Electron transport layer comprising a matrix compound mixture for an organic light-emitting diode (OLED)
Patent Information
- Application Number
- KR1020247042529
- Authority / Receiving Office
- KR · KR
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2016-02-19
- Filing Date
- 2017-02-16
- Publication Date
- 2026-09-21
- Estimated Expiration
- 2037-02-16
Smart Images
Figure 112024142592610-PAT00100_ABST
Abstract
Description
Technology Field
[0001] The present invention relates to an organic light-emitting diode (OLED) comprising an electron transport layer stack having an electron transport layer comprising a matrix compound mixture, and a method for manufacturing the organic light-emitting diode (OLED) comprising the electron transport layer stack. Background Technology
[0002] Organic light-emitting diodes (OLEDs) are self-emitting devices that possess a wide viewing angle, excellent contrast, fast response, high brightness, excellent driving voltage characteristics, and color reproduction. A typical OLED comprises an anode electrode, a hole injection layer (HIL), a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode electrode, which are sequentially stacked on a substrate. In this regard, the HIL, HTL, EML, and ETL are thin films formed from organic compounds.
[0003] When voltage is applied to the anode electrode and the cathode electrode, holes injected from the anode electrode move to the EML through the HIL and HTL, and electrons injected from the cathode electrode move to the EML through the ETL. Holes and electrons recombine in the EML to generate excitons.
[0004] WO 2016 / 001283 A1 relates to an organic light-emitting diode (OLED) comprising an electron transport layer stack comprising two or more electron transport layers, wherein the first electron transport layer and the second electron transport layer comprise one or more matrix compounds, and further, the first electron transport layer comprises a first lithium halide or a first lithium organic complex; and the second electron transport layer comprises a second lithium halide or a second lithium organic complex, wherein the first lithium organic complex is not the same as the second lithium organic complex, and the first lithium halide is not the same as the second lithium halide.
[0005] KR 2015 0115688 A relates to an organic light-emitting diode (OLED) comprising: a first electron transport layer provided between a cathode and a light-emitting layer; and a second electron transport layer provided between a cathode and the first electron transport layer, wherein the second electron transport layer comprises a host material and one or more n-type dopants selected from alkali metals and alkaline earth metals.
[0006] It is still desired to improve external quantum efficiency (EQE), reduce the operating voltage to improve the lifespan of the OLED, and / or reduce the takt time of the OLED manufacturing process.
[0007] One aspect of the present invention is to provide an OLED having improved external quantum efficiency (EQE) and / or a lower operating voltage and / or an improved lifetime and / or an increased takt time for top and / or bottom emission organic light-emitting diodes (OLEDs).
[0008] The present invention relates to an organic light-emitting diode, and such an organic light-emitting diode is:
[0009] - One or more anode electrodes;
[0010] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0011] - As an electron transport layer stack of two or more electron transport layers, where:
[0012] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0013] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0014] i) a first organic aromatic matrix compound; and
[0015] ii) a polar organic aromatic phosphine compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about > 2.5 Debye to about ≤ 10 Debye, preferably about ≥ 3 to ≤ 5 Debye.
[0016] An electron transport layer stack that is a mixture of; and
[0017] - One or more cathode electrode layers
[0018] Includes; here
[0019] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer.
[0020] Furthermore, the present invention relates to an organic light-emitting diode (OLED) comprising a substrate, an anode electrode, a hole injection layer, a hole transport layer, an optional electron blocking layer, an electron transport layer stack comprising an optional hole blocking layer, a first electron transport layer and a second electron transport layer, an optional electron injection layer and a cathode electrode layer, wherein these layers are arranged in the corresponding order.
[0021] Furthermore, the present invention relates to a method for manufacturing such an OLED.
[0022] definition
[0023] The terms "OLED," "organic light-emitting diode," and "organic photo-emitting diode" are used simultaneously and have the same meaning.
[0024] The term “electron transport layer stack,” also referred to as an ETL-stack, means two or more electron transport layers (ETLs) arranged in direct contact, for example, first and second electrode layers arranged in direct contact. The “electron transport layer stack” may include two or more electron transport layers, three or more electron transport layers, or four or more electron transport layers.
[0025] The term "first organic aromatic matrix compound" is used as a synonym for "i) a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye."
[0026] The term "polar organic aromatic phosphine compound" is used as a synonym for "ii) polar organic aromatic phosphine compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about > 2.5 Debye to about ≤ 10 Debye".
[0027] In the above, "emitter dopant" means a compound that emits visible light when an OLED is operated. In the context of the present invention, "visible light" means light having a wavelength of about ≥ 380 nm to about ≤ 780 nm.
[0028] In the context of this specification, the term “non-emitter dopant” used in relation to an electron transport layer (ETL) or an electron transport layer stack means a dopant that does not contribute to the emission spectrum of the device during operation of the OLED. That is, the non-emitter dopant is essentially non-emitting in the visible region of the electromagnetic spectrum, with wavelengths of about ≥ 380 nm to about ≤ 780 nm.
[0029] In the context of this specification, the term "essentially non-emitting" means that the contribution of a non-emitter dopant to the emission spectrum during operation of the OLED is less than 10%, preferably less than 5%, based on the emission spectrum.
[0030] In the context of this specification, the term "when operating the OLED" means that a voltage of 2 to 10 V is applied. The OLED that can be used is an OLED according to the present invention, for example, an OLED according to Table 7 of the present invention.
[0031] As used herein, “weight percent,” “wt%,” “percentage of weight,” “weight%,” and variations thereof relating to a composition, component, component, or formulation, each means the value obtained by dividing the weight of the corresponding composition, component, component, or formulation of the electron transport layer by the total weight of the composition and multiplying the result by 100. It is understood that the total weight% of all components, components, or formulations of each electron transport layer does not exceed 100 weight%.
[0032] As used herein, “volume percent,” “vol%,” “percentage of volume,” “volume%,” and variations thereof refer to metal elements, compositions, components, components, or formulations, and mean the value obtained by dividing the volume of each metal element, component, component, or formulation of the electron transport layer by the total volume of each electron transport layer and multiplying by 100. It is understood that the total volume% of all metal elements, components, components, or formulations of each cathode electrode layer does not exceed 100 volume%.
[0033] All numeric values are assumed to be modified by the term "about," regardless of whether they are explicitly indicated. As used herein, the term "about" indicates a variation in a numerical amount that may occur. Regardless of whether they are modified by the term "about," the claim includes an amount equivalent to that amount.
[0034] As used in this specification and the appended claims, the singular forms (“a,” “an,” and “the”) should be interpreted to include plural objects unless the content clearly indicates otherwise.
[0035] The terms "none," "not containing," and "not including" do not exclude impurities that may be present in the compound prior to deposition or in the layer after deposition. Impurities have no technical effect in relation to the purpose achieved by the present invention.
[0036] The term "phosphine compound" or "polar organic aromatic phosphine compound" means and includes compounds selected from the group consisting of organic phosphine oxide compounds, organic thioxophosphine compounds, or organic selenoxophosphine compounds.
[0037] The term "phosphine" as used in this specification and claims includes compounds according to Formula Ia, including phosphole and phosphepine.
[0038] The term "alkyl" refers to a straight-chain, branched, or cyclic alkyl group.
[0039] The alkyl group may be selected from the group comprising isomers of methyl, ethyl, and propyl, butyl, or pentyl, for example, isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl, and / or cyclo-hexyl.
[0040] As used herein, the term "alkan-di-yl" refers to a straight-chain, branched, or cyclic alkane-di-yl group. An alkane-di-yl group is a saturated group bonded to two phosphorus atoms.
[0041] As used herein, the term "alkan-di-yl" refers to a group comprising single and double carbon-carbon bonds. Preferably, the double and single bonds alternate to form a pentagonal, hexagonal, or heptagonal ring with a phosphorus atom.
[0042] The term "aryl" refers to an aromatic group. As used herein, the term "aryl" must include phenyl (C6-aryl), fused aromatics, such as naphthalene, anthracene, phenanthrene, tetracene, etc. Biphenyl and oligophenyl or polyphenyls, such as terphenyl, etc., are additionally included. Any additional aromatic hydrocarbon substituent, such as fluorenyl, etc., must be additionally included.
[0043] The term "arylene" refers to an aromatic group. As used herein, the term "arylene" must include phenylene (C6-arylene), fused aromatics, such as naphthalene-di-yl, anthracene-di-yl, phenanthrene-di-yl, tetracene-di-yl, vinaptylene-di-yl, etc. Biphenylene and oligophenylene or polyphenylene, such as terphenylene, etc., are additionally included. Any additional aromatic group, such as fluorene-di-yl, etc., must be additionally included.
[0044] The term "heteroarylene" refers to an aromatic heterocycle. As used herein, the term "heteroarylene" must include pyridine-di-yl, quinolone-di-yl, carbazole-di-yl, xanthen-di-yl, phenoxazine-di-yl, etc.
[0045] Here, when it is stated that a first configuration is formed or arranged "on" a second configuration, the first configuration may be arranged directly on the second configuration, or one or more other configurations may be arranged between them. When it is stated that a first configuration is formed or arranged "directly" on the second configuration, no other configurations are arranged between them.
[0046] The term "interposed in contact" refers to an arrangement of three layers in which an intermediate layer is in direct contact with two adjacent layers.
[0047] The anode electrode may be described as an anode electrode or an anode electrode layer.
[0048] The cathode electrode may be described as a cathode electrode or a cathode electrode layer.
[0049] The composition and / or components of the electron injection layer are different from those of the electron transport layer stack.
[0050] The electron transport layer stack is not the cathode electrode because their compositions are different.
[0051] The cathode electrode of the OLED according to the present invention may not include a polar organic aromatic phosphine compound or an organic aromatic matrix compound.
[0052] The cathode electrode of the OLED according to the present invention may not include or may not be composed of an organic compound.
[0053] In a preferred embodiment, the cathode electrode layer may not contain organic compounds, organometallic complexes, and metal halides.
[0054] The electron transport layer stack, electron injection layer(s) and cathode electrode layer(s) may each differ from one another in their composition.
[0055] The electron injection layers and cathode electrode layers may differ from each other in their composition.
[0056] The operating voltage, also referred to as U, is 10 milliamperes (mA / cm²) per square centimeter for bottom-emitting devices. 2 ) and 15 mA / cm² for top-emitting devices 2 It is measured in volts (V).
[0057] External quantum efficiency, also known as EQE, is measured in percentages (%).
[0058] Color spaces are described by CIE-x and CIE-y coordinates (International Commission on Illumination 1931). CIE-y is particularly important for blue emission. The smaller the CIE-y value, the deeper the blue.
[0059] The highest occupied molecular orbital, also known as HOMO, and the lowest unoccupied molecular orbital, also known as LUMO, are measured in electron volts (eV). HOMO and LUMO are measured in solution using cyclic voltammetry.
[0060] The dipole moment is verified through quantum-chemical calculations and measured in Debye (D).
[0061] The triplet level T1 is verified through quantum-chemical calculations and measured in electron volts (eV).
[0062] The term "MW" stands for molar mass and is measured in grams / mol (g / mol).
[0063] Unless otherwise noted, the relative humidity (abbreviation RH) is 40% and the temperature is 23℃.
[0064] Other embodiments
[0065] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0066] - One or more anode electrodes;
[0067] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0068] - As an electron transport layer stack of two or more electron transport layers, where:
[0069] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0070] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0071] i) a first organic aromatic matrix compound; and
[0072] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0073] An electron transport layer stack that is a mixture of; and
[0074] - One or more cathode electrode layers
[0075] Includes; here
[0076] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer; the second electron transport layer is:
[0077] - ≥ 50 wt% to ≤ 95 wt%, preferably ≥ 60 wt% to ≤ 90 wt%, more preferably ≥ 70 wt% to ≤ 90 wt%, most preferably about 80 wt% i) a first organic aromatic matrix compound; and
[0078] - ≥ 5 wt% to ≤ 90 wt%, preferably ≥ 10 wt% to ≤ 40 wt%, more preferably ≥ 10 wt% to ≤ 30 wt%, most preferably about 20 wt% of ii) polar organic aromatic phosphine compound
[0079] Includes; where weight% is based on the total weight of i) and ii) of the second electron transport layer.
[0080] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0081] - One or more anode electrodes;
[0082] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0083] - As an electron transport layer stack of two or more electron transport layers, where:
[0084] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0085] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0086] i) a first organic aromatic matrix compound; and
[0087] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0088] An electron transport layer stack that is a mixture of; and
[0089] - One or more cathode electrode layers
[0090] Includes; here
[0091] An electron transport layer stack is arranged between a light-emitting layer and a cathode electrode layer, wherein a first electron transport layer is in direct contact with a second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer; the second electron transport layer comprises one or more non-emitter dopants;
[0092] - ≥ 50 wt% to ≤ 95 wt%, preferably ≥ 60 wt% to ≤ 90 wt%, more preferably ≥ 70 wt% to ≤ 90 wt%, most preferably about 80 wt% i) a first organic aromatic matrix compound; and
[0093] - ≥ 5 wt% to ≤ 90 wt%, preferably ≥ 10 wt% to ≤ 40 wt%, more preferably ≥ 10 wt% to ≤ 30 wt%, most preferably about 20 wt% of ii) polar organic aromatic phosphine compound
[0094] It includes; where weight% is based on the total weight of i) and ii) of the second electron transport layer.
[0095] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0096] - One or more anode electrodes;
[0097] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0098] - As an electron transport layer stack of two or more electron transport layers, where:
[0099] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0100] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0101] i) a first organic aromatic matrix compound; and
[0102] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0103] An electron transport layer stack that is a mixture of; and
[0104] - One or more cathode electrode layers
[0105] Includes; here
[0106] An electron transport layer stack is arranged between a light-emitting layer and a cathode electrode layer, wherein the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer; the second electron transport layer comprises one or more non-emitter dopants, said non-emitter dopants are metal compounds, preferably the metal compounds are selected from the group consisting of metal halides, metal-organic complexes and / or zero-value metals; more preferably the metal-organic complexes have Formula VII:
[0107]
[0108] Here, M is an alkali metal ion, and A 1 To A 4 are each independently substituted or unsubstituted C6-C 20 Aryl or substituted or unsubstituted C2-C 20 Selected from heteroaryls, more preferably M is a lithium ion, most preferably lithium tetra(1H-pyrazole-1-yl)borate; and the second electron transport layer is:
[0109] - ≥ 50 wt% to ≤ 95 wt%, preferably ≥ 60 wt% to ≤ 90 wt%, more preferably ≥ 70 wt% to ≤ 90 wt%, most preferably about 80 wt% i) a first organic aromatic matrix compound; and
[0110] - ≥ 5 wt% to ≤ 90 wt%, preferably ≥ 10 wt% to ≤ 40 wt%, more preferably ≥ 10 wt% to ≤ 30 wt%, most preferably about 20 wt% of ii) polar organic aromatic phosphine compound
[0111] Includes; where weight% is based on the total weight of i) and ii) of the second electron transport layer.
[0112] According to another aspect of the present invention, the first electron transport layer may not have a non-emitter dopant.
[0113] According to another aspect of the present invention, the second electron transport layer may also include a non-emitter dopant.
[0114] According to another aspect of the present invention, the non-emitter dopant is a metal compound, and preferably, the metal compound is selected from the group consisting of metal halides, metal-organic complexes and / or zero-valence metals.
[0115] According to another aspect of the present invention, the non-emitter dopant is selected from the group consisting of metal halides, metal-organic complexes and / or zero-value metals.
[0116] According to another aspect of the present invention, the non-emitter dopant is a zero-value metal.
[0117] According to another aspect of the present invention, the second electron transport layer may also include a non-emitter dopant which is a zero-value metal.
[0118] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0119] - One or more anode electrodes;
[0120] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0121] - As an electron transport layer stack of two or more electron transport layers, where:
[0122] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0123] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0124] i) a first organic aromatic matrix compound; and
[0125] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0126] An electron transport layer stack that is a mixture of; and
[0127] - One or more cathode electrode layers
[0128] Includes; here
[0129] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer; the first electron transport layer comprises a first organic aromatic matrix compound in an amount of ≥ 90 wt% to ≤ 100 wt%, preferably ≥ 95 wt% to ≤ 98 wt%.
[0130] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0131] - One or more anode electrodes;
[0132] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0133] - As an electron transport layer stack of two or more electron transport layers, where:
[0134] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0135] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0136] i) a first organic aromatic matrix compound; and
[0137] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0138] An electron transport layer stack that is a mixture of; and
[0139] - One or more cathode electrode layers
[0140] Includes; here
[0141] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer; the first electron transport layer comprises a non-emitter dopant and comprises a first organic aromatic matrix compound in an amount of ≥ 90 wt% to ≤ 100 wt%, preferably ≥ 95 wt% to ≤ 98 wt%.
[0142] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0143] - One or more anode electrodes;
[0144] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0145] - As an electron transport layer stack of two or more electron transport layers, where:
[0146] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0147] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0148] i) a first organic aromatic matrix compound; and
[0149] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0150] An electron transport layer stack that is a mixture of; and
[0151] - One or more cathode electrode layers
[0152] Includes; here
[0153] An electron transport layer stack is arranged between a light-emitting layer and a cathode electrode layer, wherein a first electron transport layer is in direct contact with a second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer; the first electron transport layer comprises a first organic aromatic matrix compound in an amount of ≥ 90 wt% to ≤ 100 wt%, preferably ≥ 95 wt% to ≤ 98 wt%; and the second electron transport layer comprises:
[0154] - ≥ 50 wt% to ≤ 95 wt%, preferably ≥ 60 wt% to ≤ 90 wt%, more preferably ≥ 70 wt% to ≤ 90 wt%, most preferably about 80 wt% i) a first organic aromatic matrix compound; and
[0155] - ≥ 5 wt% to ≤ 90 wt%, preferably ≥ 10 wt% to ≤ 40 wt%, more preferably ≥ 10 wt% to ≤ 30 wt%, most preferably about 20 wt% of ii) polar organic aromatic phosphine compound
[0156] Includes; where weight% is based on the total weight of i) and ii) of the second electron transport layer.
[0157] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0158] - One or more anode electrodes;
[0159] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0160] - As an electron transport layer stack of two or more electron transport layers, where:
[0161] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0162] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0163] i) a first organic aromatic matrix compound; and
[0164] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0165] An electron transport layer stack that is a mixture of; and
[0166] - One or more cathode electrode layers
[0167] Includes; here
[0168] An electron transport layer stack is arranged between a light-emitting layer and a cathode electrode layer, wherein a first electron transport layer is in direct contact with a second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer; the first electron transport layer comprises a non-emitter dopant and comprises a first organic aromatic matrix compound in an amount of ≥ 90 wt% to ≤ 100 wt%, preferably ≥ 95 wt% to ≤ 98 wt%; and the second electron transport layer comprises a non-emitter dopant and:
[0169] - ≥ 50 wt% to ≤ 95 wt%, preferably ≥ 60 wt% to ≤ 90 wt%, more preferably ≥ 70 wt% to ≤ 90 wt%, most preferably about 80 wt% i) a first organic aromatic matrix compound; and
[0170] - ≥ 5 wt% to ≤ 90 wt%, preferably ≥ 10 wt% to ≤ 40 wt%, more preferably ≥ 10 wt% to ≤ 30 wt%, most preferably about 20 wt% of ii) polar organic aromatic phosphine compound
[0171] Includes; where weight% is based on the total weight of i) and ii) of the second electron transport layer.
