Patent Grant
12108655
This application claims priority to and the benefit of Korean Patent Application No. 10-2020-0063269, filed on May 26, 2020, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.
One or more embodiments relate to an organometallic compound and an organic light-emitting device including the same.
Organic light-emitting devices (OLEDs) are self-emission devices that, as compared with related art devices, have wide viewing angles, high contrast ratios, short response times, and/or suitable (e.g., excellent) characteristics in terms of luminance, driving voltage, and/or response speed, and produce full-color images.
OLEDs may include a first electrode located on a substrate, and a hole transport region, an emission layer, an electron transport region, and a second electrode sequentially stacked on the first electrode. Holes provided from the first electrode may move toward the emission layer through the hole transport region, and electrons provided from the second electrode may move toward the emission layer through the electron transport region. Carriers, such as holes and electrons, recombine in the emission layer to produce excitons. These excitons transition from an excited state to a ground state to thereby generate light.
Aspects according to one or more embodiments are directed toward novel organometallic compounds and organic light-emitting devices including the same.
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 embodiment, an organometallic compound is represented by Formula 1.
According to another embodiment, an organic light-emitting device includes a first electrode, a second electrode, and an organic layer including an emission layer located between the first electrode and the second electrode,
wherein the organic light-emitting device includes at least one of the organometallic compound represented by Formula 1.
The above and other aspects, features, and enhancements of certain embodiments of the disclosure will be more apparent from the following description taken in conjunction with the accompanying drawings, in which:
Reference will now be made in more detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. 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 of the present description. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. 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.
According to an embodiment of the present disclosure, an organometallic compound is represented by Formula 1 below:
The energy level (E3MC) of the triplet metal centered state (3MC state) of the organometallic compound may be higher than the energy level (E3MLCT) of triplet metal-to-ligand charge transfer state (3MLCT state) of the organometallic compound.
For example, the energy level of the E3MC of 3MC state of the organometallic compound may be about 0.41 kcal/mol or more. For example, E3MC may be about 0.81 kcal/mol or less, and, for example, from about 0.41 kcal/mol to about 0.81 kcal/mol.
When the organometallic compound satisfies the above described range of E3MC, the organometallic compound may less likely transition from the 3MCLT state to the non-emission state, that is, the 3MC state. Therefore, the stability of the organometallic compound in an excited state may be suitable (e.g., excellent), and the efficiency and lifespan of the organic light-emitting device including the organometallic compound may be increased.
For example, 3MLCT (%) (the ratio of presence in the 3MLCT state) of the organometallic compound may be about 10% or more. For example, 3MLCT (%) of the organometallic compound may be about 30% or less.
M1 in Formula 1 may be selected from platinum (Pt), palladium (Pd), copper (Cu), silver (Ag), gold (Au), rhodium (Rh), iridium (Ir), ruthenium (Ru), osmium (Os), titanium (T1), zirconium (Zr), hafnium (Hf), europium (Eu), Terbium (Tb), and thulium (Tm).
In an embodiment, M1 may be selected from Pt, Pd, Cu, Ag, Au, Rh, Ir, Ru, and Os.
In an embodiment, M1 may be Pt, but embodiments of the present disclosure are not limited thereto.
In an embodiment, T1 to T4 may each be a chemical bond, Y1 may be N, Y2 may be C, and at least one bond selected from a bond between Y1 and M1 and a bond between Y2 and M1 may each be a coordination bond.
For example, Y1 may be N, and Y2 and Y3 may each be C, but embodiments of the present disclosure are not limited thereto.
A1 to A3 in Formula 1 may each independently be selected from a C5-C60 carbocyclic group and a C1-C60 heterocyclic group.
In an embodiment, A1 to A3 may each independently be selected from
In an embodiment, i) A1 may be selected from a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, and a triazine group, and/or
For example, A1 may be selected from a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, and a triazine group, and A2 may be selected from an indole group, a carbazole group, an indolopyridine group, and an indolopyrimidine group. For example, A1 may be selected from a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, and a triazine group, and A3 may be selected from a benzene group, a naphthalene group, an anthracene group, and a phenanthrene group. For example, A2 may be selected from an indole group, a carbazole group, an indolopyridine group, and an indolopyrimidine group, and A3 may be selected from a benzene group, a naphthalene group, an anthracene group, and a phenanthrene group. For example, A1 may be selected from a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, and a triazine group, A2 may be selected from an indole group, a carbazole group, an indolopyridine group, and an indolopyrimidine group, and A3 may be selected from a benzene group, a naphthalene group, an anthracene group, and a phenanthrene group.
In an embodiment, ia) A1 may be a group represented by one of Formulae 2A-1 to 2A-5, and/or
In Formulae 2A-1 to 2A-5, Formulae 2B-1 to 2B-3, and Formula 2C-1,
For example, Y22 in Formulae 2A-1 to 2A-5 and 2C-1 may be C(R12a).
For example, R12a may be hydrogen, a C1-C20 alkyl group, or a C1-C20 alkyl group substituted with at least one C1-C20 alkyl group.
For example, in Formulae 2B-1 to 2B-3, Y21 may be C(R11a) and Y23 may be C(R13a). For example, R11a and R13a may each be hydrogen.
For example, in Formulae 2A-1 to 2A-5, Z21 may be C(R21a) and Z22 may be *′—C. For example, R21a may be hydrogen.
For example, in Formulae 2B-1 to 2B-3, Y21 may be C(R11a), Y22 may be C(R12a), Y23 may be C(R13a), Y24 may be C(R14a), Y25 may be C(R15a), Y26 may be C(R16a), Y27 may be C(R17a), and Y28 may be C(R18a). For example, R11a to R18a may each be hydrogen.
For example, in Formulae 2A-1 to 2A-5, Z21 may be *′—C, and Z31 may be *′—N.
For example, in Formula 2C-1, Y21 may be C(R11a), and Y23 may be C(R13a). For example, R11a may be hydrogen or a C6-C20 aryl group substituted with at least one deuterium. For example, R13a may be hydrogen.
For example, in Formulae 2A-1 and 2A-4, when Y21 is C(R11a), Y22 is C(R12a), and R12a is a C1-C20 alkyl group, R11a may be a C3-C20 aryl group substituted with at least one deuterium.
For example, in Formula 2C-1, Z21 may be *—C and Z22 may be *′—C.
For example, A1 may be a group represented by one of Formulae 2A-1 to 2A-5 and A2 may be a group represented by one of Formulae 2B-1 to 2B-3. For example, A1 may be a group represented by one of Formulae 2A-1 to 2A-5 and A3 may be a group represented by Formula 2C-1. For example, A2 may be a group represented by one of Formulae 2B-1 to 2B-3 and A3 may be a group represented by Formula 2C-1. For example, A1 may be a group represented by one of Formulae 2A-1 to 2A-5, A2 may be a group represented by one of Formulae 2B-1 to 2B-3, and A3 may be a group represented by Formula 2C-1.
L1 to L4 in Formula 1 may each independently be selected from a single bond, a double bond, *—N(R5)—*′, *—B(R5)—*′, *—P(R5)—*′, *—C(R5)(R6)—*′, *—Si(R5)(R6)—*′, *—Ge(R5)(R6)—*′, *—Se—*′, *—C(═O)—*′, *—S(═O)—*′, *—S(═O)2—*′, *—C(R5)═*′, *═C(R5)—*′, *—C(R5)═C(R6)—*′, *—C(═S)—*′, and *—C≡C—*′, and * and *′ each indicates a binding site to a neighboring atom.
In an embodiment, L1 to L4 may each independently be a single bond or *—O—*′.
a1 to a4 in Formula 1 may each independently be an integer from 0 to 3, and, when a1 is 0, A1 and A2 are not linked to each other, when a2 is 0, A2 and A3 are not linked to each other, when a3 is 0, A3 and A4 are not linked to each other, and when a4 is 0, A4 and A1 are not linked to each other.
In an embodiment, a1 to a3 may each be 1, a4 may be 0, L1 and L3 may be a single bond, and L2 may be *—O—*′.
L11 and L12 in Formula 1 may each independently be selected from *—C(R11)(R12)—*′, *—C(R11)═*′, *═C(R11)—*′, and *—C(R11)═C(R12)—*′.
a11 and a12 in Formula 1 may each independently be an integer from 1 to 3. a11 indicates the number of groups represented by L11, and a12 indicates the number of groups represented by L12, and, when a11 is 2 or more, L11(s) in the number of a11 may be identical to or different from each other and when a12 is 2 or more, L12(s) in the number of a12 may be identical to or different from each other.
In an embodiment, a11 and a12 may each independently be 1 or 2.
