Patent Application
20240244858
This application claims priority to and the benefit of Korean Patent Application No. 10-2022-0178681, filed on Dec. 19, 2022, 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.
The present subject matter relates to an organometallic compound, an organic light-emitting device including the same, and an electronic apparatus including the organic light-emitting device.
Organic light-emitting devices (OLEDs) are self-emissive devices, which have improved characteristics in terms of viewing angles, response time, brightness, driving voltage, and response speed. In addition, OLED can also produce full-color images.
In an example, an organic light-emitting device includes an anode, a cathode, and an organic layer located or arranged 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. The excitons may transition from an excited state to a ground state, thus generating light.
Provided are an organometallic compound, an organic light-emitting device including the same, and an electronic apparatus including the organic light-emitting device.
According to an aspect, provided is an organometallic compound represented by Formula 1:
wherein, in Formulae 1 and 2,
According to another aspect, an organic light-emitting device includes a first electrode, a second electrode, and an organic layer arranged between the first electrode and the second electrode, wherein the organic layer includes an emission layer, and wherein the organic layer further includes at least one organometallic compound represented by Formula 1.
According to another aspect, an electronic apparatus includes the organic light-emitting device.
Additional aspects will be set forth in part in the detailed description that follows and, in part, will be apparent from the detailed description, or may be learned by practice of the presented exemplary embodiments described herein.
The above and other aspects, features, and advantages of certain exemplary embodiments will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which:
Reference will now be made in further detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present exemplary embodiments may have different forms and should not be construed as being limited to the detailed descriptions set forth herein. Accordingly, the exemplary embodiments are merely described in further detail below, and by referring to the figures, to explain certain 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.
The terminology used herein is for the purpose of describing one or more exemplary 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.
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.
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.
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.
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.
“About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.
Hereinafter, a work function or a highest occupied molecular orbital (HOMO) energy level is expressed as an absolute value from a vacuum level. In addition, when the work function or the HOMO energy level is referred to be “deep,” “high” or “large,” the work function or the HOMO energy level has a large absolute value based on “0 electron Volts (eV)” of the vacuum level, while when the work function or the HOMO energy level is referred to be “shallow,” “low,” or “small,” the work function or HOMO energy level has a small absolute value based on “0 eV” of the vacuum level.
Provided is an organometallic compound is represented by Formula 1:
In Formula 1, M1 is a transition metal.
In one or more embodiments, M1 in Formula 1 may be 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.
For example, in Formula 1, M1 may be iridium, platinum, osmium, titanium, zirconium, hafnium, europium, terbium, thulium, rhodium, palladium, or gold.
In one or more embodiments, M1 in Formula 1 may be platinum, palladium, or gold.
For example, M1 in Formula 1 may be platinum.
In Formula 1, X11 is N or C(R11), and
For example, i) X11 may be C(R11), and X12 may be C(R12);
R11 and R12 are optionally bonded to each other to form a substituted or unsubstituted C5-C30 carbocyclic group (for example, a benzene group or the like) or a substituted or unsubstituted C1-C30 heterocyclic group (for example, a benzimidazole group or the like).
In Formula 1, X21 is N or C(R21),
In one or more embodiments, Formula 1 may satisfy one of Conditions 1-1 to 1-3:
In Conditions 1-1 and 1-2, R21 and R22 may each be as described herein.
Y2 to Y4 are each independently C or N.
In one or more embodiments, at least one of Y2 to Y4 may be N.
In one or more embodiments, Y2 may be C, Y3 may be C, and Y4 may be N;
A2 to A4 are each independently a chemical bond, O, or S.
The chemical bond may be a covalent bond, an ionic bond, or a coordinate bond, but embodiments are not limited thereto.
In Formula 1, ring CY3 and ring CY4 are each independently a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
In one or more embodiments, ring CY3 and ring CY4 may each independently be a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a cyclopentadiene group, a 1,2,3,4-tetrahydronaphthalene group, a thiophene group, a furan group, an indole group, a benzoborole group, a benzophosphole group, an indene group, a benzosilole group, a benzogermole group, a benzothiophene group, a benzoselenophene group, a benzofuran group, a carbazole group, a dibenzoborole group, a dibenzophosphole group, a fluorene group, a dibenzosilole group, a dibenzogermole group, a dibenzothiophene group, a dibenzoselenophene group, a dibenzofuran group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an iso-oxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzotriazole, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, or a 5,6,7,8-tetrahydroquinoline group.
In Formula 1, T1 is a single bond, a double bond, *—N[(L1)b1-(R1a)]—*′, *—B(R1a)—*′, *—P(R1a)—*′, *—C(R1a)(R1b)—*′, *—Si(R1a)(R1b)—*′, *—Ge(R1a)(R1b)—*′, *—S—*′, *—Se—*′, *—O—*′, *—C(═O)—*′, *—S(═O)—*′, *—S(═O)2—*′, *—C(R1a)═*′, *═C(R1a)—*′, *—C(R1a)═C(R1b)—*′, *—C(═S)—*′, or *—C≡C—*′,
a1 to a3 in Formula 1 each indicates the numbers of T1 to T3, respectively, and a1 to a3 are each independently an integer from 1 to 3 (for example, 1, 2, or 3). When a1 is two or greater, two or more of T1 are identical to or different from each other, and when a2 is two or greater, two or more of T2 are identical to or different from each other, and when a3 is two or greater, two or more of T3 are identical to or different from each other.
In one or more embodiments, at least one of T1 and T3 may be a single bond.
For example, T1 may be a single bond; T3 may be a single bond; and/or T1 and T3 may be a single bond.
In one or more embodiments, T2 may be *—N[(L2)b2-(R2a)]—*′, *—S—*′, *—Se—*′, or *—O—*′, and a2 may be 1.
In Formula 1, * and *′ each indicate a binding site to a neighboring atom.
L1 to L3 are each independently a single bond, a C5-C30 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C30 heterocyclic group unsubstituted or substituted with at least one R10a.
b1 to b3 in Formula 1 each indicates the number of L1 to L3, respectively, and b1 to b3 are each independently an integer from 1 to 3 (for example, 1, 2, or 3.) When b1 is two or greater, two or more of L1 are identical to or different from each other, and when b2 is two or greater, two or more of L2 are identical to or different from each other, and when b3 is two or greater, two or more of L3 are identical to or different from each other.
In Formula 1, R13 is a group represented by Formula 2:
In Formulae 1 and 2, R1a, R1b, R2a, R2b, R3a, R3b, R3, R4, R11, R12, R21 to R23, and E1 to E5 are each independently hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C7-C60 alkyl aryl group, a substituted or unsubstituted C7-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 C2-C60 alkyl heteroaryl group, a substituted or unsubstituted C2-C60 heteroaryl alkyl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —Si(Q1)(Q2)(Q3), —Ge(Q1)(Q2)(Q3), —N(Q4)(Q5), —B(Q6)(Q7), —P(Q8)(Q9), or —P(═O)(Q8)(Q9),
In one or more embodiments, Formula 2 may satisfy at least one of Conditions 2-1 and 2-2:
d3 and d4 in Formula 1 each indicates the number of R3 and R4, respectively, and d3 and d4 are each independently an integer from 0 to 20 (for example, 0, 1, 2, 3, or 4.) When d3 is 2 or greater, two or more of R3 are identical to or different from each other, and when d4 is 2 or greater, two or more R4 are identical to or different from each other.