[0172] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0173] - One or more anode electrodes;
[0174] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0175] - As an electron transport layer stack of two or more electron transport layers, where:
[0176] a) the first electron transport layer is composed of i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0177] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0178] i) a first organic aromatic matrix compound; and
[0179] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0180] An electron transport layer stack that is a mixture of; and
[0181] - One or more cathode electrode layers
[0182] Includes; here
[0183] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer.
[0184] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0185] - One or more anode electrodes;
[0186] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0187] - An electron transport layer stack of two or more electron transport layers, wherein the electron transport layer stack does not have an emitter dopant that emits visible light during operation of the OLED, and
[0188] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0189] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0190] i) a first organic aromatic matrix compound; and
[0191] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0192] An electron transport layer stack that is a mixture of; and
[0193] - One or more cathode electrode layers
[0194] Includes; here
[0195] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer.
[0196] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0197] - One or more anode electrodes;
[0198] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0199] - An electron transport layer stack of two or more electron transport layers, wherein the electron transport layer stack does not have an emitter dopant that emits visible light during operation of the OLED, the first electron transport layer does not have a non-emitter dopant, and the second electron transport layer includes a non-emitter dopant.
[0200] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0201] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0202] i) a first organic aromatic matrix compound; and
[0203] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0204] An electron transport layer stack that is a mixture of; and
[0205] - One or more cathode electrode layers
[0206] Includes; here
[0207] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer.
[0208] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0209] - One or more anode electrodes;
[0210] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0211] - An electron transport layer stack of two or more electron transport layers, wherein the electron transport layer stack does not have an emitter dopant that emits visible light during operation of the OLED, and
[0212] a) the first electron transport layer is composed of i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0213] b) The second electron transport layer comprises a non-emitter dopant and two organic aromatic matrix compounds, and these compounds are:
[0214] i) a first organic aromatic matrix compound; and
[0215] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0216] An electron transport layer stack that is a mixture of; and
[0217] - One or more cathode electrode layers
[0218] Includes; here
[0219] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer.
[0220] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0221] - One or more anode electrodes;
[0222] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0223] - An electron transport layer stack of two or more electron transport layers, wherein the electron transport layer stack does not have an emitter dopant that emits visible light during operation of the OLED, and
[0224] a) the first electron transport layer is composed of i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0225] b) The second electron transport layer consists of a non-emitter dopant and two organic aromatic matrix compounds, and these compounds are:
[0226] i) a first organic aromatic matrix compound; and
[0227] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0228] An electron transport layer stack that is a mixture of; and
[0229] - One or more cathode electrode layers
[0230] Includes; here
[0231] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer.
[0232] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0233] - One or more anode electrodes;
[0234] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0235] - As an electron transport layer stack of two or more electron transport layers, where:
[0236] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer comprises:
[0237] - Polar organic aromatic phosphine compounds, aryl compounds with a triplet level of 2.9 eV or higher, phenyltriazole, benzimidazole, phenanthroline, oxadiazole, benzoxazole, oxazole, quinazoline, benzo[h]quinazoline, pyrido[3,2-h]quinazoline, pyrimido[4,5-f]quinazoline, quinoline, benzoquinoline, pyrrolo[2,1-a]isoquinoline, and benzofuro[2,3-d]pyridazine
[0238] There is none;
[0239] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0240] i) a first organic aromatic matrix compound; and
[0241] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0242] An electron transport layer stack that is a mixture of; and
[0243] - One or more cathode electrode layers
[0244] Includes; here
[0245] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer.
[0246] Furthermore, the present invention provides an organic light-emitting diode (OLED) comprising a substrate, an anode electrode, a hole injection layer, a hole transport layer, an optional electron blocking layer, an electron transport layer stack including an optional hole blocking layer, a first electron transport layer and a second electron transport layer, an optional electron injection layer and a cathode electrode layer, wherein these layers are arranged in the corresponding order.
[0247] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0248] - One or more anode electrodes;
[0249] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0250] - An electron transport layer stack of two or more electron transport layers, wherein the electron transport layer stack does not have an emitter dopant that emits visible light during operation of the OLED, and
[0251] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer comprises:
[0252] - Polar organic aromatic phosphine compounds, aryl compounds with a triplet level of 2.9 eV or higher, phenyltriazole, benzimidazole, phenanthroline, oxadiazole, benzoxazole, oxazole, quinazoline, benzo[h]quinazoline, pyrido[3,2-h]quinazoline, pyrimido[4,5-f]quinazoline, quinoline, benzoquinoline, pyrrolo[2,1-a]isoquinoline, and benzofuro[2,3-d]pyridazine
[0253] There is none;
[0254] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0255] i) a first organic aromatic matrix compound; and
[0256] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0257] An electron transport layer stack that is a mixture of; and
[0258] - One or more cathode electrode layers
[0259] Includes; here
[0260] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer.
[0261] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0262] - One or more anode electrodes;
[0263] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0264] - An electron transport layer stack of two or more electron transport layers, wherein the electron transport layer stack does not have an emitter dopant that emits visible light when the OLED is operated, the first electron transport layer does not have a non-emitter dopant, and the second electron transport layer (162) includes a non-emitter dopant, and wherein
[0265] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer comprises:
[0266] - Polar organic aromatic phosphine compounds, aryl compounds with a triplet level of 2.9 eV or higher, phenyltriazole, benzimidazole, phenanthroline, oxadiazole, benzoxazole, oxazole, quinazoline, benzo[h]quinazoline, pyrido[3,2-h]quinazoline, pyrimido[4,5-f]quinazoline, quinoline, benzoquinoline, pyrrolo[2,1-a]isoquinoline, and benzofuro[2,3-d]pyridazine
[0267] There is none;
[0268] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0269] i) a first organic aromatic matrix compound; and
[0270] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0271] An electron transport layer stack that is a mixture of; and
[0272] - One or more cathode electrode layers
[0273] Includes; here
[0274] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer.
[0275] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0276] - One or more anode electrodes;
[0277] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0278] - An electron transport layer stack of two or more electron transport layers, wherein the electron transport layer stack does not have an emitter dopant that emits visible light when the OLED is operated, the first electron transport layer does not have a non-emitter dopant, and the second electron transport layer (162) includes a non-emitter dopant, and wherein
[0279] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer comprises:
[0280] - Polar organic aromatic phosphine compounds, aryl compounds with a triplet level of 2.9 eV or higher, phenyltriazole, benzimidazole, phenanthroline, oxadiazole, benzoxazole, oxazole, quinazoline, benzo[h]quinazoline, pyrido[3,2-h]quinazoline, pyrimido[4,5-f]quinazoline, quinoline, benzoquinoline, pyrrolo[2,1-a]isoquinoline, and benzofuro[2,3-d]pyridazine
[0281] There is none;
[0282] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0283] i) a first organic aromatic matrix compound; and
[0284] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0285] An electron transport layer stack that is a mixture of; and
[0286] - One or more cathode electrode layers
[0287] Includes; here
[0288] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer; the second electron transport layer is:
[0289] - ≥ 50 wt% to ≤ 95 wt%, preferably ≥ 60 wt% to ≤ 90 wt%, more preferably ≥ 70 wt% to ≤ 90 wt%, most preferably about 80 wt% i) a first organic aromatic matrix compound; and
[0290] - ≥ 5 wt% to ≤ 90 wt%, preferably ≥ 10 wt% to ≤ 40 wt%, more preferably ≥ 10 wt% to ≤ 30 wt%, most preferably about 20 wt% of ii) polar organic aromatic phosphine compound
[0291] Includes; where weight% is based on the total weight of i) and ii) of the second electron transport layer.
[0292] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided, and the organic light-emitting diode is:
[0293] - One or more anode electrodes;
[0294] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0295] - An electron transport layer stack of two or more electron transport layers, wherein the electron transport layer stack does not have an emitter dopant that emits visible light when the OLED is operated, the first electron transport layer does not have a non-emitter dopant, and the second electron transport layer (162) includes a non-emitter dopant, and wherein
[0296] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer comprises:
[0297] - Polar organic aromatic phosphine compounds, aryl compounds with a triplet level of 2.9 eV or higher, phenyltriazole, benzimidazole, phenanthroline, oxadiazole, benzoxazole, oxazole, quinazoline, benzo[h]quinazoline, pyrido[3,2-h]quinazoline, pyrimido[4,5-f]quinazoline, quinoline, benzoquinoline, pyrrolo[2,1-a]isoquinoline and benzofuro[2,3-d]pyridazine are absent;
[0298] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0299] i) a first organic aromatic matrix compound; and
[0300] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0301] An electron transport layer stack that is a mixture of; and
[0302] - One or more cathode electrode layers
[0303] Includes; here
[0304] An electron transport layer stack is arranged between a light-emitting layer and a cathode electrode layer, wherein a first electron transport layer is in direct contact with a second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer; and the second electron transport layer comprises a non-emitter dopant:
[0305] - ≥ 50 wt% to ≤ 95 wt%, preferably ≥ 60 wt% to ≤ 90 wt%, more preferably ≥ 70 wt% to ≤ 90 wt%, most preferably about 80 wt% i) a first organic aromatic matrix compound; and
[0306] - ≥ 5 wt% to ≤ 90 wt%, preferably ≥ 10 wt% to ≤ 40 wt%, more preferably ≥ 10 wt% to ≤ 30 wt%, most preferably about 20 wt% of ii) polar organic aromatic phosphine compound
[0307] Includes; where weight% is based on the total weight of i) and ii) of the second electron transport layer.
[0308] Electron transport layer stack
[0309] The electron transport layer stack according to the present invention comprises two or more electron transport layers, wherein
[0310] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0311] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0312] i) a first organic aromatic matrix compound; and
[0313] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0314] It is a mixture of
[0315] According to another embodiment, the second electron transport layer may comprise i) a first organic aromatic matrix compound and ii) a polar organic aromatic phosphine compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about > 2.5 Debye to about ≤ 10 Debye, preferably about ≥ 3 to ≤ 5 Debye, more preferably ≥ 2.5 to less than ≤ 4 Debye.
[0316] The use of a first organic aromatic matrix compound and a polar organic aromatic phosphine compound having an MW of about ≥ 400 to about ≤ 1000 provides the benefit of positive control of the deposition rate during vacuum thermal evaporation and high reproducibility in the manufacturing process. If the MW is less than 400, the evaporation rate is too high and the deposition rate cannot be controlled. If the MW is greater than 1000, the evaporation rate is too slow and the deposition rate cannot be controlled.
[0317] When the dipole moment of the first organic aromatic matrix compound is ≥ 0 to ≤ 2.5 debye, highly efficient electron transport is achieved, the OLED can be operated at a very low operating voltage, and high external quantum efficiency EQE and / or a very long lifetime are obtained.
[0318] The use of a polar organic aromatic phosphine compound having a dipole moment of about > 2.5 Debye to about ≤ 10 Debye provides the benefit of efficient electron injection from the cathode and / or electron injection layer and efficient electron transport into the first electron transport layer.
[0319] Another advantage of the electron transport layer stack according to the present invention is that it has a stacked structure so that electron injection and transport can be balanced and holes can be efficiently blocked, and preferably, it can have a stacked structure of two ETL layers. In conventional OLEDs, since the amounts of electrons and holes vary over time, the number of excitons generated in the light-emitting region may decrease after driving begins. As a result, carrier balance is not maintained, and the lifespan of the OLED may be shortened.
[0320] In a preferred embodiment, the triplet level T1 of the first organic aromatic matrix compound is selected to be lower than the triplet level T1 of the polar organic aromatic phosphine compound, preferably the T1 of the first organic aromatic matrix compound is at least 0.1 eV lower than the triplet level T1 of the polar organic aromatic phosphine compound, and more preferably at least 0.2 eV lower.
[0321] According to various embodiments, the reduction potential of the first organic aromatic matrix compound is less negative than the reduction potential of the polar organic aromatic phosphine compound.
[0322] According to various embodiments, the LUMO of the first organic aromatic matrix compound is more negative than the LUMO of the polar organic aromatic phosphine compound.
[0323] When organic aromatic matrix compounds and polar organic aromatic phosphine compounds are selected within this range, very low operating voltage and / or high external quantum efficiency and / or long lifespan are obtained, and charge balance can be maintained during the operation of the OLED.
[0324] The present invention provides significant gains in terms of takt time and yield because layers can be deposited rapidly since the VTE (vacuum thermal evaporation) source moves back and forth below the substrate.
[0325] In a preferred embodiment, a first VTE source containing a first organic aromatic matrix compound moves first from below the substrate, and a first electron transport layer is deposited on the light-emitting layer. A shutter of a second VTE source containing a polar organic aromatic phosphine compound remains closed. Then, the shutter is opened on the second VTE source, and a second electron transport layer is deposited while the first and second VTE sources move backward from below the substrate. When a non-emitter dopant is deposited simultaneously with the polar organic aromatic phosphine compound, the shutter of a third VTE source is opened and closed simultaneously with the shutter of the second VTE source.
[0326] In another preferred embodiment, the shutters of the first, second, and optional third VTE sources are opened while the third electron transport layer (163) is deposited on the light-emitting layer. Then, the shutters are closed on the second and third VTE sources, and the shutters remain open on the first VTE source, while the sources move backward from below the substrate to deposit the first electron transport layer (161). Then, the shutters of the second and optional third VTE sources are opened again, and the first, second, and third VTE sources move forward to deposit the second electron transport layer (162). Thus, alternating layers of the first and second electron transport layers can be deposited rapidly until the desired layer thickness is obtained.
[0327] Preferably, the first organic aromatic matrix compound in the first electron transport layer and the first organic aromatic matrix compound in the second electron transport layer are selected from the same compound. More preferably, the first organic aromatic matrix compound in all layers of the ETL-stack is selected to be the same compound.
[0328] According to another embodiment, the electron transport layer stack does not have an emitter dopant that emits visible light during the operation of the OLED.
[0329] According to another embodiment, the first electron transport layer does not have a non-emitter dopant, and the second electron transport layer includes a non-emitter dopant, wherein the non-emitter dopant is a metal compound, and preferably the metal compound is selected from the group consisting of metal halides, metal-organic complexes and / or zero-value metals.
[0330] The electron transport layer stack is arranged between the emissive layer and the electron cathode layer. If the OLED includes an injection layer, the electron transport layer stack can be arranged between the emissive layer and the electron injection layer.
[0331] Preferably, the ETL-stack is interposed and in contact between the light-emitting layer and the electron injection layer.
[0332] In another preferred embodiment, the ETL-stack is interposed between the light-emitting layer and the cathode electrode and contacts them.
[0333] In another embodiment, when the OLED includes a hole blocking layer and an injection layer, the electron transport layer may be interposed between the hole blocking layer and the electron injection layer and contact them.
[0334] According to various embodiments of the OLED of the present invention, the electron transport layer stack comprises two or more electron transport layers, wherein
[0335] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0336] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0337] i) a first organic aromatic matrix compound; and
[0338] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0339] It is a mixture of
[0340] The organic light-emitting device may include additional electron transport layers, preferably a third and optional fourth electron transport layer. The first, second, third, and fourth electron transport layers may form an electron transport layer stack, wherein the first electron transport layer is in direct contact with the second electron transport layer, the second electron transport layer is in direct contact with the third electron transport layer, and the third electron transport layer is in direct contact with the fourth electron transport layer. In an alternative embodiment, the first and second electron transport layers may form an individual electron transport layer stack, and the third and optional fourth electron transport layers may form an individual electron transport layer stack and be arranged between the charge generation layer and the cathode.
[0341] According to another embodiment, the OLED may comprise an electron transport layer stack of a first electron transport layer, a second electron transport layer, a third electron transport layer, and a fourth electron transport layer, wherein the fourth electron transport layer comprises a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the fourth electron transport layer does not contain a polar organic aromatic phosphine compound.
[0342] Preferably, the first electron transport layer and the fourth electron transport layer may be selected to be the same, and the second electron transport layer and the third electron transport layer may be selected to be the same.
[0343] According to a more preferred embodiment, an organic light-emitting diode (OLED) is provided, wherein the organic light-emitting diode comprises an electron transport layer stack of a first electron transport layer, a second electron transport layer, and a third electron transport layer, wherein the third electron transport layer is arranged closest to the anode, the second electron transport layer is arranged closest to the cathode, and the first electron transport layer is arranged between the third electron transport layer and the second electron transport layer.
[0344] According to a more preferred embodiment, an organic light-emitting diode (OLED) is provided, wherein the organic light-emitting diode comprises an electron transport layer stack of a first electron transport layer, a second electron transport layer, and a third electron transport layer, wherein the third electron transport layer is arranged closest to the anode, the second electron transport layer is arranged closest to the cathode, the first electron transport layer is arranged between the third electron transport layer and the second electron transport layer, and the third electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0345] i) a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, and free of polar organic aromatic phosphine compounds; and
[0346] ii) a polar organic aromatic phosphine compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye; and
[0347] iii) an optional non-emitter dopant, wherein the non-emitter dopant is a metal compound, preferably the metal compound is selected from the group consisting of metal halides, metal-organic complexes and / or zero-valence metals.
[0348] It is a mixture of
[0349] According to a further embodiment, an organic light-emitting diode (OLED) is provided, wherein the organic light-emitting diode comprises an electron transport layer stack of a first electron transport layer, a second electron transport layer, a third electron transport layer, and a fourth electron transport layer, wherein the third electron transport layer is arranged closest to the anode, followed by the first electron transport layer, followed by the second electron transport layer, and followed by the fourth electron transport layer, the fourth electron transport layer is arranged closest to the cathode, and the first electron transport layer and the second electron transport layer are arranged between the third electron transport layer and the fourth electron transport layer.
[0350] According to another aspect, an organic light-emitting diode (OLED) is provided, wherein the organic light-emitting diode comprises an electron transport layer stack of a first electron transport layer and a second electron transport layer and an electron transport layer stack of a third electron transport layer and a fourth electron transport layer, wherein the third electron transport layer is arranged closest to the cathode, and the fourth electron transport layer is in contact with the third electron transport layer and is arranged closest to the anode; and the second electron transport layer is arranged closest to the cathode, and the first electron transport layer is in contact with the second electron transport layer and is arranged closest to the anode.