In an embodiment, i) L11 and L12 may each be *—C(R11)(R12)—*′, a11 may be 2, and a12 may be 1,
R′, R″, R1 to R6, and R11 to R12 in Formula 1 may each independently be selected from 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 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 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 C1-C60 heteroaryl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C30 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), —B(Q1)(Q2), —N(Q1)(Q2), —P(Q1)(Q2), —C(═O)(Q1), —S(═O)(Q1), —S(═O)2(Q1), —P(═O)(Q1)(Q2), —P(═S)(Q1)(Q2), ═O, ═S, ═N(Q1), and ═C(Q1)(Q2)
In an embodiment, R′, R″, R1 to R6, R11, and R12 may each independently be selected from: 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, and a C1-C20 alkoxy group;
In an embodiment, when L12 is *—C(R11)═C(R12)—*′ and a12 is 1, R11 and R12 may be linked to each other to form a substituted or unsubstituted C5-C60 carbocyclic group or a substituted or unsubstituted C1-C60 heterocyclic group.
In an embodiment, the organometallic compound represented by Formula 1 may be a group represented by one of Formulae 1-1 to 1-6:
For example, A21 may be a benzene group.
For example, Ra may be a C1-C20 alkyl group substituted with at least one deuterium, a C6-C20 aryl group substituted with at least one deuterium, or a C6-C20 aryl group substituted with at least one C6-C20 aryl group substituted with at least one deuterium.
In an embodiment, the organometallic compound represented by Formula 1 may be represented by Formula 1A:
In an embodiment, the organometallic compound represented by Formula 1 may include at least one deuterium.
In an embodiment, the organometallic compound represented by Formula 1 may include at least one selected from a C1-C20 alkyl group substituted with at least one deuterium and a C6-C20 aryl group substituted with at least one deuterium.
In an embodiment, the organometallic compound represented by Formula 1 may be selected from Compounds 1 to 44, but embodiments of the present disclosure are not limited thereto:
Because in the organometallic compound represented by Formula 1, a carbene ligand that is linked to the central metal thereof (M1 in Formula 1) includes a bridge structure, the binding force between the central metal and the carbene ligand is strengthened and thus, rigidity of the organometallic compound may be increased. Therefore, the lifespan characteristics of an organic light-emitting device utilizing the organometallic compound may be improved.
In addition, due to the inclusion of one or more deuterium in the organometallic compound represented by Formula 1, an intermolecular vibration mode is decreased, resulting in an increase in rigidity of the organometallic compound, and thus, stability of the organometallic compound is increased and a long lifespan effect of the organic light-emitting device utilizing the organometallic compound is obtained.
In an embodiment, because in the organometallic compound represented by Formula 1, the carbene ligand has a condensed cyclic structure, stability may be increased due to an increase in 3MC energy level in correspondence to the increase in the sigma electron donor effect.
In addition, in the organometallic compound represented by Formula 1, the element of the carbene ligand that is connected to the central metal is carbon, and the carbene ligand has a covalent bond rather than a coordination bond with the central metal, so that the binding force is increased and hole transport characteristics and electron transport characteristics may be simultaneously enhanced.
As a result, when the organometallic compound is applied to an organic light-emitting device, the phenomenon that the triplet exciton is transferred to the non-emissive 3MC state due to ligand rupture may be reduced or prevented, so that the stability in the excited state is suitable (e.g., excellent) and the organic light-emitting device may have suitable (e.g., excellent) lifespan and efficiency characteristics.
In an embodiment, the organometallic compound represented by Formula 1 may satisfy the range of E3MC described above. At this time, the transition of the organometallic compound represented by Formula 1 from the 3MCLT state to the 3MC state, which is the non-emission state, may less likely to occur. Therefore, the stability of the organometallic compound in the excited state may be suitable (e.g., excellent), and the efficiency and lifespan of the organic light-emitting device including the organometallic compound may be increased.
The organometallic compound may emit blue light. For example, the organometallic compound may emit blue light (bottom emission CIEx,y color coordinates X=0.13, Y=0.05 to 0.18) having a maximum emission wavelength of about 440 nm or more and about 490 nm or less, but embodiments of the present disclosure are not limited thereto. Accordingly, the organometallic compound represented by Formula 1 may be useful for the manufacturing of an organic light-emitting device that emits blue light.
Synthesis methods of the organometallic compound represented by Formula 1 may be recognizable by one of ordinary skill in the art by referring to Examples provided below.
At least one of such organometallic compounds represented by Formula 1 may be utilized between a pair of electrodes of an organic light-emitting device. In an embodiment, the organometallic compound may be included in an emission layer. The organometallic compound included in the emission layer may act as a dopant. In one or more embodiments, the organometallic compound of Formula 1 may be utilized as a material for a capping layer located outside a pair of electrodes of an organic light-emitting device.
Accordingly, according to another embodiment of the present disclosure, an organic light-emitting device includes: a first electrode; a second electrode facing the first electrode; an organic layer located between the first electrode and the second electrode; and at least one organometallic compound represented by Formula 1. For example, the organic layer includes at least one of organometallic compounds.
The expression “(an organic layer) includes at least one of organometallic compounds” 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 the organometallic compound, and may include 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 organometallic compound, 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 may both exist in an emission layer), or different layers (for example, Compound 1 may exist in an emission layer and Compound 2 may exist in an electron transport region).
In some embodiments,
The term “organic layer” as used herein refers to a single layer and/or multiple layers located between the first electrode and the second electrode of the organic light-emitting device. A material included in the “organic layer” is not limited to an organic material.
In an embodiment, the emission layer includes the organometallic compound represented by Formula 1, the emission layer further includes a host, and an amount of the host of the emission layer may be greater than the amount of the organometallic compound in the emission layer.
In an embodiment, the emission layer may further include a host, and the amount of the organometallic compound may be from 0.1 parts by weight to 50 parts by weight based on 100 parts by weight of the emission layer.
In an embodiment, the hole transport region may include a p-dopant having a lowest unoccupied molecular orbital (LUMO) energy level of less than about −3.5 eV.
Description of
Hereinafter, the structure of the organic light-emitting device 10 according to an embodiment and a method of manufacturing the organic light-emitting device 10 will be described in connection with
First Electrode 110
In
The first electrode 110 may be formed by, for example, depositing or sputtering a material for forming the first electrode 110 on the substrate. When the first electrode 110 is an anode, the material for forming the first electrode 110 may be selected from materials with a high work function to facilitate hole injection.
The first electrode 110 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. When the first electrode 110 is a transmissive electrode, a material for forming the first electrode 110 may be selected from indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), and any combination thereof, but embodiments of the present disclosure are not limited thereto. In one or more embodiments, when the first electrode 110 is a semi-transmissive electrode or a reflective electrode, a material for forming the first electrode 110 may be selected from magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), and any combination thereof, but embodiments of the present disclosure are not limited thereto.
The first electrode 110 may have a single-layered structure or a multi-layered structure including two or more layers. For example, the first electrode 110 may have a three-layered structure of ITO/Ag/ITO, but the structure of the first electrode 110 is not limited thereto.
Organic Layer 150
The organic layer 150 is located on the first electrode 110. The organic layer 150 may include an emission layer.
The organic layer 150 may further include a hole transport region located between the first electrode 110 and the emission layer and an electron transport region located between the emission layer and the second electrode 190.
Hole Transport Region in Organic Layer 150
The hole transport region may have i) a single-layered structure including (e.g., consisting of) a single material, ii) a single-layered structure including a plurality of different materials, or iii) a multi-layered structure having a plurality of layers including a plurality of different materials.
The hole transport region may include at least one layer selected from a hole injection layer, a hole transport layer, an emission auxiliary layer, and an electron blocking layer.
In an embodiment, the hole transport region may have a single-layered structure including a plurality of different materials, or a multi-layered structure having a hole injection layer/hole transport layer structure, a hole injection layer/hole transport layer/emission auxiliary layer structure, a hole injection layer/emission auxiliary layer structure, a hole transport layer/emission auxiliary layer structure, or a hole injection layer/hole transport layer/electron blocking layer structure, wherein for each structure, constituting layers are sequentially stacked from the first electrode 110 in the respective stated order, but the structure of the hole transport region is not limited thereto.
The hole transport region may include at least one selected from m-MTDATA, TDATA, 2-TNATA, NPB(NPD), β-NPB, TPD, spiro-TPD, spiro-NPB, methylated-NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (PANI/CSA), polyaniline/poly(4-styrenesulfonate) (PANI/PSS), a compound represented by Formula 201, and a compound represented by Formula 202:
For example, R201 and R202 in Formula 202 may optionally be linked to each other via a single bond, a dimethyl-methylene group, or a diphenyl-methylene group, and R203 and R204 may optionally be linked to each other via a single bond, a dimethyl-methylene group, or a diphenyl-methylene group.
In an embodiment, in Formulae 201 and 202,
In one or more embodiments, xa1 to xa4 may each independently be 0, 1, or 2.
In one or more embodiments, xa5 may be 1, 2, 3, or 4.
In one or more embodiments, R201 to R204 and Q201 may each independently be selected from: a phenyl group, a biphenyl group, a terphenyl group, a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptalenyl group, an indacenyl group, an acenaphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenalenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a naphthacenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group, an ovalenyl 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, and a pyridinyl group; and
In one or more embodiments, at least one selected from R201 to R203 in Formula 201 may each independently be selected from:
In one or more embodiments, in Formula 202, i) R201 and R202 may be linked to each other via a single bond, and/or ii) R203 and R204 may be linked to each other via a single bond.
