Patent Grant
12114563
This application is based on and claims priority to Korean Patent Application No. 10-2020-0130411, filed on Oct. 8, 2020, in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. § 119, the entire content of which is incorporated by reference herein.
Provided is an organic light-emitting device.
Organic light-emitting devices (OLEDs) are self-emission devices that produce full-color images, and also have wide viewing angles, high contrast ratios, short response times, and excellent characteristics in terms of brightness, driving voltage, and response speed, compared to devices in the art.
In an example, an organic light-emitting device includes an anode, a cathode, and an organic layer between the anode and the cathode, wherein the organic layer includes an emission layer. A hole transport region may be located between the anode and the emission layer, and an electron transport region may be located between the emission layer and the cathode. Holes provided from the anode may move toward the emission layer through the hole transport region, and electrons provided from the cathode may move toward the emission layer through the electron transport region. The holes and the electrons recombine in the emission layer to produce excitons. These excitons transit from an excited state to a ground state to thereby generate light.
Provided is an organic light-emitting device with low driving voltage, high efficiency, and long lifespan.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.
According to an aspect, provided is an organic light-emitting device including a first electrode, a second electrode facing the first electrode, and an organic layer located between the first electrode and the second electrode and including an emission layer, wherein the emission layer includes a host compound, a first dopant compound, and a second dopant compound, and the second dopant compound is represented by Formula 1 below.
A-(Ar1)n11 Formula 1
wherein, in Formula 1,
According to an aspect, provided is an electronic apparatus including the organic light-emitting device.
The above and other aspects, features, and advantages of certain embodiments of the disclosure will be more apparent from the following description taken in conjunction with the accompanying drawing, in which
FIGURE is a cross-sectional view schematically illustrating an organic light-emitting device according to an embodiment.
Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout the specification. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the figures, to explain aspects. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list. Throughout the disclosure, the expression “at least one of a, b, or c” indicates only a, only b, only c, both a and b, both a and c, both b and c, all of a, b, and c, or variations thereof.
It will be understood that when an element is referred to as being “on” another element, it can be directly in contact with the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
It will be understood that, although the terms first, second, third etc. may be used herein to describe various elements, components, regions, layers, and/or sections, these elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of the present embodiments.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The term “or” means “and/or.” It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this general inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
“About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ±20%, 10%, 5% of the stated value.
In any formula, * and *′ each indicate a binding site to a neighboring atom or a neighboring functional group.
According to an aspect, provided is an organic light-emitting device including: a first electrode; a second electrode facing the first electrode; and an organic layer located between the first electrode and the second electrode and including an emission layer, wherein the emission layer includes a host compound, a first dopant compound, and a second dopant compound, and the second dopant compound is represented by Formula 1 below.
A-(Ar1)n11 Formula 1
In Formula 1, Ar1 may be a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group.
In an embodiment, Ar1 may be: a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a phenyl group, a biphenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an isoindolyl group, an indolyl group, an indazolyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a phenanthrolinyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzoisothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, a triazinyl group, a dibenzofuranyl group, a dibenzothiophenyl group, or a carbazolyl group;
In an embodiment, Ar1 may be:
In an embodiment, Ar1 may be a group of Formulae 3-1 to 3-78, but embodiments of the present disclosure are not limited thereto:
In Formula 1, n11 may be an integer of 4 or more, Ar1(s) in the number of n11 may be identical to or different from each other.
In an embodiment, Ar1(s) in the number of n11 may be identical to each other.
M in Formula 1-1 may be B, Al, Si(R1), Ge(R1), P, P(═O), or P(═S).
In an embodiment, M may be B, Al, Si(R1), P, or P(═O), but embodiments of the present disclosure are not limited thereto.
In an embodiment, M may be B.
In Formula 1-1, ring CY1 to ring CY5 may each independently be a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
In an embodiment, ring CY1 to ring CY5 may each independently be a first ring, a second ring, a condensed ring in which two or more groups selected from the first ring are condensed with each other, a condensed ring in which two or more groups selected from the second ring are condensed with each other, or a condensed ring in which at least one first ring and at least one second ring are condensed with each other, but embodiments of the present disclosure are not limited thereto.
The first ring may be a cyclopenta-1,3-diene group, an indene group, an azulene group, a phenyl group, a naphthalene group, an anthracene group, a phenanthrene group, a tetracene group, a tetraphene group, a pyrene group, a chrysene group, a triphenylene group, or a fluorene group, and
In an embodiment, ring CY1 to ring CY5 may each independently be a phenyl group, a naphthalene group, an anthracene group, a fluorene group, a pyridine group, a pyrimidine group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, or a dibenzosilole group.
In Formula 1-1, Ra and R1 to R5 may each independently be a binding site to Ar1 in Formula 1, hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C2-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryl alkyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted C1-C60 heteroalkyl aryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —B(Q6)(Q7), or —P(═O)(Q8)(Q9).
In an embodiment, Ra and R1 to R5 may each independently be:
In an embodiment, Ra may be: hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group (CN), a nitro group, an amino group, a C1-C60 alkyl group, a C1-C60 alkylthio group, or a C1-C60 alkoxy group; a C1-C60 alkyl group, a C1-C60 alkylthio group, or a C1-C60 alkoxy group, each independently substituted with at least one of deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group (CN), a nitro group, an amino group, a phenyl group, or a biphenyl group.
In an embodiment, when at least one group of R1(s) in the number of a1 may be a binding site to Ar1 in Formula 1, the remaining R1 groups may each be hydrogen.
In an embodiment, when at least one group of R2(s) in the number of a2 may be a binding site to Ar1 in Formula 1, the remaining R2 groups may each be hydrogen.
In an embodiment, when at least one group of R3(s) in the number of a3 may be a binding site to Ar1 in Formula 1, the remaining R3 groups may each be hydrogen.
In an embodiment, when at least one group of R4(s) in the number of a4 may be a binding site to Ar1 in Formula 1, the remaining R4 groups may each be hydrogen.
In an embodiment, when at least one group of R5(s) in the number of a5 may be a binding site to Ar1 in Formula 1, the remaining R5 groups may each be hydrogen.
In Formula 1-1, a1 to a5 may each independently an integer from 1 to 10. Here, a1 may indicate the number of R1 groups, wherein, when a1 is an integer of 2 or more, two or more of R1(s) may be identical to or different from each other, a2 may indicate the number of R2 groups, wherein, when a2 is an integer of 2 or more, two or more of R2(s) may be identical to or different from each other, a3 may indicate the number of R3 groups, wherein, when a3 is an integer of 2 or more, two or more of R3(s) may be identical to or different from each other, a4 may indicate the number of R4 groups, wherein, when a4 is an integer of 2 or more, two or more of R4(s) may be identical to or different from each other, and a5 may indicate the number of R5 groups, wherein, when a5 is an integer of 2 or more, two or more of R5(s) may be identical to or different from each other.
In Formula 1-1, two neighboring groups of R1 to R5 may optionally linked to each other to thereby form a C5-C30 carbocyclic group unsubstituted or substituted with R10 a C1-C30 heterocyclic group unsubstituted or substituted with R10. In this regard, R10 is the same as described in connection with R1.
In an embodiment, Formula 1 may be represented by Formula 1-2:
In Formula 1-2,
In an embodiment, when b1 is 2 or more, two or more of Ar11(s) may be identical to or different from each other, when b2 is 2 or more, two or more of Ar12(s) may be identical to or different from each other, when b3 is 2 or more, two or more of Ar13(s) may be identical to or different from each other, when b4 is 2 or more, two or more of Ar14(s) may be identical to or different from each other, and when b5 is 2 or more, two or more of Ar15(s) may be identical to or different from each other.
In an embodiment, when b1 is 0, Ar11 does not exist, when b2 is 0, Ar12 does not exist, when b3 is 0, Ar13 does not exist, when b4 is 0, Ar14 does not exist, and when b5 is 0, Ar15 does not exist.
In an embodiment, in Formula 1-2, Ar11(s) in the number of b1, Ar12(s) in the number of b2, Ar13(s) in the number of b3, Ar14(s) in the number of b4, and Ar15(s) in the number of b5 may be identical to each other.
In an embodiment, in Formula 1-2,
In an embodiment, the second dopant compound may be Compounds 1 to 229:
wherein in the formulae Ph is a phenyl group.
While not wishing to be bound by theory, it is understood that because the second dopant compound represented by Formula 1 includes four or more substituents (Ar1) which are substituted on a central condensed ring core (A), stability of a molecule is improved, and thus, an organic light-emitting device including the second dopant compound represented by Formula 1 has an improved lifespan characteristics
While not wishing to be bound by theory, it is understood that because the organic light-emitting device includes the emission layer including a host compound and a first dopant compound together with the second dopant compound represented by Formula 1, a decrease in efficiency according to triplet-triplet annihilation may be easily prevented, and because excitons are transferred to the light-emitting dopant without loss of excitons through a Forster resonance energy transfer (FRET) mechanism and a dexter energy transfer (DET) mechanism, efficiency may be improved.
A highest occupied molecular orbital (HOMO) energy level, a lowest unoccupied molecular orbital (LUMO) energy level, a S1 energy level, and a T1 energy level of the exemplary second dopant compound represented by Formula 1 are evaluated using Gaussian 09 program with molecular structure optimization by density functional theory (DFT) based on B3LYP, and results thereof are shown in Table 1 below.