[0351] According to a more preferred embodiment, an organic light-emitting diode (OLED) is provided, wherein the organic light-emitting diode comprises an electron transport layer stack of a first electron transport layer, a second electron transport layer, a third electron transport layer, and a fourth electron transport layer, wherein the third electron transport layer is arranged closest to the anode, followed by the first electron transport layer, followed by the second electron transport layer, and followed by the fourth electron transport layer, wherein the fourth electron transport layer is arranged closest to the cathode, and the first electron transport layer and the second electron transport layer are arranged between the third electron transport layer and the fourth electron transport layer, wherein
[0352] The third electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0353] i) a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, and free of polar organic aromatic phosphine compounds; and
[0354] ii) a polar organic aromatic phosphine compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye; and
[0355] iii) an optional non-emitter dopant, wherein the non-emitter dopant is a metal compound, preferably the metal compound is selected from the group consisting of metal halides, metal-organic complexes and / or zero-valence metals.
[0356] It is a mixture of; here
[0357] The fourth electron transport layer is:
[0358] - It comprises a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the fourth electron transport layer does not contain a polar organic aromatic phosphine compound.
[0359] According to a more preferred embodiment, an organic light-emitting diode (OLED) is provided, wherein the organic light-emitting diode is:
[0360] - One or more anode electrodes;
[0361] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated, the light-emitting layer (100);
[0362] - One or more cathode electrode layers;
[0363] - Electron transport layer stack of a first electron transport layer (161), a second electron transport layer (162), and a third electron transport layer (163), wherein the third electron transport layer (163) comprises two organic aromatic matrix compounds, and these compounds are:
[0364] i) a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, and free of polar organic aromatic phosphine compounds; and
[0365] ii) a polar organic aromatic phosphine compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye; and
[0366] iii) an optional non-emitter dopant, wherein the non-emitter dopant is a metal compound, preferably the metal compound is selected from the group consisting of metal halides, metal-organic complexes and / or zero-valence metals.
[0367] It is a mixture of
[0368] In a preferred embodiment, the second electron transport layer (162) and the third electron transport layer (163) may have the same composition.
[0369] According to a more preferred embodiment, an organic light-emitting diode (OLED) is provided, wherein the organic light-emitting diode (OLED) comprises an electron transport layer stack (160) of a first electron transport layer (161), a second electron transport layer (162), a third electron transport layer (163) and a fourth electron transport layer (164), wherein the fourth electron transport layer (164) is:
[0370] - Includes a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the fourth electron transport layer (161) does not contain a polar organic aromatic phosphine compound.
[0371] In another embodiment, an electron transport layer stack comprising five or more electron transport layers is provided, wherein the electron transport layer comprises i) a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not have a polar organic aromatic phosphine compound; and the electron transport layer comprises two organic aromatic matrix compounds, the compounds being a mixture of i) the first organic aromatic matrix compound; and ii) a polar organic aromatic phosphine compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about > 2.5 Debye to about ≤ 10 Debye, and the electron transport layer is arranged alternately.
[0372] In a preferred embodiment, the first electron transport layer (161) and the fourth electron transport layer (164) may have the same composition.
[0373] In a more preferred embodiment, the second electron transport layer (162) and the third electron transport layer (163) may have the same composition, and the first electron transport layer (161) and the fourth electron transport layer (164) may have the same composition.
[0374] Preferably, the second electron transport layer and the optional third electron transport layer according to the present invention comprise a polar organic aromatic phosphine oxide compound.
[0375] In a preferred embodiment of the OLED, the electron transport layer stack does not contain an emitter compound, also known as an emitter dopant, that emits visible light during operation of the OLED.
[0376] According to another embodiment, the electron transport layer stack may not contain metals, metal halides, metal salts, and / or lithium organometallic complexes.
[0377] The thickness of the first electron transport layer may be in the range of ≥ 2 nm to about ≤ 10 nm, preferably ≥ 3 nm to about ≤ 5 nm.
[0378] The thickness of the second electron transport layer may be in the range of ≥ 20 nm to about ≤ 50 nm, preferably ≥ 25 nm to about ≤ 40 nm.
[0379] According to various embodiments of the OLED of the present invention, the thickness of the electron transport layer stack may be in the range of about ≥ 20 nm to about ≤ 100 nm, preferably about ≥ 30 nm to about ≤ 80 nm, more preferably about ≥ 35 nm to about ≤ 60 nm, and more preferably about ≥ 33 nm to about ≤ 40 nm.
[0380] The electron transport layer of the ETL-stack can be formed on the EML by vacuum deposition, spin coating, slot-die coating, printing, casting, etc. When the electron transport layer of the ETL-stack is formed by vacuum deposition or spin coating, the deposition and coating conditions may be similar to the conditions for the formation of the HIL. However, the deposition and coating conditions may vary depending on the compound used to form the electron transport layer of the ETL-stack.
[0381] First organic aromatic matrix compound
[0382] According to one embodiment, the first organic aromatic matrix compounds have a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye. When the first organic aromatic matrix compounds have a MW within this range, the evaporation rate can be controlled to a level sufficient for manufacturing, and a high takt time can be realized while maintaining high reproducibility.
[0383] When the first organic aromatic matrix compound has a dipole moment of ≥ 0 to ≤ 2.5 debye, particularly high external quantum efficiency EQE, low operating voltage and / or lifetime are obtained. When the first organic aromatic matrix compound has a dipole moment within this range, it can also be described as a non-polar matrix compound.
[0384] Dipole moment of a molecule containing an N atom is given by the following equation:
[0385]
[0386] Here, and is the partial charge and position of atom i within the molecule. The dipole moment is determined by the semi-empirical molecular orbital method. The values in Table 2 were calculated using the methods described below. Partial charges and atomic positions are obtained using the DFT function of Becke and Perdew BP based on def-SV(P) as set in the program package TURBOMOLE V6.5, or the hybrid function B3LYP based on def2-TZVP. If more than one stereoconfiguration is feasible, the stereoconfiguration with the lowest total energy is selected to determine the dipole moment.
[0387] When the first organic aromatic matrix compound has a dipole moment of 0 to 2.5 Debye, the first organic aromatic matrix compound is the center of inversion I, the horizontal mirror plane, and more than one C n Axis (n>1) and / or C n It can contain n C2s perpendicular to it.
[0388] The first organic aromatic matrix compound is an electron transport compound. Accordingly, the triplet level T1 of the first organic aromatic matrix compound can be selected within a range that supports electron transport. Preferably, the first organic aromatic matrix compound is selected from organic aromatic matrix compounds having a triplet level of > 1 eV to < 2.9 eV, preferably > 1.2 to < 2.8 eV, more preferably > 1.3 to < 2.7 eV.
[0389] The triplet level T1 is verified through quantum-chemical calculations. For this purpose, the software package "Gaussion-03 W" is used. First, geometry optimization is performed using the "ground state / semi-empirical / default spin / AM1 / charge 0 / spin singlet" method. Subsequently, energy calculations based on the optimized geometry are performed. Subsequently, energy calculations based on the optimized geometry are performed. The "TD-SFC / DFT / default spin / B3PW91" method is used with the "6-31G(d)" base set (charge 0, spin singlet). The result can be further optimized using B3PW91.
[0390] According to various embodiments, the reduction potential of the first organic aromatic matrix compound is Fc under the same conditions. +When measured by cyclic voltammetry in tetrahydrofuran for the redox couple / Fc, it is less negative than the reduction potential of pyrene, preferably less negative than the reduction potential of 1,3,5-tris(1-phenyl-1H-benzimidazole-2-yl)benzene, more preferably less negative than the reduction potential of (9-phenyl-9H-carbazole-2,7-diyl)bis(diphenylphosphine oxide), more negative than the reduction potential of 4,4'-bis(4,6-diphenyl-1,3,5-triazine-2-yl)biphenyl, and preferably more negative than the reduction potential of 4-(naphthalene-1-yl)-2,7,9-triphenylpyrido[3,2-h]quinazolin.
[0391] Redox potentials were determined by cyclic voltammetry at room temperature using the Metrohm PGSTAT30 potentiostatic device and Metrohm Autolab GPES software. The redox potential given to a specific compound was measured at a scan rate of 100 mV / s in an argon-deaerated, dry 0.1 M THF solution of the tested component in an argon atmosphere with a 0.1 M tetrabutylammonium hexafluorophosphate-supported electrolyte, consisting of a silver wire covered with silver chloride and directly immersed in the solution being measured, present alongside an Ag / AgCl pseudo-standard electrode (Metrohm silver rod electrode) between platinum working electrodes. The first run was performed at the widest potential range set on the working electrode, and the range was then appropriately adjusted in subsequent runs. The last three runs were performed with the addition of ferrocene (0.1 M concentration) as a standard. After subtracting the average of the cathode and anode potentials observed for a standard Fc+ / Fc oxidation source couple, the average of the potentials corresponding to the cathode and anode peaks of the studied compounds finally yielded the values reported above. All studied compounds, as well as the reported comparative compounds, exhibited well-defined, reversible electrochemical behavior.
[0392] Under these conditions, the reduction potential of pyrene is -2.64 V, the reduction potential of 1,3,5-tris(1-phenyl-1H-benzimidazole-2-yl)benzene is -2.58 V, the reduction potential of (9-phenyl-9H-carbazole-2,7-diyl)bis(diphenylphosphine oxide) is -2.51 V, the reduction potential of 4,4'-bis(4,6-diphenyl-1,3,5-triazine-2-yl)biphenyl is -2.03 V, and the reduction potential of 4-(naphthalene-1-yl)-2,7,9-triphenylpyrido[3,2-h]quinazolin is -2.18 V.
[0393] A simple rule is very frequently used to convert redox potential into electron affinity and ionization potential: IP(eV) = 4.84 eV + e*Eox (where Eox is given as volts vs. ferrocene / ferrocenium (Fc / Fc+)) and EA(eV) = 4.84 eV + e*Ered (where Ered is given as volts vs. Fc / Fc+) (see BW D'Andrade, Org. Electron. 6, 11-20 (2005)), where e* is the elemental charge. Although it is not strictly correct to use the terms "HOMO energy" E(HOMO) and "LUMO energy" E(LUMO) as synonyms for ionization energy and electron affinity, respectively, it is a common practice (Koopman's Theorem).
[0394] Thus, the LUMO of pyrene is -2.2 eV, the LUMO of 1,3,5-tris(1-phenyl-1H-benzimidazole-2-yl)benzene is -2.26 eV, the LUMO of (9-phenyl-9H-carbazole-2,7-diyl)bis(diphenylphosphine oxide) is -2.33 eV, the LUMO of 4,4'-bis(4,6-diphenyl-1,3,5-triazine-2-yl)biphenyl is -2.81 eV, and the LUMO of 4-(naphthalene-1-yl)-2,7,9-triphenylpyrido[3,2-h]quinazolin is -2.66 eV.
[0395] According to a more preferred embodiment, the first organic aromatic matrix compound may comprise at least 10, preferably at least 14, conjugated systems of delocalized electrons.
[0396] Examples of conjugated systems of delocalized electrons include systems in which pi and sigma bonds alternate. Optionally, one or more 2-atom structural units having pi bonds between atoms of the structural units may be replaced by atoms having one or more lone pairs of electrons, typically by divalent atoms selected from O, S, or Se, or by trivalent atoms selected from N or P. Preferably, the conjugated system of delocalized electrons comprises one or more aromatic or heteroaromatic rings according to the Huekel rule. Also preferably, the first organic aromatic matrix compound may comprise at least two aromatic or heteroaromatic rings connected by covalent bonds or condensed.
[0397] According to a more preferred embodiment, the first organic aromatic matrix compound is selected from the group consisting of benzo[k]fluorantene, pyrene, anthracene, fluorene, spiro(bifluorene), phenanthrene, perylene, tryptycene, spiro[fluorene-9,9'-xantene], coronene, triphenylene, xantene, benzofuran, dibenzofuran, dinaphthofuran, acridine, benzo[c]acridine, dibenzo[c,h]acridine, dibenzo[a,j]acridine, triazine, pyridine, pyrimidine, carbazole, thienopyrimidine, dithienothiophene, benzothienopyrimidine, benzothienopyrimidine, triarylborane, or mixtures thereof.
[0398] According to a more preferred embodiment, the first organic aromatic matrix compound does not have phosphine groups, phenanthroline groups, benzimidazole groups, or metal cations.
[0399] It may be more preferable that the first organic aromatic matrix compound comprises a triarylborane compound of formula (1):
[0400]
[0401] In the above equation (1), R 1 , R 3and R 7 H, D, C1-C independently 16 Alkyl and C1-C 16 Selected from a group consisting of alkoxy groups;
[0402] R 2 , R 4 , R 5 and R 6 H, D, C1-C independently 16 Alkyl, C1-C 16 Alkoxy and C6-C 20 Selected from a group composed of Aryl;
[0403] Ar 0 is substituted or unsubstituted C6-C 20 Selected from Aril, Ar 0 In this substitution case, the substituents are independently D, C1-C 12 Alkyl, C1-C 16 Alkoxy and C6-C 20 Selected from a group composed of Aryl;
[0404] Ar 1 is substituted or unsubstituted C6-C 20 Selected from Arilen, Ar 1 In this substitution case, the substituents are independently D, C1-C 12 Alkyl, C1-C 16 Alkoxy and C6-C 20 Selected from a group composed of aryls;
[0405] Ar 2 is H, D, substituted or unsubstituted C6-C 40 Aryl and C5-C 40 It is selected from the group consisting of heteroaryls.
[0406] Preferably, Ar 0 is selected from substituted or unsubstituted phenyl or naphthyl, and Ar 0 In this substitution case, the substituents are independently D, C1-C 12 Alkyl, C1-C 16 Alkoxy and C6-C 20It is selected from a group composed of Aril.
[0407] Triarylborane compound of formula (1):
[0408]
[0409] It is disclosed in WO2015049030A2 and EP15187135.7.
[0410] In a more preferred embodiment, the first organic aromatic matrix compound is a dibenzo[c,h]acridine compound of formula (2):
[0411]
[0412] and / or dibenzo[a,j]acridine compounds of formula (3):
[0413]
[0414] and / or benzo[c]acridine compounds of formula (4):
[0415]
[0416] Includes,
[0417] Here, Ar 3 is independently C6-C 20 Aryllene, preferably selected from phenylene, biphenylene, or fluorenylene;
[0418] Ar 4 is independently unsubstituted or substituted C6-C 40 aryl, preferably selected from phenyl, naphthyl, anthranil, pyrenyl, or phenanthril;
[0419] Ar 4 In the case where is substituted, one or more substituents independently C1-C 12 Alkyl and C1-C 12 It is selected from the group consisting of heteroalkyls, wherein C1-C5 alkyls are preferred.
[0420] Suitable dibenzo[c,h]acridine compounds are disclosed in EP 2 395 571. Suitable dibenzo[a,j]acridine compounds are disclosed in EP 2 312 663. Suitable benzo[c]acridine compounds are disclosed in WO 2015 / 083948.
[0421] In a further embodiment, the first organic aromatic matrix compound is C6-C 40 Aryl, C5-C 40 Heteroaryl and / or C1-C 12 It is preferable to include a dibenzo[c,h]acridine compound substituted with an alkyl group, preferably 7-(naphthalene-2-yl)dibenzo[c,h]acridine, 7-(3-(pyrene-1-yl)phenyl)dibenzo[c,h]acridine, and 7-(3-(pyridine-4-yl)phenyl)dibenzo[c,h]acridine.
[0422] In a further embodiment, the first organic aromatic matrix compound is C6-C 40 Aryl, C5-C 40 Heteroaryl and / or C1-C 12 It is preferable to include a dibenzo[a,j]acridine compound substituted with an alkyl group, preferably 14-(3-(pyrene-1-yl)phenyl)dibenzo[a,j]acridine.
[0423] In a further embodiment, the first organic aromatic matrix compound is C6-C 40 Aryl, C5-C 40 Heteroaryl and / or C1-C 12 It is preferable to include a benzo[c]acridine compound substituted with an alkyl group, preferably 7-(3-(pyrene-1-yl)phenyl)benzo[c]acridine.
[0424] It may be more preferable that the first organic aromatic matrix compound comprises a triazine compound of formula (5):
[0425]
[0426] In the above equation (5), Ar 5 is independently, unsubstituted or substituted C6-C 20Aryl or Ar 5.1 -Ar 5.2 Selected from,
[0427] Ar 5.1 It is unsubstituted or substituted C6-C 20 Selected by Arilen,
[0428] Ar 5,2 is unsubstituted or substituted C6-C 20 Aryl or unsubstituted and substituted C5-C 20 Selected from heteroaryls;
[0429] Ar 6 It is unsubstituted or substituted C6-C 20 Aryllene, preferably selected from phenylene, biphenylene, terphenylene, and fluorenylene;
[0430] Ar 7 The is independently selected from the group consisting of substituted or unsubstituted aryls, substituted or unsubstituted heteroaryls, preferably phenyl, naphthyl, phenanthryl, fluorenyl, terphenyl, pyridyl, quinolyl, pyrimidyl, triazinyl, benzo[h]quinolinyl, or benzo[4,5]thieno[3,2-d]pyrimidine, and said aryl and said heteroaryl have 6 to 40 ring-forming atoms;
[0431] x is selected from 1 or 2, and
[0432] Ar 5 In the case of substitution, one or more substituents independently, C1-C 12 Alkyl and C1-C 12 It can be selected from heteroalkyl, preferably C1-C5alkyl;
[0433] Ar 7 In the case of this substitution, one or more substituents independently, C1-C 12 Alkyl and C1-C 12 Heteroalkyl, preferably C1-C5 alkyl and C6-C 20 Can be selected from Aril.
[0434] Suitable triazine compounds are disclosed in US 2011 / 284832, WO 2014 / 171541, WO 2015 / 008866, WO2015 / 105313, JP 2015-074649 A, JP 2015-126140, KR 2015 / 0088712, KR2015-012551 and WO16171358A1.
[0435] Furthermore, the first organic aromatic matrix compound is C6-C 40 Aryl, C5-C 40 Heteroaryl and / or C1-C 12 A triazine compound substituted with an alkyl group, preferably 3-[4-(4,6-di-2-naphthalenyl-1,3,5-triazine-2-yl)phenyl]quinolone, 2-[3-(6'-methyl[2,2'-bipyridine]-5-yl)-5-(9-phenanthrenyl)phenyl]-4,6-diphenyl-1,3,5-triazine, 2-(3-(phenanthren-9-yl)-5-(pyridine-2-yl)phenyl)-4,6-diphenyl-1,3,5-triazine, 2,4-diphenyl-6-(5'''-phenyl-[1,1':3',1'':3'',1''':3''',1''''-quinquophenyl]-3-yl)-1,3,5-triazine, It is preferable to include 2-([1,1'-biphenyl]-3-yl)-4-(3'-(4,6-diphenyl-1,3,5-triazine-2-yl)-[1,1'-biphenyl]-3-yl)-6-phenyl-1,3,5-triazine and / or 2-(3'-(4,6-diphenyl-1,3,5-triazine-2-yl)-[1,1'-biphenyl]-3-yl)-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine.