In one or more embodiments, at least one of R201 to R204 in Formula 202 may be selected from:
In one or more embodiments, the compound represented by Formula 201 may be represented by Formula 201A below:
In one or more embodiments, the compound represented by Formula 201 may be represented by Formula 201A(1) below, but embodiments of the present disclosure are not limited thereto:
In one or more embodiments, the compound represented by Formula 201 may be represented by Formula 201A-1 below, but embodiments of the present disclosure are not limited thereto:
In one or more embodiments, the compound represented by Formula 202 may be represented by Formula 202A below:
In one or more embodiments, the compound represented by Formula 202 may be represented by Formula 202A-1 below:
In Formulae 201A, 201A(1), 201A-1, 202A, and 202A-1,
The hole transport region may include at least one compound selected from compounds HT1 to HT39, but compounds to be included in the hole transport region are not limited thereto:
A thickness of the hole transport region may be in a range of 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 selected from a hole injection layer and a hole transport layer, the thickness of the hole injection layer may be in a range of about 100 Å to about 9,000 Å, for example, about 100 Å to about 1,000 Å, and the thickness of the hole transport layer may be in a range of about 50 Å to about 2,000 Å, for example, about 100 Å to about 1,500 Å. When the thicknesses of the hole transport region, the hole injection layer and the hole transport layer are within these ranges, satisfactory hole transporting characteristics may be obtained without a substantial increase in driving voltage.
The emission auxiliary layer may increase light-emission efficiency by compensating for an optical resonance distance according to the wavelength of light emitted by an emission layer, and the electron blocking layer may block the flow of electrons from an electron transport region. The emission auxiliary layer and the electron blocking layer may include the materials as described above.
P-Dopant
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.
In an embodiment, the p-dopant may have a lowest unoccupied molecular orbital (LUMO) energy level of −3.5 eV or less.
The p-dopant may include at least one selected from a quinone derivative, a metal oxide, and 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 selected from:
R221 to R223 may each independently be selected from 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 C1-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, and a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, and at least one selected from R221 to R223 may have at least one substituent selected from a cyano group, —F, —Cl, —Br, —I, a C1-C20 alkyl group substituted with —F, a C1-C20 alkyl group substituted with —Cl, a C1-C20 alkyl group substituted with —Br, and a C1-C20 alkyl group substituted with —I.
Emission Layer in Organic Layer 150
When the organic light-emitting device 10 is a full-color organic light-emitting device, the emission layer may be patterned into a red emission layer, a green emission layer, or a blue emission layer, according to a sub-pixel. In one or more embodiments, the emission layer may have a stacked structure of two or more layers selected from a red emission layer, a green emission layer, and a blue emission layer, in which the two or more layers may contact each other or may be separated from each other. In one or more embodiments, the emission layer may include two or more materials selected from a red light-emitting material, a green light-emitting material, and a blue light-emitting material, in which the two or more materials are mixed with each other in a single layer to emit white light.
The emission layer may include a host and a dopant. The dopant may include at least one selected from a phosphorescent dopant and a fluorescent dopant. The phosphorescent dopant may include the organometallic compound represented by Formula 1.
An amount of a dopant in the emission layer may be, based on about 100 parts by weight of the host, in the range of about 0.01 to about 15 parts by weight, 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. When the thickness of the emission layer is within these ranges, suitable (e.g., excellent) light-emission characteristics may be obtained without a substantial increase in driving voltage.
Host in Emission Layer
In one or more embodiments, the host may include a compound represented by Formula 301 below.
[Ar301]xb11-[(L301)xb1-R301]xb21 Formula 301
In an embodiment, Ar301 in Formula 301 may be selected from:
When xb11 in Formula 301 is two or more, two or more of Ar301(s) may be linked via a single bond.
In one or more embodiments, the compound represented by Formula 301 may be represented by one of Formula 301-1 and Formula 301-2:
In Formulae 301-1 and 301-2
For example, L301 to L304 in Formulae 301, 301-1, and 301-2 may each independently be selected from:
In an embodiment, R301 to R304 in Formulae 301, 301-1, and 301-2 may each independently be selected from:
In one or more embodiments, the host may include an alkaline earth metal complex. For example, the host may be selected from a Be complex (for example, Compound H55), an Mg complex, and a Zn complex.
The host may include at least one selected from 9,10-di(2-naphthyl)anthracene (ADN), 2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN), 9,10-di-(2-naphthyl)-2-t-butyl-anthracene (TBADN), 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP), 1,3-di-9-carbazolylbenzene (mCP), 1,3,5-tri(carbazol-9-yl)benzene (TCP), and Compounds H1 to H55, but embodiments of the present disclosure are not limited thereto:
In an embodiment, the host may include at least one selected from a silicon-containing compound (for example, BCPDS utilized in the following examples and/or the like) and a phosphine oxide-containing compound (for example, POPCPA utilized in the following examples and/or the like).
The host may include only one compound or may include two or more compounds that are different from each other (for example, the host of the following Examples includes BCPDS and POPCPA). In one or more embodiment, the host may instead have various suitable modifications.
Phosphorescent Dopant Included in Emission Layer in Organic Layer 150
The phosphorescent dopant may include the organometallic compound represented by Formula 1:
In addition, the phosphorescent dopant may include an organometallic complex represented by Formula 401 below:
In an embodiment, A401 and A402 in Formula 402 may each independently be selected from a benzene group, a naphthalene group, a fluorene group, a spiro-bifluorene group, an indene group, a pyrrole group, a thiophene group, a furan 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, a quinoline group, an isoquinoline group, a benzoquinoline group, a quinoxaline group, a quinazoline group, a carbazole group, a benzimidazole group, a benzofuran group, a benzothiophene group, an isobenzothiophene group, a benzoxazole group, an isobenzoxazole group, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, a dibenzofuran group, and a dibenzothiophene group.
In one or more embodiments, in Formula 402, i) X401 may be nitrogen and X402 may be carbon, or ii) X401 and X402 may each be nitrogen at the same time.
In one or more embodiments, R401 and R402 in Formula 402 may each independently be selected from:
In one or more embodiments, when xc1 in Formula 401 is two or more, two A401(s) in two or more L401(s) may optionally be linked to each other via X407, which is a linking group, two A402(s) may optionally be linked to each other via X408, which is a linking group (see Compounds PD1 to PD4 and PD7). X407 and X408 may each independently be a single bond, *—O—*′, *—S—*′, *—C(═O)—*′, *—N(Q413)-*′, *—C(Q413)(Q414)-*′ or *—C(Q413)═C(Q414)-*′(where Q413 and Q414 may each independently be hydrogen, deuterium, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group), but embodiments of the present disclosure are not limited thereto.
L402 in Formula 401 may be a monovalent, divalent, or trivalent organic ligand. For example, L402 may be selected from halogen, diketone (for example, acetylacetonate), carboxylic acid (for example, picolinate), —C(═O), isonitrile, —CN, and a phosphorus-containing material (for example, phosphine, or phosphite), but embodiments of the present disclosure are not limited thereto.
In one or more embodiments, the phosphorescent dopant may be selected from, for example, Compounds PD1 to PD25, but embodiments of the present disclosure are not limited thereto:
Fluorescent Dopant in Emission Layer
The fluorescent dopant may include an arylamine compound or a styrylamine compound.
The fluorescent dopant may include a compound represented by Formula 501 below.
In an embodiment, Ar501 in Formula 501 may be selected from:
In one or more embodiments, L501 to L503 in Formula 501 may each independently be selected from:
In one or more embodiments, R501 and R502 in Formula 501 may each independently be selected from:
In one or more embodiments, xd4 in Formula 501 may be 2, but embodiments of the present disclosure are not limited thereto.
In one or more embodiments, the fluorescent dopant may be selected from the following compounds, but embodiments of the present disclosure are not limited thereto.
Electron Transport Region in Organic Layer 150
The electron transport region may have i) a single-layered structure including (e.g., consisting of) a single material, ii) a single-layered structure including a plurality of different materials, or iii) a multi-layered structure having a plurality of layers including a plurality of different materials.
The electron transport region may include at least one selected from a buffer layer, a hole blocking layer, an electron control layer, an electron transport layer, and an electron injection layer, but embodiments of the present disclosure are not limited thereto.
For example, the electron transport region may have an electron transport layer/electron injection layer structure, a hole blocking layer/electron transport layer/electron injection layer structure, an electron control layer/electron transport layer/electron injection layer structure, or a buffer layer/electron transport layer/electron injection layer structure, wherein for each structure, constituting layers are sequentially stacked from an emission layer in this stated order. However, embodiments of the structure of the electron transport region are not limited thereto.
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 TT electron-depleted nitrogen-containing ring.
The “TT electron-depleted nitrogen-containing ring” refers to a C1-C60 heterocyclic group having at least one *—N═*′ moiety as a ring-forming moiety.