Referring to Table 1, it is confirmed that the second dopant compound represented by Formula 1 has electric characteristics that are suitable for use as a light-emitting dopant for an electronic device, for example, an organic light-emitting device.
Synthesis method of the second dopant compound represented by Formula 1 may be recognized by those skilled in the art with reference to the following Synthesis Examples.
In an embodiment, the host may consist of one kind of host. When the host consists of one kind of host, the one kind of host may be a bipolar host, an electron transport host, or a hole transport host, which will be described later.
In an embodiment, the host compound included in the emission layer may include two different compounds.
In an embodiment, the host compound included in the emission layer may include a common host forming an exciplex.
In an embodiment, the host compound may include a hole transport host compound and an electron transport host compound, but embodiments of the present disclosure are not limited thereto. The electron transport host compound and a hole transport host may be understood by referring to the related description to be presented later.
In an embodiment, the host may include an electron transport host including at least one electron transport moiety and a hole transport host that does not include an electron transport moiety.
The electron transport moiety used herein may be a cyano group, a π-electron-deficient nitrogen-containing cyclic group, or a group represented by one of the following formulae:
In the formulae, *, *′, and *″ are each binding sites to neighboring atoms.
In an embodiment, the electron transport host in the emission layer may include at least one of a cyano group and a π-electron-deficient nitrogen-containing cyclic group.
In an embodiment, the electron transport host in the emission layer may include at least one cyano group.
In an embodiment, the electron transport host in the emission layer may include at least one cyano group and at least one π-electron-deficient nitrogen-containing cyclic group.
In an embodiment, the host may include an electron transport host and a hole transport host, wherein the electron transport host may include at least one π-electron-deficient nitrogen-free cyclic group and at least one electron transport moiety, and the hole transport host may include at least one π-electron-deficient nitrogen-free cyclic group and may not include an electron transport moiety.
In the present specification, the term “π-electron-deficient nitrogen-containing cyclic group” refers to a cyclic group having at least one *—N═*′ moiety, and for example, may be: an imidazole group, a pyrazole group, a thiazole group, an isothiazole group, an oxazole group, an isoxazole group, a pyridine group, a pyrazine group, a pyridazine group, a pyrimidine group, an indazole group, a purine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a phthalazine group, a naphthyridine group, a quinoxaline group, a quinazoline group, a cinnoline group, a phenanthridine group, an acridine group, a phenanthroline group, a phenazine group, a benzimidazole group, an isobenzothiazole group, a benzoxazole group, a benzoisoxazole group, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, a thiadiazole group, an imidazopyridine group, an imidazopyrimidine group, and an azacarbazole group; or a condensed cyclic group of two or more π-electron-deficient nitrogen-containing cyclic groups.
In an embodiment, the π-electron-deficient nitrogen-free cyclic group may be a phenyl group, a heptalene group, an indene group, a naphthalene group, an azulene group, an indacene group, an acenaphthylene group, a fluorene group, a spiro-bifluorene group, a benzofluorene group, a dibenzofluorene group, a phenalene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a naphthacene group, a picene group, a perylene group, a pentacene group, a hexacene group, a pentacene group, a rubicene group, a coronene group, an ovalene group, a pyrrole group, an isoindole group, an indole group, a furan group, a thiophene group, a benzofuran group, a benzothiophene group, a benzocarbazole group, a dibenzocarbazole group, a dibenzofuran group, a dibenzothiophene group, a dibenzothiophene sulfone group, a carbazole group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, and a triindolobenzene group; or a condensed cyclic of two or more π-electron-deficient nitrogen-free cyclic group, but embodiments of the present disclosure are not limited thereto.
In an embodiment, the electron transport host may be compounds represented by Formula E-1 below, and
Condition 3:
In an embodiment, at least one of A21 and A22 in Formula 12 is not a single bond.
In an embodiment, in Formula E-1, Ar301 and L301 may each independently be a phenyl group, a naphthalene group, a fluorene group, a spiro-bifluorene group, a benzofluorene group, a dibenzofluorene group, a phenalene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a naphthacene group, a picene group, a perylene group, a pentaphene group, an indenoanthracene group, a dibenzofuran group, a dibenzothiophene group, an imidazole group, a pyrazole group, a thiazole group, an isothiazole group, an oxazole group, an isoxazole group, a pyridine group, a pyrazine group, a pyridazine group, a pyrimidine group, an indazole group, a purine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a phthalazine group, a naphthyridine group, a quinoxaline group, a quinazoline group, a cinnoline group, a phenanthridine group, an acridine group, a phenanthroline group, a phenazine group, a benzimidazole group, an isobenzothiazole group, a benzoxazole group, an isobenzoxazole group, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, a thiadiazole group, an imidazopyridine group, an imidazopyrimidine group, or an azacarbazole group, each independently unsubstituted or substituted with at least one deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazine group, a hydrazone group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a cyano-containing phenyl group, a cyano-containing biphenyl group, a cyano-containing terphenyl group, a cyano-containing naphthyl group, a pyridinyl group, a phenylpyridinyl group, a diphenylpyridinyl group, a biphenylpyridinyl group, a di(biphenyl)pyridinyl group, a pyrazinyl group, a phenylpyrazinyl group, a diphenylpyrazinyl group, a biphenylpyrazinyl group, a di(biphenyl)pyrazinyl group, a pyridazinyl group, a phenylpyridazinyl group, a diphenylpyridazinyl group, a biphenylpyridazinyl group, a di(biphenyl)pyridazinyl group, a pyrimidinyl group, a phenylpyrimidinyl group, a diphenylpyrimidinyl group, a biphenylpyrimidinyl group, a di(biphenyl)pyrimidinyl group, a triazinyl group, a phenyltriazinyl group, a diphenyltriazinyl group, a biphenyltriazinyl group, a di(biphenyl)triazinyl group, —Si(Q31)(Q32)(Q33), —N(Q31)(Q32), —B(Q31)(Q32), —C(═O)(Q31), —S(═O)2(Q31), or —P(═O)(Q31)(Q32),
In an embodiment,
In Formulae 5-1 to 5-3 and 6-1 to 6-33,
Q31 to Q33 are the same as described above.
In an embodiment, L301 may be groups represented by Formulae 5-2, 5-3, or 6-8 to 6-33.
In an embodiment, R301 may be a cyano group and groups represented by Formulae 7-1 to 7-18, or at least one of Ar402(s) in the number of xd11 may be groups represented by Formulae 7-1 to 7-18, but embodiments of the present disclosure are not limited thereto:
In Formulae 7-1 to 7-18,
In an embodiment, at least one of the following conditions is satisfied:
Two or more of Ar301(s) in Formula E-1 may be identical to or different from each other, two or more of L301(s) in Formula E-1 may be identical to or different from each other, two or more of L401(s) in Formula H-1 may be identical to or different from each other, and two or more of Ar402(s) in Formula H-1 may be identical to or different from each other.
In an embodiment, the electron transport host may include i) at least one of a cyano group, a pyrimidine group, a pyrazine group, and a triazine group and ii) a triphenylene group, and the hole transport host may include a carbazole group.
In an embodiment, the electron transport host may include at least one cyano group.
The electron transport host may be, for example, a compound of Groups HE1 to HE7, but embodiments of the present disclosure are not limited thereto:
In an embodiment, the hole transport host may be Compounds H-H1 to H-H104, but embodiments of the present disclosure are not limited thereto:
In an embodiment, the bipolar host may be the following Group HEH1, but embodiments of the present disclosure are not limited thereto:
In Compound 1 to 432,
Ph is a phenyl group.
When the host is a mixture of an electron transport host and a hole transport host, the weight ratio of the electron transport host to the hole transport host may be 1:9 to 9:1, for example, 2:8 to 8:2, for example, 4:6 to 6:4, for example, 5:5. When the weight ratio of the electron transport host to the hole transport host satisfies the above-described ranges, the hole-and-electron transport balance in the emission layer may be achieved.
In an embodiment, the host may include at least one of TPBi, TBADN, ADN (also referred to as “DNA”), CBP, CDBP, TCP, mCP, or Compounds H50 to H52:
In an embodiment, the host may further include a compound represented by Formula 301 below:
In Formula 301, Ar111 and Ar112 may each independently be:
Ar113 to Ar116 in Formula 301 may each independently be:
g, h, i, and j in Formula 301 may each independently be an integer from 0 to 4, for example, 0, 1, or 2.
In Formula 301, Ar113 to Ar116 may each independently be:
In an embodiment, the host may include a compound represented by Formula 302:
Detailed descriptions of Ar122 to Ar125 in Formula 302 are the same as described in connection with Ar113 in Formula 301.
Ar126 and Ar127 in Formula 302 may each independently be a C1-C10 alkyl group (for example, a methyl group, an ethyl group, or a propyl group).
k and l in Formula 302 may each independently be an integer from 0 to 4. In an embodiment, k and l may be 0, 1, or 2.
When the organic light-emitting device is a full-color organic light-emitting device, emission layer may be patterned into a red emission layer, a green emission layer, and a blue emission layer. In an embodiment, the emission layer may have a structure in which the red emission layer, the green emission layer, and/or the blue emission layer are stacked, the emission layer may emit white light, and various modifications are possible.