In Formula 1, R10a is as described herein in connection with R3.
* in Formula 2 indicate a binding site to a neighboring atom.
At least one substituent of the substituted C5-C30 carbocyclic group, the substituted C1-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 C7-C60 alkyl aryl group, the substituted C7-C60 aryl alkyl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl group, the substituted C2-C60 alkyl heteroaryl group, the substituted C2-C60 heteroaryl alkyl group, the substituted C1-C60 heteroaryloxy group, the substituted C1-C60 heteroarylthio group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group is:
In one or more embodiments, R1a, R1b, R2a, R2b, R3a, R3b, R3, R4, R11, R12, R21 to R23, and E1 to E5 may each independently be:
In one or more embodiments, at least one of E2 and E4 may be:
In one or more embodiments, R11, R12, R21 to R23, R3, R4, R1a, R1b, R2a, R2b, R3a, R3b, and E1 to E5 may each independently be:
* in Formulae 9-1 to 9-61, 9-201 to 9-237, 10-1 to 10-129, and 10-201 to 10-355 indicates a binding site to a neighboring atom, “Ph” is a phenyl group, “TMS” is a trimethylsilyl group, “TMG” is a trimethylgermyl group, and “t-Bu” is a t-butyl group.
In one or more embodiments, at least one of E2 and E4 may be:
* in Formulae 9-1 to 9-61, 9-201 to 9-237, 10-1 to 10-129, and 10-201 to 10-355 indicates a binding site to a neighboring atom, “Ph” is a phenyl group, “TMS” is a trimethylsilyl group, “TMG” is a trimethylgermyl group, and “t-Bu” is a t-butyl group.
In one or more embodiments, a group represented by
In one or more embodiments, a group represented by
In one or more embodiments, a group represented by
In one or more embodiments, a group represented by
In one or more embodiments, in Formulae CY3-15-1 to CY3-15-9, R34 may not be hydrogen; however, embodiments are not limited thereto.
In one or more embodiments, a group represented by
In one or more embodiments, the organometallic compound represented by Formula 1 may be represented by one of Formulae 1-1 and 1-2:
In Formulae 1-1 and 1-2,
In another embodiment, the organometallic compound represented by Formula 1 may be represented by one of Formulae 1-11 and 1-12:
In one or more embodiments, Formula 2 may be represented by one of Formulae 2-1 to 2-16:
In one or more embodiments, the organometallic compound may be represented by one of Compounds 1 to 405, but embodiments are not limited thereto:
The organometallic compound represented by Formula 1 has a structure including a 5-membered moiety including a carbene structure substituted with a group represented by Formula 2 and a ligand including a benzene moiety including at least one nitrogen.
As the organometallic compound has a 5-membered moiety including a carbene structure substituted with a group represented by Formula 2, interaction with other molecules may be prevented, and efficiency by the electron-donating effect may be increased.
Moreover, as the organometallic compound includes a ligand including a benzene moiety including at least one nitrogen, the photoluminescence quantum yield (PLQY) may be increased, which leads to improved efficiency. Accordingly, by introducing nitrogen with great electronegativity while maintaining the deep blue emission area, the organometallic compound may have a deep highest occupied molecular orbital (HOMO) energy level, which facilitates the hole injection, and thus, may have a lower driving voltage. In addition, as the energy bandgap increases due to the introduction of nitrogen, the organometallic compound may have luminescence characteristics that make it suitable for use as a dopant of a blue organic light-emitting device.
Synthesis methods of the organometallic compound represented by Formula 1 may be recognizable by one of ordinary skill in the art and by referring to Synthesis Examples provided herein.
The highest occupied molecular orbital (HOMO) energy level, the lowest unoccupied molecular orbital (LUMO) energy level, and the lowest excitation triplet (T1) energy level of selected organometallic compounds represented by Formula 1, and Comparative Compounds C1 to C3, were calculated using a density functional theory (DFT) method of the Gaussian 09 program with the molecular structure optimized at the B3LYP level, and results thereof are shown in Table 1. The energy levels are expressed in electron volts (eV).
From Table 1, it was confirmed that the organometallic compound represented by Formula 1 according to one or more embodiments have a greater T1 energy level than Comparative Compounds C1 to C3, and have a deeper HOMO energy level, and thus, have electrical characteristics suitable for use as a material for an organic light-emitting device, for example, as a dopant of an organic light-emitting device.
Accordingly, according to another aspect, also provided is an organic light-emitting device that may include a first electrode; a second electrode; and an organic layer arranged between the first electrode and the second electrode, wherein the organic layer includes an emission layer, and wherein the organic layer further includes at least one organometallic compound represented by Formula 1 as described herein.
Since the organic light-emitting device has an organic layer including at least one of the organometallic compounds represented by Formula 1, the organic light-emitting device may have a low driving voltage, a high efficiency, a high luminance, a high quantum efficiency, and a long lifespan.
The expression “(an organic layer) includes at least one of the organometallic compound(s) represented by Formula 1” and the expression “(an organic layer) includes at least one organometallic compound represented by Formula 1” as used herein may include a case in which “(an organic layer) includes identical organometallic compounds represented by Formula 1” and a case in which “(an organic layer) includes two or more different organometallic compounds represented by Formula 1.”
For example, the organic layer may include, as the at least one organometallic compound represented by Formula 1, only Compound 1. In this embodiment, Compound 1 may be included in the emission layer of the organic light-emitting device. In one or more embodiments, the organic layer may include, as the at least one organometallic compound represented by Formula 1, Compound 1 and Compound 2. In this regard, Compound 1 and Compound 2 may exist in an identical layer (for example, Compound 1 and Compound 2 both may be included in an emission layer).
In one or more embodiments, the at least one organometallic compound represented by Formula 1 may be included in the emission layer of the organic light-emitting device.
In the emission layer, the at least one organometallic compound represented by Formula 1 may serve as an emitter. In some embodiments, an emission layer including the at least one organometallic compound represented by Formula 1 may emit phosphorescence produced upon transition of triplet excitons to a ground state of the at least one organometallic compound represented by Formula 1.
In one or more embodiments, the emission layer of the organic light-emitting device may further include a host, and an amount of the host in the emission layer may be greater than an amount of the at least one organometallic compound represented Formula 1 based on their weights.
For example, the emission layer in the organic light-emitting device may include a host and a dopant, and the dopant may include the at least one organometallic compound represented by Formula 1. The host may be selected from any suitable hosts. That is, the organometallic compound represented by Formula 1 may act as a dopant.
In one or more embodiments, a full width at half maximum (FWHM) of an emission peak of an emission spectrum or electroluminescence spectrum of the organometallic compound represented by Formula 1 may be about 50 nanometers (nm) or less. For example, the FWHM of the emission peak of the emission spectrum or the electroluminescence spectrum of the organometallic compound may be from about 5 nm to about 50 nm, about 5 nm to about 40 nm, or about 5 nm to about 20 nm.