[0436] In a preferred embodiment, the first organic aromatic matrix compound is C6-C 40 Aryl, C5-C 40 Heteroaryl and / or C1-C 12Benzothienopyrimidine compounds substituted with alkyl groups, preferably 2-phenyl-4-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-quaternphenyl]-3'''-yl)benzo[4,5]thieno[3,2-d]pyrimidine. Suitable benzothienopyrimidine compounds are disclosed in WO 2015 / 0105316.
[0437] In a preferred embodiment, the first organic aromatic matrix compound is C6-C 40 Aryl, C5-C 40 Heteroaryl and / or C1-C 12 It includes benzo[k]fluoranthene compounds substituted with alkyl groups, preferably 7,12-diphenylbenzo[k]fluoranthene. Suitable benzo[k]fluoranthene compounds are disclosed in JP10189247 A2.
[0438] In a preferred embodiment, the first organic aromatic matrix compound is C6-C 40 Aryl, C5-C 40 Heteroaryl and / or C1-C 12 Perylene compounds substituted with alkyl groups, preferably 3,9-bis([1,1'-biphenyl]-2-yl)perylene, 3,9-di(naphthalene-2-yl)perylene, or 3,10-di(naphthalene-2-yl)perylene. Suitable perylene compounds are disclosed in US 2007202354.
[0439] In a preferred embodiment, the first organic aromatic matrix compound comprises a pyrene compound. Suitable pyrene compounds are disclosed in US20050025993.
[0440] In a preferred embodiment, the first organic aromatic matrix compound comprises a spiro-fluorene compound. A suitable spiro-fluorene compound is disclosed in JP2005032686.
[0441] In a preferred embodiment, the first organic aromatic matrix compound comprises a xanthen compound. Suitable xanthen compounds are disclosed in US2003168970A and WO 2013149958.
[0442] In a preferred embodiment, the first organic aromatic matrix compound comprises a coronene compound. Suitable coronene compounds are disclosed in Adachi, C.; Tokito, S.; Tsutsui, T.; Saito, S., Japanese Journal of Applied Physics, Part 2: Letters (1988), 27(2), L269-L271.
[0443] In a preferred embodiment, the first organic aromatic matrix compound is selected from triphenylene compounds. Suitable triphenylene compounds are disclosed in US20050025993.
[0444] In a preferred embodiment, the first organic aromatic matrix compound is selected from carbazole compounds. Suitable carbazole compounds are disclosed in US2015207079.
[0445] In a preferred embodiment, the first organic aromatic matrix compound is selected from dithienothiophene compounds. Suitable dithienothiophene compounds are disclosed in KR2011085784.
[0446] In a preferred embodiment, the first organic aromatic matrix compound comprises an anthracene compound. An anthracene compound represented by the following formula 400 is particularly preferred:
[0447]
[0448] In Equation 400, Ar 111 and Ar 112 are each independently substituted or unsubstituted C6-C 60 It may be an arylene group; Ar 113 or Ar 116Each independently, substituted or unsubstituted C1-C 10 Alkyl groups or substituted or unsubstituted C6-C 60 It may be an aryl group; g, h, i and j may each independently be integers from 0 to 4.
[0449] In some embodiments, Ar in Formula 400 111 and Ar 112 Each independently,
[0450] Phenylene group, naphthylene group, phenanthrenylene group, or pyrenylene group; or
[0451] Phenylene, naphthylene, phenanthrenylene, fluorenyl, or pyrenylene groups, each substituted with one or more of a phenyl group, naphthyl group, or anthryl group
[0452] It could be one of them.
[0453] In Equation 400, g, h, i, and j can each independently be integers of 0, 1, or 2.
[0454] In Equation 400, Ar 113 or Ar 116 Each independently,
[0455] C1-C substituted with one or more of a phenyl group, a naphthyl group, or anthryl group 10 Alkyl group;
[0456] Phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthrenyl group, or fluorenyl group;
[0457] Each is a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, C1-C 60 Alkyl group, C2-C 60 alkenyl group, C2-C 60 alkynyl group, C1-C 60A phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthrenyl group, or fluorenyl group substituted with one or more of an alkoxy group, a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthrenyl group, or a fluorenyl group; or a structure having the following structure
[0458] It could be one of them.
[0459] .
[0460] According to a further more preferred embodiment, the first organic aromatic matrix compound may be selected from the compounds in Table 1 below. These have been found to have particularly beneficial effects on operating voltage, external quantum efficiency, and / or lifetime.
[0461]
[0462]
[0463]
[0464]
[0465]
[0466]
[0467]
[0468]
[0469]
[0470] Table 2 below shows the dipole moments of representative examples of the first organic aromatic matrix compounds with dipole moments ranging from ≥ 0 debye to ≤ 2.5 debye.
[0471]
[0472]
[0473] In another embodiment, the first electron transport layer may comprise a second organic aromatic matrix compound, preferably the second organic aromatic matrix compound is selected from an emitter matrix compound and / or a hole-blocking matrix compound.
[0474] Polar organic aromatic phosphine compounds
[0475] Examples of polar organic aromatic phosphine compounds are mainly compounds composed of covalently bonded C, H, O, N, S, P, and Se, preferably C, H, O, N, and P.
[0476] According to a more preferred embodiment, polar organic aromatic phosphine compounds do not have metal cations.
[0477] According to a more preferred embodiment, the polar organic aromatic phosphine compound comprises a conjugated system of six or more, more preferably ten or more, delocalized electrons.
[0478] Examples of conjugated systems of delocalized electrons include systems in which pi bonds and sigma bonds alternate. Optionally, one or more 2-atom structural units having pi bonds between atoms of the structural units may be replaced by atoms having one or more lone pairs of electrons, typically by divalent atoms selected from O, S, or Se, or by trivalent atoms selected from N or P.
[0479] Preferably, the conjugated system of delocalized electrons comprises one or more aromatic or heteroaromatic rings according to the Hueckel rule. Also preferably, the polar organic aromatic phosphine compound may comprise at least two aromatic or heteroaromatic rings connected by covalent bonds or condensed.
[0480] According to another embodiment, the polar organic aromatic phosphine compound is an electron transport compound. To support electron transport, the polar organic aromatic phosphine compound may be selected from compounds having a triplet level of > 1 eV to < 2.9 eV, preferably > 1.2 to < 2.8 eV, more preferably > 1.3 to < 2.7 eV.
[0481] According to another embodiment, the polar organic aromatic phosphine compound does not participate in electron transport, and electron transport is supported by the first organic aromatic matrix compound. The polar organic aromatic phosphine compound may be selected from compounds having a triplet level of < 3.5 to > 2.7 eV, more preferably < 3.2 to > 2.8 eV, and more preferably < 3.5 to > 2.9 eV.
[0482] According to various embodiments, the reduction potential of polar organic aromatic phosphine compounds is Fc under the same conditions + When measured by cyclic voltammetry in tetrahydrofuran for the redox couple / Fc, it is more negative than the reduction potential of 9-phenyl-9H-carbazole-2,7-diylbis(diphenylphosphine oxide), preferably more negative than the reduction potential of [1,1':4',1''-terphenyl]-3,5-diylbis(diphenylphosphine oxide), equal to or less negative than the reduction potential of ethane-1,2-diylbis(diphenylphosphine oxide), and preferably less negative than the reduction potential of triphenylene.
[0483] Under these conditions, the reduction potential of 9-phenyl-9H-carbazole-2,7-diylbis(diphenylphosphine oxide) is -2.51 V, the reduction potential of [1,1':4',1''-terphenyl]-3,5-diylbis(diphenylphosphine oxide) is -2.58 V, the reduction potential of ethane-1,2-diylbis(diphenylphosphine oxide) is -3.17 V, and the reduction potential of triphenylene is -3.04 V.
[0484] The LUMO of 9-phenyl-9H-carbazole-2,7-diylbis(diphenylphosphine oxide) is -2.33 eV, the LUMO of [1,1':4',1''-terphenyl]-3,5-diylbis(diphenylphosphine oxide) is -2.26 eV, the LUMO of ethane-1,2-diylbis(diphenylphosphine oxide) is -1.67 eV, and the LUMO of triphenylene is -1.8 eV.
[0485] According to another embodiment, the polar organic aromatic phosphine compound may be selected from the group consisting of organic phosphine oxide compounds, organic thioxophosphine compounds, or organic selenophosphine compounds.
[0486] Preferably, the polar aromatic phosphine compound is selected from phosphine oxide compounds.
[0487] According to another aspect, an organic light-emitting diode (OLED) is provided, wherein the polar organic aromatic phosphine compound of the second electron transport layer has the formula Ia:
[0488]
[0489] Here:
[0490] X is selected from O, S, and Se;
[0491] R 1 and R 2 is independently, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 Selected from heteroaryls; or R 1 and R 2 is cross-linked with an alkene-diyl group forming a substituted or unsubstituted 5, 6, or 7-membered ring together with a P atom;
[0492] A 1 is phenyl or selected from formula (II):
[0493]
[0494] Here:
[0495] R 3 C1 to C8 alkane-diyl, substituted or unsubstituted C6 to C 20 Aryllene, and substituted or unsubstituted C5 to C 20 Selected from heteroarylenes; or
[0496] A 1 is selected from Equation (III):
[0497]
[0498] Here:
[0499] n is selected from 0 or 1;
[0500] m is selected from 1 or 2;
[0501] o is selected from 1 or 2;
[0502] If o is 2, m is 1, and;
[0503] Ar 1 ...substituted or unsubstituted C6 to C 20 Aryllene and substituted or unsubstituted C5 to C 20 Selected from heteroarylenes;
[0504] Ar 2 is substituted or unsubstituted C 18 to C 40 Aryllene and substituted or unsubstituted C 10 to C 40 Selected from heteroarylenes;
[0505] R 4 is H, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 It is selected from heteroaryls.
[0506] According to another embodiment, an organic light-emitting diode (OLED) is provided, wherein the organic light-emitting diode is
[0507] - One or more anode electrodes;
[0508] - One or more light-emitting layers, wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED is operated;
[0509] - As an electron transport layer stack of two or more electron transport layers, where:
[0510] a) the first electron transport layer comprises i) a first organic aromatic matrix compound having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer does not contain a polar organic aromatic phosphine compound;
[0511] b) The second electron transport layer comprises two organic aromatic matrix compounds, and these compounds are:
[0512] i) a first organic aromatic matrix compound; and
[0513] ii) Polar organic aromatic phosphine compounds having a MW of about ≥ 400 to about ≤ 1000 and a dipole moment of about > 2.5 Debye to about ≤ 10 Debye
[0514] It is a mixture of, where, the polar organic aromatic phosphine compound has formula Ia and:
[0515]
[0516] Here:
[0517] X is selected from O, S, and Se;
[0518] R 1 and R 2 is independently, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 Selected from heteroaryls; or R 1 and R 2is cross-linked with an alkene-diyl group forming a substituted or unsubstituted 5, 6, or 7-membered ring together with a P atom;
[0519] A 1 is phenyl or selected from formula (II):
[0520]
[0521] Here:
[0522] R 3 C1 to C8 alkane-diyl, substituted or unsubstituted C6 to C 20 Aryllene and substituted or unsubstituted C5 to C 20 Selected from heteroarylenes; or
[0523] A 1 is selected from Equation (III):
[0524]
[0525] Here:
[0526] n is selected from 0 or 1;
[0527] m is selected from 1 or 2;
[0528] o is selected from 1 or 2;
[0529] If o is 2, m is 1, and;
[0530] Ar 1 ...substituted or unsubstituted C6 to C 20 Aryllene and substituted or unsubstituted C5 to C 20 Selected from heteroarylenes;
[0531] Ar 2 is substituted or unsubstituted C 18 to C 40 Aryllene and substituted or unsubstituted C 10 to C 40 Selected from heteroarylenes;
[0532] R 4 is H, C1 to C 12Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 An electron transport layer stack selected from heteroaryls; and
[0533] - One or more cathode electrode layers
[0534] Includes; here
[0535] The electron transport layer stack is arranged between the light-emitting layer and the cathode electrode layer, the first electron transport layer is in direct contact with the second electron transport layer, the first electron transport layer is arranged closer to the light-emitting layer, and the second electron transport layer is arranged closer to the cathode electrode layer.
[0536] According to another embodiment, an organic light-emitting diode (OLED) is provided, wherein a polar organic aromatic phosphine compound has the formula Ia:
[0537]
[0538] Here:
[0539] X is selected from O, S, and Se;
[0540] R 1 and R 2 is independently, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 Selected from heteroaryls; or R 1 and R 2 is cross-linked with an alkene-diyl group forming a substituted or unsubstituted 5, 6, or 7-membered ring together with a P atom;
[0541] A 1 is phenyl or selected from formula (II):
[0542]
[0543] Here:
[0544] R 3C1 to C8 alkane-diyl, substituted or unsubstituted C6 to C 20 Aryllene and substituted or unsubstituted C5 to C 20 Selected from heteroarylenes; or
[0545] A 1 is selected from Equation (III):
[0546]
[0547] Here:
[0548] n is selected from 0 or 1;
[0549] m is selected from 1 or 2;
[0550] o is selected from 1 or 2;
[0551] If o is 2, m is 1, and;
[0552] Ar 1 ...substituted or unsubstituted C6 to C 20 Aryllene and substituted or unsubstituted C5 to C 20 Selected from heteroarylenes;
[0553] Ar 2 is substituted or unsubstituted C 18 to C 40 Aryllene and substituted or unsubstituted C 10 to C 40 Selected from heteroarylenes;
[0554] R 4 is H, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 It is selected from heteroaryls.
[0555] According to another aspect, an organic light-emitting diode (OLED) is provided in which the substituent X in formula Ia is selected from O.
[0556] According to another aspect, the polar organic aromatic phosphine compound is of general formula Ia, where o can be 1 or 2, and:
[0557] - When o = 2, the polar organic aromatic phosphine compound is a compound having formula Ib or:
[0558]
[0559] - When o = 1, polar organic aromatic phosphine compounds are compounds with the formula Ic, Id, Ie, or If:
[0560] .
[0561] According to another embodiment, a polar organic aromatic phosphine compound can be selected from formula Ib and:
[0562]
[0563] Here:
[0564] X is selected from O, S, and Se;
[0565] R 1 and R 2 is independently, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 Selected from heteroaryls; or R 1 and R 2 is cross-linked with an alkene-diyl group forming a substituted or unsubstituted 5, 6, or 7-membered ring together with a P atom;
[0566] Ar 1 ...substituted or unsubstituted C6 to C 20 Aryllene and substituted or unsubstituted C5 to C 20 Selected from heteroarylenes;
[0567] Ar 2 is substituted or unsubstituted C 18 to C 40 Aryllene and substituted or unsubstituted C10 to C 40 Selected from heteroarylenes;
[0568] R 4 is H, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 It is selected from heteroaryls.
[0569] According to another aspect, the polar organic aromatic phosphine compound may be selected from the group comprising polar organic aromatic phosphine compounds of formula Ic and / or Id, and:
[0570]
[0571] Here:
[0572] X is selected from O, S, and Se;
[0573] R 1 and R 2 is independently, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 Selected from heteroaryls; or R 1 and R 2 is cross-linked with an alkene-diyl group forming a substituted or unsubstituted 5, 6, or 7-membered ring together with a P atom;
[0574] A 1 ...substituted or unsubstituted C6 to C 20 Aryllene and substituted or unsubstituted C5 to C 20 Selected from heteroarylenes;
[0575] R 4 is H, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 It is selected from heteroaryls.
[0576] According to another aspect, the polar organic aromatic phosphine compound may be selected from the group comprising polar organic aromatic phosphine compounds of formula Id or If:
[0577]
[0578] Here:
[0579] X is selected from O, S, and Se;
[0580] R 1 and R 2 is independently, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 Selected from heteroaryls; or R 1 and R 2 is cross-linked with an alkene-diyl group forming a substituted or unsubstituted 5, 6, or 7-membered ring together with a P atom;
[0581] A 1 ...substituted or unsubstituted C6 to C 20 Aryllene and substituted or unsubstituted C5 to C 20 Selected from heteroarylenes;
[0582] Ar 2 is substituted or unsubstituted C 18 to C 40 Aryllene and substituted or unsubstituted C 10 to C 40 Selected from heteroarylenes;
[0583] R 4 is H, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 It is selected from heteroaryls.
[0584] According to another embodiment, Ar of a polar organic aromatic phosphine compound according to Formula Ia, preferably an organic aromatic phosphine oxide compound 1and Ar 2 can be defined, where
[0585] - Ar 1 is substituted C6 to C 20 Arrylene, and / or substituted C5 to C 20 Selected from heteroarylenes, wherein C6 to C 20 Arrylene, and / or C5 to C 20 Heteroarylenes have one or more C1 to C1 12 alkyl and / or one or more C1 to C 12 Substituted with heteroalkyl groups;
[0586] Ar 2 is substituted C 18 to C 40 Aryllene and / or substituted C 10 to C 40 Selected from heteroarylenes, where C 18 to C 40 Arrylene and / or C 10 to C 40 Heteroarylenes have one or more C1 to C1 12 alkyl and / or one or more C1 to C 12 Substituted with a heteroalkyl group; or
[0587] - Preferably Ar 1 is substituted C6 to C 20 Aryllene and / or substituted C5 to C 20 It is a heteroarylene, where C6 to C 20 Aryllene and / or C5 to C 20 The heteroarylene is substituted with one or more C1 to C6 alkyl and / or C1 to C6 heteroalkyl groups;
[0588] Ar 2 is substituted C 18 to C 40 Aryllene and / or substituted C 10 to C 40 It is a heteroarylene, where C 18 to C 40 Arrylene and / or C 10 to C40 The heteroarylene is substituted with one or more C1 to C6 alkyl and / or C1 to C6 heteroalkyl groups; or
[0589] - More preferably Ar 1 is substituted C6 to C 20 Aryllene and / or substituted C5 to C 20 It is a heteroarylene, where C6 to C 20 Aryllene and / or C5 to C 20 The heteroarylene is substituted with one or more C1 to C4 alkyl and / or C1 to C4 heteroalkyl groups;
[0590] Ar 2 is substituted C 18 to C 40 Aryllene and / or substituted C 10 to C 40 It is a heteroarylene, where C 18 to C 40 Arrylene and / or C 10 to C 40 The heteroarylene is substituted with one or more C1 to C4 alkyl and / or C1 to C4 heteroalkyl groups.