For example, the “TT electron-depleted nitrogen-containing ring” may be i) a 5-membered to 7-membered heteromonocyclic group having at least one *—N═*′ moiety, ii) a heteropolycyclic group in which two or more 5-membered to 7-membered heteromonocyclic groups each having at least one *—N═*′ moiety are condensed with each other, or iii) a heteropolycyclic group in which at least one of 5-membered to 7-membered heteromonocyclic groups, each having at least one *—N═*′ moiety, is condensed with at least one C5-C60 carbocyclic group.
Examples of the TT electron-deficient nitrogen-containing ring include an imidazole ring, a pyrazole ring, a thiazole ring, an isothiazole ring, an oxazole ring, an isoxazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indazole ring, a purine ring, a quinoline ring, an isoquinoline ring, a benzoquinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a phenazine ring, a benzimidazole ring, an isobenzothiazole ring, a benzoxazole ring, an isobenzoxazole ring, a triazole ring, a tetrazole ring, an oxadiazole ring, a triazine ring, a thiadiazole ring, an imidazopyridine ring, an imidazopyrimidine ring, and an azacarbazole ring, but are not limited thereto.
For example, the electron transport region may include a compound represented by Formula 601 below:
[Ar601]xe11-[(L601)xe1-R601]xe21 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 TT electron-deficient nitrogen-containing ring.
In an embodiment, ring Ar601 in Formula 601 may be selected from:
When xe11 in Formula 601 is 2 or more, two or more Ar601(s) may be linked to each other via a single bond.
In one or more embodiments, Ar601 in Formula 601 may be an anthracene group.
In one or more embodiments, the compound represented by Formula 601 may be represented by Formula 601-1:
In an embodiment, L601 and L611 to L613 in Formulae 601 and 601-1 may each independently be selected from:
a phenylene group, a naphthylene group, a fluorenylene group, a spiro-bifluorenylene group, a benzofluorenylene group, a dibenzofluorenylene group, a phenanthrenylene group, an anthracenylene group, a fluoranthenylene group, a triphenylenylene group, a pyrenylene group, a chrysenylene group, a perylenylene group, a pentaphenylene group, a hexacenylene group, a pentacenylene group, a thiophenylene group, a furanylene group, a carbazolylene group, an indolylene group, an isoindolylene group, a benzofuranylene group, a benzothiophenylene group, a dibenzofuranylene group, a dibenzothiophenylene group, a benzocarbazolylene group, a dibenzocarbazolylene group, a dibenzosilolylene group, a pyridinylene group, an imidazolylene group, a pyrazolylene group, a thiazolylene group, an isothiazolylene group, an oxazolylene group, an isoxazolylene group, a thiadiazolylene group, an oxadiazolylene group, a pyrazinylene group, a pyrimidinylene group, a pyridazinylene group, a triazinylene group, a quinolinylene group, an isoquinolinylene group, a benzoquinolinylene group, a phthalazinylene group, a naphthyridinylene group, a quinoxalinylene group, a quinazolinylene group, a cinnolinylene group, a phenanthridinylene group, an acridinylene group, a phenanthrolinylene group, a phenazinylene group, a benzimidazolylene group, an isobenzothiazolylene group, a benzoxazolylene group, an isobenzoxazolylene group, a triazolylene group, a tetrazolylene group, an imidazopyridinylene group, an imidazopyrimidinylene group, and an azacarbazolylene group; and
In one or more embodiments, xe1 and xe611 to xe613 in Formulae 601 and 601-1 may each independently be 0, 1, or 2.
In one or more embodiments, R601 and R611 to R613 in Formulae 601 and 601-1 may each independently be selected from:
The electron transport region may include at least one compound selected from Compounds ET1 to ET36, but embodiments of the present disclosure are not limited thereto:
In one or more embodiments, the electron transport region may include at least one selected from 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), Alq3, BAlq, 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), and NTAZ:
In one or more embodiments, the electron transport region may include a phosphine oxide-containing compound, but embodiments of the present disclosure are not limited thereto. In an embodiment, the phosphine oxide-containing compound may be utilized in a hole blocking layer in the electron transport region, but embodiments of the present disclosure are not limited thereto.
Thicknesses of the buffer layer, the hole blocking layer, and the electron control layer may each independently be in a range of about 20 Å to about 1,000 Å, for example, about 30 Å to about 300 Å. When the thicknesses of the buffer layer, the hole blocking layer, and the electron control layer are within these ranges, suitable (e.g., excellent) hole blocking characteristics or suitable (e.g., excellent) electron control characteristics may be obtained 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. When the thickness of the electron transport layer is within the ranges described above, the electron transport layer may have satisfactory electron transport characteristics without a substantial increase in driving voltage.
The electron transport region (for example, the electron transport layer in the electron transport region) may further include, in addition to the materials described above, a metal-containing material.
The metal-containing material may include at least one selected from alkali metal complex and alkaline earth-metal complex. The alkali metal complex may include a metal ion selected from a Li ion, a Na ion, a K ion, a Rb ion, and a Cs ion, and the alkaline earth-metal complex may include a metal ion selected from a Be ion, a Mg ion, a Ca ion, a Sr ion, and a Ba ion. A ligand coordinated with the metal ion of the alkali metal complex or the alkaline earth-metal complex may be selected from a hydroxy quinoline, a hydroxy isoquinoline, a hydroxy benzoquinoline, a hydroxy acridine, a hydroxy phenanthridine, a hydroxy phenyloxazole, a hydroxy phenylthiazole, a hydroxy phenyloxadiazole, a hydroxy phenylthiadiazole, a hydroxy phenylpyridine, a hydroxy phenylbenzimidazole, a hydroxy phenylbenzothiazole, a bipyridine, a phenanthroline, and a cyclopentadiene, but embodiments of the present disclosure are not limited thereto.
For example, 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:
The electron transport region may include an electron injection layer that facilitates the injection of electrons from the second electrode 190. The electron injection layer may directly contact the second electrode 190.
The electron injection layer may have i) a single-layered structure including (e.g., consisting of) a single material, ii) a single-layered structure including 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 combinations thereof.
The alkali metal may be selected from Li, Na, K, Rb, and Cs. In an embodiment, the alkali metal may be Li, Na, or Cs. In one or more embodiments, the alkali metal may be Li or Cs, but embodiments of the present disclosure are not limited thereto.
The alkaline earth metal may be selected from Mg, Ca, Sr, and Ba.
The rare earth metal may be selected from Sc, Y, Ce, Tb, Yb, and Gd.
The alkali metal compound, the alkaline earth-metal compound, and the rare earth metal compound may be selected from oxides and halides (for example, fluorides, chlorides, bromides, or iodides) of the alkali metal, the alkaline earth-metal, and the rare earth metal.
The alkali metal compound may be selected from alkali metal oxides, such as Li2O, Cs2O, and/or K2O, and alkali metal halides, such as LiF, NaF, CsF, KF, LiI, NaI, CsI, and/or KI. In an embodiment, the alkali metal compound may be selected from LiF, Li2O, NaF, LiI, NaI, CsI, and KI, but embodiments of the present disclosure are not limited thereto.
The alkaline earth-metal compound may be selected from alkaline earth-metal oxides, such as BaO, SrO, CaO, BaxSr1-xO (0<x<1), and/or BaxCa1-xO (0<x<1). In an embodiment, the alkaline earth-metal compound may be selected from BaO, SrO, and CaO, but embodiments of the present disclosure are not limited thereto.
The rare earth metal compound may be selected from YbF3, ScF3, Sc2O3, Y2O3, Ce2O3, GdF3 and TbF3. In an embodiment, the rare earth metal compound may be selected from YbF3, ScF3, TbF3, YbI3, ScI3, and 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 selected from hydroxy quinoline, hydroxy isoquinoline, hydroxy benzoquinoline, hydroxy acridine, hydroxy phenanthridine, hydroxy phenyloxazole, hydroxy phenylthiazole, hydroxy phenyloxadiazole, hydroxy phenylthiadiazole, hydroxy phenylpyridine, hydroxy phenylbenzimidazole, hydroxy phenylbenzothiazole, bipyridine, phenanthroline, and cyclopentadiene, but embodiments of the present disclosure are not limited thereto.
The electron injection layer may include (e.g., consist of) 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 one or more embodiments, the electron injection layer may further include an organic material. When the electron injection layer further includes an organic material, the alkali metal, the alkaline earth metal, the rare earth metal, the alkali metal compound, the alkaline earth-metal compound, the rare earth metal compound, the alkali metal complex, the alkaline earth-metal complex, the rare earth metal complex, or any combination 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. When the thickness of the electron injection layer is within the ranges described above, the electron injection layer may have satisfactory electron injection characteristics without a substantial increase in driving voltage.
Second Electrode 190
The second electrode 190 is located on the organic layer 150 having such a structure. The second electrode 190 may be a cathode which is an electron injection electrode, and in this regard, a material for forming the second electrode 190 may be selected from a metal, an alloy, an electrically conductive compound, and a combination thereof, each having a relatively low work function.