When the emission layer includes a host and a light-emitting dopant, an amount of the light-emitting dopant may be from about 0.01 parts by weight to about 15 parts by weight based on about 100 parts by weight of the host, for example, about 0.01 parts by weight to about 12 parts by weight, about 0.01 parts by weight to about 10 parts by weight, about 0.01 parts by weight to about 8 parts by weight, about 0.01 parts by weight to about 6 parts by weight, about 0.01 parts by weight to about 4 parts by weight, or about 0.01 parts by weight to about 2 parts by weight based on 100 parts by weight of the host, but embodiments of the present disclosure are not limited thereto.
A thickness of the emission layer may be in a range of about 100 Å to about 1,000 Å, for example, about 200 Å to about 600 Å, for example, about 100 Å to about 800 Å, about 200 Å to about 600 Å, or about 300 Å to about 400 Å. When the thickness of the emission layer is within these ranges, improved light-emission characteristics may be obtained without a substantial increase in driving voltage.
In the emission layer of the organic light-emitting device, the first dopant compound may include an organometallic compound including a transition metal.
The first dopant compound may include a polycyclic compound represented by Formula 1.
In an embodiment, the first dopant compound may include an organometallic compound including at least one a first-row transition metal of the Periodic Table of Elements, a second-row transition metal of the Periodic Table of Elements, or a third-row transition metal of the Periodic Table of Elements.
In an embodiment, the first dopant compound may include an organic ligand (L1) and at least one metal (M11) a first-row transition metal of the Periodic Table of Elements, a second-row transition metal of the Periodic Table of Elements, or a third-row transition metal of the Periodic Table of Elements, and L1 and M11 may form one cyclometallated ring, two cyclometallated rings, three cyclometallated rings, or four cyclometallated rings.
In an embodiment, the first dopant compound may include an organometallic compound represented by Formula 101 below:
M11(L1)n1(L2)n2 Formula 101
In Formula 101,
In an embodiment, the first dopant compound may be Groups I to VI, but embodiments of the present disclosure are not limited thereto:
Group V
A compound represented by the following Formula A:
(L101)n101-M101-(L102)m101 Formula A
In Formula A, L101, n101, M101, L102, and m101 are the same as described in Tables 2 to 4:
In Tables 2 to 4, LM1 to LM243, LFM1 to LFM7 and LFP1 to LFP7 may be understood by referring to Formulae 11-1 to 11-3 and Tables 5 to 7:
X1 to X10 and Y1 to Y18 in Tables 5 to 7 are the same as described below, and Ph in the tables refers to a phenyl group:
In an embodiment, the first dopant compound may be a thermally activated delayed fluorescence (TADF) emitter satisfying the following Condition 7:
ΔEST≤0.3 eV Condition 7
In Condition 7,
ΔEST is a difference between a lowest excited singlet energy level of the first dopant compound and a lowest excited triplet energy level of the first dopant compound.
In an embodiment, the first dopant compound may include a thermally activated delayed fluorescence emitter represented by Formula 201 or 202:
In Formulae 201 and 202,
In an embodiment, in Formulae 201 and 202, A21 may be a substituted unsubstituted π-electron-deficient nitrogen-free cyclic group.
In an embodiment, the π-electron-deficient nitrogen-free cyclic group may be a phenyl group, a heptalene group, an indene group, a naphthalene group, an azulene group, an indacene group, an acenaphthylene group, a fluorene group, a spiro-bifluorene group, a benzofluorene group, a dibenzofluorene group, a phenalene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a naphthacene group, a picene group, a perylene group, a pentacene group, a hexacene group, a pentacene group, a rubicene group, a coronene group, an ovalene group, a pyrrole group, an isoindole group, an indole group, a furan group, a thiophene group, a benzofuran group, a benzothiophene group, a benzocarbazole group, a dibenzocarbazole group, a dibenzofuran group, a dibenzothiophene group, a dibenzothiophene sulfone group, a carbazole group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, or a triindolobenzene group; or a condensed cyclic of two or more π-electron-deficient nitrogen-free cyclic group, but embodiments of the present disclosure are not limited thereto.
In an embodiment, in Formulae 201 and 202, D21 may be: —F, a cyano group, or a π-electron-deficient nitrogen-containing cyclic group;
In an embodiment, the π-electron-deficient nitrogen-free cyclic group is the same as described above.
In an embodiment, the π-electron-deficient nitrogen-containing cyclic group may be a cyclic group having at least one *—N═*′ moiety, or for example, may be an imidazole group, a pyrazole group, a thiazole group, an isothiazole group, an oxazole group, an isoxazole group, a pyridine group, a pyrazine group, a pyridazine group, a pyrimidine group, an indazole group, a purine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a phthalazine group, a naphthyridine group, a quinoxaline group, a quinazoline group, a cinnoline group, a phenanthridine group, an acridine group, a phenanthroline group, a phenazine group, a benzimidazole group, an isobenzothiazole group, a benzoxazole group, a benzoisoxazole group, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, a thiadiazole group, an imidazopyridine group, an imidazopyrimidine group, an azacarbazole group, or a benzimidazolobenzimidazole group; or a condensed cyclic of two or more π-electron-deficient nitrogen-containing cyclic groups.
In an embodiment, the first dopant compound may be a compound of one of Groups VII to XI, but embodiments of the present disclosure are not limited thereto:
In an embodiment, the first electrode may be an anode, which is a hole injection electrode, and the second electrode may be a cathode, which is an electron injection electrode, or the first electrode may be a cathode, which is an electron injection electrode, and the second electrode may be an anode, which is a hole injection electrode.
In an embodiment, in the organic light-emitting device, the first electrode may be an anode, the second electrode may be a cathode, the organic layer may further include a hole transport region between the first electrode and the emission layer and an electron transport region between the emission layer and the second electrode, the hole transport region may include a hole injection layer, a hole transport layer, an electron blocking layer, a buffer layer, or any combination thereof, and the electron transport region may include a hole blocking layer, an electron transport layer, an electron injection layer, or any combination thereof.
The term “organic layer” used herein refers to a single layer and/or a plurality of layers between the first electrode and the second electrode of the organic light-emitting device. The “organic layer” may include, in addition to an organic compound, an organometallic complex including metal.
The term “sensitizer” used herein refers to a compound that is included in an organic layer (for example, an emission layer) and may deliver excitation energy to a light-emitting dopant compound.
OLED System
An organic light-emitting device according to an embodiment of the present disclosure may include an emission layer including a host compound, a first dopant compound, and a second dopant compound. An amount of the host in the emission layer may be greater than an amount of the dopant. In an embodiment, an amount of the host may be greater than a total amount of a first dopant and a second dopant.
An organic light-emitting device according to an embodiment of the present disclosure may include an emission layer including a host, a sensitizer, and a light-emitting dopant. In an embodiment, at least one of the first dopant compound and the second dopant compound may be a sensitizer, and the other may be a light-emitting dopant.
In an embodiment, the second dopant compound may include a compound having an energy relationship suitable for transferring excited singlet and/or excited triplet energy to the first dopant compound in a relationship with the first dopant compound.
In an embodiment, the sensitizer may include the second dopant, and the light-emitting dopant may be the organometallic compound.
Singlet excitons and triplet excitons of the second dopant compound may be respectively delivered to the excited singlet and excited triplet energy levels of the organometallic compound through a FRET mechanism and a DET mechanism, and triplet excitons of a phosphorescent dopant exhibit phosphorescent emission.
In an embodiment, the sensitizer may include the second dopant compound represented by Formula 1, and the light-emitting dopant may include a thermally activated delayed fluorescence (TADF) compound.
The singlet excitons and triplet excitons of the second dopant compound may be respectively delivered to the excited singlet and excited triplet energy levels of the first dopant compound through a FRET mechanism and a DET mechanism, and triplet excitons in the TADF compound may be converted to singlet excitons by reverse inter system crossing (RISC), and accumulated singlet excitons may be sequentially transitioned to a ground state, thereby exhibiting fluorescence.
In an embodiment, the sensitizer may include the second dopant compound represented by Formula 1, wherein the second dopant compound may be a TADF compound, and the light-emitting dopant may include the organometallic compound or a TADF compound.
In the TADF second dopant compound, triplet excitons are converted into singlet excitons by RISC, and at the same time, energy transfer to the light-emitting dopant by FRET and DET mechanisms may occur.
Since the sensitizer contains the second dopant compound represented by Formula 1, the triplet-triplet annihilation of the triplet excitons may be suppressed and the luminescence efficiency of the light-emitting dopant may be improved.
In an embodiment, the light-emitting dopant may include the second dopant compound represented by Formula 1, and the sensitizer may include the TADF compound or the organometallic compound. However, embodiments of the present disclosure are not limited thereto. Any suitable compound having an energy relationship in which excitons may be transferred to the second dopant compound may be included.
Excitons formed in the sensitizer are transferred to a light-emitting dopant compound through a DET mechanism or a FRET mechanism, and exciton energy transferred to the light-emitting dopant compound may emit light while being transitioned to a ground state.
In an embodiment, the excitons of the sensitizer may be formed by the FRET mechanism from the host compound, or may be formed by the delivery of excitons generated from the host by the DET mechanism.
In an embodiment, the sensitizer may be a TADF compound.
In addition, the sensitizer may satisfy Equation 1 below:
ΔEST≤0.3 eV Equation 1
In an embodiment, ΔEST refers to an energy difference between the lowest excited singlet (S1) and the lowest excited triplet (T1).