[0591] According to another aspect, R of a polar organic aromatic phosphine compound according to Formula Ia, preferably an organic aromatic phosphine oxide compound 1 to R 4 can be defined, where
[0592] R 1 and R 2 is independently, substituted C6 to C 20 Aryl, and / or substituted C5 to C 20 Selected from heteroaryls, wherein C6 to C 20 Aryl, and / or C5 to C 20 Heteroaryl consists of one or more C1 to C1 12 alkyl and / or one or more C1 to C 12 Substituted with a heteroalkyl group, preferably R 1 and R 2is selected identically; and / or
[0593] R 3 is independently, substituted C6 to C 20 Arrylene, and / or substituted C5 to C 20 Selected from heteroarylenes, wherein C6 to C 20 Arrylene, and / or C5 to C 20 Heteroarylenes have one or more C1 to C1 12 alkyl and / or one or more C1 to C 12 Substituted with a heteroalkyl group, and / or
[0594] R 4 is independently, substituted C6 to C 20 Aryl, and / or substituted C5 to C 20 Selected from heteroaryls, wherein C6 to C 20 Aryl, and / or C5 to C 20 Heteroaryl consists of one or more C1 to C1 12 alkyl and / or one or more C1 to C 12 It is substituted with a heteroalkyl group.
[0595] According to another aspect, R of a polar organic aromatic phosphine compound according to Formula Ia, preferably an organic aromatic phosphine oxide compound 1 to R 4 , X, n, m, Ar 1 and Ar 2 can be defined, where
[0596] R 1 and R 2 is independently C1 to C4 alkyl, unsubstituted or substituted C6 to C 10 Aryl or unsubstituted or substituted C5 to C 10 Selected from heteroaryls; preferably R 1 and R 2 is independently selected from methyl, phenyl, naphthyl, phenanthril, pyrenyl, or pyridyl; more preferably R 1 and R 2is independently selected from methyl, phenyl, and pyridyl; more preferably, R 1 and R 2 is selected identically; and / or
[0597] X is selected from O or S, preferably O; and / or
[0598] R 3 C1 to C6 alkane-diyl, unsubstituted or substituted C6 to C 10 Aryllene or unsubstituted or substituted C5 to C 10 Selected from heteroarylenes, preferably selected from C1 to C4 alkanes-diyls; and / or
[0599] R 4 is selected from H, phenyl, biphenyl, terphenyl, fluorenyl, naphthyl, anthranil, phenanthril, pyrenyl, carbazoyl, dibenzofuranil, dinaphthofuranil, preferably H, phenyl, biphenyl, or naphthyl, more preferably H; and / or
[0600] When n is 0 or 1, preferably n is 1, and preferably n = 2, Ar 1 is phenyl, and more preferably, when n = 1, R 1 and R 2 is phenyl and R 4 is H;
[0601] If n is 0 or 1, m is 1 or 2, and if n is 2, m is 2; and / or
[0602] Ar 1 is preferably selected from phenylene, biphenylene, terphenylene, naphthylene, fluorenylene, pyridylene, quinolinylene, and pyrimidinylene; and / or
[0603] Ar 2 is selected from fluorenylene, anthranylene, pyrenylene, phenanthrylene, carbazoylene, benzo[c]acridinylene, dibenzo[c,h]acridinylene, and dibenzo[a,j]acridinylene.
[0604] According to another aspect, R of a polar organic aromatic phosphine compound according to Formula Ia, preferably an organic aromatic phosphine oxide compound 1 to R 4 , Ar 1 and Ar 2 can be defined, where R 1 , R 2 , R 3 , R 4 , Ar 1 and / or Ar 2 is non-substituted.
[0605] According to another aspect, R of a polar organic aromatic phosphine compound according to Formula Ia, preferably an organic aromatic phosphine oxide compound 1 and R 2 is independently, C1 to C 12 Alkyl, preferably selected from C1 to C8, more preferably from C1 to C6, and most preferably from C1 to C4.
[0606] According to another aspect, R of a polar organic aromatic phosphine compound according to Formula Ia, preferably an organic aromatic phosphine oxide compound 4 is C1 to C 12 Alkyl, preferably C1 to C8, more preferably C1 to C6, most preferably C1 to C4.
[0607] According to another embodiment, Ar of a polar organic aromatic phosphine compound according to Formula Ia, preferably an organic aromatic phosphine oxide compound 2 can be defined, where Ar 2 is selected from compounds according to formulas IVa to IVh:
[0608]
[0609] According to another embodiment, a polar organic aromatic phosphine compound of formula (Ia) is defined, where A1 is selected from Equation (II).
[0610] Preferably, R 3 C1 to C6 alkane-diyl, unsubstituted or substituted C6 to C 10 Aryllene or unsubstituted or substituted C5 to C 10 It is selected from heteroarylenes, and preferably from C1 to C4 alkanes-diyls.
[0611] Preferred examples are shown in Table 3 below. These compounds have been found to have particularly beneficial effects on operating voltage, external quantum efficiency (EQE), and / or lifetime.
[0612]
[0613]
[0614] According to another embodiment, a polar organic aromatic phosphine compound of formula (Ia) is defined, where A 1 It can be selected from Formula (III). Preferably, o is 1, n is 0 or 1, and m is 1 or 2. The molecular weight of these compounds is within a range that is particularly suitable for vacuum deposition and in which particularly low operating voltage, high efficiency, and / or long lifetime are achieved. Particularly preferred examples are shown in Table 4 below.
[0615]
[0616]
[0617] According to another preferred embodiment, o is 2, n is 0 or 1, and m is 1. The crystallinity of these compounds is reduced, and a low operating voltage is achieved. Particularly preferred examples are shown in Table 4 above.
[0618] A polar organic aromatic phosphine compound suitable for use in polar organic aromatic phosphine compounds comprising electron transport layers / s has the formula (Ia), where A 1 is phenyl, and R 1 and R 2 It is cross-linked with alkene-diyl groups to form five to seven-membered rings with P atoms. These polar organic aromatic phosphine compounds can provide a high glass transition temperature Tg and, in particular, a low operating voltage, high external quantum efficiency (EQE), and / or a long lifetime. Particularly preferred compounds are the polar organic aromatic phosphine compounds shown in Table 5.
[0619]
[0620] According to another aspect, the organic aromatic phosphine oxide compound according to the present invention may be selected from compounds according to the following formulas A1 to A41:
[0621]
[0622]
[0623]
[0624]
[0625]
[0626]
[0627] Organic aromatic phosphine oxide compounds are C6-C 40 Aryl, C5-C 40 Heteroaryl and / or C1-C 12Substituted with an alkyl group, preferably (3-(dibenzo[c,h]acridine-7-yl)phenyl)diphenylphosphine oxide, 3-phenyl-3H-benzo[b]di-naphtho[2,1-d:1',2'-f]phosphine-3-oxide, phenyledi(pyrene-1-yl)phosphine oxide, bis(4-(anthracene-9-yl)phenyl)(phenyl)phosphine oxide, (3-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)diphenylphosphine oxide, phenyledi(pyrene-1-yl)phosphine oxide, diphenyl(5-(pyrene-1-yl)pyridine-2-yl)phosphine oxide, diphenyl(4'-(pyrene-1-yl)-[1,1'-biphenyl]-3-yl)phosphine oxide, It is more preferable that it be diphenyl(4'-(pyrene-1-yl)-[1,1'-biphenyl]-3-yl)phosphine oxide, (3'-(dibenzo[c,h]acridine-7-yl)-[1,1'-biphenyl]-4-yl)diphenylphosphine oxide and / or phenyl bis(3-(pyrene-1-yl)phenyl)phosphine oxide.
[0628] According to another aspect, polar organic aromatic phosphine compounds are not emitter dopants and do not emit visible light when the OLED is in operation.
[0629] According to another aspect, polar organic aromatic phosphine compounds are not emitter matrix compounds.
[0630] According to another embodiment of the electron transport layer stack:
[0631] - A first organic aromatic matrix compound having a dipole moment ≥ 0 debye to ≤ 2.5 debye may be selected from the following compounds:
[0632]
[0633]
[0634] - Polar organic aromatic phosphine compounds may be the following compounds:
[0635]
[0636] non-emitter dopant
[0637] According to various embodiments of the OLED of the present invention, the first electron transport layer (161) does not have a non-emitter dopant, and the second electron transport layer (162) includes a non-emitter dopant, wherein the non-emitter dopant is a metal compound, and preferably the metal compound is selected from the group consisting of metal halides, metal-organic complexes and / or zero-value metals.
[0638] According to various embodiments of the OLED of the present invention, the metal halide may be selected from the group consisting of halides, wherein the metal is selected from the group consisting of Li, Na, K, Cs, Mg, Ca, and Ba; the halide is selected from the group consisting of F, Cl, Br, and J; and preferably, it is a lithium halide.
[0639] The lithium halide can be selected from the group consisting of LiF, LiCl, LiBr, or LiJ, and preferably is LiF.
[0640] According to various embodiments of the OLED of the present invention, the metal-organic complex may be selected from the group consisting of metal quinolates, metal borates, metal phenolates and / or metal Schiff bases.
[0641] Preferably, the metal-organic complex may be an alkali-organic complex, preferably a lithium-organic complex.
[0642] Preferably, the lithium organic complex may be selected from the group consisting of lithium quinolates, lithium borates, lithium phenolates and / or lithium Schiff bases, and preferably, the lithium quinolate complex has Formula I, II or III:
[0643]
[0644] Here,
[0645] - A1 to A6 are identical or independently selected from CH, CR, N, and O, and
[0646] - R is selected from hydrogen, halogen, alkyl, aryl, or heteroaryl having 1 to 20 carbon atoms, either identically or independently, and more preferably is lithium 8-hydroxyquinolate.
[0647] According to various embodiments of the organic electroluminescent device of the present invention, the organic ligand of the lithium organic complex may be a borate-based organic ligand. Preferably, the lithium organic complex is a compound of formula (VII):
[0648]
[0649] Here, M is an alkali metal ion, and A 1 To A 4 are each independently substituted or unsubstituted C6-C 20 Aryl or substituted or unsubstituted C2-C 20 It is selected from heteroaryls.
[0650] Preferably, the alkali organic complex is a complex of formula (VIII):
[0651]
[0652] Here, A 1 To A 4 are each independently substituted or unsubstituted C6-C 20 Aryl or substituted or unsubstituted C2-C 20 It is selected from heteroaryls.
[0653] Preferably, the lithium organic complex is lithium tetra(1H-pyrazol-1-yl)borate. Borate-based organic ligands that can be suitably used are disclosed in WO 2013079676 A1.
[0654] According to various embodiments of the organic electroluminescent device of the present invention, the organic ligand of the lithium organic complex may be a phenolate ligand.
[0655] According to various embodiments of the organic electroluminescent device of the present invention, the organic ligand of the lithium organic complex may be a phosphoryl phenolate ligand.
[0656] Preferably, the lithium organic complex is a phosphoryl phenolate compound of formula (IX):
[0657]
[0658] Here, A 5 is C6-C 20 It is Arilen, and A 6 To A 7 Each independently C6-C 20 Selected from Aril, where A 5 , A 6 and A 7 The group may be unsubstituted or substituted with a group selected from the group consisting of C and H or an additional LiO group, provided that a given C coefficient in the aryl or arylene group also includes all substituents present in the group. Preferably, the lithium organic complex is lithium 2-(diphenylphosphoryl)phenolate. A phenolate ligand that can be suitably used is disclosed in WO 2013079678 A1.
[0659] Furthermore, the phenolate ligand may be selected from the group consisting of pyridine oleates, preferably 2-(diphenylphosphoryl)pyridine-3-oleates. Pyridine phenolate ligands that can be suitably used are disclosed in JP 2008195623.
[0660] In addition, the phenolate ligand may be selected from the group consisting of imidazole phenolates, preferably 2-(1-phenyl-1H-benzo[d]imidazole-2-yl)phenolate. An imidazole phenolate ligand that can be suitably used is disclosed in JP 2001291593.
[0661] Additionally, the phenolate ligand may be selected from the group consisting of oxazole phenolates, preferably 2-(benzo[d]oxazole-2-yl)phenolates. Oxazole phenolate ligands that can be suitably used are disclosed in US 20030165711.
[0662] According to various embodiments of the organic electroluminescent device of the present invention, the organic ligand of the lithium organic complex may be a phosphoryl heteroaryl oligoate ligand.
[0663] Preferably, the lithium organic complex is a phosphoryl heteroaryl oate compound of formula (X):
[0664]
[0665] Here, A 8 , A 9 and A 10 C1-C independently 30 -alkyl, C3-C 30 -cycloalkyl, C2-C 30 -heteroalkyl, C6-C 30 -Aryl, C2-C 30 -Heteroaryl, C1-C 30 -Alkoxy, C3-C 30 -cycloalkyloxy, C6-C 30 Selected from aryloxy, and structural units having the general formula EZ-,
[0666] Z is a spacer unit containing a trivalent nitrogen atom having a lone electron pair, wherein the spacer unit has a structure that allows the formation of a 5-, 6-, or 7-membered chelate ring with a metal cation, the chelate ring comprises an oxygen atom of a phosphine oxide group and a trivalent nitrogen atom of the spacer unit coordinated to the metal cation, and E is an electron transport unit comprising a conjugated system of 10 or more delocalized electrons, and
[0667] A 8 , A 9 and A 10One or more devices selected from have the general formula EZ-.
[0668] Preferably, the lithium organic complex is lithium 2-(diphenyl-phosphoryl)pyridine-3-oleate. Heteroaryloleate ligands that can be suitably used are disclosed in EP 2724388 and are included by reference.
[0669] According to various embodiments of the organic electroluminescent device of the present invention, the organic ligand of the alkali organic complex may be selected from borate ligands, phosphoryl phenolate ligands, and heteroaryloleate ligands. Preferably, the organic ligand of the alkali organic complex is selected from borate ligands and phosphoryl phenolate ligands.
[0670] More preferably, the lithium organic complex may be selected from the group consisting of lithium quinolate, lithium borate, lithium phenolate, lithium pyridinooleate, or lithium Schiff base; preferably
[0671] - The lithium organic complex is selected from the group consisting of lithium quinolate, lithium borate, lithium phenolate, lithium pyridinooleate, or lithium Schiff base;
[0672] - Preferably, the lithium quinolate has formula XI, XII, or XIII and:
[0673]
[0674] Here,
[0675] A1 to A6 are identical or independently selected from CH, CR, N, and O;
[0676] R is selected from hydrogen, halogen, alkyl, aryl, or heteroaryl having 1 to 20 carbon atoms, either identically or independently; more preferably, A1 to A6 are CH;
[0677] - Preferably, the lithium borate is lithium tetra(1H-pyrazol-1-yl)borate;
[0678] - Preferably, the lithium phenolate is lithium 2-(pyridine-2-yl)phenolate, lithium 2-(diphenylphosphoryl)phenolate, lithium imidazole phenolate, or lithium 2-(pyridine-2-yl)phenolate, and more preferably, lithium 2-(1-phenyl-1H-benzo[d]imidazole-2-yl)phenolate or lithium 2-(benzo[d]oxazole-2-yl)phenolate;
[0679] - Preferably, the lithium pyridine oleate is lithium 2-(diphenylphosphoryl)pyridine-3-oleate, and
[0680] - Preferably, the lithium Schiff base has the structure 100, 101, 102, or 103:
[0681]
[0682] Quinoleates suitable for use are disclosed in WO 2013079217 A1.
[0683] According to various embodiments of the organic electroluminescent device of the present invention, the organic ligand of the lithium organic complex may be a phenolate ligand, and preferably, the lithium organic complex is lithium 2-(diphenylphosphoryl)phenolate. A phenolate ligand that can be suitably used is disclosed in WO 2013079678 A1.
[0684] Furthermore, the phenolate ligand may be selected from the group consisting of pyridine oleates, preferably 2-(diphenylphosphoryl)pyridine-3-oleates. Pyridine phenolate ligands that can be suitably used are disclosed in JP 2008195623.
[0685] In addition, the phenolate ligand may be selected from the group consisting of imidazole phenolates, preferably 2-(1-phenyl-1H-benzo[d]imidazole-2-yl)phenolate. An imidazole phenolate ligand that can be suitably used is disclosed in JP 2001291593.
[0686] Additionally, the phenolate ligand may be selected from the group consisting of oxazole phenolates, preferably 2-(benzo[d]oxazole-2-yl)phenolates. Oxazole phenolate ligands that can be suitably used are disclosed in US 20030165711.
[0687] The lithium Schiff base organic complex may be a lithium Schiff base organic complex having the structure 100, 101, 102, or 103 that can be suitably used:
[0688]
[0689] Organic ligands suitable for forming lithium organic complexes that can be used in electron injection layers are disclosed in US 2014 / 0048792 and Kathirgamanathan, Poopathy; Arkley, Vincent; Surendrakumar, Sivagnanasundram; Chan, Yun F.; Ravichandran, Seenivasagam; Ganeshamurugan, Subramaniam; Kumaraverl, Muttulingam; Antipan-Lara, Juan; Paramaswara, Gnanamolly; Reddy, Vanga R., Digest of Technical Papers - Society for Information Display International Symposium (2010), 41(Bk. 1), 465-468.
[0690] Exceptionally desirable lithium organic complexes that can be used in the present invention are summarized in Table 6 below.
[0691]
[0692]
[0693] According to various embodiments of the OLED of the present invention, the zero-valent metal is selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals and / or group 3 transition metals, preferably the zero-valent metal is selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Yb, Sm, Eu, Nd, Tb, Gd, Ce, La, Sc and Y, more preferably the zero-valent metal is selected from the group consisting of Li, Na, Mg, Ca, Ba, and Yb, and even more preferably the zero-valent metal is selected from the group consisting of Li, Mg, Ba, and Yb.
[0694] According to another embodiment, the second electron transport layer comprises a non-emitter dopant, wherein the non-emitter dopant is a metal-organic complex of lithium quinolate, lithium borate, lithium phenolate and / or lithium Schiff base, preferably a lithium quinolate complex having formula I, II or III.
[0695] According to another embodiment, the second electron transport layer comprises a non-emitter dopant, wherein the non-emitter dopant is a metal-organic complex of a borate-based organic ligand, preferably, the lithium organic complex is a compound of formula (VII) or:
[0696]
[0697] Here, M is an alkali metal ion, and A 1 To A 4 are each independently substituted or unsubstituted C6-C 20 Aryl or substituted or unsubstituted C2-C 20 Selected from heteroaryls; or an alkali organic complex of formula (VIII); or:
[0698]
[0699] Here, A 1 To A 4 are each independently substituted or unsubstituted C6-C 20 Aryl or substituted or unsubstituted C2-C 20 Selected from heteroaryls; or a Li organic complex of formula (VIII):
[0700]
[0701] Here, A 1 To A 4 are each independently substituted or unsubstituted C6-C 20 Aryl or substituted or unsubstituted C2-C 20 It is selected from heteroaryls.