The second electrode 190 may include at least one selected from lithium (Li), silver (Ag), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), ytterbium (Yb), silver-ytterbium (Ag—Yb), ITO, and IZO, but embodiments of the present disclosure are not limited thereto. The second electrode 190 may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode.
The second electrode 190 may have a single-layered structure or a multi-layered structure including two or more layers.
Description of
An organic light-emitting device 20 of
Regarding
In the organic layer 150 of each of the organic light-emitting devices 20 and 40, light generated in an emission layer may pass through the first electrode 110, which is a semi-transmissive electrode or a transmissive electrode, and the first capping layer 210 toward the outside, and in the organic layer 150 of each of the organic light-emitting devices 30 and 40, light generated in an emission layer may pass through the second electrode 190, which is a semi-transmissive electrode or a transmissive electrode, and the second capping layer 220 toward the outside.
The first capping layer 210 and the second capping layer 220 may increase external luminescence efficiency according to the principle of constructive interference. Accordingly, the light extraction efficiency of the organic light-emitting device 10 is increased, so that the luminescence efficiency of the organic light-emitting device 10 may be improved.
Each of the first capping layer 210 and the second capping layer 220 may include a material having a refractive index of 1.6 or more (at 589 nm).
The first capping layer 210 and the second capping layer 220 may increase external luminescence efficiency according to the principle of constructive interference.
The first capping layer 210 and the second capping layer 220 may each independently be an organic capping layer including an organic material, an inorganic capping layer including an inorganic material, or a composite capping layer including an organic material and an inorganic material.
At least one selected from the first capping layer 210 and the second capping layer 220 may each independently include at least one material selected from carbocyclic compounds, heterocyclic compounds, amine-based compounds, porphyrin derivatives, phthalocyanine derivatives, naphthalocyanine derivatives, alkali metal complexes, and alkaline earth metal complexes. The carbocyclic compound, the heterocyclic compound, and the amine-based compound may be optionally substituted with a substituent containing at least one element selected from O, N, S, Se, Si, F, Cl, Br, and I. In an embodiment, at least one of the first capping layer 210 and the second capping layer 220 may each independently include an amine-based compound.
In an embodiment, at least one selected from the first capping layer 210 and the second capping layer 220 may each independently include the compound represented by Formula 201 or the compound represented by Formula 202.
In one or more embodiments, at least one of the first capping layer 210 and the second capping layer 220 may each independently include a compound selected from Compounds HT28 to HT33, Compounds CP1 to CP6, and β-NPB, but embodiments of the present disclosure are not limited thereto.
Hereinbefore, the organic light-emitting device according to an embodiment has been described in connection with
Layers constituting the hole transport region, the emission layer, and layers constituting the electron transport region may be formed in a certain region by utilizing one or more suitable methods selected from vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) deposition, ink-jet printing, laser-printing, and laser-induced thermal imaging.
When layers constituting the hole transport region, the emission layer, and layers constituting the electron transport region are formed by vacuum deposition, the vacuum deposition may be performed at a deposition temperature of about 100° C. to about 500° C., a vacuum degree of about 10−8 torr to about 10−3 torr, and a deposition speed of about 0.01 Å/sec to about 100 Å/sec by taking into account a material to be included in the layer to be formed and the structure of the layer to be formed.
When layers constituting the hole transport region, the emission layer, and layers constituting the electron transport region are formed by spin coating, the spin coating may be performed at a coating speed of about 2,000 rpm to about 5,000 rpm and at a heat treatment temperature of about 80° C. to 200° C. by taking into account a material to be included in the layer to be formed and the structure of the layer to be formed.
The term “C1-C60 alkyl group” as used herein refers to a linear or branched aliphatic saturated 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, 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 “C2-C60 alkenyl group” as used herein refers to a hydrocarbon group having 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, 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 refers to a hydrocarbon group having 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, 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 “C1-C60 alkoxy group” as 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, and an isopropyloxy 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, 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 selected from N, O, Si, P, and S as a ring-forming atom and 1 to 10 carbon atoms, and non-limiting examples thereof include a 1,2,3,4-oxatriazolidinyl group, 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 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, 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 selected from N, O, Si, P, and S as a ring-forming atom, 1 to 10 carbon atoms, and at least one double bond in its ring. Non-limiting examples of the C1-C10 heterocycloalkenyl group include a 4,5-dihydro-1,2,3,4-oxatriazolyl group, 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 the term “C6-C60 arylene group” as used herein refers to a divalent group having a carbocyclic aromatic 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 fluorenyl group and a chrysenyl group. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the two or more rings may be fused to each other.
The term “C1-C60 heteroaryl group” as used herein refers to a monovalent group having a heterocyclic aromatic system that has at least one heteroatom selected from N, O, Si, P, and S as a ring-forming atom, in addition to 1 to 60 carbon atoms. The term “C1-C60 heteroarylene group” as used herein refers to a divalent group having a heterocyclic aromatic system that has at least one heteroatom selected from N, O, Si, P, and S as a ring-forming atom, in addition to 1 to 60 carbon atoms. 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, a carbazolyl group, a dibenzofuranyl group and a dibenzothiophenyl group. When the C1-C60 heteroaryl group and the C1-C60 heteroarylene group each include two or more rings, the two or more rings may be condensed with each other.
The term “C6-C60 aryloxy group” as used herein refers to a group represented by —OA102 (wherein A102 is the C6-C60 aryl group), and the term “C6-C60 arylthio group” as used herein refers to a group represented by —SA103 (wherein A103 is the C6-C60 aryl group).
The term “monovalent non-aromatic condensed polycyclic group” as used herein refers to a monovalent group having two or more rings condensed with each other, only carbon atoms (for example, having 8 to 60 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 and an adamantyl 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 having two or more rings condensed to each other, at least one heteroatom selected from N, O, Si, P, and S, other than carbon atoms (for example, having 1 to 60 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 and a 9H-xanthenyl 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-C60 carbocyclic group” as used herein refers to a monocyclic or polycyclic group that includes only carbon atoms as a ring-forming atom and includes 5 to 60 carbon atoms. The term “C5-C60 carbocyclic group” as used herein refers to an aromatic carbocyclic group or a non-aromatic carbocyclic group. The C5-C60 carbocyclic group may be a ring, such as benzene, a monovalent group, such as a phenyl group, or a divalent group, such as a phenylene group. In one or more embodiments, depending on the number of substituents connected to the C5-C60 carbocyclic group, the C5-C60 carbocyclic group may be a trivalent group or a quadrivalent group.
The term “C1-C60 heterocyclic group” as used herein refers to a group having the same structure as the C5-C60 carbocyclic group, except that as a ring-forming atom, at least one heteroatom selected from N, O, Si, P, and S is used in addition to carbon (the number of carbon atoms may be in a range of 1 to 60).
In the present specification, at least one substituent of the substituted C5-C60 carbocyclic group, the substituted C1-C60 heterocyclic group, the substituted C1-C20 alkylene group, the substituted C2-C20 alkenylene group, the substituted C3-C10 cycloalkylene group, the substituted C1-C10 heterocycloalkylene group, the substituted C3-C10 cycloalkenylene group, the substituted C1-C10 heterocycloalkenylene group, the substituted C6-C60 arylene group, the substituted C1-C60 heteroarylene group, the substituted divalent non-aromatic condensed polycyclic group, the substituted divalent non-aromatic condensed heteropolycyclic 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 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 C1-C60 heteroaryl 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 selected from:
The term “Ph” as used herein refers to a phenyl group, the term “Me” as used herein refers to a methyl group, the term “Et” as used herein refers to an ethyl group, the term “ter-Bu” or “But” as used herein refers to a tert-butyl group, and the term “OMe” as used herein refers to a methoxy group.
The term “biphenyl group” as used herein refers to “a phenyl group substituted with a phenyl group.” In other words, the “biphenyl group” is a substituted phenyl group having a C6-C60 aryl group as a substituent.
The term “terphenyl group” as used herein refers to “a phenyl group substituted with a biphenyl group”. In other words, the “terphenyl group” is a substituted phenyl group having, as a substituent, a C6-C60 aryl group substituted with a C6-C60 aryl group.
*, and *′, as used herein, unless defined otherwise, each refer to a binding site to a neighboring atom in a corresponding formula.
Hereinafter, a compound according to embodiments and an organic light-emitting device according to embodiments will be described in more detail with reference to Synthesis Examples and Examples. The wording “B was utilized instead of A” utilized in describing Synthesis Examples refers to that an identical molar equivalent of B was utilized in place of an identical molar equivalent of A.
1,3-diacetylimidazolin-2-one (1.0 equiv.) and cyclopentadiene (1.0 mol, 10 equiv.) were dissolved in m-xylene and stirred at a temperature of 150° C. for 72 hours. After the pressure was reduced, n-hexane was added to the reaction mixture and the precipitate was removed therefrom by filtration. The filtered precipitate was dissolved in MeOH (250 ml) and 2 M HCl (250 ml), stirred at room temperature for 30 minutes, and then subjected to reduced pressure. The reaction mixture was extracted with water and dichloromethane to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize Intermediate compound 1-A (yield of 54%).