The emission layer may emit a light having a maximum emission wavelength from about 410 nm to about 490 nm, for example, from about 440 nm to about 480 nm, or from about 440 nm to about 470 nm. For example, the emission layer may emit a blue light, such as a blue light having a maximum emission wavelength from about 410 nm to about 490 nm, for example, from about 440 nm to about 480 nm, or from about 440 nm to about 470 nm.
In one or more embodiments, the emission layer may include a host and a dopant, the host may be any suitable host, and the dopant may include at least one organometallic compound represented by Formula 1, and the emission layer may further include a fluorescent dopant. The emission layer may emit fluorescent light that is generated by the transfer of the triplet excitons of the organometallic compound represented by Formula 1 to the fluorescent dopant, and then transition thereof.
The first electrode may be anode, which is a hole injection electrode, and the second electrode may be a cathode, which is an electron injection electrode. Alternatively, 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 some embodiments, the first electrode may be an anode, the second electrode may be a cathode, and the organic layer may include a hole transport region arranged between the first electrode and the emission layer, and an electron transport region arranged between the emission layer and the second electrode, wherein the hole transport region may include a hole injection layer, a hole transport layer, an electron blocking layer, or a combination thereof, and the electron transport region may include a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof.
For example, the organometallic compound represented by Formula 1 may be included in at least one of the hole transport region and the electron transport region.
According to another aspect, an electronic apparatus including the organic light-emitting device is provided.
The organic light-emitting device 10 in
A substrate may be additionally disposed under the first electrode 11 or on the second electrode 19. The substrate may be a conventional substrate that is commonly used in organic light-emitting devices, e.g., a glass substrate or a transparent plastic substrate, each having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and/or water repellency.
The first electrode 11 may be produced by depositing or sputtering, onto the substrate, a material for forming the first electrode 11. The first electrode 11 may be an anode. The material for forming the first electrode 11 may be selected from materials with a high work function for easy hole injection.
The first electrode 11 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. The material for forming the first electrode 11 may be indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), or zinc oxide (ZnO). In one or more embodiments, the material for forming the first electrode 11 may be metal, such as magnesium (Mg), aluminum (Al), silver (Ag), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), or magnesium-silver (Mg—Ag), or the like, but embodiments are not limited thereto.
The first electrode 11 may have a single-layered structure or a multi-layered structure including a plurality of layers. For example, the first electrode 11 may have a three-layered structure of ITO/Ag/ITO, but the structure of the first electrode 11 is not limited thereto.
The organic layer 15 may be located on the first electrode 11.
The organic layer 15 may include a hole transport region, an emission layer, an electron transport region, or a combination thereof.
The hole transport region may be arranged between the first electrode 11 and the emission layer.
The hole transport region may include at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a buffer layer, or a combination thereof.
The hole transport region may include only either a hole injection layer or a hole transport layer. In one or more embodiments, the hole transport region may have a hole injection layer/hole transport layer structure, or a hole injection layer/hole transport layer/electron blocking layer structure, wherein, for each structure, respective layers are sequentially stacked in this stated order from the first electrode 11.
When the hole transport region includes a hole injection layer, the hole injection layer may be formed on the first electrode 11 by using one or more suitable methods, such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) deposition, or the like, but embodiments are not limited thereto.
When a hole injection layer is formed by vacuum deposition, the deposition conditions may vary according to a material that is used to form the hole injection layer, and the structure and thermal characteristics of the hole injection layer. For example, the deposition conditions may include a deposition temperature of about 100° C. to about 500° C., a vacuum pressure of about 10−8 torr to about 10−3 torr, and a deposition rate of about 0.01 angstroms per second (Å/sec) to about 100 Å/sec. However, the deposition conditions are not limited thereto.
When a hole injection layer is formed by spin coating, the spin coating may be performed at a rate in a range of about 2,000 revolutions per minute (rpm) to about 5,000 rpm and at a temperature of about 80° C. to 200° C. to facilitate removal of a solvent after the spin coating, though the conditions may vary depending on a compound used as a hole injection material and a structure and thermal properties of a desired hole injection layer, but embodiments are not limited thereto.
The conditions for forming the hole transport layer and the electron blocking layer may be similar to or the same as the conditions for forming the hole injection layer.
The hole transport region may include, for example, at least one of 4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (TDATA), 4,4′,4″-tris{N-(2-naphthyl)-N-phenylamino}-triphenylamine (2-TNATA), N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine (NPB), β-NPB, N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1-biphenyl]-4,4′-diamine (TPD), spiro-TPD, spiro-NPB, methylated NPB, 4,4′-cyclohexylidene bis[N,N-bis(4-methylphenyl)benzenamine] (TAPC), 4,4′-bis[N,N′-(3-tolyl)amino]-3,3′-dimethylbiphenyl (HMTPD), 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (PANI/CSA), polyaniline/poly(4-styrenesulfonate) (PANI/PSS), a compound represented by Formula 201, or a compound represented by Formula 202, but embodiments are not limited thereto:
Ar101 and Ar102 in Formula 201 may each independently be a phenylene group, a pentalenylene group, an indenylene group, a naphthylene group, an azulenylene group, a heptalenylene group, an acenaphthylene group, a fluorenylene group, a phenalenylene group, a phenanthrenylene group, an anthracenylene group, a fluoranthenylene group, a triphenylenylene group, a pyrenylene group, a chrysenylenylene group, a naphthacenylene group, a pienylene group, a perylenylene group, or a pentacenylene group, each unsubstituted or substituted with at least one of deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a 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 C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C7-C60 alkyl aryl group, a C7-C60 aryl alkyl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C1-C60 heteroaryl group, a C2-C60 alkyl heteroaryl group, a C2-C60 heteroaryl alkyl 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, or a combination thereof.
xa and xb in Formula 201 may each independently be an integer from 0 to 5, or 0, 1, or 2. For example, xa may be 1 and xb may be 0, but xa and xb are not limited thereto.
R101 to R108, R111 to R119 and R121 to R124 in Formulae 201 and 202 may each independently be:
In Formula 201, R109 may be a phenyl group, a naphthyl group, an anthracenyl group, or a pyridinyl group, each unsubstituted or substituted with at least one of deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a phenyl group, a naphthyl group, an anthracenyl group, a pyridinyl group, or a combination thereof.
In one embodiment, the compound represented by Formula 201 may be represented by Formula 201A:
R101, R111, R112, and R109 in Formula 201A are each as described herein.
For example, the hole transport region may include at least one of Compounds HT1 to HT20, or a combination thereof, but embodiments are not limited thereto:
A thickness of the hole transport region may be about 100 Å to about 10,000 Å, for example, about 100 Å to about 1,000 Å. When the hole transport region includes at least one of a hole injection layer and a hole transport layer, a thickness of the hole injection layer may be about 100 Å to about 10,000 Å, for example, about 100 Å to about 1,000 Å, and a thickness of the hole transport layer may be about 50 Å to about 2,000 Å, for example, about 100 Å to about 1,500 Å. Without wishing to be bound to theory, when the thicknesses of the hole transport region, the hole injection layer, and the hole transport layer are within these ranges, satisfactory hole transporting characteristics may be obtained without a substantial increase in driving voltage.
The hole transport region may further include, in addition to these materials, a charge-generation material for the improvement of conductive properties. The charge-generation material may be homogeneously or non-homogeneously dispersed in the hole transport region.