[0702] According to another embodiment, the second electron transport layer comprises a non-emitter dopant, wherein the non-emitter dopant is a metal compound, preferably the metal compound is selected from the group consisting of metal halides, metal-organic complexes and / or zero-valence metals; more preferably the metal-organic complex has Formula VII:
[0703]
[0704] Also, preferably, the metal-organic complex is lithium borate, and most preferably, lithium tetra(1H-pyrazol-1-yl)borate.
[0705] According to another embodiment, the first electron transport layer has no non-emitter dopant, and the second electron transport layer comprises a non-emitter dopant, wherein the non-emitter dopant is a metal compound, preferably the metal compound is selected from the group consisting of metal halides, metal-organic complexes and / or zero-valence metals; more preferably the metal-organic complex has Formula VII:
[0706]
[0707] Here, M is an alkali metal ion, and A1 To A 4 are each independently substituted or unsubstituted C6-C 20 Aryl or substituted or unsubstituted C2-C 20 It is selected from heteroaryls, more preferably M is a lithium ion, and most preferably lithium tetra(1H-pyrazol-1-yl)borate.
[0708] substrate
[0709] The substrate may be any substrate commonly used in the manufacture of organic light-emitting diodes. When light is emitted through the substrate, the substrate may be a transparent material having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance, for example, a glass substrate or a transparent plastic substrate. When light is emitted through the top surface, the substrate may be a transparent or opaque material, for example, a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.
[0710] anode electrode
[0711] The anode electrode may be formed by depositing or sputtering a compound used to form the anode electrode. The compound used to form the anode electrode may be a compound with a large work function to facilitate hole injection. The anode material may be selected from a material with a low work function (i.e., aluminum). The anode electrode may be a transparent electrode or a reflective electrode. Transparent conductive compounds, such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), and zinc oxide (ZnO), may be used to form the anode electrode (120). The anode electrode (120) may also be formed using magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), silver (Ag), gold (Au), etc.
[0712] The anode electrode can be formed of a highly conductive metal, for example, copper (Cu) or silver (Ag).
[0713] HIL
[0714] A hole injection layer (HIL) comprising a first and / or second hole injection layer suitable for use in the OLED of the present invention is described in US2002158242 AA, EP1596445A1 and EP1988587A1.
[0715] The first HIL can be formed on the anode electrode by vacuum deposition, spin coating, printing, casting, slot-die coating, Langmuir-Blodgett (LB) deposition, etc.
[0716] The second HIL can be formed on an n-type charge generation layer by vacuum deposition, spin coating, slot-die coating, printing, casting, Langmuir-bloodjet (LB) deposition, etc.
[0717] When HIL is formed using vacuum deposition, the deposition conditions may vary depending on the compound used to form the HIL, and the desired structure and thermal properties of the HIL. However, generally, the conditions for vacuum deposition include a deposition temperature of 100°C to 500°C, 10 -8 to 10 -3 It may include a pressure of torr (1 torr is equal to 133.322 Pa) and a deposition rate of 0.1 to 10 nm / sec.
[0718] For example, coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. The heat treatment removes the solvent after the coating is performed.
[0719] HTL
[0720] A hole transport layer (HTL) comprising a first and / or second hole transport layer suitable for use in the OLED of the present invention is described in Shirota and Kageyama, Chem. Rev. 2007, 107, 953-1010.
[0721] The first hole transport layer (HTL) can be formed on the HIL by vacuum deposition, spin coating, slot-die coating, printing, casting, Langmoor-bloodjet (LB) deposition, etc.
[0722] The second hole transport layer (HTL) can be formed on the second hole injection layer by vacuum deposition, spin coating, slot-die coating, printing, casting, Langmoor-bloodjet (LB) deposition, etc.
[0723] When HTL is formed by vacuum deposition or spin coating, the deposition and coating conditions may be similar to those used to form HIL. However, vacuum or solution deposition conditions may vary depending on the compound used to form the HTL.
[0724] Electromagnetic blocking layer
[0725] The function of the electron blocking layer (EBL) (150) is to prevent electrons from transferring from the emitting layer to the hole transport layer, thereby confining the electrons to the emitting layer. This improves efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer comprises a triarylamine compound. The triarylamine compound may have a LUMO level closer to the vacuum level than the LUMO level of the hole transport layer. The electron blocking layer may have a HOMO level further from the vacuum level compared to the HOMO level of the hole transport layer. The thickness of the electron blocking layer is selected from 2 nm to 20 nm.
[0726] The electron blocking layer may include a compound of the following formula Z:
[0727]
[0728] In equation Z,
[0729] CY1 and CY2 are identical or different from each other, and each independently represents a benzene cycle or a naphthalene cycle, and
[0730] Ar1 to Ar3 are identical or different from each other and are each independently selected from the group consisting of hydrogen; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; and a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, and
[0731] Ar4 is selected from the group consisting of a substituted or unsubstituted phenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted triphenylene group and a substituted or unsubstituted heteroaryl group, and
[0732] L is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.
[0733] If the electron blocking layer has a high triplet level, it can also be described as a triplet control layer.
[0734] The function of the triplet control layer is to reduce the quenching of triplets when a phosphorescent green or blue emitting layer is used. This allows for a higher luminous efficiency from the phosphorescent emitting layer. The triplet control layer is selected from triarylamine compounds in which the triplet level is higher than the triplet level of the phosphorescent emitter in an adjacent emitting layer. Suitable triplet control layers, in particular triarylamine compounds, are described in EP 2 722 908 A1, the entirety of which is incorporated by reference.
[0735] Emissive layer (EML)
[0736] EML can be formed on HTL by vacuum deposition, spin coating, slot-die coating, printing, casting, LB, etc. When forming EML using vacuum deposition or spin coating, the deposition and coating conditions may be similar to those for forming HIL.
[0737] The first light-emitting layer can be formed on the first hole transport layer.
[0738] The second light-emitting layer can be formed on the second hole transport layer.
[0739] However, deposition and coating conditions may vary depending on the compounds used to form the EML.
[0740] The emissive layer (EML) can be formed by a combination of a host and a dopant. Examples of hosts include Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 4,4',4''-tris(carbazole-9-yl)-triphenyl-amine (TCTA), 1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), bis(2-(2-hydroxyphenyl)benzothiazolate)zinc (Zn(BTZ)2), the following E3, AND, the following compound 12 and the following compound 13.
[0741]
[0742]
[0743] In a preferred embodiment, the light-emitting layer comprises one or more emitter dopants that emit visible light during operation of the OLED.
[0744] The dopant can be a phosphorescent emitter or a fluorescent emitter. Phosphorescent emitters and emitters that emit light via a thermally activated delayed fluorescence (TADF) mechanism are preferred due to their higher efficiency. The emitter can be a small molecule or a polymer. Examples of red dopants include, but are not limited to, PtOEP, Ir(piq)3, and Btp2lr(acac). While these compounds are phosphorescent emitters, fluorescent red dopants may also be used.
[0745]
[0746] Examples of phosphorescent green dopants include Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2 (acac), and Ir(mpyp)3. Compound 14 is an example of a fluorescent green emitter, and its structure is shown below.
[0747]
[0748]
[0749] Examples of phosphorescent blue dopants include F2Irpic, (F2ppy)2Ir(tmd) and Ir(dfppz)3, and ter-fluorene, the structures of which are as follows. 4,4'-bis(4-diphenylamiostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe), and the following compound 15 are examples of fluorescent blue dopants.
[0750]
[0751] The amount of dopant may be in the range of about 0.01 parts by weight to about 50 parts by weight based on 100 parts by weight of the host. Alternatively, the light-emitting layer may include or be composed of a light-emitting polymer. The EML may have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, excellent light-emitting characteristics can be achieved without substantially increasing the driving voltage.
[0752] In a preferred embodiment, the light-emitting layer comprising or constituting a light-emitting polymer is in direct contact with the electron transport layer stack.
[0753] Hole Blocking Layer (HBL)
[0754] When the EML contains a phosphorescent dopant, a hole blocking layer (HBL) can be formed on the EML using vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, etc., to prevent triplet excitons or holes from diffusing into the ETL.
[0755] A hole blocking layer suitable for use in the OLED of the present invention is described in US2015207093A and US2015060794A and is incorporated herein by reference.
[0756] When HBL is formed using vacuum deposition or spin coating, the deposition and coating conditions may be similar to those for forming HIL. However, the deposition and coating conditions may vary depending on the compound used to form the HBL. Any compound commonly used to form HBL may be used. Examples of compounds for forming HBL include oxadiazole derivatives, triazole derivatives, triazine derivatives, acridine derivatives, and phenanthroline derivatives.
[0757] If the hole blocking layer has a high triplet level, such a hole blocking layer may also be described as a triplet control layer. The function of the triplet control layer is to reduce the dissolution of triplets when a phosphorescent green or blue emitting layer is used. This allows for a higher luminescence efficiency from the phosphorescent emitting layer. The triplet control layer is selected from heteroaryl compounds in which the triplet level is higher than the triplet level of the phosphorescent emitter in an adjacent emitting layer.
[0758] A first hole blocking layer can be formed on a first light-emitting layer.
[0759] A second hole blocking layer can be formed on the second light-emitting layer.
[0760] The HBL can have a thickness of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. If the thickness of the HBL is within this range, the HBL can have excellent hole blocking properties without substantially increasing the driving voltage.
[0761] charge generation layer
[0762] A charge generating layer (CGL) suitable for use in the OLED of the present invention is described in US 2012098012 A.
[0763] The charge generation layer can generally be composed of a double layer. The charge generation layer may be a pn junction charge generation layer that junctions an n-type charge generation layer and a p-type charge generation layer. The pn junction charge generation layer generates charges or separates these charges into holes and electrons; and injects said charges into individual photoluminescent layers. That is, the n-type charge generation layer provides electrons to a first photoluminescent layer adjacent to the anode electrode, while the p-type charge generation layer provides electrons to a second photoluminescent layer adjacent to the cathode electrode, thereby further improving the luminous efficiency of an organic light-emitting device incorporating multiple photoluminescent layers and simultaneously lowering the driving voltage.
[0764] The p-type charge generating layer may be composed of a metal or organic material doped with a p-type dopant. Here, the metal may be a single metal selected from the group consisting of Al, Cu, Fe, Pb, Zn, Au, Pt, W, In, Mo, Ni, and Ti, or an alloy composed of two or more. Additionally, the p-type dopant and host used in the p-type doped organic material may be conventional materials. For example, the p-type dopant may be a dopant selected from the group consisting of tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), derivatives of tetracyanoquinodimethane, radialene derivatives, iodine, FeCl3, FeF3, and SbCl5. Additionally, the host may be selected from the group consisting of N,N'-di(naphthalene-1-yl)-N,N-diphenyl-benzidine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenyl-4,4'-diamine (TPD), and N,N',N'-tetranaphthyl-benzidine (TNB).
[0765] The n-type charge generating layer may be composed of an n-type doped metal or organic material. The metal may be a metal selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. Additionally, the n-type dopant and host used in the n-type doped organic material may be conventional materials. For example, the n-type dopant may be an alkali metal, an alkali metal compound, an alkaline earth metal, or an alkaline earth metal compound. More specifically, the n-type dopant may be selected from the group consisting of Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. The host material may be selected from the group consisting of tris(8-hydroxyquinoline)aluminum, triazine, hydroxyquinoline derivatives, benzazole derivatives, and silole derivatives.
[0766] In another preferred embodiment, the n-type charge generating layer is arranged adjacent to the electron transport layer. The n-type charge generating layer according to one embodiment may include a compound of Formula 16 below.
[0767]
[0768] Here,
[0769] A 1 To A 6Each may be hydrogen, a halogen atom, nitrile (-CN), nitro (-NO2), sulfonyl (-SO2R), sulfoxide (-SOR), sulfonamide (-SO2NR), sulfonate (-SO3R), trifluoromethyl (-CF3), ester (-COOR), amide (-CONHR or -CONRR'), substituted or unsubstituted straight-chain or branched-chain C1-C12 alkoxy, substituted or unsubstituted straight-chain or branched-chain C1-C12 alkyl, substituted or unsubstituted straight-chain or branched-chain C2-C12 alkenyl, substituted or unsubstituted aromatic or non-aromatic heterocycle, substituted or unsubstituted aryl, substituted or unsubstituted mono- or di-arylamine, substituted or unsubstituted alkylamine, etc.
[0770] In the present invention, R and R' are each substituted or unsubstituted C1-C 60 It may be an alkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted 5- to 7-membered heterocycle, etc.
[0771] An n-type charge generating layer containing the compound of formula (17) is particularly preferred:
[0772] .
[0773] A p-type charge generating layer is arranged on top of an n-type charge generating layer. As a material for the p-type charge generating layer, an arylamine-based compound may be used. One embodiment of an arylamine-based compound comprises a compound of the following formula 18:
[0774]
[0775] Here,
[0776] Ar1, Ar2, and Ar3 are each independently hydrogen or hydrocarbon groups. In the same invention, one or more of Ar1, Ar2, and Ar3 may comprise aromatic hydrocarbon substituents, and each substituent may be identical or may consist of different substituents. Where Ar1, Ar2, and Ar3 are not aromatic hydrocarbons, they may be hydrogen; straight-chain, branched-chain, or cyclic aliphatic hydrocarbons; or heterocyclic groups comprising N, O, S, or Se.
[0777] In another aspect of the present invention, the organic light-emitting diode (100) further comprises an n-type CGL (185), a p-type CGL (135), and an ETL stack (160), wherein the ETL stack (160) comprises a first electron transport layer (160a) comprising a first organic aromatic matrix compound selected from polar organic aromatic phosphine compounds, and a second electron transport layer (160b) comprising a second organic matrix compound. Preferably, the polar organic aromatic phosphine compound is selected from the group consisting of organic phosphine oxide, organic thioxophosphine compounds and / or organic selenoxophosphine compounds, and the second organic matrix compound is selected from organic compounds having a dipole moment of about ≥ 0 debye to about ≤ 2.5 debye. In a particularly preferred embodiment, the electron injection layer (180) and the first electron transport layer (160) comprise the same polar organic aromatic phosphine compound.
[0778] In a preferred embodiment, the n-type CGL comprises or is composed of a first zero-valent metal.
[0779] Electron injection layer (EIL)
[0780] An organic light-emitting diode may include an electron injection layer. The electron injection layer may be composed of one or more metal compounds.
[0781] The metal compound may be selected from the group consisting of metal halides, metal-organic complexes and / or zero-valence metals.
[0782] Preferably, the metal compound is selected from the group consisting of metal halides, metal-organic complexes and / or zero-valent metals, preferably alkali halides, alkali-organic complexes, more preferably alkali halides, alkali-organic complexes, and most preferably lithium fluoride and lithium quinolate (LiQ).
[0783] The metal halide can be selected from the group consisting of halides, wherein the metal can be selected from the group consisting of Li, Na, K, Cs, Mg, Ca and Ba; the halide is selected from the group consisting of F, Cl, Br and J; and preferably, it is a lithium halide.
[0784] The lithium halide can be selected from the group consisting of LiF, LiCl, LiBr, or LiJ, and preferably is LiF.
[0785] Metal-organic complexes can be selected from the group consisting of metal quinolates, metal borates, metal phenolates and / or metal Schiff bases.
[0786] Preferably, the metal-organic complex may be a lithium-organic complex.
[0787] Preferably, the lithium organic complex may be selected from the group consisting of lithium quinolates, lithium borates, lithium phenolates and / or lithium Schiff bases, and preferably, the lithium quinolate complex has Formula I, II or III:
[0788]
[0789] Here,
[0790] - A1 to A6 are identical or independently selected from CH, CR, N, and O, and
[0791] - R is selected from hydrogen, halogen, alkyl, aryl, or heteroaryl having 1 to 20 carbon atoms, either identically or independently, and more preferably is lithium 8-hydroxyquinolate.
[0792] Unless otherwise defined in the specification, the zero-valent metal is selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals and / or group 3 transition metals, preferably the zero-valent metal is selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Yb, Sm, Eu, Nd, Tb, Gd, Ce, La, Sc and Y, more preferably the zero-valent metal is selected from the group consisting of Li, Na, Mg, Ca, Ba, and Yb, and even more preferably the zero-valent metal is selected from the group consisting of Li, Mg, Ba, and Yb.
[0793] Preferably, the electron injection layer does not contain an organic matrix compound. Therefore, the electron injection layer is not an electron transport layer.
[0794] The electron injection layer is positioned interposed between the electron transport layer stack and the cathode electrode layer, and preferably, the electron injection layer is arranged in direct contact with the cathode electrode layer.
[0795] If the EIL exists, it can be formed directly on the electron transport layer stack. The deposition and coating conditions for forming the EIL are similar to those for forming the hole injection layer (HIL), but these conditions may vary depending on the material used for forming the EIL.
[0796] The thickness of the EIL may be in the range of about 1 nm to 10 nm. According to a preferred embodiment, the thickness of the electron injection layer may be ≥ 1 nm to ≤ 10 nm, preferably ≥ 2 nm to ≤ 6 nm, preferably ≥ 3 nm to ≤ 5 nm, more preferably ≥ 3 nm to ≤ 4 nm. When the thickness of the EIL is within this range, the EIL according to the present invention may have improved electron-injection characteristics, in particular a substantial reduction in operating voltage and / or an increase in external quantum efficiency EQE.
[0797] According to another aspect of the OLED, the second electron transport layer and / or the second electron transport layer and the fourth electron transport layer comprise a polar organic aromatic phosphine compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about > 2.5 Debye to about ≤ 10 Debye, wherein the electron injection layer does not have a polar organic aromatic phosphine compound and does not have a first organic aromatic matrix compound.
[0798] Preferably, if the second electron transport layer does not contain a non-emitter dopant, an electron injection layer is present.
[0799] If the second electron transport layer contains a non-emitter dopant, the electron injection layer may not exist.
[0800] cathode electrode
[0801] A cathode electrode is formed on the EIL. The cathode electrode is an electron injection layer. The cathode electrode can be formed from a metal, an alloy, an electrically conductive compound, or a mixture thereof. The cathode electrode may have a low work function. For example, the cathode can be formed from lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), etc. Additionally, the cathode electrode can be formed from a transparent conductive material, such as ITO or IZO.
[0802] The thickness of the cathode electrode may be in the range of about 5 nm to 1000 nm, for example, 10 nm to 100 nm. If the cathode is in the range of 5 nm to 50 nm, the electrode will be transparent even if a metal or metal alloy is used.
[0803] The cathode electrode is not an electron injection layer or an electron transport layer.
[0804] In a preferred embodiment, the cathode electrode is in direct contact with the electron transport layer stack. Surprisingly, it has been found that when the electron transport layer in direct contact with the cathode comprises a non-emitter dopant, very good electron injection from the cathode electrode into the electron transport layer stack can be achieved. Preferably, a second electron transport layer is in direct contact with the cathode electrode.