The TADF compound may include singlet excitons and triplet excitons, and triplet excitons may be transferred to singlet excitons by RISC, and the singlet excitons accumulated in the excited singlet of the sensitizer may be energy-transitioned to the polycyclic compound by FRET and/or DET.
In an embodiment, the sensitizer may be the organometallic compound. In an embodiment, the sensitizer may be an organometallic compound including Pt as a central metal, but embodiments of the present disclosure are not limited thereto.
The organometallic compound may include singlet excitons and triplet excitons, and triplet excitons may be energy-transitioned to the excited triplet energy of the second dopant compound by the DET mechanism.
The organometallic compound may satisfy Equation 1 above, and when Equation 1 is satisfied, excitons may be delivered to the excited singlet and excited triplet energy levels of the second dopant compound by a mechanism similar to the TADF compound, that is, the FRET and/or DET mechanism.
In an embodiment, the excited singlet energy level and the excited triplet energy level of the sensitizer may be lower than the excited singlet energy and excited triplet energy of the host. Accordingly, excited singlet and triplet energy transfer from the host to the sensitizer may easily occur.
In an embodiment, the sensitizer and the light-emitting dopant may each independently include the second dopant compound represented by Formula 1.
In an embodiment, energy transfer between the sensitizer and the light-emitting dopant may be facilitated by FRET and DET mechanisms, and it is easy to manufacture a high-efficiency organic light-emitting device by suppressing triplet-triplet annihilation.
In general, it is known that since triplet excitons stay long in an excited state, they influence the decrease in the lifespan of organic light-emitting devices. While not wishing to be bound by theory, it is understood that due to the use of the second dopant compound, the time during which the sensitizer stays in the triplet excitons is reduced, and thus, the lifespan of an organic light-emitting device including the same may be improved.
In an embodiment, the second dopant compound may be a material capable of emitting fluorescent light. An emission layer emitting the fluorescent light may be clearly distinguished from an emission layer of the related art that emits phosphorescent light.
In an embodiment, the second dopant compound may emit TADF light.
The excited singlet and excited triplet energy levels of the second dopant compound may be lower than the excited singlet and excited triplet energy levels of the host compound described later. In an embodiment, singlet excitons and/or triplet excitons may be easily transitioned from the host compound to the second dopant compound.
The second dopant compound may receive singlet excitons and/or triplet excitons from the sensitizer.
In an embodiment, when the sensitizer is a TADF compound, the excited singlet energy level of the second dopant compound is lower than the excited singlet energy level of the sensitizer, and the second dopant compound may receive singlet excitons from the excited singlet of the sensitizer by the FRET and/or DET mechanism.
In an embodiment, when the sensitizer may be an organometallic compound, the excited triplet energy level of the second dopant compound may be lower than the excited triplet level of the sensitizer, and the second dopant compound may receive triplet excitons from the sensitizer by DET mechanism.
In an embodiment, when the sensitizer may be a TADF compound or an organometallic compound, the second dopant compound may further receive singlet excitons and/or triplet excitons from the host, and the triplet excitons received from the host may be transitioned to singlet energy of the second dopant compound by RISC.
While not wishing to be bound by theory, it is understood that due to this mechanism, triplet-triplet annihilation may be suppressed by reducing the time during which excitons stay in the excited triplet energy of the second dopant compound, and high-efficiency fluorescent light emission may be realized through the transition of multiple singlet excitons to the ground state.
An amount of the sensitizer in the emission layer may be from about 5 weight percentage (wt %) to less than about 50 wt %, for example, from about 5 wt % to about 40 wt %, from about 5 wt % to about 30 wt %, from about 5 wt % to about 20 wt %, from about 5 wt % to about 10 wt %, from about 10 wt % to about 50 wt %, from about 15 wt % to about 50 wt %, from about 20 wt % to about 50 wt %, from about 25 wt % to about 50 wt %, from about 30 wt % to about 50 wt %, from about 35 wt % to about 50 wt %, from about 40 wt % to about 50 wt %, or from about 45 wt % to about 50 wt %. Within these ranges, it is possible to achieve effective energy transfer in the emission layer, and accordingly, an organic light-emitting device having high efficiency and long lifespan may be obtained.
In an embodiment, the host, the first dopant compound, and the second dopant compound may satisfy the following Equation 2:
T1(H)/S1(H)≥T1(1D)/S1(1D)≥T1(2D)/S1(2D) Equation 2
In Equation 2,
While not wishing to be bound by theory, it is understood that when the host, the first dopant compound, and the second dopant compound further satisfy Equation 2 above, triplet excitons may be effectively transferred from the emission layer to the second dopant compound, and thus an organic light-emitting device having improved efficiency may be obtained.
A thickness of the emission layer may be in a range of about 100 Å to about 1,000 Å, for example, about 100 Å to about 600 Å, about 200 Å to about 600 Å, about 300 Å to about 500 Å, about 400 Å to about 800 Å, or about 500 Å to about 900 Å. When the thickness of the emission layer is within these ranges, improved light-emission characteristics may be obtained without a substantial increase in driving voltage.
Hereinafter, a configuration of an organic light-emitting device excluding an emission layer will be described with reference to FIGURE.
FIGURE is a schematic cross-sectional view of an organic light-emitting device 10 according to an embodiment. Hereinafter, a structure and a manufacturing method of an organic light-emitting device according to an embodiment of the present disclosure will be described with reference to FIGURE.
The organic light-emitting device 10 of FIGURE includes a first electrode 11, a second electrode 19 facing the first electrode 11, and an organic layer 10A between the first electrode 11 and the second electrode 19.
The organic layer 10A includes an emission layer 15, a hole transport region 12 is located between the first electrode 11 and the emission layer 15, and an electron transport region 17 is located between the emission layer 15 and the second electrode 19.
A substrate may be additionally located under the first electrode 11 or above the second electrode 19. For use as the substrate, any suitable substrate that is used in general organic light-emitting devices may be used, and the substrate may be a glass substrate or a transparent plastic substrate, each having suitable mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance.
First Electrode 11
In an embodiment, the first electrode 11 may be formed by depositing or sputtering a material for forming the first electrode 11 on the substrate. The first electrode 11 may be an anode. The material for forming the first electrode 11 may be materials with a suitable work function to facilitate hole injection. The first electrode 11 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. For use as the material for forming the first electrode 11, Indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), or zinc oxide (ZnO) may be used. In an embodiment, metals such as magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), or magnesium-silver (Mg—Ag) may be used.
The first electrode 11 may have a single-layered structure or a multi-layered structure including two or more layers. In an embodiment, the first electrode 11 may have a three-layered structure of ITO/Ag/ITO, but embodiments of the present disclosure are not limited thereto.
The organic layer 10A may be located on the first electrode 11.
The organic layer 10A may include: the hole transport region 12; the emission layer 15; and the electron transport region 17.
Hole Transport Region 12
In the organic light-emitting device 10, the hole transport region 12 may be located between the first electrode 11 and the emission layer 15.
The hole transport region 12 may have a single-layered structure or a multi-layered structure.
In an embodiment, the hole transport region 12 may have a hole injection layer, a hole transport layer, a hole injection layer/hole transport layer structure, a hole injection layer/first hole transport layer/second hole transport layer structure, a hole transport layer/interlayer structure, a hole injection layer/hole transport layer/interlayer structure, a hole transport layer/electron blocking layer structure, or a hole injection layer/hole transport layer/electron blocking layer structure, but embodiments of the present disclosure are not limited thereto.
The hole transport region 12 may include any suitable compound that has hole transportation characteristics.
In an embodiment, the hole transport region 12 may include an amine-based compound.
In an embodiment, the hole transport region 12 may include at least one a compound represented by Formula 201 to a compound represented by Formula 205, but embodiments of the present disclosure are not limited thereto:
In Formulae 201 to 205,
L201 to L209 may each independently be *—O—*′, *—S—*′, a substituted or unsubstituted C5-C60 carbocyclic group, or a substituted or unsubstituted C1-C60 heterocyclic group,
xa1 to xa9 may each independently an integer from 0 to 5, and
R201 to R206 may each independently be a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C6-C60 aryl alkyl group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted C1-C60 heteroalkyl aryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, and two neighboring groups of R201 to R206 may optionally be linked to each other via a single bond, a dimethyl-methylene group, or a diphenyl-methylene group.
In an embodiment,
In an embodiment, the hole transport region 12 may include a carbazole-containing amine-based compound.
In one or more embodiments, the hole transport region 12 may include a carbazole-containing amine-based compound and a carbazole-free amine-based compound.
The carbazole-containing amine-based compound may be, for example, compounds represented by Formula 201 including a carbazole group and further including at least one of a dibenzofuran group, a dibenzothiophene group, a fluorene group, a spiro-bifluorene group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, or a benzothienocarbazole group.
The carbazole-free amine-based compound may be, for example, compounds represented by Formula 201 that do not include a carbazole group and that include at least one of a dibenzofuran group, a dibenzothiophene group, a fluorene group, a spiro-bifluorene group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, or a benzothienocarbazole group.
In an embodiment, the hole transport region 12 may include at least one compounds represented by Formulae 201 or 202.