The charge-generation material may be, for example, a p-dopant. The p-dopant may include a quinone derivative, a metal oxide, a cyano group-containing compound, or a combination thereof, but embodiments are not limited thereto. For example, non-limiting examples of the p-dopant include a quinone derivative, such as tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4-TCNQ), 1,3,4,5,7,8-hexafluorotetracyanonaphthoquinodimethane (F6-TCNQ), or the like; a metal oxide, such as a tungsten oxide, a molybdenum oxide, or the like; or a compound containing a cyano group, such as Compound HT-D1 or Compound HT-D2, but embodiments are not limited thereto:
The hole transport region may include a buffer layer.
In some embodiments, the buffer layer may compensate for an optical resonance distance according to a wavelength of light emitted from the emission layer, and thus, efficiency of a formed organic light-emitting device may be improved.
The emission layer may be formed on the hole transport region by using one or more suitable methods, such as vacuum deposition, spin coating, casting, LB deposition, or the like. When the emission layer is formed by vacuum deposition or spin coating, the deposition or coating conditions may be similar to those applied in forming the hole injection layer although the deposition or coating conditions may vary according to a material that is used to form the emission layer.
The hole transport region may further include an electron blocking layer. The electron blocking layer may include a material available in the art, for example, 1,3-bis(N-carbazolyl)benzene (mCP), but embodiments are not limited thereto.
A thickness of the electron blocking layer may be about 50 Å to about 1,000 Å, for example about 70 Å to about 500 Å. Without wishing to be bound to theory, when the thickness of the electron blocking layer is within the range described above, the electron blocking layer may have satisfactory electron blocking characteristics without a substantial increase in driving voltage.
When the organic light-emitting device 10 is a full-color organic light-emitting device 10, the emission layer may be patterned into a red emission layer, a green emission layer, and/or a blue emission layer. In one or more embodiments, due to a stacked structure including a red emission layer, a green emission layer, and/or a blue emission layer, the emission layer may emit a white light.
The emission layer may include at least one of the organometallic compounds represented by Formula 1.
The emission layer may include a host and a dopant, and the dopant may include at least one of the organometallic compounds represented by Formula 1.
The host may include, for example, at least one of 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene (TPBi), 3-tert-butyl-9,10-di(naphth-2-yl)anthracene (TBADN), 9,10-di(naphthalene-2-yl)anthracene (ADN) (also referred to as “DNA”), 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP), 4,4′-bis(9-carbazolyl)-2,2′-dimethyl-biphenyl (CDBP), 1,3,5-tris(carbazole-9-yl)benzene (TCP), 1,3-bis(N-carbazolyl)benzene (mCP), Compound H50, Compound H51, Compound H52, or a combination thereof, but embodiments are not limited thereto:
In one or more embodiments, the host may further include a compound represented by Formula 301, but embodiments are not limited thereto:
Ar111 and Ar112 in Formula 301 may each independently be:
Ar113 to Ar116 in Formula 301 may each independently be:
In Formula 301, g, h, i, and j may each independently be 0, 1, 2, 3, or 4, for example, g, h, i, and j may each independently be 0, 1, or 2.
Ar113 to Ar116 in Formula 301 may each independently be:
but embodiments are not limited thereto.
In one or more embodiments, the host may include a compound represented by Formula 302, but embodiments are not limited thereto:
Ar122 to Ar125 in Formula 302 may be as described in detail 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, a propyl group, or the like).
In Formula 302, k and l may each independently be an integer of 0, 1, 2, 3, or 4. For example, k and l may each independently be 0, 1, or 2.
When the organic light-emitting device 10 is a full-color organic light-emitting device 10, the emission layer may be patterned into a red emission layer, a green emission layer, and/or a blue emission layer. In one or more embodiments, due to a stacked structure including a red emission layer, a green emission layer, and/or a blue emission layer, the emission layer may emit a white light.
When the emission layer includes a host and a dopant, the amount of the dopant in the emission layer may be about 0.01 parts by weight to about 20 parts by weight, based on 100 parts by weight of the emission layer. However, the amount of the dopant included in the emission layer is not limited thereto. When the amount of the dopant satisfies the above range, it may be possible to realize emission without extinction phenomenon.
In one embodiment, the organic layer of the organic light-emitting device may further include a fluorescent dopant in addition to at least one of the organometallic compounds represented by Formula 1.
In some embodiments, the fluorescent dopant may be a condensed polycyclic compound, a styryl-containing compound, or a combination thereof.
According to one or more embodiments, the fluorescent dopant may include a compound represented by Formula 501:
For example, in Formula 50,
The fluorescent dopant may include, for example, at least one of Compounds FD(1) to FD(16), Compounds FD1 to FD13, or a combination thereof, but embodiments are not limited thereto:
The thickness of the emission layer may be about 100 Å to about 1,000 Å, for example, about 200 Å to about 600 Å. Without wishing to be bound to theory, when the thickness of the emission layer 120 is within these ranges, excellent luminescence characteristics may be obtained without a substantial increase in driving voltage.
An electron transport region may be located on the emission layer.
The electron transport region may include at least one of a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof.
For example, the electron transport region may have a hole blocking layer/electron transport layer/electron injection layer structure, or an electron transport layer/electron injection layer structure, and the structure of the electron transport region is not limited thereto. The electron transport layer may have a single-layered structure or a multi-layered structure including two or more different materials.
Conditions for forming the hole blocking layer, the electron transport layer, and the electron injection layer which constitute the electron transport region may be understood by referring to the conditions for forming the hole injection layer.
When the electron transport region includes a hole blocking layer, the hole blocking layer may include, for example, at least one of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), or a combination thereof, but embodiments are not limited thereto:
A thickness of the hole blocking layer may be about 20 Å to about 1,000 Å, for example, about 30 Å to about 300 Å. Without wishing to be bound to theory, when the thickness of the hole blocking layer is within these ranges, excellent hole blocking characteristics may be obtained without a substantial increase in driving voltage.
The electron transport layer may include, for example, at least one of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), tris(8-hydroxy-quinolinato)aluminum (Alq3), bis(2-methyl-8-quinolinolato-N1,O8)-(1,1′-biphenyl-4-olato)aluminum (BAlq), 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole (TAZ), 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole (NTAZ), or a combination thereof, but embodiments are not limited thereto:
In one or more embodiments, the electron transport layer may include at least one of ET1 to ET25, but embodiments are not limited thereto:
A thickness of the electron transport layer may be about 100 Å to about 1,000 Å, for example, about 150 Å to about 500 Å. Without wishing to be bound to theory, when the thickness of the electron transport layer is within the range described above, the electron transport layer may have satisfactory electron transporting characteristics without a substantial increase in driving voltage.
The electron transport layer may include a metal-containing material in addition to the material as described herein.
The metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 (lithium quinolate, LiQ) or ET-D2, but embodiments are not limited thereto:
The electron transport region may include an electron injection layer that facilitates injection of electrons from the second electrode 19.
The electron injection layer may include at least one of LiQ, LiF, NaCl, CsF, Li2O, or BaO, but embodiments are not limited thereto.