[0805] When the cathode electrode layer is in direct contact with the electron injection layer, a very low operating voltage and a high external quantum efficiency (EQE) are achieved. This increases the battery life of the mobile device. However, if the cathode electrode and the electron injection layer are present, their constituent components are different.
[0806] Light Emitting Diode (OLED)
[0807] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided comprising a substrate, an anode electrode, a hole injection layer, a hole transport layer, an optional electron blocking layer, a light-emitting layer, an optional hole blocking layer, an optional electron transport layer, an electron injection layer, and a first cathode electrode layer, wherein these layers are arranged in the corresponding order.
[0808] According to another aspect of the present invention, an organic light-emitting diode (OLED) is provided comprising a substrate, an anode electrode, a first hole injection layer, a first hole transport layer, an optional first electron blocking layer, a first light-emitting layer, an optional first hole blocking layer, an optional first electron transport layer, an n-type charge generating layer, a p-type charge generating layer, a second hole transport layer, an optional second electron blocking layer, a second light-emitting layer, an optional second hole blocking layer, an optional second electron transport layer, an electron injection layer, and a cathode electrode layer, wherein these layers are arranged in the corresponding order.
[0809] According to various embodiments of the OLED of the present invention, the OLED may not include an electron injection layer.
[0810] According to various embodiments of the OLED of the present invention, the OLED may not include an electron blocking layer.
[0811] According to various embodiments of the OLED of the present invention, the OLED may not include a hole blocking layer.
[0812] According to various embodiments of the OLED of the present invention, the OLED may not include a charge generating layer.
[0813] According to various embodiments of the OLED of the present invention, the OLED may not include a second light-emitting layer.
[0814] Manufacturing method
[0815] According to various embodiments of the present invention, the manufacturing method may further include the step of forming other layers of an anode electrode, a hole injection layer, a hole transport layer, an optional electron blocking layer, an emitting layer, an optional hole blocking layer, an electron transport layer stack comprising one or more first electron transport layers and second electron transport layers, an optional electron injection layer, and a cathode electrode layer on a substrate, wherein these layers are deposited in a corresponding order; or these layers are deposited in the reverse order starting with the cathode electrode layer.
[0816] According to various embodiments of the present invention, the method may further include the step of depositing an anode electrode on a substrate, and depositing on the anode electrode in the corresponding order an electron transport layer stack comprising a hole injection layer, a hole transport layer, an optional electron blocking layer, an emitting layer, an optional hole blocking layer, at least a first electron transport layer and a second electron transport layer, an optional electron injection layer, and other layers of a cathode electrode layer; or depositing these layers starting with the first cathode electrode layer and in the reverse order.
[0817] According to various embodiments of the present invention, the manufacturing method may further include the step of forming an anode electrode, a first hole injection layer, a first hole transport layer, an optional first electron blocking layer, a first light-emitting layer, an optional first hole blocking layer, a first electron transport layer stack, an n-type charge generating layer, a p-type charge generating layer, a second hole transport layer, an optional second electron blocking layer, a second light-emitting layer, an optional second hole blocking layer, an optional second electron transport layer stack, an optional electron injection layer, and a cathode electrode layer on a substrate, wherein these layers are arranged in a corresponding order; or these layers are deposited in the reverse order starting with the cathode electrode layer.
[0818] However, according to one embodiment, the layers are deposited in opposite directions starting from the cathode electrode and interposed between the cathode electrode and the anode electrode.
[0819] The anode electrode and / or cathode electrode may be deposited on a substrate. Preferably, the anode is deposited on the substrate.
[0820] According to another aspect of the present invention, a method for manufacturing an organic light-emitting diode (OLED) is provided, and said manufacturing method
[0821] - One or more deposition sources, preferably two deposition sources, more preferably three or more deposition sources; and / or
[0822] - Deposition via vacuum thermal evaporation; and / or
[0823] - Deposition via solution processing, preferably the processing is selected from spin-coating, printing, casting, and / or slot-die coating.
[0824] Uses
[0825] electronic devices
[0826] Another aspect relates to an electronic device comprising one or more organic light-emitting diodes (OLEDs). The device comprising the organic light-emitting diodes (OLEDs) is, for example, a display or a lightning panel.
[0827] Additional embodiments and / or advantages of the invention will be described in the following description, some of which may become apparent from the detailed description or be learned from the embodiments of the invention. Brief explanation of the drawing
[0828] These and / or other aspects and advantages of the present invention will become clear and more easily understood from the following description of exemplary embodiments with reference to the accompanying drawings: FIG. 1 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention, comprising two electron transport layers. FIG. 2 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention, comprising three electron transport layers. FIG. 3 is a schematic cross-sectional view of an OLED according to another exemplary embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of an OLED according to another exemplary embodiment of the present invention. FIG. 5 is a schematic cross-sectional view of an OLED according to another exemplary embodiment of the present invention. FIG. 6 is a schematic cross-sectional view of an OLED according to another exemplary embodiment of the present invention. FIG. 7 is a schematic cross-sectional view of a tandem OLED including a charge generating layer according to an exemplary embodiment of the present invention. Specific details for implementing the invention
[0829] Now, we will refer in detail to exemplary embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein similar reference numerals refer to elements that are generally similar. Exemplary embodiments are described below to explain aspects of the present invention by reference to the drawings.
[0830] Here, when it is stated that the first configuration is formed or arranged "on" the second configuration, the first configuration may be arranged directly on the second configuration, or one or more other configurations may be arranged between them. When it is stated that the first configuration is formed or arranged "directly" on the second configuration, no other configurations are arranged between them.
[0831] FIG. 1 is a schematic cross-sectional view of an organic light-emitting diode (OLED) (100) according to an exemplary embodiment of the present invention. The OLED (100) comprises a substrate (110), an anode electrode (120), a hole injection layer (HIL) (130), a hole transport layer (HTL) (140), a light-emitting layer (EML) (150), and an electron transport layer stack (ETL) (160) of a first electron transport layer (161) and a second electron transport layer (162). The first electron transport layer (161) comprises i) a first organic aromatic matrix compound having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about ≥ 0 Debye to about ≤ 2.5 Debye, wherein the first electron transport layer (161) does not contain a polar organic aromatic phosphine compound; The second electron transport layer (162) comprises two organic aromatic matrix materials, which are:
[0832] i) a first organic aromatic matrix compound; and ii) a mixture of polar organic aromatic phosphine compounds having a dipole moment of about ≥ 400 to about ≤ 1000 MW and about > 2.5 Debye to about ≤ 10 Debye.
[0833] The polar organic aromatic phosphine compound is selected from the group consisting of organic aromatic phosphine oxide compounds, organic aromatic thioxophosphine compounds, or organic aromatic selenophosphine compounds. The cathode electrode layer (190) is placed directly on the second electron transport layer (ETL) (162).
[0834] FIG. 2 is a schematic cross-sectional view of an OLED according to another exemplary embodiment of the present invention. FIG. 2 differs from FIG. 1 in that the OLED (100) of FIG. 2 comprises an electron transport layer stack (160) of a first electron transport layer (161), a second electron transport layer (162), and a third electron transport layer (163). The third electron transport layer (163) may have the same composition as the first electron transport layer (161).
[0835] FIG. 3 is a schematic cross-sectional view of an OLED according to another exemplary embodiment of the present invention. FIG. 3 differs from FIG. 1 in that the OLED (100) of FIG. 3 includes an electron transport layer stack (160) of a first electron transport layer (161), a second electron transport layer (162), a third electron transport layer (163), and a fourth electron transport layer (164).
[0836] FIG. 4 is a schematic cross-sectional view of an OLED according to another exemplary embodiment of the present invention. FIG. 4 differs from FIG. 1 in that the OLED (100) of FIG. 4 includes an electron blocking layer (EBL) (145) and an electron injection layer (EIL) (180).
[0837] FIG. 5 is a schematic cross-sectional view of an OLED according to another exemplary embodiment of the present invention. FIG. 5 differs from FIG. 2 in that the OLED (100) of FIG. 5 includes an electron injection layer (EIL) (180).
[0838] FIG. 6 is a schematic cross-sectional view of an OLED according to another exemplary embodiment of the present invention. FIG. 6 differs from FIG. 5 in that the OLED (100) of FIG. 6 includes an electron blocking layer (EBL) (145).
[0839] FIG. 7 shows a substrate (110), an anode electrode (120), an electron transport layer stack (160) of a first hole injection layer (HIL) (130), a first hole transport layer (HTL) (140), a first electron blocking layer (EBL) (145), a first emitting layer (EML) (150), a first hole blocking layer (HBL) (155), a first electron transport layer (ETL) (161) and a second electron transport layer (ETL) (162), an n-type charge generation layer (n-type CGL) (185), a p-type charge generation layer (p-type GCL) (186), a second hole transport layer (HTL) (141), a second electron blocking layer (EBL) (146), a second emitting layer (EML) (151), a second hole blocking layer (EBL) (156), a fourth electron transport layer (ETL) (164) and a third electron This is a schematic cross-sectional view of a tandem OLED (100) comprising a second electron transport layer stack (ETL) (160) of a transport layer (ETL) (163), an electron injection layer (EIL) (180), a first cathode electrode layer (191), and a second cathode electrode layer (192). The second electron transport layer (162) and the third electron transport layer (163) comprise a polar organic aromatic phosphine compound selected from the group consisting of an organic aromatic phosphine oxide compound, an organic aromatic thioxophosphine compound, or an organic aromatic selenophosphine compound.
[0840] In the above description, the method for manufacturing an OLED (100) of the present invention may start with a substrate (110), and an anode electrode (120) is formed on the substrate (110), and on the anode electrode (120), an ETL-stack (160) comprising a first hole injection layer (130), a first hole transport layer (140), an optional first electron blocking layer (145), a first light-emitting layer (150), an optional first hole blocking layer (155), a first electron transport layer (161), and a second electron transport layer (162), an optional n-type CGL (185), an optional p-type CGL (135), an optional second hole transport layer (141), an optional second electron blocking layer (146), an optional second light-emitting layer (151), an optional second hole blocking layer (156), a fourth electron transport layer (164), and a third electron transport layer (163). An additional ETL stack (160), an optional electron injection layer (180), a first cathode electrode layer (191), and an optional second cathode electrode layer (192) are formed in that order or in the reverse order.
[0841] Although not illustrated in FIGS. 1, 2, 3, 4, 5, 6 and 7, a sealing layer may be further formed on the second electrode (190) to seal the OLED (100). Additionally, various other variations may be applied.
[0842] Examples
[0843] General procedure
[0844] Bottom emission device having an evaporating light-emitting layer
[0845] Bottom emission device - For Examples 1 to 10 and Comparative Examples 1 to 2, 15 Ω / cm having 100 nm ITO 2A glass substrate (available from Corning Co.) was cut to a size of 50 mm x 50 mm x 0.7 mm, ultrasonically cleaned with isopropyl alcohol for 5 minutes, then cleaned with pure water for 5 minutes, and then cleaned again with UV ozone for 30 minutes to produce a first electrode.
[0846] Then, 97 wt% of biphenyl-4-yl(9,9-diphenyl-9H-fluorene-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-amine (CAS 1242056-42-3) and 3 wt% of 2,2',2''-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) were vacuum deposited on an ITO electrode to form a HIL with a thickness of 10 nm. Then, biphenyl-4-yl(9,9-diphenyl-9H-fluorene-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-amine was vacuum deposited on the HIL to form an HTL with a thickness of 120 nm. 97 wt% of ABH113 (Sun Fine Chemicals) as a host and 3 wt% of NUBD370 (Sun Fine Chemicals) as a dopant were deposited on the HTL to form a blue emitting EML with a thickness of 20 nm.
[0847] Then, a first electron transport layer is formed by depositing a first organic aromatic matrix compound ETM1 according to Examples 1 to 11 and Comparative Examples 1 to 29 by directly depositing a compound derived from a first deposition source onto the EML. Additionally, the thickness d (nm) of ETL1 can be taken from Tables 7, 8, and 9.
[0848] Then, a second electron transport layer is formed by directly depositing a polar organic aromatic phosphine compound ETM2 according to Examples 1 to 11 and Comparative Examples 1 to 29 onto the first electron transport layer. The composition and thickness of the second electron transport layer can be taken from Tables 7, 8, and 9.
[0849] If an electron injection layer exists, such electron injection layer is formed by directly depositing LiQ or Yb on the second electron transport layer. The composition and thickness of the second electron transport layer can be taken from Tables 7, 8, and 9.
[0850] 10 cathode electrode layers -7 Evaporation is performed in an ultra-high vacuum of bar. Thus, thermal single-cavity evaporation of one or several metals is carried out at a rate of 0, 1 to 10 nm / s (0.01 to 1 Å / s) to produce a homogeneous cathode electrode with a thickness of 5 nm to 1000 nm. 100 nm aluminum is used as the cathode layer in Examples 1 to 11 and Comparative Examples 1 to 29.
[0851] The OLED stack is protected from ambient conditions by encapsulating the device with a glass slide. By doing so, a cavity containing a getter material for additional protection is formed.
[0852] Top emission device
[0853] For the top-emitting device, the anode electrode is formed from 100 nm silver on glass and manufactured by the same method as described above.
[0854] Then, 97 wt% of biphenyl-4-yl(9,9-diphenyl-9H-fluorene-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-amine (CAS 1242056-42-3) and 3 wt% of 2,2',2''-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) are vacuum deposited on an ITO electrode to form a HIL with a thickness of 10 nm. Then, biphenyl-4-yl(9,9-diphenyl-9H-fluorene-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-amine (CAS 1242056-42-3) is vacuum deposited on the HIL to form an HTL with a thickness of 125 nm. N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1''-terphenyl]-4-amine is directly deposited on the upper surface of HTL to form an EBL with a thickness of 5 nm.
[0855] 97 wt% of 2-(10-phenyl-9-anthracenyl)-benzo[b]naphtho[2,3-d]furan as a host and 3 wt% of NUBD370 (Sun Fine Chemicals) as a dopant are deposited on the EBL to form a blue-emitting EML with a thickness of 20 nm.
[0856] Then, first and second electron transport layers and an optional electron injection layer are deposited on the EML as described for the lower emission device.
[0857] 10 cathode electrode layers -7 Evaporation is performed in an ultra-high vacuum of bar. Thus, thermal single-cavity evaporation of one or several metals is carried out at a rate of 0, 1 to 10 nm / s (0.01 to 1 Å / s) to produce a homogeneous cathode electrode with a thickness of 5 nm to 1000 nm.
[0858] 60 nm biphenyl-4-yl(9,9-diphenyl-9H-fluorene-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-amine (CAS 1242056-42-3) is placed directly on the upper surface of the second cathode electrode layer.
[0859] The OLED stack is protected from ambient conditions by encapsulating the device with a glass slide. By doing so, a cavity containing a getter material for additional protection is formed.
[0860] To evaluate the performance of an embodiment of the present invention compared with prior art, current efficiency is measured under ambient conditions (20°C). Current-voltage measurements are performed using a Keithley 2400 source meter and recorded in V. For a bottom-emitting device, 10 mA / cm² 2 and 10 mA / cm² for top-emitting devices 2 In this case, Instrument Systems' calibrated spectrometer CAS140 is used for CIE coordinates in candela and brightness measurements. The lifetime LT of the bottom-emitting device is determined using a Keithley 2400 source meter under ambient conditions (20°C) and 10 mA / cm². 2 Measure at and record after a few hours. The lifetime LT of the top-emitting device is under ambient conditions (20°C) and 8 mA / cm² 2 It is measured at. The brightness of the device is measured using a calibrated photodiode. Lifetime LT is defined as the time until the brightness of the device decreases to 97% of its initial value.
[0861] In bottom-emitting devices, emission is primarily Lambertian and is quantified as an external quantum efficiency (EQE) percentage. To verify the EQE efficiency in percentages, the device's light output is set to 10 mA / cm². 2 Measure using a calibrated photodiode.
[0862] In top-emitting devices, emission is forward-directed, non-Lambertian, and highly dependent on the microcavity. Therefore, the efficiency EQE will be higher compared to bottom-emitting devices. To verify the efficiency EQE in %, the device's optical output was set to 10 mA / cm² 2 Measure using a calibrated photodiode.
[0863] Technical effects of the present invention
[0864] The beneficial effects of the electron injection layer according to the present invention on the performance of the bottom emission device can be seen in Tables 7, 8, and 9.
[0865] Table 7 shows the results for a fluorescent blue device comprising a first electron transport layer composed of a first organic aromatic matrix compound, a second electron transport layer composed of a polar organic aromatic phosphine compound, and an electron injection layer composed of a lithium organic complex LiQ (Comparative Examples 1 to 10 and Examples 1 to 4) or Yb (Comparative Examples 11 to 13 and Example 4).
[0866] In Comparative Example 1, the first and second electron transport layers comprise polar organic aromatic phosphine oxide A26. The dipole moment of A26 is 2.68 eV, the reduction potential is -2.2 V, and the LUMO is -2.64 eV. The operating voltage is 4.9 V, and the external quantum efficiency EQE is 5.5%. Since the efficiency is quite low, the lifetime was not measured. In Comparative Example 2, the first and second electron transport layers comprise different polar phosphine oxide compounds. A18 is used instead of A26. The dipole moment of A18 is 4.64 eV, the reduction potential is -2.62 V, and the LUMO is -2.22 eV. Since the operating voltage is slightly higher and the efficiency is reduced, the performance is worse.
[0867] In Comparative Example 3, the first electron transport layer comprises a polar organic aromatic phosphine compound A26, and the second electron transport layer comprises a mixture of polar organic aromatic phosphine compounds A26 and A18. No improvement is observed in either operating voltage or efficiency.
[0868] In Comparative Example 4, the first electron transport layer comprises a polar phenanthroline compound PHEN-1, the structure of which is referenced below. PHEN-1 has a dipole moment of approximately 3.6 Debye, a reduction potential of -2.29 V, and a LUMO of -2.55 eV.
[0869]
[0870] The second electron transport layer comprises a mixture of the polar phenanthroline compound PHEN-1 and the polar organic aromatic phosphine compound A18. A small improvement in efficiency and a decrease in operating voltage are observed.
[0871] In Comparative Example 5, the first and second electron transport layers comprise the first organic aromatic matrix compound ETM1-1. The dipole moment of ETM1-1 is close to 0 Debye, the reduction potential is -2.45 V, and the LUMO is -2.55 eV. The efficiency is low at 4.6%, and the operating voltage is high at 7.4 V.
[0872] In Comparative Example 6, the first electron transport layer comprises non-polar ETM1-1, and the second electron transport layer comprises polar phosphine compound A18. No improvement is observed in either efficiency or operating voltage.