In an embodiment, the hole transport region 12 may include at least one compound represented by Formulae 201-1, 202-1, or 201-2, but embodiments of the present disclosure are not limited thereto:
In Formulae 201-1, 202-1, and 201-2, L201 to L203, L205, xa1 to xa3, xa5, R201, and R202 are the same as described herein, and R211 to R213 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazine group, a hydrazone group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a phenyl group, a biphenyl group, a terphenyl group, a phenyl group substituted with a C1-C10 alkyl group, a phenyl group substituted with —F, a naphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a dimethylfluorenyl group, a diphenyl fluorenyl group, a triphenylenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, or a pyridinyl group.
In an embodiment, the hole transport region 12 may include at least one Compounds HT1 to HT39, but embodiments of the present disclosure are not limited thereto.
In an embodiment, the hole transport region 12 of the organic light-emitting device 10 may further include a p-dopant. When the hole transport region 12 further includes a p-dopant, the hole transport region 12 may have a structure including a matrix (for example, at least one of compounds represented by Formulae 201 to 205) and a p-dopant included in the matrix. The p-dopant may be uniformly or non-uniformly doped in the hole transport region 12.
In an embodiment, a LUMO energy level of the p-dopant may be −3.5 electronvolt (eV) or less.
The p-dopant may include at least one a quinone derivative, a metal oxide, or a cyano group-containing compound, but embodiments of the present disclosure are not limited thereto.
In an embodiment, the p-dopant may include at least one:
In Formula 221,
The hole transport region 12 may have a thickness of about 100 Å to about 10,000 Å, for example, about 200 Å to about 1000 Å, about 400 Å to about 2,000 Å, about 500 Å to about 3000 Å, about 600 Å to about 4000 Å, about 700 Å to about 5000 Å, about 800 Å to about 6000 Å, about 900 Å to about 7000 Å, about 1000 Å to about 8000 Å, or about 2000 Å to about 9000 Å, and the emission layer 15 may have a thickness of about 100 Å to about 3,000 Å, for example, about 100 Å to about 500 Å, about 300 Å to about 1,000 Å, about 400 Å to about 1500 Å, about 500 Å to about 2000 Å, or about 600 Å to about 2500 Å. When the thickness of each of the hole transport region 12 and the emission layer 15 is within these ranges described above, satisfactory hole transportation characteristics and/or luminescence characteristics may be obtained without a substantial increase in driving voltage.
Emission Layer 15
The emission layer is the same as described in above.
In an embodiment, the emission layer may emit blue light, for example, blue light having a maximum emission wavelength of 450 or more (for example, 450 nanometers (nm) or more and 500 nm or less).
Electron Transport Region 17
Next, an electron transport region is located on the emission layer.
The electron transport region 17 may be located between the emission layer 15 and the second electrode 19 of the organic light-emitting device 10.
The electron transport region 17 may have a single-layered structure or a multi-layered structure.
In an embodiment, the electron transport region 17 may have an electron transport layer, an electron transport layer/electron injection layer structure, a buffer layer/electron transport layer structure, a hole blocking layer/electron transport layer structure, a buffer layer/electron transport layer/electron injection layer structure, or a hole blocking layer/electron transport layer/electron injection layer structure, but embodiments of the present disclosure are not limited thereto. The electron transport region 17 may further include an electron control layer.
The electron transport region 17 may include a known electron transport material.
The electron transport region (for example, a buffer layer, a hole blocking layer, an electron control layer, or an electron transport layer in the electron transport region) may include a metal-free compound containing at least one π-electron-deficient nitrogen-containing C1-C60 cyclic group. The π-electron-deficient nitrogen-containing C1-C60 cyclic group is the same as described above.
In an embodiment, the electron transport region may include a compound represented by Formula 601 below.
[Ar601]xe11-[(L601)xe1-R601]xe21 Formula 601
In Formula 601,
In an embodiment, at least one of Ar601(s) in the number of xe11 and R601(s) in the number of xe21 may include the π-electron-deficient nitrogen-containing C1-C60 cyclic group.
In an embodiment, ring Ar601 and L601 in Formula 601 may each independently be a phenyl group, a naphthalene group, a fluorene group, a spiro-bifluorene group, a benzofluorene group, a dibenzofluorene group, a phenalene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a naphthacene group, a picene group, a perylene group, a pentaphene group, an indenoanthracene group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, an imidazole group, a pyrazole group, a thiazole group, an isothiazole group, an oxazole group, an isoxazole group, a pyridine group, a pyrazine group, a pyrimidine group, a pyridazine group, an indazole group, a purine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a phthalazine group, a naphthyridine group, a quinoxaline group, a quinazoline group, a cinnoline group, a phenanthridine group, an acridine group, a phenanthroline group, a phenazine group, a benzimidazole group, an isobenzothiazole group, a benzoxazole group, a benzoisoxazole group, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, a thiadiazole group, an imidazopyridine group, an imidazopyrimidine group, or an azacarbazole group, each independently unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, —Si(Q31)(Q32)(Q33), —S(═O)2(Q31), —P(═O)(Q31)(Q32), or any combination thereof, and
When xe11 in Formula 601 is 2 or more, two or more of Ar601(s) may be linked via a single bond.
In an embodiment, Ar601 in Formula 601 may be an anthracene group.
In an embodiment, a compound represented by Formula 601 may be represented by Formula 601-1 below:
In Formula 601-1,
In an embodiment, xe1 and xe611 to xe613 in Formulae 601 and 601-1 may each independently be 0, 1, or 2.
In an embodiment, R601 and R611 to R613 in Formulae 601 and 601-1 may each independently be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, a pyridinyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a thiadiazolyl group, an oxadiazolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a benzimidazolyl group, a benzoisothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, or azacarbazolyl group, each independently unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, a pyridinyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a thiadiazolyl group, an oxadiazolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a benzimidazolyl group, a benzoisothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an azacarbazolyl group, or any combination thereof; or
The electron transport region may include at least one Compounds ET1 to ET36 below, but embodiments of the present disclosure are not limited thereto:
In an embodiment, the electron transport region may include at least one 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-dphenyl-1,10-phenanthroline (Bphen), Alq3, BAlq, 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), or NTAZ.
Thicknesses of the buffer layer, the hole blocking layer, and the electron control layer may each be in a range of about 20 Å to about 1,000 Å, for example, about 10 Å to about 100 Å, about 20 Å to about 200 Å, about 30 Å to about 300 Å, about 40 Å to about 400 Å, about 50 Å to about 500 Å, about 60 Å to about 600 Å, about 70 Å to about 700 Å, about 80 Å to about 800 Å, about 90 Å to about 900 Å, or about 100 Å to about 1000 Å. When the thicknesses of the buffer layer, the hole blocking layer, and the electron control layer are within these ranges, the electron blocking layer may have improved electron blocking characteristics or electron control characteristics without a substantial increase in driving voltage.
A thickness of the electron transport layer may be in a range of about 100 Å to about 1,000 Å, for example, about 150 Å to about 500 Å, about 200 Å to about 600 Å, about 250 Å to about 700 Å, about 300 Å to about 800 Å, about 350 Å to about 900 Å, or about 400 Å to about 1000 Å. When the thickness of the electron transport layer is within the range described above, the electron transport layer may have suitable electron transportation characteristics without a substantial increase in driving voltage.
The electron transport region 17 (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 at least one alkali metal complex or alkaline earth-metal complex. A metal ion of the alkali metal complex may be a Li ion, a Na ion, a K ion, a Rb ion, or a Cs ion, and a metal ion of the 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 alkaline earth-metal complex may be hydroxy quinoline, hydroxy isoquinoline, hydroxy benzoquinoline, hydroxy acridine, hydroxy phenanthridine, hydroxy phenyloxazole, hydroxy phenylthiazole, hydroxy diphenyloxadiazole, hydroxy diphenylthiadiazole, hydroxy phenylpyridine, hydroxy phenylbenzimidazole, hydroxy phenylbenzothiazole, bipyridine, phenanthroline, or cyclopentadiene, but embodiments of the present disclosure are not limited thereto.
In an embodiment, the metal-containing material may include a Li complex. The Li complex may include, for example, the following Compound ET-D1 (Liq) or ET-D2.
The electron transport region 17 may include an electron injection layer that facilitates the injection of electrons from the second electrode 19. The electron injection layer may be in direct contact with the second electrode 19.
The electron injection layer may have i) a single-layered structure including a single layer consisting of a single material, ii) a single-layered structure including a single layer consisting of a plurality of different materials, or iii) a multi-layered structure having a plurality of layers including a plurality of different materials.
The electron injection layer may include an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal compound, an alkaline earth-metal compound, a rare earth metal compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or any combination thereof.
The alkali metal may be Li, Na, K, Rb, or Cs. In an embodiment, the alkali metal may be Li, Na, or Cs. In an embodiment, the alkali metal may be Li or Cs, but embodiments of the present disclosure are not limited thereto.
The alkaline earth metal may be Mg, Ca, Sr, or Ba.
The rare earth metal may be Sc, Y, Ce, Tb, Yb, or Gd.
The alkali metal compound, the alkaline earth-metal compound, and the rare earth metal compound may be oxides or halides (for example, fluorides, chlorides, bromides, or iodides) of the alkali metal, the alkaline earth-metal, or the rare earth metal.
The alkali metal compound may be alkali metal oxides, such as Li2O, Cs2O, or K2O, or alkali metal halides, such as LiF, NaF, CsF, KF, Lil, Nal, Csl, or KI. In an embodiment, the alkali metal compound may be LiF, Li2O, NaF, Lil, Nal, Csl, or KI, but embodiments of the present disclosure are not limited thereto.