A thickness of the electron injection layer may be in a range of about 1 Å to about 100 Å, and, for example, about 3 Å to about 90 Å. Without wishing to be bound to theory, when the thickness of the electron injection layer is within the ranges above, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.
The second electrode 19 may be located on the organic layer 15. The second electrode 19 may be a cathode. 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. For example, lithium (Li), magnesium (Mg), aluminum (Al), silver (Ag), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), or magnesium-silver (Mg—Ag) may be used as the material for forming the second electrode 19. In one or more embodiments, to manufacture a top-emission type light-emitting device, a transmissive electrode formed using ITO or IZO may be used as the second electrode 19.
Hereinbefore, the organic light-emitting device has been described with reference to
According to another aspect, the organic light-emitting device may be included in an electronic apparatus. Thus, an electronic apparatus including the organic light-emitting device is provided. The electronic apparatus may include, for example, a display, an illumination, a sensor, or the like, but embodiments are not limited thereto.
According to another aspect, a diagnostic composition may include at least one organometallic compound represented by Formula 1.
As the organometallic compound represented by Formula 1 provides a high luminescence efficiency, the diagnostic composition including at least one of the organometallic compounds represented by Formula 1 may have a high diagnostic efficiency.
The diagnostic composition may be used in various applications, for example, including a diagnosis kit, a diagnosis reagent, a biosensor, a biomarker, or the like, but embodiments are not limited thereto.
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 non-limiting 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, a hexyl group, or the like. 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” used herein refers to a monovalent group represented by —OA101 (wherein A101 is the C1-C60 alkyl group), and non-limiting examples thereof include a methoxy group, an ethoxy group, an isopropyloxy group, or the like.
The term “C2-C60 alkenyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60 alkyl group, and non-limiting examples thereof include an ethenyl group, a propenyl group, a butenyl group, or the like. 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 refers to a hydrocarbon group formed by substituting at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60 alkyl group, and non-limiting examples thereof include an ethynyl group, a propynyl group, or the like. 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 non-limiting examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or the like. 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 monocyclic group having at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and 1 to 10 carbon atoms as ring-forming atom(s), and non-limiting examples thereof include a tetrahydrofuranyl group, a tetrahydrothiophenyl group, or the like. 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 non-limiting examples thereof include a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, or the like. 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 selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom, 1 to 10 carbon atoms as ring-forming atom(s), and at least one double bond in its ring. Non-limiting examples of the C1-C10 heterocycloalkenyl group include a 2,3-dihydrofuranyl group, a 2,3-dihydrothiophenyl group, or the like. 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 ring system having 6 to 60 carbon atoms, and the term “C6-C60 arylene group” as used herein refers to a divalent group having a carbocyclic aromatic ring system having 6 to 60 carbon atoms. Non-limiting examples of the C6-C60 aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a chrysenyl group, or the like. 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 “C1-C60 heteroaryl group” as used herein refers to a monovalent group having a carbocyclic aromatic ring system that has at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom, and 1 to 60 carbon atoms as ring-forming atom(s). The term “C1-C60 heteroarylene group” as used herein refers to a divalent group having a carbocyclic aromatic ring system that has at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom, and 1 to 60 carbon atoms as ring-forming atom(s). Non-limiting 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, an isoquinolinyl group, or the like. 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 indicates —OA102 (wherein A102 is the C6-C60 aryl group), and the term “C6-C60 arylthio group” as used herein indicates —SA103 (wherein A103 is the C6-C60 aryl group).
The term “C1-C60 heteroaryloxy group” as used herein indicates —OA102′ (wherein A102 is the C1-C60 heteroaryl group), and the term “C1-C60 heteroarylthio group” as used herein indicates —SA103′ (wherein A103′ is the C1-C60 heteroaryl 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 to each other, only carbon atoms as ring-forming atoms, and no aromaticity in its entire molecular structure. Non-limiting examples of the monovalent non-aromatic condensed polycyclic group include a fluorenyl group or the like. The term “divalent non-aromatic condensed polycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed polycyclic group described above.
The term “monovalent non-aromatic condensed heteropolycyclic group” as used herein refers to a monovalent group (for example, having 2 to 60 carbon atoms) having two or more rings condensed with each other, at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B, other than carbon atoms, as a ring-forming atom, and no aromaticity in its entire molecular structure. Non-limiting examples of the monovalent non-aromatic condensed heteropolycyclic group include a carbazolyl group or the like. 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 described above.
The term “C5-C30 carbocyclic group” as used herein refers to a saturated or unsaturated ring group having, as a ring-forming atom, 5 to 30 carbon atoms only. The C5-C30 carbocyclic group may be a monocyclic group or a polycyclic group.
The term “C1-C30 heterocyclic group” as used herein refers to a saturated or unsaturated ring group having, as a ring-forming atom, at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B, other than 1 to 30 carbon atoms as ring-forming atom(s). The C1-C30 heterocyclic group may be a monocyclic group or a polycyclic group.
At least one substituent of the substituted C5-C30 carbocyclic group, the substituted C1-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 C7-C60 alkyl aryl group, the substituted C7-C60 aryl alkyl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl group, the substituted C2-C60 alkyl heteroaryl group, the substituted C2-C60 heteroaryl alkyl group, the substituted C1-C60 heteroaryloxy group, the substituted C1-C60 heteroarylthio group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may be:
For example, Q1 to Q9, Q11 to Q19, Q21 to Q29 and Q31 to Q39 as described herein may each independently be:
The term “room temperature” used herein refers to a temperature of about 25° C.
The terms “a biphenyl group, a terphenyl group, and a tetraphenyl group” as used herein each refers to a monovalent group having two, three, or four phenyl groups linked via a single bond, respectively.
Hereinafter, a compound and an organic light-emitting device according to exemplary embodiments are described in further detail with reference to Synthesis Example 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.
After 59.2 millimoles (mmol) (18.7 grams (g)) of 9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-ol and 71.1 mmol (12.5 g) of 2-bromo-4-fluoropyridine were dissolved in 300 milliliters (mL) of dimethyl sulfoxide (DMSO), 118.5 mmol (16.4 g) of K2CO3 was added thereto, followed by heating at reflux at 150° C. for 12 hours. After completion of the reaction, the resultant mixture was allowed to cool to room temperature, and an organic layer was extracted therefrom using a mixture of ethyl acetate and water. The organic layer was washed three times with water and dried using anhydrous magnesium sulfate. Then, a solvent was removed therefrom under a reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (eluents: ethyl acetate:hexane) to obtain Intermediate 1(1) (yield: 72%). The product was identified by high-performance liquid chromatography-mass spectrometry (HPLC-MS).
HPLC-MS: m/z=474.09 [M+H]+.
After 14.8 mmol (7.0 g) of Intermediate 1(1) and 19.3 mmol (2.3 g) of 1H-benzo[d]imidazole were dissolved in 75 mL of DMSO, 3.0 mmol (0.6 g) of CuI, 5.9 mmol (0.7 g) of (±)-trans-1,2-diaminocyclohexane, and 44.4 mmol (6.1 g) of K2CO3 were added thereto, followed by heating at reflux at 90° C. for 12 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, and an organic layer was extracted therefrom using the mixture including ethyl acetate and water. The organic layer was washed three times with water and dried using anhydrous magnesium sulfate, and then, a solvent was removed therefrom under a reduced pressure, thereby obtaining a crude product. The crude product was purified by silica gel column chromatography (eluents: ethyl acetate:hexane) to obtain Intermediate 1(2) (yield: 56%). The product was identified by HPLC-MS.