[0873] In Example 1, the first electron transport layer comprises non-polar ETM1-1, and the second electron transport layer comprises a mixture of non-polar ETM1-1 and a polar phosphine compound A18. Efficiency is substantially improved to 7.1% EQE, and the operating voltage is very low at 4.3 V. Life is dramatically improved to 119 hours compared to 15 hours and 32 hours of Comparative Examples 3 and 4. In summary, substantial gains are observed for the electron transport layer stack according to the present invention.
[0874] In Example 2, the first electron transport layer comprises a non-polar triazine compound ETM1-32, and the second electron transport layer comprises a polar phosphine compound A18. The triazine compound ETM1-32 has a dipole moment of 1.03 Debye, a reduction potential of -2.22 V, and a LUMO of -2.62 eV. Additionally, the efficiency is very high at 7.2% EQE, and the operating voltage is relatively low at 4.5 V. The lifetime is good at 83 hours. All performance parameters are improved compared to Comparative Examples 7 to 9, which do not contain a mixture of non-polar and polar matrix compounds in the second electron transport layer.
[0875] In Example 3, the first electron transport layer comprises a non-polar dibenzo[c,h]acridine compound ETM1-15 and a polar phosphine compound A18. The dibenzo[c,h]acridine compound ETM1-15 has a dipole moment of 1.8 Debye, a reduction potential of -2.26 V, and a LUMO of -2.58 eV. The efficiency and operating voltage are improved compared to Comparative Example 10, which does not contain a mixture of matrix compounds in the second electron transport layer.
[0876] In Example 4, the first electron transport layer comprises a non-polar triazine compound ETM1-32, and the second electron transport layer comprises a polar phosphine compound A18. The electron injection layer comprises 2 nm Yb. Additionally, the efficiency is very high at 6.9% EQE, and the operating voltage is relatively low at 4.7 V. The lifetime is good at 59 hours. All performance parameters are improved compared to Comparative Examples 11 to 13, which do not contain a mixture of non-polar and polar matrix compounds in the second electron transport layer.
[0877] Table 8 shows results for a fluorescent blue bottom-emitting device comprising a first electron transport layer comprising a first organic aromatic matrix compound, and a second electron transport layer comprising the first and second matrix compounds and a non-emitter dopant selected from the lithium organic complex Li-1. Comparative Examples 14 to 18 and Examples 5 and 6 do not contain an electron injection layer. Comparative Examples 19 and 20 and Example 7 contain an electron injection layer formed from 1.5 nm LiQ. Comparative Examples 21 and 22 and Example 8 contain an electron injection layer formed from 2 nm Yb.
[0878] In Comparative Example 14, the first electron transport layer comprises a polar phenanthroline compound PHEN-1, and the second electron transport layer comprises a mixture of PHEN-1, a polar phosphine compound A18, and a lithium organic complex Li-1. The efficiency is 6.4% EQE, and the operating voltage is 5 V. The lifetime is very short at 15 hours.
[0879] In Comparative Example 15, the first electron transport layer comprises a non-polar dibenzo[c,h]acridine compound ETM1-15, and the second electron transport layer comprises ETM1-15 and Li-1. The efficiency is increased to 5.7% EQE, and the operating voltage is reduced to 6.6 V.
[0880] In Comparative Example 16, the first electron transport layer comprises a non-polar dibenzo[c,h]acridine compound ETM1-15, and the second electron transport layer comprises a polar phosphine compound A18 and Li-1. The efficiency is increased to 6.3% EQE, and the operating voltage is reduced to 3.7 V.
[0881] In Example 5, the first electron transport layer comprises a non-polar dibenzo[c,h]acridine compound ETM1-15, and the second electron transport layer comprises a mixture of ETM1-15, a polar phosphine compound A18, and Li-1. The efficiency is increased to 7% EQE, and the operating voltage remains low at 4 V. The lifetime is 30 hours. All performance parameters are improved to surpass Comparative Examples 14 to 16.
[0882] In Example 6, the first electron transport layer comprises a non-polar triazine compound ETM1-32, and the second electron transport layer comprises a mixture of ETM1-32, a polar phosphine compound A18, and Li-1. The efficiency is substantially increased to 9.9% EQE, and the operating voltage remains low at 4.6 V. The lifetime is 21 hours. All performance parameters are improved to surpass Comparative Examples 14 to 18.
[0883] In Comparative Example 19, the first and second electron transport layers contain the same matrix non-polar triazine matrix compound ETM1-32. The second electron transport layer additionally contains Li-1. LiQ is used as the electron injection layer. Although the efficiency is still high at 7.3% EQE, the operating voltage is also high at 6.2 V.
[0884] In Comparative Example 20, the first electron transport layer comprises a non-polar triazine compound ETM1-32, and the second electron transport layer comprises polar phosphine compounds A18 and Li-1. The efficiency remains high at 7.6% EQE, and the operating voltage is reduced compared to Example 5, but this is achieved by depositing an additional layer compared to Example 5.
[0885] In Example 7, the same ETL stack as in Example 6 is used, but the device additionally contains an electron injection layer containing LiQ. While the efficiency remains very high at 10% EQE, the operating voltage is reduced to 4.4 V, thereby demonstrating the beneficial effect of EIL on the operating voltage.
[0886] In Example 8, the same ETL stack as in Examples 6 and 7 is used, but this device additionally contains an electron injection layer containing Yb. The efficiency remains high at 9.7% EQE, and the voltage is further improved to 4.3 V. The lifetime is unaffected. In particular, the efficiency is improved compared to Comparative Examples 14 to 22.
[0887] In summary, very high efficiency and good lifespan can be obtained using the ETL stack according to the present invention. If a further reduction in operating voltage is desired, this can be achieved by an electron injection layer. However, even without an electron injection layer, the operating voltage remains within a range suitable for mass production of the device.
[0888] Table 9 shows results for a fluorescent blue bottom-emitting device comprising a first electron transport layer comprising a first organic aromatic matrix compound, and a second electron transport layer comprising a mixture of the first organic aromatic matrix compound, a polar organic aromatic phosphine compound, and a non-emitter dopant selected from zero-valent ytterbium metal.
[0889] Comparative Examples 23 to 25 and Example 9 do not contain an electron injection layer. Comparative Examples 26 and 27 and Example 10 contain an electron injection layer formed from 1.5 nm LiQ. Comparative Examples 28 and 29 and Example 11 contain an electron injection layer formed from 2 nm Yb.
[0890] In Comparative Example 23, the first electron transport layer comprises a polar phenanthroline compound PHEN-2, and the second electron transport layer comprises a mixture of PHEN-2, a polar phosphine compound A18, and 2.5 wt% Yb. The dipole moment of PHEN-2 is 2.53 Debye, the reduction potential is -2.45 V, and the LUMO is -2.39 eV. The efficiency is 5.7% EQE, and the operating voltage is 3.3 V.
[0891]
[0892] In Comparative Example 24, the first and second electron transport layers comprise the non-polar dibenzo[c,h]acridine compound ETM1-15. The second electron transport layer additionally comprises 5 wt% Yb. The efficiency is reduced compared to Comparative Example 23, and the operating voltage is increased sharply.
[0893] In Comparative Example 25, the first electron transport layer comprises a non-polar dibenzo[c,h]acridine compound ETM1-15, and the second electron transport layer comprises a polar phosphine compound A18 and 5 wt% Yb. The efficiency is increased to 6.5% EQE, and the operating voltage is very low at 3.4 V.
[0894] In Example 9, the first electron transport layer comprises a non-polar dibenzo[c,h]acridine compound ETM1-15, and the second electron transport layer comprises a mixture of ETM1-15, a polar phosphine compound A18, and 2.5 wt% Yb. The efficiency is substantially increased to 8.5% EQE, and the operating voltage is still very low at 3.6 V. The lifetime is 32 hours. In particular, the efficiency is improved to surpass Comparative Examples 23 to 25.
[0895] In Example 10, the ETL-stack is the same as in Example 9, but the device additionally contains an electron injection layer formed of 1.5 nm LiQ. The efficiency and operating voltage do not change compared to Example 9. The performance is improved, surpassing Comparative Examples 26 and 27, which do not contain a mixture of matrix compounds in the second electron transport layer.
[0896] In Example 11, the same ETL stack is used as in Examples 9 and 10. The efficiency, operating voltage, and lifetime do not change compared to Examples 9 and 10.
[0897] In summary, if the second electron transport layer includes a non-emitter dopant selected from zero-value metals, high performance can be achieved even without an electron injection layer.
[0898] Substantial time savings are achieved when no electron injection layer is to be deposited.
[0899] Another embodiment relates to an organic light-emitting diode (OLED) comprising more than one light-emitting layer (EML) (150), for example, two, three, or four light-emitting layers may exist. An organic light-emitting diode (OLED) comprising more than one light-emitting layer is also described as a tandem OLED or a stacked OLED.
[0900] Another aspect relates to a device comprising one or more organic light-emitting diodes (OLEDs). The device comprising the organic light-emitting diodes (OLEDs) is, for example, a display or a lighting panel.
[0901]
[0902]
[0903]
[0904]
[0905]
[0906]
[0907] From the detailed description and embodiments of the invention described above, it is evident that modifications and alterations to the compositions and methods of the present invention may be made without departing from the spirit and scope of the invention. Accordingly, all modifications to the present invention that do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims
Claim 1 As an organic light-emitting diode (100), - one or more anode electrodes (120); - one or more light-emitting layers (150), wherein the light-emitting layer comprises one or more emitter dopants that emit visible light when the OLED (100) is operated; - as an electron transport layer stack (160) of two or more electron transport layers (161 / 162): a) the first electron transport layer (161) comprises i) a first organic aromatic matrix compound having a dipole moment of ≥ 400 to ≤ 1000 MW and ≥ 0 Debye to ≤ 2.5 Debye, wherein the first electron transport layer (161) does not contain a polar organic aromatic phosphine compound; b) the second electron transport layer (162) comprises two organic aromatic matrix compounds, wherein these compounds are: i) the first organic aromatic matrix compound; and ii) MW of ≥ 400 to ≤ 1000 and > 2.Electron transport layer stack (160), which is a mixture of polar organic aromatic phosphine compounds having a dipole moment of 5 to ≤ 10 Debyes; and - comprising one or more cathode electrode layers (190); Here, the electron transport layer stack (160) is arranged between the light-emitting layer (150) and the cathode electrode layer (190), the first electron transport layer (161) is in direct contact with the second electron transport layer (162), the first electron transport layer (161) is arranged closer to the light-emitting layer (150), and the second electron transport layer (162) is arranged closer to the cathode electrode layer (190), the polar organic aromatic phosphine compound is a phosphine oxide compound, and the second electron transport layer comprises: - ≥ 50 wt% to ≤ 95 wt%, or ≥ 60 wt% to ≤ 90 wt%, or ≥ 70 wt% to ≤ 90 wt%, or 80 wt% i) a first organic aromatic matrix compound; and- ≥ 5 wt% to ≤ 50 wt%, or ≥ 10 wt% to ≤ 40 wt%, or ≥ 10 wt% to ≤ 30 wt%, or 20 wt% ii) a polar organic aromatic phosphine compound; wherein the wt% is based on the total weight of i) and ii) of the second electron transport layer, an organic light-emitting diode (100). Claim 2 In claim 1, the organic light-emitting diode (100) in the electron transport layer stack (160) does not have an emitter dopant that emits visible light when the OLED (100) is operated. Claim 3 In claim 1, the first electron transport layer (161) does not have a non-emitter dopant, and the second electron transport layer (162) comprises a non-emitter dopant, wherein the non-emitter dopant is a metal compound; or a metal compound selected from the group consisting of metal halides, metal organic complexes and / or zero-value metals; or a metal organic complex having Formula VII: Here, M is an alkali metal ion, and A 1 To A 4 are each independently, unsubstituted C6-C 20 Aryl or unsubstituted C2-C 20 Organic light-emitting diode (100) selected from heteroaryls. Claim 4 The organic light-emitting diode (100) of claim 1 further comprises an electron injection layer (180), wherein the electron injection layer (180) comprises a metal compound; or a metal compound selected from the group consisting of a metal halide, a metal-organic complex and / or a zero-valent metal, or an alkali halide, an alkali-organic complex, or lithium fluoride and lithium quinolate (LiQ); and wherein the electron injection layer (180) is positioned interposed between the electron transport layer stack (160) and the cathode electrode layer (190), or wherein the electron injection layer (180) is arranged in direct contact with the cathode electrode layer (190). Claim 5 An organic light-emitting diode (100), wherein, in claim 3 or 4, the zero-value metal is selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals and / or group 3 transition metals, or the zero-value metal is selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Yb, Sm, Eu, Nd, Tb, Gd, Ce, La, Sc and Y. Claim 6 In claim 1, the polar organic aromatic phosphine compound of the second electron transport layer (162) is a compound having the formula Ia: Here: X is O and;R 1 and R 2 is independently, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl or substituted or unsubstituted C5 to C 20 Selected from heteroaryls; or R 1 and R 2 is cross-linked with an alkene-diyl group forming a substituted or unsubstituted 5, 6, or 7-membered ring together with a P atom; A 1 is phenyl or selected from formula (II): Here: R 3 C1 to C8 alkane-diyl, substituted or unsubstituted C6 to C 20 Aryllene, or substituted or unsubstituted C5 to C 20 Selected from heteroarylenes; or A 1 is selected from Equation (III): Here: n is selected from 0 or 1; m is selected from 1 or 2; o is selected from 1 or 2; if o is 2, m is 1 and; Ar 1 ...substituted or unsubstituted C6 to C 20 Aryllene and substituted or unsubstituted C5 to C 20 Selected from heteroarylene; Ar 2 is substituted or unsubstituted C 18 to C 40 Aryllene and substituted or unsubstituted C 10 to C 40 Selected from heteroarylenes; R 4 is H, C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 20 Aryl and substituted or unsubstituted C5 to C 20 Selected from heteroaryls; R 1 , R 2 , R 3 , R 4 , Ar 1 or Ar 2 In the case where is substituted, the substituent is C1 to C 12 Alkyl group and C1 to C 12 Organic light-emitting diode (100), one or more selected from heteroalkyl groups. Claim 7 In Paragraph 6,- Ar 1 This, substituted C6 to C 20 Aryllene and / or substituted C5 to C 20 Selected from heteroarylenes, wherein C6 to C 20 Aryllene and / or C5 to C 20 Heteroarylenes have one or more C1 to C1 12 alkyl and / or one or more C1 to C 12 Substituted with a heteroalkyl group; Ar 2 a, substituted C 18 to C 40 Aryllene and / or substituted C 10 to C 40 Selected from heteroarylenes, where C 18 to C 40 Arrylene and / or C 10 to C 40 Heteroarylenes have one or more C1 to C1 12 alkyl and / or one or more C1 to C 12 Organic light-emitting diode (100) substituted with a heteroalkyl group. Claim 8 In Paragraph 6, R 1 and R 2 independently, substituted C6 to C 20 aryl or substituted C5 to C 20 Selected from heteroaryls, wherein C6 to C 20 Aryl and / or C5 to C 20 Heteroaryl consists of one or more C1 to C1 12 alkyl and / or one or more C1 to C 12 Substituted with a heteroalkyl group; and / or R 3 This independently substituted C6 to C 20 Aryllene or substituted C5 to C 20 Selected from heteroarylenes, wherein C6 to C 20 Aryllene and / or C5 to C 20 Heteroarylenes have one or more C1 to C1 12 alkyl and / or one or more C1 to C 12 Substituted with a heteroalkyl group; and / or R 4 independently, substituted C6 to C 20 aryl or substituted C5 to C 20 Selected from heteroaryls, wherein C6 to C 20 Aryl and / or C5 to C 20 Heteroaryl consists of one or more C1 to C1 12 alkyl and / or one or more C1 to C 12 Organic light-emitting diode (100) substituted with a heteroalkyl group. Claim 9 In paragraph 6, where o = 2, the polar organic aromatic phosphine compound is a compound having formula Ib or: - When o = 1, the above polar organic aromatic phosphine compound is a compound having the formula Ic, Id, Ie or If, organic light-emitting diode (100): . Claim 10 In Paragraph 6, R 1 and R 2 independently, C1 to C4 alkyl, unsubstituted or substituted C6 to C 10 Aryl or unsubstituted or substituted C5 to C 10 Selected from heteroaryls, wherein C6 to C 10 Aryl and / or C5 to C 10 Heteroaryl consists of one or more C1 to C1 12 alkyl and / or one or more C1 to C 12 Substituted with a heteroalkyl group, or R 1 and R 2 is independently selected from methyl, phenyl, naphthyl, phenanthril, pyrenyl, or pyridyl; and / or X is O; and / or R 3 This C1 to C6 alkane-diyl, unsubstituted or substituted C6 to C 10 Aryllene or unsubstituted or substituted C5 to C 10 Selected from heteroarylenes; and / or R 4 g is selected from H, phenyl, biphenyl, terphenyl, fluorenyl, naphthyl, anthranil, phenanthril, pyrenyl, carbazoyl, dibenzofuranil, dinaphthofuranil; and / or n is 0, 1, or 2; m is 1 or 2 and n is 0 or 1, or m is 2 and n is 2; and / or Ar 1 This is selected from phenylene, biphenylene, terphenylene, naphthylene, fluorenylene, pyridylene, quinolinylene, and pyrimidinylene; and / or Ar 2 An organic light-emitting diode (100) selected from fluorenylene, anthranilene, pyrenylene, phenanthrylene, carbazoylene, benzo[c]acrydinylene, dibenzo[c,h]acrydinylene, and dibenzo[a,j]acrydinylene. Claim 11 In Paragraph 6, R 1 , R 2 , R 3 , R 4 , Ar 1 and / or Ar 2 An organic light-emitting diode (100) that is not substituted. Claim 12 In Paragraph 6, Ar 2 Organic light-emitting diode (100) selected from substituents according to formula IVa to IVh: . Claim 13 In claim 6, the organic light-emitting diode (100) wherein the polar organic aromatic phosphine compound is one compound selected from compounds according to the following formulas A1 to A41: Claim 14 A method for manufacturing an organic light-emitting diode (100) according to claim 1, comprising: a step of depositing an anode electrode on a substrate (110), and depositing other layers on the anode electrode in the corresponding order, such as a hole injection layer (130), a hole transport layer (140), an optional electron blocking layer (145), a light-emitting layer (150), an optional hole blocking layer (155), an electron transport layer stack (160) including at least a first electron transport layer (161) and a second electron transport layer (162), an optional electron injection layer (180), and a cathode electrode layer (191); or a step of depositing the layers in the reverse order, starting with the first cathode electrode layer (191). Claim 15 An electronic device comprising one or more organic light-emitting diodes (100) according to claim 1.
Citation Information
Patent Citations
Organic light emitting device and method for preparing the same
KR1020130037186A
Organic light-emitting diode (OLED) including an electron transport layer stack comprising different lithium compounds
WO2016001283A1
Organic electroluminescence device
KR1020140054330A
Organic light emitting diode
KR1020150115688A