A 20 ml ethyl acetate (EtOAc) solution of 10% Pd/C (70 mg) was added to a solution in which Intermediate compound 1-A (30 mmol) was dissolved in EtOAc (20 ml) under the Ar condition (e.g., under an Ar inert atmosphere). After filling with the hydrogen gas, stirring was performed thereon at room temperature for 1 hour. The reaction mixture was washed with EtOAc and filtered utilizing Celite. The filtrate was concentrated to obtain Intermediate compound 1-B (yield of 99%).
Intermediate compound 1-B (2.0 equiv.) was dissolved in MeOH and dichloromethane and stirred at room temperature. After adding NaH (60% in mineral oil, 1.0 equiv.) at 0° C., the resultant mixture was stirred for 4 hours at room temperature. After quenching with a NH4Cl solution at 0° C., an extraction process was performed utilizing water and dichloromethane. The obtained organic layer was dried utilizing anhydrous magnesium sulfate, concentrated, and recrystallized utilizing n-hexane to synthesize Intermediate compound 1-C (yield of 93%).
Intermediate Compound 1-C (1.0 eq), Iodomethane-d3 (3.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 12 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography was utilized to obtain Intermediate compound 1-D (yield: 75%).
Intermediate Compound 1-D (1.2 eq), 2-(3-bromo-5-(tert-butyl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 3 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (ethyl acetate:hexane=1:9) was utilized to obtain Intermediate compound 1-E (yield: 78%).
Intermediate Compound 1-E (3.5 mmol) was dissolved in tetrahydrofuran (THF) and then stirred at room temperature. LiAlH4 (7.0 mmol) was added at a temperature of 0° C., followed by stirring for 2 hours at a temperature of 50° C. After adding THF, a NaOH solution and H2O to the reaction mixture at a temperature of 0° C., the resultant mixture was stirred for 30 minutes at room temperature. The reaction mixture was filtered by celite/silica gel utilizing THF and EtOAc and subjected to reduced pressure. After the reaction mixture (1.0 eq) was dissolved in triethyl orthoformate (30 eq) at 80° C., 37% HCl (1.5 eq) was added thereto and stirred at a temperature of 80° C. for 12 hours. After cooling at room temperature, triethyl orthoformate (e.g., the triethyl orthoformate solution) was concentrated and extracted three times with dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC, MC:5 vol % methanol) was utilized to obtain Intermediate compound 1-F (yield: 87%).
Intermediate compound 1-F (1.0 eq) and ammonium hexafluorophosphate (3.0 eq) were dissolved in methanol (0.5 M), and then, distilled water was added thereto, and stirred at room temperature for 3 to 12 hours. After washing with distilled water and filtering to obtain a solid, an extraction process was performed thereon three times utilizing dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize Intermediate compound 1-G (yield of 96%).
Intermediate compound 1-G (1.0 eq), dichloro(1,5-cyclooctadiene)platinum (II) (1.1 eq), and sodium acetate (3.0 eq) were dissolved in anhydrous 1,4-dioxane, and then, stirred in the nitrogen condition (e.g., stirred under a nitrogen inert atmosphere) at a temperature of 120° C. for 4 days. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC:50 vol % hexane) was utilized to obtain Compound 1 (yield: 21%).
1,3-diacetylimidazolin-2-one (1.0 equiv.) and cyclopentadiene (1.0 mol, 10 equiv.) were dissolved in m-xylene and stirred at a temperature of 150° C. for 72 hours. After the pressure was reduced, n-hexane was added to the reaction mixture and the precipitate was removed therefrom by filtration. The filtered precipitate was dissolved in MeOH (250 ml) and 2 M HCl (250 ml), stirred at room temperature for 30 minutes, and then subjected to reduced pressure. The reaction mixture was extracted with water and dichloromethane to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize Intermediate compound 2-A (yield of 53%).
A 20 ml EtOAc solution of 10% Pd/C (70 mg) was added to a solution in which Intermediate compound 2-A (30 mmol) was dissolved in EtOAc (20 ml) under the Ar condition (e.g., under an Ar inert atmosphere). After filling with the hydrogen gas, stirring was performed thereon at room temperature for 1 hour. The reaction mixture was washed with EtOAc and filtered utilizing Celite. The filtrate was concentrated to obtain synthesized Intermediate compound 2-B (yield of 99%).
Intermediate compound 2-B (2.0 equiv.) was dissolved in MeOH and dichloromethane and stirred at room temperature. After adding NaH (60% in mineral oil, 1.0 equiv.) at 0° C., the resultant mixture was stirred for 4 hours at room temperature. After quenching with a NH4Cl solution at 0° C., an extraction process was performed utilizing water and dichloromethane. The obtained organic layer was dried utilizing anhydrous magnesium sulfate, concentrated, and recrystallized utilizing n-hexane to synthesize Intermediate compound 2-C (yield of 91%).
Intermediate Compound 2-C (1.0 eq), Iodomethane-d3 (3.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 12 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography was utilized to obtain Intermediate compound 2-D (yield: 75%).
Intermediate compound 2-D (1.2 eq), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 3 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (ethyl acetate:hexane=1:9) was utilized to obtain Intermediate compound 2-E (yield: 78%).
Intermediate Compound 2-E (3.5 mmol) was dissolved in THF and then stirred at room temperature. LiAlH4 (7.0 mmol) was added at a temperature of 0° C., followed by stirring for 2 hours at 50° C. After adding THF, a NaOH solution and H2O to the reaction mixture at a temperature of 0° C., the resultant mixture was stirred for 30 minutes at room temperature. The reaction mixture was filtered by celite/silica gel utilizing THF and EtOAc and subjected to reduced pressure. After the reaction mixture (1.0 eq) was dissolved in triethyl orthoformate (30 eq) at 80° C., 37% HCl (1.5 eq) was added thereto and stirred at a temperature of 80° C. for 12 hours. After cooling at room temperature, triethyl orthoformate (e.g., the triethyl orthoformate solution) was concentrated and extracted three times with dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC, MC:5 vol % methanol) was utilized to obtain Intermediate compound 2-F (yield: 87%).
Intermediate compound 2-F (1.0 eq) and ammonium hexafluorophosphate (3.0 eq) were dissolved in methanol (0.5 M), and then, distilled water was added thereto, and stirred at room temperature for 3 hours to 12 hours. After washing with distilled water and filtering to obtain a solid, an extraction process was performed thereon three times utilizing dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize Intermediate compound 2-G (yield of 93%).
Intermediate compound 2-G (1.0 eq), dichloro(1,5-cyclooctadiene)platinum (II) (1.1 eq), and sodium acetate (3.0 eq) were dissolved in anhydrous 1,4-dioxane, and then, stirred in the nitrogen condition (e.g., stirred under a nitrogen inert atmosphere) at a temperature of 120° C. for 4 days. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC:50 vol % hexane) was utilized to obtain Compound 2 (yield: 18%).
Intermediate compound 1-C (1.0 eq), bromobenzene-d5 (2.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 12 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography was utilized to obtain Intermediate compound 4-D (yield: 77%).
Intermediate compound 4-D (1.2 eq), 2-(3-bromo-5-(tert-butyl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 3 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (ethyl acetate:hexane=1:9) was utilized to obtain Intermediate compound 4-E (yield: 70%).
Intermediate compound 4-E (1.0 eq) and ammonium hexafluorophosphate (3.0 eq) were dissolved in methanol (0.5 M), and then, distilled water was added thereto, and stirred at room temperature for 3 hours to 12 hours. After washing with distilled water and filtering to obtain a solid, an extraction process was performed thereon three times utilizing dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize Intermediate compound 4-F (yield of 93%).
Intermediate compound 4-F (1.0 eq), dichloro(1,5-cyclooctadiene)platinum (II) (1.1 eq), and sodium acetate (3.0 eq) were dissolved in anhydrous 1,4-dioxane, and then, stirred in the nitrogen condition (e.g., stirred under a nitrogen inert atmosphere) at a temperature of 120° C. for 4 days. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC:50 vol % hexane) was utilized to obtain Compound 4 (yield: 19%).
Intermediate compound 4-D (1.2 eq), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 3 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (ethyl acetate:hexane=1:9) was utilized to obtain Intermediate compound 5-E (yield: 68%).
Intermediate compound 5-E (1.0 eq) and ammonium hexafluorophosphate (3.0 eq) were dissolved in methanol (0.5 M), and then, distilled water was added thereto, and stirred at room temperature for 3 hours to 12 hours. After washing with distilled water and filtering to obtain a solid, an extraction process was performed thereon three times utilizing dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize Intermediate compound 5-F (yield of 93%).
Intermediate compound 5-F (1.0 eq), dichloro(1,5-cyclooctadiene)platinum (II) (1.1 eq), and sodium acetate (3.0 eq) were dissolved in anhydrous 1,4-dioxane, and then, stirred in the nitrogen condition (e.g., stirred under a nitrogen inert atmosphere) at a temperature of 120° C. for 4 days. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC:50 vol % hexane) was utilized to obtain Compound 5 (yield: 17%).