HPLC-MS: m/z=510.18 [M+H]+.
8.3 mmol (4.35 g) of Intermediate 1(2), 10.3 mmol (6.3 g) of (3,5-di-tert-butylphenyl)(mesityl)iodonium triflate (−OTf), and 0.8 mmol (0.2 g) copper (II) acetate (Cu(Oac)2) were added to 50 mL of dimethylformamide (DMF), followed by heating at reflux at 100° C. for 3 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, and an organic layer was extracted therefrom using a mixture including ethyl acetate and water. The organic layer was washed three times with water and dried using anhydrous magnesium sulfate, and then, a solvent was removed therefrom under a reduced pressure, thereby obtaining a crude product. The crude product was purified by silica gel column chromatography (eluents: dichloromethane:acetone) to obtain Intermediate 1(3) (yield: 89%). The product was identified by HPLC-MS.
HPLC-MS: m/z=698.39 [M-OTf]+.
7.4 mmol (6.3 g) of Intermediate 1(3), 8.1 mmol (3.0 g) of (1,5-cyclooctadiene)platinum(II) dichloride (Pt(COD)Cl2), and 22.2 mmol (1.8 g) of sodium acetate were mixed with 130 mL of benzonitrile, followed by stirring and heating at 180° C. for 18 hours. Once the reaction was completed, the mixture was allowed to cool to room temperature, and the solvent was removed under reduced pressure. The resultant product thus obtained was purified by silica gel column chromatography to obtain Compound 1 (yield=18%). The product was identified by HPLC-MS.
HPLC-MS: m/z=891.34 [M+H]+.
After 51.0 mmol (20.0 g) of 9-(4-(tert-butyl)pyridin-2-yl)-6-phenyl-9H-carbazol-2-ol, and 66.3 mmol (11.7 g) of 2-bromo-4-fluoropyridine were dissolved in 250 mL of DMSO, 101.9 mmol (14.1 g) of potassium carbonate (K2CO3) was added thereto, followed by heating at reflux at 150° C. for 12 hours. After completion of the reaction, the resultant mixture was allowed to cool to room temperature, and an organic layer was extracted therefrom using a mixture of ethyl acetate and water. The organic layer was washed three times with water and dried using anhydrous magnesium sulfate. Then, a solvent was removed therefrom under a reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (eluents: ethyl acetate:hexane) to obtain Intermediate 2(1) (yield: 79%). The product was identified by HPLC-MS.
HPLC-MS: m/z=550.08 [M+H]+.
Intermediate 2(2) was synthesized in a similar manner as in Synthesis of Intermediate 1(2) in Synthesis Example 1, except that Intermediate 2(1) was used instead of Intermediate 1(1) (yield: 83%). The product was identified by HPLC-MS.
HPLC-MS: m/z=586.31 [M+H]+.
Intermediate 2(3) was synthesized in a similar manner as in Synthesis of Intermediate 1(3) in Synthesis Example 1, except that Intermediate 2(2) was used instead of Intermediate 1(2) (yield: 82%). The product was identified by HPLC-MS.
HPLC-MS: m/z=774.43 [M-OTf]+.
Compound 2 was synthesized in a similar manner as in Synthesis of Compound 1 in Synthesis Example 1, except that Intermediate 2(3) was used instead of Intermediate 1(3) (yield: 20%). The product was identified by HPLC-MS.
HPLC-MS: m/z=967.15 [M+H]+.
After 23.4 mmol (10.0 g) of 2-((2-bromopyridin-4-yl)oxy)-9-(4-(4-(tert-butyl)-2,6-bis(methyl-d3)phenyl)pyridin-2-yl)-9H-carbazole and 28.1 mmol (4.9 g) of 2-bromo-4-fluoropyridine were dissolved in 120 mL of DMSO, 46.9 mmol (6.5 g) of K2CO3 was added thereto, followed by heating at reflux at 150° C. for 12 hours. After completion of the reaction, the resultant mixture was allowed to cool to room temperature, and an organic layer was extracted therefrom using a mixture of ethyl acetate and water. The organic layer was washed three times with water and dried using anhydrous magnesium sulfate. Then, a solvent was removed therefrom under a reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (eluents: ethyl acetate:hexane) to obtain Intermediate 3(1) (yield: 94%). The product was identified by HPLC-MS.
HPLC-MS: m/z=584.21 [M+H]+.
Intermediate 3(2) was synthesized in a similar manner as in Synthesis of Intermediate 1(2) in Synthesis Example 1, except that Intermediate 3(1) was used instead of Intermediate 1(1) (yield: 78%). The product was identified by HPLC-MS.
HPLC-MS: m/z=620.33 [M+H]+.
Intermediate 3(3) was synthesized in a similar manner as in Synthesis of Intermediate 1(3) in Synthesis Example 1, except that Intermediate 3(2) was used instead of Intermediate 1(2) (yield: 79%). The product was identified by HPLC-MS.
HPLC-MS: m/z=808.48 [M-OTf]+.
Compound 3 was synthesized in a similar manner as in Synthesis of Compound 1 in Synthesis Example 1, except that Intermediate 3(3) was used instead of Intermediate 1(3) (yield: 25%). The product was identified by HPLC-MS.
HPLC-MS: m/z=1001.44 [M+H]+.
After 25.4 mmol (5.4 g) of 3-nitro-[1,1′-biphenyl]-4-amine (4(1)) and 21.2 mmol (10.0 g) of 2-((2-bromopyridin-4-yl)oxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1(1)) were dissolved in 210 mL of toluene, 4.2 mmol (3.9 g) of tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), 8.5 mmol (3.5 g) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos), and 31.8 mmol (3.1 g) of sodium tert-butoxide (NaOtBu) were added thereto, followed by heating at reflux at 110° C. for 6 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, and an organic layer was extracted therefrom using ethyl acetate and water. The organic layer was washed three times with water and dried using anhydrous magnesium sulfate, and then, a solvent was removed therefrom under a reduced pressure, thereby obtaining a crude product. The crude product was purified by silica gel column chromatography (eluents: ethyl acetate:hexane) to obtain Intermediate 4(2) (yield: 64%). The product was identified by HPLC-MS.
HPLC-MS: m/z=606.25 [M+H]+.
After 13.5 mmol (8.2 g) of Intermediate 4(2) and 13.5 mmol (1.4 g) of palladium on carbon (Pd/C) were dissolved in 130 mL of ethanol, 270 mmol (13.5 g) of hydrazine monohydrate (N2H4 H2O, also referred to as H2NNH2 H2O) was added thereto, followed by heating at reflux at 85° C. for 4 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, filtered using celite, and an organic layer was extracted therefrom using ethyl acetate and water. The organic layer was washed three times with water and dried using anhydrous magnesium sulfate, and then, a solvent was removed therefrom under a reduced pressure, thereby obtaining a crude product. The crude product was purified by silica gel column chromatography (eluents: dichloromethane:methanol) to obtain Intermediate 4(3) (yield: 96%). The product was identified by HPLC-MS.