The alkaline earth-metal compound may be alkaline earth-metal oxides, such as BaO, SrO, CaO, BaxSri-xO (wherein 0<x<1), or BaxCai-xO (wherein 0<x<1). In an embodiment, the alkaline earth-metal compound may be BaO, SrO, or CaO, but embodiments of the present disclosure are not limited thereto.
The rare earth metal compound may be YbF3, ScF3, Sc2O3, Y2O3, Ce2O3, GdF3, or TbF3. In an embodiment, the rare earth metal compound may be YbF3, ScF3, TbF3, YbI3, ScI3, or TbI3, but embodiments of the present disclosure are not limited thereto.
The alkali metal complex, the alkaline earth-metal complex, and the rare earth metal complex may include an ion of alkali metal, alkaline earth-metal, and rare earth metal as described above, and a ligand coordinated with a metal ion of the alkali metal complex, the alkaline earth-metal complex, or the rare earth metal complex may be hydroxy quinoline, hydroxy isoquinoline, hydroxy benzoquinoline, hydroxy acridine, hydroxy phenanthridine, hydroxy phenyloxazole, hydroxy phenylthiazole, hydroxy diphenyloxadiazole, hydroxy diphenylthiadiazole, hydroxy phenylpyridine, hydroxy phenylbenzimidazole, hydroxy phenylbenzothiazole, bipyridine, phenanthroline, or cyclopentadiene, but embodiments of the present disclosure are not limited thereto.
The electron injection layer may include an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal compound, an alkaline earth-metal compound, a rare earth metal compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or any combinations thereof, as described above. In an embodiment, the electron injection layer may further include an organic material. When the electron injection layer further includes an organic material, an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal compound, an alkaline earth-metal compound, a rare earth metal compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or any combinations thereof may be homogeneously or non-homogeneously 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, about 3 Å to about 90 Å, about 6 Å to about 80 Å, about 9 Å to about 70 Å, about 12 Å to about 60 Å, about 15 Å to about 50 Å, about 18 Å to about 40 Å, or about 20 Å to about 30 Å. When the thickness of the electron injection layer is within the range described above, the electron injection layer may have satisfactory electron injection characteristics without a substantial increase in driving voltage.
Second Electrode 19
The second electrode 19 is located on the organic layer 10A having such a structure. The second electrode 19 may be a cathode which is an electron injection electrode, and in this regard, a material for forming the second electrode 19 may be a metal, an alloy, an electrically conductive compound, or a combination thereof, which have a relatively low work function.
The second electrode 19 may include at least one lithium (Li), silver (Ag), magnesium (Mg), aluminum (AI), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), ITO, or IZO, but embodiments of the present disclosure are not limited thereto. The second electrode 19 may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode.
The second electrode 19 may have a single-layered structure having a single layer or a multi-layered structure including two or more layers.
Hereinbefore, the organic light-emitting device has been described with reference to FIGURE, but embodiments of the present disclosure are not limited thereto.
According to an aspect of the invention, provided is an electronic apparatus including the organic light-emitting device.
According to an embodiment, the electronic apparatus may be applied in various fields such as a diagnostic kit, a biosensor, a biomarker, a display, and a lighting device.
The term “C1-C60 alkyl group” as used herein refers to a linear or branched saturated aliphatic hydrocarbon monovalent group having 1 to 60 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, and a hexyl group. The term “C1-C60 alkylene group” as used herein refers to a divalent group having the same structure as the C1-C60 alkyl group.
The term “C1-C60 alkoxy group” as used herein refers to a monovalent group represented by —OA101 (wherein A101 is the C1-C60 alkyl group), and examples thereof include a methoxy group, an ethoxy group, and an isopropyloxy group.
The term “C1-C60 alkylthio group” used herein refers to a monovalent group represented by —SA105 (wherein A105 is the C1-C60 alkyl group), and examples thereof include a thiomethyl group, a thioethyl group, and a thioisopropyl group.
The term “C2-C60 alkenyl group” as used herein has a structure including at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethenyl group, a propenyl group, and a butenyl group. The term “C2-C60 alkenylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein has a structure including at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethynyl group and a propynyl group. The term “C2-C60 alkynylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkynyl group.
The term “C3-C10 cycloalkyl group” as used herein refers to a monovalent saturated hydrocarbon monocyclic group having 3 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. The term “C3-C10 cycloalkylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkyl group.
The term “C1-C10 heterocycloalkyl group” as used herein refers to a monovalent saturated monocyclic group having at least one heteroatom N, O, P, Si, or S as a ring-forming atom and 1 to 10 carbon atoms, and examples thereof include a tetrahydrofuranyl group and a tetrahydrothiophenyl group. The term “C1-C10 heterocycloalkylene group” as used herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkyl group.
The term “C3-C10 cycloalkenyl group” as used herein refers to a monovalent monocyclic group that has 3 to 10 carbon atoms and at least one carbon-carbon double bond in the ring thereof and no aromaticity, and examples thereof include a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group. The term “C3-C10 cycloalkenylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkenyl group.
The term “C1-C10 heterocycloalkenyl group” as used herein refers to a monovalent monocyclic group that has at least one heteroatom N, O, P, Si, or S as a ring-forming atom, 1 to 10 carbon atoms, and at least one double bond in its ring. Examples of the C1-C10 heterocycloalkenyl group are a 2,3-dihydrofuranyl group and a 2,3-dihydrothiophenyl group. The term “C1-C10 heterocycloalkenylene group” as used herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as used herein refers to a monovalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms, and a C6-C60 arylene group used herein refers to a divalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms. Examples of the C6-C60 aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a chrysenyl group. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the rings may be fused to each other.
The term “C6-C60 alkylaryl group” as used herein refers to a C6-C59 aryl group substituted with at least one C1-C54 alkyl or alkylene group, and the term “C6-C60 aryl alkyl group” as used herein indicates -A106A107 (wherein A106 is the C6-C59 aryl group and A107 is the C1-C54 alkyl or alkylene group).
The term “C1-C60 heteroaryl group” as used herein refers to a monovalent group having a cyclic aromatic system that has at least one heteroatom N, O, P, Si, or S as a ring-forming atom, and 1 to 60 carbon atoms. The term “C1-C60 heteroarylene group” as used herein refers to a divalent group having a carbocyclic aromatic system that has at least one heteroatom N, O, P, or S as a ring-forming atom, and 1 to 60 carbon atoms. Examples of the C1-C60 heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, and an isoquinolinyl group. When the C1-C60 heteroaryl group and the C1-C60 heteroarylene group each include two or more rings, the rings may be fused to each other.
The term “C6-C60 aryloxy group” as used herein refers to —OA102 (here, A102 is the C6-C60 aryl group), the C6-C60 arylthio group refers to —SA103 (here, A103 is the C6-C60 aryl group), and the C6-C60 aryl alkyl group refers to —(CH2)nA104 (here, A104 is a C6-C59 aryl group, and n is an integer from 1 to 10).
The term “C1-C60 heteroaryloxy group” as used herein refers to —OA108 (wherein A108 is the C1-C60 heteroaryl group), the term “C1-C60 heteroarylthio group” as used herein indicates —SA109 (wherein A109 is the C1-C60 heteroaryl group), and the term “C1-C60 heteroalkyl aryl group” as used herein refers to -A110A111 (A110 is a C1-C55 heteroalkylene or heteroalkyl group, and A111 is a C1-C59 heteroaryl group).
The term “C1-C60 heteroalkyl aryl group” as used herein refers to a C1-C60 heteroaryl group substituted with at least one C1-C59 alkyl or alkylene group.
The term “monovalent non-aromatic condensed polycyclic group” as used herein refers to a monovalent group (for example, having 8 to 60 carbon atoms) having two or more rings condensed with each other, only carbon atoms as ring-forming atoms, and non-aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic condensed polycyclic group include a fluorenyl group. The term “divalent non-aromatic condensed polycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed polycyclic group.
The term “monovalent non-aromatic condensed heteropolycyclic group” as used herein refers to a monovalent group (for example, having 1 to 60 carbon atoms) having two or more rings condensed to each other, a heteroatom N, O, P, Si, or S, other than carbon atoms, as a ring-forming atom, and non-aromaticity in its entire molecular structure. The monovalent non-aromatic condensed heteropolycyclic group includes a carbazolyl group. The term “divalent non-aromatic condensed heteropolycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed heteropolycyclic group.
The term “C5-C30 carbocyclic group” as used herein refers to, as a ring-forming atom, a saturated or unsaturated cyclic group including aromatic group having 5 to 30 carbon atoms. The C5-C30 carbocyclic group may be a monocyclic group or a polycyclic group. For example, the C5-C30 carbocyclic group may be a cyclopentane group, a cyclohexane group, a cyclohexene group, a phenyl group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, or like.
The term “C1-C30 heterocyclic group” as used herein refers to a saturated or unsaturated cyclic group having, as a ring-forming atom, at least one heteroatom N, O, P, Si, or S other than 1 to 30 carbon atoms. The C1-C30 heterocyclic group may be a monocyclic group or a polycyclic group.