Intermediate compound 1-C (1.0 eq), 2,6-diphenyl-d10-aniline (2.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 12 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography was utilized to obtain Intermediate compound 7-A (yield: 74%).
Intermediate compound 7-A (1.2 eq), 2-(3-bromo-5-(tert-butyl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 3 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (ethyl acetate:hexane=1:9) was utilized to obtain Intermediate compound 7-B (yield: 72%).
Intermediate compound 7-B (1.0 eq) and ammonium hexafluorophosphate (3.0 eq) were dissolved in methanol (0.5 M), and then, distilled water was added thereto, and stirred at room temperature for 3 hours to 12 hours. After washing with distilled water and filtering to obtain a solid, an extraction process was performed thereon three times utilizing dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize Intermediate compound 7-C (yield of 93%).
Intermediate compound 7-C (1.0 eq), dichloro(1,5-cyclooctadiene)platinum (II) (1.1 eq), and sodium acetate (3.0 eq) were dissolved in anhydrous 1,4-dioxane, and then, stirred in the nitrogen condition (e.g., stirred under a nitrogen inert atmosphere) at a temperature of 120° C. for 4 days. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC:50 vol % hexane) was utilized to obtain Compound 7 (yield: 17%).
Intermediate compound 7-A (1.2 eq), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 3 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (ethyl acetate:hexane=1:9) was utilized to obtain Intermediate compound 8-A (yield: 70%).
Intermediate compound 8-A (1.0 eq) and ammonium hexafluorophosphate (3.0 eq) were dissolved in methanol (0.5 M), and then, distilled water was added thereto, and stirred at room temperature for 3 hours to 12 hours. After washing with distilled water and filtering to obtain a solid, an extraction process was performed thereon three times utilizing dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize Intermediate compound 8-B (yield of 93%).
Intermediate compound 8-B (1.0 eq), dichloro(1,5-cyclooctadiene)platinum (II) (1.1 eq), and sodium acetate (3.0 eq) were dissolved in anhydrous 1,4-dioxane, and then, stirred in the nitrogen condition (e.g., stirred under a nitrogen inert atmosphere) at a temperature of 120° C. for 4 days. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC 30 vol %:hexane) was utilized to obtain Compound 8 (yield: 18%).
1,3-diacetylimidazolin-2-one (1.0 equiv.) and cyclopentadiene (1.0 mol, 10 equiv.) were dissolved in m-xylene and stirred at a temperature of 150° C. for 72 hours. After the pressure was reduced, n-hexane was added to the reaction mixture and the precipitate was removed therefrom by filtration. The filtered precipitate was dissolved in MeOH (250 ml) and 2 M HCl (250 ml), stirred at room temperature for 30 minutes, and then subjected to reduced pressure. The reaction mixture was extracted with water and dichloromethane to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize an intermediate compound. The intermediate compound was dissolved in MeOH and dichloromethane and stirred at room temperature. After adding NaH (60% in mineral oil, 1.0 equiv.) at a temperature of 0° C., the resultant mixture was stirred for 4 hours at room temperature. After quenching with a NH4Cl solution at 0° C., an extraction process was performed utilizing water and dichloromethane. The obtained organic layer was dried utilizing anhydrous magnesium sulfate, concentrated, and recrystallized utilizing n-hexane to synthesize Intermediate compound 12-A (yield of 91%).
Intermediate compound 12-A (1.0 eq), Iodomethane-d3 (3.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 12 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography was utilized to obtain Intermediate compound 12-B (yield: 80%).
Intermediate compound 12-B (1.2 eq), 2-(3-bromo-5-(tert-butyl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 3 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (ethyl acetate:hexane=1:9) was utilized to obtain Intermediate compound 12-C(yield: 78%).
Intermediate compound 12-C (3.5 mmol) was dissolved in THF and then stirred at room temperature. LiAlH4 (7.0 mmol) was added at a temperature of 0° C., followed by stirring for 2 hours at 50° C. After adding THF, a NaOH solution and H2O to the reaction mixture at a temperature of 0° C., the resultant mixture was stirred for 30 minutes at room temperature. The reaction mixture was filtered by celite/silica gel utilizing THF and EtOAc and subjected to reduced pressure. After the reaction mixture (1.0 eq) was dissolved in triethyl orthoformate (30 eq) at 80° C., 37% HCl (1.5 eq) was added thereto and stirred at a temperature of 80° C. for 12 hours. After cooling at room temperature, triethyl orthoformate (e.g., the triethyl orthoformate solution) was concentrated and extracted three times with dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC, MC:5 vol % methanol) was utilized to obtain Intermediate compound 12-D (yield: 87%).
Intermediate compound 12-D (1.0 eq) and ammonium hexafluorophosphate (3.0 eq) were dissolved in methanol (0.5 M), and then, distilled water was added thereto, and stirred at room temperature for 3 hours to 12 hours. After washing with distilled water and filtering to obtain a solid, an extraction process was performed thereon three times utilizing dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize Intermediate compound 12-E (yield of 96%).
Intermediate compound 12-E (1.0 eq), dichloro(1,5-cyclooctadiene)platinum (II) (1.1 eq), and sodium acetate (3.0 eq) were dissolved in anhydrous 1,4-dioxane, and then, stirred in the nitrogen condition (e.g., stirred under a nitrogen inert atmosphere) at a temperature of 120° C. for 4 days. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC:50 vol % hexane) was utilized to obtain Compound 12 (yield: 21%).
1,3-diacetylimidazolin-2-one (1.0 equiv.) and 5,5-dimethylcyclopenta-1,3-diene (1.0 mol, 10 equiv.) were dissolved in m-xylene and stirred at a temperature of 150° C. for 72 hours. After the pressure was reduced, n-hexane was added to the reaction mixture and the precipitate was removed therefrom by filtration. The filtered precipitate was dissolved in MeOH (250 ml) and 2 M HCl (250 ml), stirred at room temperature for 30 minutes, and then subjected to reduced pressure. The reaction mixture was extracted with water and dichloromethane to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize Intermediate compound 23-A (yield of 56%).
A 20 ml EtOAc solution of 10% Pd/C (70 mg) was added to a solution in which Intermediate compound 23-A (15 mmol) was dissolved in EtOAc (10 ml) under the Ar condition (e.g., under the Ar inert atmosphere). After filling with the hydrogen gas, stirring was performed thereon at room temperature for 1 hour. The reaction mixture was washed with EtOAc and filtered utilizing Celite. The filtrate was concentrated to obtain synthesized Intermediate compound 23-B (yield of 99%).
Intermediate compound 23-B (2.0 equiv.) was dissolved in methanol (MeOH) and dichloromethane and stirred at room temperature. After adding NaH (60% in mineral oil, 1.0 equiv.) at a temperature of 0° C., the resultant mixture was stirred for 4 hours at room temperature. After quenching with a NH4Cl solution at 0° C., an extraction process was performed utilizing water and dichloromethane. The obtained organic layer was dried utilizing anhydrous magnesium sulfate, concentrated, and recrystallized utilizing n-hexane to synthesize Intermediate compound 23-C (yield of 94%).
Intermediate compound 23-C (1.0 eq), Iodomethane-d3 (3.0 eq), Pd2(dba)3 (2 mol %), Sphos (1 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 12 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography was utilized to obtain Intermediate compound 23-D (yield: 78%).
Intermediate compound 23-D (1.2 eq), 2-(3-bromo-5-(tert-butyl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 3 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (ethyl acetate:hexane=1:9) was utilized to obtain Intermediate compound 23-E (yield: 68%).
Intermediate Compound 23-E (7.0 mmol) was dissolved in THF and then stirred at room temperature. LiAlH4 (14 mmol) was added at a temperature of 0° C., followed by stirring for 2 hours at a temperature of 50° C. After adding THF, a NaOH solution and H2O to the reaction mixture at a temperature of 0° C., the resultant mixture was stirred for 30 minutes at room temperature. The reaction mixture was filtered by celite/silica gel utilizing THF and EtOAc and subjected to reduced pressure. After the reaction mixture (1.0 eq) was dissolved in triethyl orthoformate (30 eq) at 80° C., 37% HCl (1.5 eq) was added thereto and stirred at a temperature of 80° C. for 12 hours. After cooling at room temperature, triethyl orthoformate (e.g., the triethyl orthoformate solution) was concentrated and extracted three times with dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC, MC:5 vol % methanol) was utilized to obtain Intermediate compound 23-F (yield: 85%).
Intermediate compound 23-F (1.0 eq) and ammonium hexafluorophosphate (3.0 eq) were dissolved in methanol (0.5 M), and then, distilled water was added thereto, and stirred at room temperature for 3 hours to 12 hours. After washing with distilled water and filtering to obtain a solid, an extraction process was performed thereon three times utilizing dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize Intermediate compound 23-G (yield of 97%).