HPLC-MS: m/z=576.27 [M+H]+.
12.2 mmol (7.0 g) of Intermediate 4(3) was dissolved in 270 mmol (13.5 g) of formic acid, followed by heating at reflux at 110° C. for 4 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, neutralized using NaHCO3, and an organic layer was extracted using therefrom using ethyl acetate and water. The organic layer was washed three times with water and dried using anhydrous magnesium sulfate, and then, a solvent was removed therefrom under a reduced pressure, thereby obtaining a crude product. The crude product was purified by silica gel column chromatography (eluents: dichloromethane:methanol) to obtain Intermediate 4(4) (yield: 75%). The product was identified by HPLC-MS.
HPLC-MS: m/z=586.07 [M+H]+.
Intermediate 4(5) was synthesized in a similar manner as in Synthesis of Intermediate 1(3) in Synthesis Example 1, except that Intermediate 4(4) was used instead of Intermediate 1(2) (yield: 74%). The product was identified by HPLC-MS.
HPLC-MS: m/z=774.41 [M-OTf]+.
Compound 4 was synthesized in a similar manner as in Synthesis of Compound 1 in Synthesis Example 1, except that Intermediate 4(5) was used instead of Intermediate 1(3) (yield: 29%). The product was identified by HPLC-MS.
HPLC-MS: m/z=967.29 [M+H]+.
After 41.2 mmol (13.7 g) of 9-(4-(2,2-dimethylpropyl-1,1-d2)pyridin-2-yl)-9H-carbazol-2-ol and 49.5 mmol (8.7 g) of 2-bromo-4-fluoropyridine were dissolved in 205 mL of DMSO, 82.4 mmol (11.4 g) of K2CO3 was added thereto, followed by heating at reflux at 150° C. (“° C.” is written as “C” in the reaction scheme below) for 12 hours. After completion of the reaction, the resultant mixture was allowed to cool to room temperature, and an organic layer was extracted therefrom using a mixture of ethyl acetate and water. The organic layer was washed three times with water and dried using anhydrous magnesium sulfate. Then, a solvent was removed therefrom under a reduced pressure to obtain a crude product. The crude product was subjected to purification by silica gel column chromatography (eluents: ethyl acetate:hexane) to obtain Intermediate 5(1) (yield: 99%). The product was identified by HPLC-MS.
HPLC-MS: m/z=490.13 [M+H]+.
Intermediate 5(2) was synthesized in a similar manner as in Synthesis of Intermediate 1(2) in Synthesis Example 1, except that Intermediate 5(1) was used instead of Intermediate 1(1) (yield: 63%). The product was identified by HPLC-MS.
HPLC-MS: m/z=526.25 [M+H]+.
12.8 mmol (6.7 g) of Intermediate 5(2), 16.6 mmol (8.8 g) of (3-(tert-butyl)phenyl)(mesityl)iodonium triflate, and 1.2 mmol (0.2 g) of copper (II) acetate were added to 65 mL of DMF, followed heating at reflux at 100° C. for 3 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, and an organic layer was extracted therefrom using ethyl acetate and water. The organic layer was washed three times with water and dried using anhydrous magnesium sulfate, and then, a solvent was removed therefrom under a reduced pressure, thereby obtaining a crude product. The crude product was purified by silica gel column chromatography (eluents: dichloromethane:acetone) to obtain Intermediate 5(3) (yield: 84%). The product was identified by HPLC-MS.
HPLC-MS: m/z=659.36 [M-OTf]+.
Compound 5 was synthesized in a similar manner as in Synthesis of Compound 1 in Synthesis Example 1, except that Intermediate 5(3) was used instead of Intermediate 1(3) (yield: 13%). The product was identified by HPLC-MS.
HPLC-MS: m/z=851.29 [M+H]+.
Intermediate 6(1) was synthesized in a similar manner as in Synthesis of Intermediate 1(3) in Synthesis Example 1, except that Intermediate 5(2) was used instead of Intermediate 1(2) (yield: 74%). The product was identified by HPLC-MS.
HPLC-MS: m/z=714.41 [M-OTf]+.
Compound 6 was synthesized in a similar manner as in Synthesis of Compound 1 in Synthesis Example 1, except that Intermediate 6(1) was used instead of Intermediate 1(3) (yield: 24%). The product was identified by HPLC-MS.
HPLC-MS: m/z=908.36 [M+H]+.
Compound 7(1) was synthesized in a similar manner as in Synthesis of Compound 1(1) in Synthesis Example 1, except that 3-bromo-5-fluoropyridine was used instead of 2-bromo-4-fluoropyridine (yield: 54%). The product was identified by HPLC-MS.
HPLC-MS: m/z=472.10 [M+H]+.
Compound 7(2) was synthesized in a similar manner as in Synthesis of Compound 1(2) in Synthesis Example 1, except that Intermediate 7(1) was used instead of Intermediate 1(1) (yield: 45%). The product was identified by HPLC-MS.
HPLC-MS: m/z=510.19 [M+H]+.
Compound 7(3) was synthesized in a similar manner as in Synthesis of Compound 1(3) in Synthesis Example 1, except that Intermediate 7(2) was used instead of Intermediate 1(2) (yield: 76%). The product was identified by HPLC-MS.
HPLC-MS: m/z=698.34 [M-OTf]+.
Compound 7 was synthesized in a similar manner as in Synthesis of Compound 1 in Synthesis Example 1, except that Intermediate 7(3) was used instead of Intermediate 1(3) (yield: 21%). The product was identified by HPLC-MS.
HPLC-MS: m/z=891.27 [M+H]+.
Compounds 1 and 7 and Comparative Compound C1 were each diluted in toluene at a concentration of 10−4 molar (M). Then, the PL spectrum of each of the compounds was measured by using an ISC PC1 spectrofluorometer, in which a xenon lamp was mounted. The results thereof are shown in
The maximum emission wavelength (λmax, nm), the FWHM (nm), and the PLQY were obtained from the PL spectrum of each compound and shown in Table 3.
The HOMO and LUMO energy levels were measured by differential pulse voltammetry (DPV). The solvent used for the measurement was DMF, and tetrabutylammonium fluoride (TBAF) was used as an electrolyte. In addition, the reference electrode Ag/Ag+ was used, and the counter electrode Pt and the working electrode Pt were used. During the measurement, ferrocene (Fc) as used as a reference material, and the HOMO of Fc was known to be −4.8 eV. Therefore, the HOMO and LUMO energy levels of the compounds were calculated by applying the potential values measured by DPV to the data calculation method used to obtain results shown in Table 2 below.
From Table 3, it was confirmed that Compounds 1 to 7 have a deeper HOMO energy level, emit a blue light having higher energy, have an equal or less FWHM, and have a higher PLQY, as compared to Comparative Example Compound C1.
A glass substrate having 500 Å of indium tin oxide (ITO) electrode (first electrode, anode) deposited thereon was washed with DI water in the presence of ultrasonic waves. After the DI water ultrasonication, ultrasonic cleaning was performed with isopropyl alcohol, acetone, and then, methanol, in this stated order, and the glass substrate was dried and transferred to a plasma cleaner. The glass substrate was cleaned by using oxygen plasma for 5 minutes, and then transferred to a vacuum laminator.