For example, the π-electron-deficient nitrogen-containing C1-C60 cyclic group may be an imidazole group, a pyrazole group, a thiazole group, an isothiazole group, an oxazole group, an isoxazole group, a pyridine group, a pyrazine group, a pyridazine group, a pyrimidine group, an indazole group, a purine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a benzoisoquinoline group, a phthalazine group, a naphthyridine group, a quinoxaline group, a benzoquinoxaline group, a quinazoline group, a cinnoline group, a phenanthridine group, an acridine group, a phenanthroline group, a phenazine group, a benzimidazole group, an isobenzothiazole group, a benzoxazole group, a benzoisoxazole group, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, a thiadiazole group, an imidazopyridine group, an imidazopyrimidine group, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, an acridine group, or a pyridopyrazine group.
In an embodiment, the π-electron-rich C3-C60 cyclic group may be a phenyl group, a heptalene group, an indene group, a naphthalene group, an azulene group, an indacene group, an acenaphthylene group, a fluorene group, a spiro-bifluorene group, a benzofluorene group, a dibenzofluorene group, a phenalene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a naphthacene group, a picene group, a perylene group, a pentacene group, a hexacene group, a pentaphene group, a rubicene group, a coronene group, an ovalene group, a pyrrole group, a furan group, a thiophene group, an isoindole group, an indole group, an indene group, a benzofuran group, a benzothiophene group, a benzosilole group, a naphthopyrrole group, a naphthofuran group, a naphthothiophene group, a naphthosilole group, a benzocarbazole group, a dibenzocarbazole group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, a triindolobenzene group, a pyrrolophenanthrene group, a furanophenanthrene group, a thienophenanthrene group, a benzonaphthofuran group, a benzonaphthothiophene group, a (indolo)phenanthrene group, a (benzofurano)phenanthrene group, or a (benzothieno)phenanthrene group.
In an embodiment, the C5-C60 cyclic group may be a cyclopentane group, a cyclohexane group, a cyclohexene group, a phenyl or benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a 1,2,3,4-tetrahydronaphthalene group, a cyclopentadiene group, an indene group, a fluorene group, a 5,6,7,8-tetrahydroisoquinoline group, a 5,6,7,8-tetrahydroquinoline group, an adamantane group, a norbornane group, or a norbornene group.
For example, the C1-C60 heterocyclic group may be a thiophene group, a furan group, a pyrrole group, a cyclopentadiene group, a silole group, a borole group, a phosphole group, a selenophene group, a germole group, a benzothiophene group, a benzofuran group, an indole group, an indene group, a benzosilole group, a benzoborole group, a benzophosphole group, a benzoselenophene group, a benzogermole group, a dibenzothiophene group, a dibenzofuran group, a carbazole group, a dibenzosilole group, a dibenzoborole group, a dibenzophosphole group, a dibenzoselenophene group, a dibenzogermole group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azabenzothiophene group, an azabenzofuran group, an azaindole group, an azaindene group, an azabenzosilole group, an azabenzoborole group, an azabenzophosphole group, an azabenzoselenophene group, an azabenzogermole group, an azadibenzothiophene group, an azadibenzofuran group, an azacarbazole group, an azafluorene group, an azadibenzosilole group, an azadibenzoborole group, an azadibenzophosphole group, an azadibenzoselenophene group, an azadibenzogermole group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isooxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, or a benzothiadiazole group.
In the present specification, each of the π-electron-deficient nitrogen-containing C1-C60 cyclic group, the π-electron-rich C3-C60 cyclic group, the C5-C60 cyclic group, and the C1-C60 heterocyclic group may be part of a condensed cyclic or may be a monovalent, a divalent, a trivalent, a tetravalent, a pentavalent, or a hexavalent group, depending on a formula structure.
At least one substituent of the substituted π-electron-deficient nitrogen-containing C1-C60 cyclic group, the substituted π-electron-rich C3-C60 cyclic group, the substituted C5-C30 carbocyclic group, the substituted C2-C30 heterocyclic group, the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted C1-C60 alkylthio group, the substituted C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C1-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C6-C60 aryl alkyl group, the substituted C1-C60 heteroaryl group, the substituted C1-C60 heteroaryloxy group, the substituted C1-C60 heteroarylthio group, the substituted C1-C60 heteroalkyl aryl group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group is:
deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkylthio group, or a C1-C60 alkoxy group;
a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkylthio group, or a C1-C60 alkoxy group, each independently substituted with at least one deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a 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 C6-C60 aryloxy group, a C6-C60 arylthio group, a C6-C60 aryl alkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C1-C60 heteroalkyl aryl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, —N(Q11)(Q12), —Si(Q13)(Q14)(Q15), —B(Q16)(Q17), or —P(═O)(Q18)(Q19);
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 C6-C60 aryloxy group, a C6-C60 arylthio group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C1-C60 heteroalkyl aryl group, a monovalent non-aromatic condensed polycyclic group, or a monovalent non-aromatic condensed heteropolycyclic group;
a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C6-C60 aryl alkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C1-C60 heteroalkyl aryl group, a monovalent non-aromatic condensed polycyclic group, or a monovalent non-aromatic condensed heteropolycyclic group, each independently substituted with at least one deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C1-C60 alkylthio group, a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C6-C60 aryl alkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, —N(Q21)(Q22), —Si(Q23)(Q24)(Q25), —B(Q26)(Q27), or —P(═O)(Q28)(Q29); or
—N(Q31)(Q32), —Si(Q33)(Q34)(Q35), —B(Q36)(Q37), or —P(═O)(Q38)(Q39), and
Q1 to Q9, Q11 to Q19, Q21 to Q29, and Q31 to Q39 are each independently hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C1-C60 alkylthio group, a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C6-C60 aryl alkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C1-C60 heteroalkyl aryl group, a monovalent non-aromatic condensed polycyclic group, or a monovalent non-aromatic condensed heteropolycyclic group.
In an embodiment, Q1 to Q9, Q11 to Q19, Q21 to Q29, and Q31 to Q39 as used herein may each independently be:
—CH3, —CD3, —CD2H, —CDH2, —CH2CH3, —CH2CD3, —CH2CD2H, —CH2CDH2, —CHDCH3, —CHDCD2H, —CHDCDH2, —CHDCD3, —CD2CD3, —CD2CD2H, or —CD2CDH2; or
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, a phenyl group, a biphenyl group, or a naphthyl group, each independently unsubstituted or substituted with deuterium, a C1-C10 alkyl group, a phenyl group, or any combination thereof.
The term “room temperature” used herein refers to a temperature of about 25° C.
The terms “a biphenyl group, a terphenyl group, and a tetraphenyl group” used herein respectively refer to monovalent groups in which two, three, or four phenyl groups which are linked together via a single bond.
The terms “a cyano-containing phenyl group, a cyano-containing biphenyl group, a cyano-containing terphenyl group, and a cyano-containing tetraphenyl group” used herein respectively refer to a phenyl group, a biphenyl group, a terphenyl group, and a tetraphenyl group, each of which is substituted with at least one cyano group. In “a cyano-containing phenyl group, a cyano-containing biphenyl group, a cyano-containing terphenyl group, and a cyano-containing tetraphenyl group”, a cyano group may be substituted to any position of the corresponding group, and the “cyano-containing phenyl group, the cyano-containing biphenyl group, the cyano-containing terphenyl group, and the cyano-containing tetraphenyl group” may further include substituents other than a cyano group. In an embodiment, a phenyl group substituted with a cyano group, and a phenyl group substituted with a cyano group and a methyl group may all belong to “a cyano-containing phenyl group.”
Hereinafter, a compound and an organic light-emitting device according to embodiments are described in detail with reference to Synthesis Examples and Examples. However, the organic light-emitting device is not limited thereto. The wording “‘B’ was used instead of ‘A’” used in describing Synthesis Examples means that an amount of ‘A’ used was identical to an amount of ‘B’ used, in terms of a molar equivalent.
1-Bromo-2,3-dichlorobenzene (4.0 gram (g)), bis(4-biphenylyl)amine (12.0 g), sodium tert-butoxide (4.3 g), Pd(dba)2 (Palladium(0) bis(dibenzylideneacetone), 0.81 g), and SPhos (2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, 0.44 g) were dissolved in toluene (350 milliliter (mL)), and then heated at 100° C. for 15 hours using an oil bath. The reaction product was cooled to room temperature, and a target product was extracted using ethyl acetate, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. A compound obtained therefrom was purified through silica gel column chromatography to thereby obtain 11.4 g (yield: 86%, purity: 98%) of Intermediate 1-a.
A tert-butyl benzene solution (70 mL) of Intermediate 1-a (5.1 g) obtained therefrom was cooled to −78° C. A tert-BuLi solution (9.9 mL, 1.5 M in pentane) was added thereto, the resulting reaction mixture was heated at 60° C., and then stirred for an hour. Subsequently, the reaction mixture was cooled at −78° C., and boron tribromide (1.4 mL) was added thereto and then stirred at 0° C. for two hours. Again, the reaction mixture was cooled at −78° C., and diisopropylethylamine (2.4 mL) was added thereto, and then heated at 110° C. for three hours. The reaction mixture was cooled to room temperature, diluted using dichloromethane, subjected to filtration using FLORISIL®, and then concentrated under reduced pressure. A compound obtained therefrom was recrystallized using a toluene/dichloromethane solvent to thereby obtain 2.2 g (yield: 44%, purity: 98%) of Compound 1. Also, a target molecular weight ([M+H]+ 725.3) was confirmed through ESI-MS measurement.