Intermediate compound 23-G (1.0 eq), dichloro(1,5-cyclooctadiene)platinum (II) (1.1 eq), and sodium acetate (3.0 eq) were dissolved in anhydrous 1,4-dioxane, and then, stirred in the nitrogen condition (e.g., stirred under a nitrogen inert atmosphere) at a temperature of 120° C. for 4 days. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC:50 vol % hexane) was utilized to obtain Compound 23 (yield: 22%).
1,4-dihydro-1,4-methanonaphthalene (1.00 g) was dissolved in tert-butanol (7.8 ml) and H2O (2.3 ml). N-methylmorpholine N-oxide solution (4.8 M in H2O, 6.4 mL, 30.7 mmol) was added thereto, and after about 5 minutes, an OsO4 solution (0.02 mL, 2 wt % in water) was added thereto and stirred at a temperature of 60° C. for 20 hours. After cooling the reaction mixture, the solvent was removed therefrom under reduced pressure, and extracted with water and ethyl acetate to obtain an organic layer. After washing with acetone, the resultant product was filtered to synthesize Intermediate compound 35-A (yield of 86%).
Trifluoroacetic anhydride (0.62 mL, 4.50 mmol) was slowly added to dimethyl sulfoxide (DMSO), and then the solution was stirred at a temperature of −78° C. for 10 minutes. The resultant mixture was added to a solution in which Intermediate compound 35-A (264 mg, 1.50 mmol) was dissolved in THF (5 ml), and then, stirred at a temperature of −78° C. for 2 hours. After the addition of Et3N (1.11 mL), the resultant mixture was stirred at a temperature of −78° C. for 3 hours, and transferred to an ice bath and stirred therein at a temperature of 0° C. The result was quenched utilizing NH4Cl solution (10 ml), and then, extracted with water and Et2O to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (30% EtOAc) was utilized to obtain Intermediate compound 35-B (yield: 96%).
Intermediate Compound 35-B (400 mg, 1.98 mmol) was dissolved in 10 ml MeOH, and then, NaOAc (389 mg, 4.75 mmol) and NH2OH HCl (550 mg, 7.92 mmol) were added thereto, followed by stirring at room temperature for 4 hours. The reaction mixture was extracted with water and EtOAc to obtain an organic layer. The obtained organic layer was dried utilizing anhydrous magnesium sulfate, concentrated, and recrystallized utilizing hexane and EtOAc at the volume ratio of 1:1 to synthesize Intermediate compound 35-C (yield of 89%).
Intermediate compound 35-C (1.75 mmol) was dissolved in MeOH, and then, NiCl2 (3.50 mmol) was added thereto and stirred at room temperature for 10 minutes. NaBH4 (17.5 mmol) was added thereto at a temperature of 0° C., and then, stirred at room temperature for 4 hours. The reaction mixture was subjected to reduced pressure, dissolved in dichloromethane, and filtered utilizing a celite pad. After extraction with 2 M HCl and dichloromethane, the pressure was reduced to obtain Intermediate compound 35-D (yield: 82%).
Intermediate Compound 35-D (1.0 eq), Iodomethane-d3 (3.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 12 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography was utilized to obtain Intermediate compound 35-E (yield: 75%).
Intermediate compound 35-E (1.2 eq), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.0 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M), and then, stirred at a temperature of 110° C. for 3 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (ethyl acetate:hexane=1:9) was utilized to obtain Intermediate compound 35-F (yield: 77%).
After Intermediate compound 35-F (1.0 eq) was dissolved in triethyl orthoformate (30 eq) at 80° C., 37% HCl (1.5 eq) was added thereto and stirred at a temperature of 80° C. for 12 hours. After cooling at room temperature, triethyl orthoformate (e.g., the triethyl orthoformate solution) was concentrated and extracted three times with dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC, MC:5 vol % methanol) was utilized to obtain Intermediate compound 35-G (yield: 37%).
Intermediate compound 35-G (1.0 eq) and ammonium hexafluorophosphate (3.0 eq) were dissolved in methanol (0.5 M), and then, distilled water was added thereto, and stirred at room temperature for 3 hours to 12 hours. After washing with distilled water and filtering to obtain a solid, an extraction process was performed thereon three times utilizing dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate, and concentrated to synthesize Intermediate compound 35-H (yield of 94%).
Intermediate compound 35-H (1.0 eq), dichloro(1,5-cyclooctadiene)platinum (II) (1.1 eq), and sodium acetate (3.0 eq) were dissolved in anhydrous 1,4-dioxane, and then, stirred in the nitrogen condition (e.g., stirred under a nitrogen inert atmosphere) at a temperature of 120° C. for 4 days. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing water to obtain an organic layer. The obtained organic layer was dried by utilizing anhydrous magnesium sulfate and concentrated, and column chromatography (MC:50 vol % hexane) was utilized to obtain Compound 35 (yield: 23%).
The 3MLCT (%), simulation maximum emission wavelength (λmaxsim), and 3MC energy level of each of the compounds of Synthesis Examples 1 to 9 and Comparative Example 1 were evaluated by quantum simulation. Actual maximum emission wavelength (λmaxexp) for each was also measured. Results thereof are shown in Table 1.
In more detail, characteristics of Compounds 5 and 7 and Compound A as a comparative compound were evaluated, and the energy level value of 3MC state for each was evaluated utilizing a B3LYP functional method. The 3MLCT (%) value was measured by structural optimization at the level of B3LYP, 6-31 G(d,p) utilizing a density functional theory (DFT) calculation method of the Gaussian program.
3MC
3MLCT(%)
From Table 1, it can be seen that the 3MC values of Compounds 1, 2, 4, 5, 7, 8, 12, 23, and 35 were each significantly higher than the 3MC value of Compound A. Accordingly, each of Compounds 1, 2, 4, 5, 7, 8, 12, 23, and 35 may less likely transition from the 3MCLT state to the non-emission state, that is, the 3MC state. Therefore, the stability thereof in an excited state may be suitable (e.g., excellent), and the efficiency and lifespan of the organic light-emitting device including the organometallic compounds may be increased.
As a substrate and an anode, a glass substrate with 15 Ω/cm2 (1,200 Å) ITO thereon, which was manufactured by Corning Inc., was cut to a size of 50 mm×50 mm×0.7 mm, and the glass substrate was sonicated by utilizing isopropyl alcohol and pure water for 5 minutes each, and then ultraviolet (UV) light was irradiated for 30 minutes thereto and ozone was exposed thereto for cleaning. Then, the resultant glass substrate was loaded onto a vacuum deposition apparatus.
2-TNATA was vacuum-deposited on the ITO anode on the glass substrate to form a hole injection layer having a thickness of 600 Å, and then, NPB was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 300 Å.
Co-hosts bis(4-(9H-carbazol-9-yl)phenyl)diphenylsilane) (BCPDS) and (4-(1-(4-(diphenylamino)phenyl)cyclohexyl)phenyl)diphenyl-phosphine oxide (POPCPA) (the weight ratio of BCPDS to POPCPA was 1:1) and Compound 1, which is a dopant, were co-deposited on the hole transport layer at a co-host to dopant weight ratio of 90:10 to form an emission layer having a thickness of 300 Å.
Diphenyl(4-(triphenylsilyl)phenyl)-phosphine oxide (TSPO1) was deposited on the emission layer to form a hole blocking layer having a thickness of 50 Å, Alq3 was deposited on the hole blocking layer to form an electron transport layer having a thickness of 300 Å, LiF was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and Al was vacuum-deposited on the electron injection layer to form a cathode having a thickness of 3,000 Å, thereby completing the manufacture of an organic light-emitting device.
Organic light-emitting devices were manufactured in the same manner as in Example 1, except that in forming an emission layer, for usage as a dopant, corresponding compounds shown in Table 1 were utilized instead of Compound 1.
The driving voltage, current density, luminance, luminescence efficiency, emission color, and maximum emission wavelength of each of the organic light-emitting devices manufactured according to Examples 1 to 9, and Comparative Example 1 were measured by utilizing a Keithley SMU 236 and a luminance photometer PR650, and results thereof are shown in Table 2. PGP 54 TRE
Referring to Table 2, it was confirmed that each of the organic light-emitting devices of Examples 1 to 9 had a higher level of luminance and a higher luminescence efficiency than the organic light-emitting device of Comparative Example 1.
According to the one or more embodiments, the organic light-emitting device including the organometallic compound may have high luminance, high efficiency, and long lifespan.
The use of “may” when describing embodiments of the present invention refers to “one or more embodiments of the present invention.” Also, the term “exemplary” is intended to refer to an example or illustration.
As used herein, the term “substantially,” “about,” and similar terms are used as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art. Moreover, any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range. For example, a range of “1.0 to 10.0” is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein. All such ranges are intended to be inherently described in this specification such that amending to expressly recite any such subranges would comply with the requirements of 35 U.S.C. § 112(a), and 35 U.S.C. § 132(a).
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 suitable changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims, and equivalents thereof.
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