Compound HT3 was vacuum-deposited on the ITO electrode of the glass substrate to form a first hole injection layer having a thickness of 3,500 Å, Compound HT-D1 was vacuum-deposited on the first hole injection layer to form a second hole injection layer having a thickness of 300 Å, and then, TAPC was vacuum-deposited on the second hole injection layer to form an electron blocking layer having a thickness of 100 Å, thereby completing the manufacture of a hole transport region.
Compound H52 and Compound 1 (10 wt %) were co-deposited on the hole transport region to form an emission layer having a thickness of 300 Å.
Compound ET3 was vacuum-deposited on the emission layer to form an electron transport layer having a thickness of 250 Å, and then, ET-D1 (Liq) was deposited on the electron transport layer to form an electron injection layer having a thickness of 5 Å, and then, an Al second electrode (cathode) having a thickness of 1,000 Å was formed on the electron injection layer, thereby completing the manufacture of an organic light-emitting device.
Organic light-emitting devices were manufactured in a similar manner as in Example 1-1, except that the dopant compounds shown in Table 4 were each used instead of Compound 1 in forming an emission layer.
A glass substrate, having 500 Å of indium tin oxide (ITO) electrode (first electrode, anode) deposited thereon, was washed with DI water in the presence of ultrasonic waves. After the DI water ultrasonication, ultrasonic cleaning was performed with isopropyl alcohol, acetone, and then, methanol, in this stated order, and the glass substrate was dried and transferred to a plasma cleaner. The glass substrate was cleaned by using oxygen plasma for 5 minutes, and then transferred to a vacuum laminator.
Compound HT3 was vacuum-deposited on the ITO electrode of the glass substrate to form a first hole injection layer having a thickness of 3,500 Å, Compound HT-D1 was vacuum-deposited on the first hole injection layer to form a second hole injection layer having a thickness of 300 Å, and then, TAPC was vacuum-deposited on the second hole injection layer to form an electron blocking layer having a thickness of 100 Å, thereby completing the manufacture of a hole transport region.
Compound H52 and Compound 1 (10 wt %) were co-deposited on the hole transport region to form an emission layer having a thickness of 300 Å.
Compound ET3 was vacuum-deposited on the emission layer to form an electron transport layer having a thickness of 250 Å, and then, ET-D1 (Liq) was vacuum deposited on the electron transport layer to form an electron injection layer having a thickness of 5 Å, and then, an Al second electrode (cathode) having a thickness of 1,000 Å was formed on the electron injection layer, thereby completing the manufacture of an organic light-emitting device.
Organic light-emitting devices were manufactured in a similar manner as in Example 2-1, except that the dopant compounds shown in Table 5 were each used instead of Compound 1 in forming an emission layer.
A glass substrate having 500 Å of an indium tin oxide (ITO) electrode (first electrode, anode) deposited thereon was washed with DI water in the presence of ultrasonic waves. After the DI water ultrasonication, ultrasonic cleaning was performed with isopropyl alcohol, acetone, and then, methanol, in this stated order, and the glass substrate was dried and transferred to a plasma cleaner. The glass substrate was cleaned by using oxygen plasma for 5 minutes, and then transferred to a vacuum laminator.
Compound HT3 was vacuum-deposited on the ITO electrode of the glass substrate to form a first hole injection layer having a thickness of 3,500 Å, Compound HT-D1 was vacuum-deposited on the first hole injection layer to form a second hole injection layer having a thickness of 300 Å, and then, TAPC was vacuum-deposited on the second hole injection layer to form an electron blocking layer having a thickness of 100 Å, thereby completing the manufacture of a hole transport region.
Compound H52 and Compound 1 (10 wt %) were co-deposited on the hole transport region to form an emission layer having a thickness of 300 Å.
Compound ET3 was vacuum-deposited on the emission layer to form an electron transport layer having a thickness of 250 Å, and then, ET-D1 (Liq) was deposited on the electron transport layer to form an electron injection layer having a thickness of 5 Å, and then, an Al second electrode (cathode) having a thickness of 1,000 Å was formed on the electron injection layer, thereby completing the manufacture of an organic light-emitting device.
Organic light-emitting devices were manufactured in a similar manner as in Example 3-1, except that the dopant compounds shown in Table 6 were each used instead of Compound 1 in forming an emission layer.
The EL spectrum of each of the organic light-emitting devices manufactured in Examples 1-1 to 1-6 and Comparative Examples 1-1 and 1-2, Examples 2-1 to 2-5 and Comparative Examples 2-1 and 2-2, and Examples 3-1 to 3-6 and Comparative Examples 3-1 and 3-2 was measured, and from the EL spectrum of each device, various properties were measured. The results thereof are shown in Tables 4, 5, and 6. In Table 4, the driving voltage (Volts, V), maximum emission wavelength (λmax, nm), CIE y color coordinate (CIEy), and external quantum luminescence efficiency (EQE, relative %) were evaluated for Comparative Examples 1-1 and 1-2, and Examples 1-1 to 1-6. In Table 5, the driving voltage (V), CIE y color coordinate (CIEy), conversion efficiency (cd/A/y, relative value, %), and the lifespan (T95, relative %) were evaluated for Comparative Examples 2-1 and 2-2, and Examples 2-1 to 2-5. In Table 6, the driving voltage (V), CIE y color coordinate (CIEy), photoluminescence quantum yield (PLQY), and external quantum luminescence efficiency (EQE, relative %) were evaluated for Comparative Examples 3-1 and 3-2, and Examples 3-1 to 3-6. The EL spectra of the manufactured organic light-emitting devices at a luminance of 1,000 candela per square meter (cd/m2) were measured by using a luminance meter (Minolta Cs-1000A). Then, the maximum emission wavelength was evaluated. The driving voltage and the external quantum luminescence efficiency were evaluated by using a current-voltage meter (Keithley 2400) and a luminance meter (Minolta Cs-1000A), and the lifespan was evaluated based on the time taken for the luminance to decrease to 95% of the initial luminance. In addition, the conversion efficiency (cd/A/y) was obtained by dividing the EQE by the CIEy value.
From Table 4, it was confirmed that the organic light-emitting devices of Examples 1-1 to 1-6 have lower driving voltages and higher external quantum luminescence efficiencies, compared to the organic light-emitting devices of Comparative Examples 1-1 and 1-2.
From Table 5, it was confirmed that the organic light-emitting devices of Examples 2-1 to 2-5 have lower driving voltages, higher conversion efficiencies, and longer lifespans, compared to the organic light-emitting devices of Comparative Examples 2-1 and 2-2.
From Table 6, it was confirmed that the organic light-emitting devices of Examples 3-1 to 6-6 have lower driving voltages, higher PLQYs, and higher external quantum luminescence efficiencies, compared to the organic light-emitting devices of Comparative Examples 3-1 and 3-2.
By using at least one of the organometallic compounds represented by Formula 1 in an emission layer, an organic light-emitting device having excellent luminescence efficiency characteristics, and an electronic apparatus including the same may be provided.
It should be understood that exemplary embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each exemplary embodiment should typically be considered as available for other similar features or aspects in other exemplary embodiments. While one or more exemplary embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0178681 | Dec 2022 | KR | national |