1-Bromo-2,3-dichlorobenzene (1.4 g), bis(4′-(tert-butyl)-[1,1′-biphenyl]-4-yl)amine (5.7 g), sodium tert-butoxide (1.7 g), Pd(OAc)2 (27 mg), and SPhos (125 milligrams (mg)) were dissolved in o-xylene (50 mL), and then refluxed while heating for an hour using an oil bath. The reaction mixture was cooled to room temperature, and a target product was extracted using ethyl acetate, dried over magnesium sulfate, and then concentrated under reduced pressure. A compound obtained therefrom was purified by silica gel column chromatography to thereby obtain 5.5 g (yield: 94%, purity: >99%) of Intermediate 224-a.
A tert-butyl benzene solution (12 mL) of Intermediate 224-a (0.5 g) obtained therefrom was cooled at −78° C. A tert-BuLi solution (0.72 mL, 1.5 M in pentane) was added thereto, the resulting reaction mixture was heated at 80° C., and then stirred for two hours. Subsequently, the reaction mixture was cooled to −78° C., and boron tribromide (0.11 mL) was added thereto and then stirred at 0° C. for an hour. Again, the reaction mixture was cooled at −78° C., and diisopropylethylamine (0.18 mL) was added thereto and then heated at 110° C. for three hours. The reaction mixture was diluted using dichloromethane, subjected to filtration using FLORISIL®, and then concentrated under reduced pressure. A compound obtained therefrom was purified by silica gel column chromatography to thereby obtain 0.13 g (yield: 15%, purity: 95%) of Compound 224. Also, a target molecular weight ([M+H]+ 949.6) was confirmed through ESI-MS measurement.
5-Bromo-m-terphenyl (10 g), aniline (4.2 mL), sodium tert-butoxide (4.7 g), Pd(dba)2 (1.48 g), and SPhos (0.81 mg) were dissolved in toluene (150 mL), and then heated at 100° C. for 15 hours using an oil bath. The reaction mixture was cooled at room temperature, and a target product was extracted using ethyl acetate, dried over magnesium sulfate, and then concentrated under reduced pressure. A compound obtained therefrom was purified by silica gel column chromatography to thereby obtain 6.2 g (yield: 60%, purity: 97%) of Intermediate 95-b.
Intermediate 95-b (6.2 g) obtained therefrom, 1-bromo-2,3-dichlorobenzene (2.0 g), sodium tert-butoxide (2.5 g), Pd(dba)2 (0.44 mg), and SPhos (0.24 mg) were dissolved in toluene (100 mL), and then heated 100° C. for 15 hours using an oil bath. The reaction mixture was cooled to room temperature, and a target product was extracted using ethyl acetate, dried over magnesium sulfate, and then concentrated under reduced pressure. A compound obtained therefrom was purified by silica gel column chromatography to thereby obtain 5.2 g (yield: 72%, purity: 97%) of Intermediate 95-a.
A tert-butyl benzene solution (12 mL) of Intermediate 95-a (0.5 g) obtained therefrom was cooled at −78° C. A tert-BuLi solution (0.98 mL, 1.5 M in pentane) was added thereto, heated at 80° C., and then stirred for two hours. Next, the reaction mixture was cooled to −78° C., and boron tribromide (0.16 mL) was added thereto and then stirred at 0° C. for an hour. Again, the reaction mixture was cooled to −78° C., and diisopropylethylamine (0.29 mL) was added thereto and then heated at 110° C. for three hours. The reaction mixture was cooled to room temperature, diluted using dichloromethane, subjected to filtration using FLORISIL®, and then concentrated under reduced pressure. A compound obtained therefrom was purified by silica gel column chromatography to thereby obtain 0.15 g (yield: 31%, purity: 91%) of Compound 95. Also, a target molecular weight ([M+H]+ 725.3) was confirmed through ESI-MS measurement.
1-Bromo-2,3-dichlorobenzene (2.0 g), bis(3-biphenylyl)amine (6.0 g), sodium tert-butoxide (2.2 g), Pd2(dba)3 (0.21 g), and SPhos (0.22 g) were dissolved in toluene (150 mL), and then heated at 100° C. for 15 hours using an oil bath. The reaction mixture was cooled to room temperature, and a target product was extracted using ethyl acetate, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. A compound obtained therefrom was purified by silica gel column chromatography to thereby obtain 5.8 g (yield: 88%, purity: 98%) of Intermediate 229-a.
A tert-butyl benzene solution (12 mL) of Intermediate 229-a (1.0 g) obtained therefrom was cooled at −78° C. A tert-BuLi solution (0.28 mL, 1.5 M in pentane) was added thereto, heated at 60° C., and then stirred for an hour. Next, the reaction mixture was cooled to −78° C., and boron tribromide (0.28 mL) was added thereto and then stirred at 0° C. for two hours. Again, the reaction result was cooled to −78° C., and diisopropylethylamine (0.48 mL) was added thereto and then heated at 110° C. for three hours. The reaction mixture was cooled to room temperature, diluted using dichloromethane, subjected to filtration using FLORISIL®, and then concentrated under reduced pressure. A compound obtained therefrom was recrystallized using a toluene/dichloromethane solvent to thereby obtain 0.36 g (yield: 38%, purity: 92%) of Compound 229. Also, a target molecular weight ([M+H]+ 725.3) was confirmed through ESI-MS measurement.
A glass substrate with an ITO electrode located thereon was cut to a size of 50 millimeters (mm)×50 mm×0.5 mm and then, sonicated in acetone isopropyl alcohol and pure water, each for 15 minutes, and then, washed by exposure of UV ozone thereto for 30 minutes.
Then, HAT-CN was deposited on the ITO electrode (anode) on the glass substrate to form a hole injection layer having a thickness of 100 angstrom (A), NPB was deposited on the hole injection layer to form a first hole transport layer having a thickness of 500 Å, TCTA was deposited on the first hole transport layer to form a second hole transport layer having a thickness of 50 Å, and mCP was deposited on the second hole transport layer to form an electron blocking layer having a thickness of 50 Å.
A first host (H1), a second host (H2), a sensitizer (S-1), and an emitter (Compound 1) were co-deposited on the electron blocking layer to form an emission layer having a thickness of 400 Å. At this time, the first host and the second host were mixed at a ratio of 60:40, and amounts of the sensitizer and the emitter were adjusted to be 10 wt % and 1.5 wt %, respectively, based on the total weight of the first host, the second host, the sensitizer, and the emitter.
2,8-bis(diphenylphosphine oxide) dibenzofuran (DBFPO) was deposited on the emission layer to form a hole blocking layer having a thickness of 100 Å, DBFPO and Liq were co-deposited thereon at a weight ratio of 5:5 to form an electron transport layer having a thickness of 300 Å, Liq was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and Al was deposited on the electron injection layer to form a cathode having a thickness of 1000 Å, thereby completing the manufacture of an organic light-emitting device.
An organic light-emitting device was manufactured in the same manner as in Example 1, except that, in forming an emission layer, 0.5 wt % of an emitter (Compound 1) was used.
An organic light-emitting device was manufactured in the same manner as in Example 1, except that, in forming an emission layer, corresponding compounds shown in Table 2 were used.
H1
H2
S-1
1
A
B
C
For each of the organic light-emitting devices manufactured in Examples 1 and 2 and Comparative Examples 1 to 7, driving voltage, T95 lifespan, which is the time taken for initial luminance to decrease to 95%, and quantum efficiency were measured, and relative values with respect to Comparative Example 1 are shown in Table 3.
As described in Tables 2 and 3, the organic light-emitting devices of Examples 1 and 2 each include an emission layer including two hosts, a sensitizer, and a dopant of Compound 1, thereby having low driving voltage, high efficiency, and long lifespan, compared to the organic light-emitting devices manufactured in Comparative Examples 1 (free of a sensitizer), 2 to 4, and 5 to 7.
An organic light-emitting device including a host, a first dopant, and a second dopant described herein has improved efficiency, low driving voltage, and improved lifespan.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present detailed description as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0130411 | Oct 2020 | KR | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20200028084 | Song | Jan 2020 | A1 |
| 20200058874 | Kim et al. | Feb 2020 | A1 |
| 20200144503 | Hayano | May 2020 | A1 |
| 20210053998 | Kim et al. | Feb 2021 | A1 |
| 20210202876 | Kim | Jul 2021 | A1 |
| 20220102636 | Dück | Mar 2022 | A1 |
| 20220285621 | Thirion | Sep 2022 | A1 |
| 20220289769 | Dück | Sep 2022 | A1 |
| 20230084208 | Kim et al. | Mar 2023 | A1 |
| 20230159568 | Zink | May 2023 | A1 |
| 20230345748 | Kim | Oct 2023 | A1 |
| Number | Date | Country |
|---|---|---|
| 1020200011383 | Feb 2020 | KR |
| 1020200019272 | Feb 2020 | KR |
| 1020200020538 | Feb 2020 | KR |
| 1020200047400 | May 2020 | KR |
| 1020200052513 | May 2020 | KR |
| Entry |
|---|
| English Abstract of KR 10-2020-0011383. |
| English Abstract of KR 10-2020-0047400. |
| Number | Date | Country | |
|---|---|---|---|
| 20230069900 A1 | Mar 2023 | US |
