Organic light emitting device

Abstract

The present invention provides an organic light emitting device having improved driving voltage, efficiency, and lifespan.

Description

Technical Field

[0001] Cross-references to related applications

[0002] This application claims priority based on Korean Patent Application No. 10-2022-0165647 filed on December 1, 2022 and Korean Patent Application No. 10-2023-0168055 filed on November 28, 2023, and incorporates all the contents disclosed in the documents of the Korean patent applications as part of this specification.

[0003] The present invention relates to an organic light emitting device having improved driving voltage, efficiency and lifespan. Background Art

[0004] Generally speaking, the organic light-emitting phenomenon refers to the phenomenon of converting electrical energy into light energy using organic substances. Organic light-emitting devices using the organic light-emitting phenomenon have wide viewing angles, excellent contrast, fast response time, and excellent brightness, driving voltage, and response speed characteristics, so a lot of research is being carried out.

[0005] An organic light-emitting device generally has a structure including an anode and a cathode and an organic layer located between the anode and the cathode. In order to improve the efficiency and stability of the organic light-emitting device, the organic layer is usually formed by a multilayer structure composed of different substances, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. For such an organic light-emitting device structure, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition back to the ground state, light is emitted.

[0006] For the organic light emitting devices as described above, there is a continuous demand for the development of organic light emitting devices having improved driving voltage, efficiency, and lifespan.

[0007] Prior art literature

[0008] Patent Literature

[0009] (Patent Document 0001) Korean Patent Publication No. 10-2000-0051826 Summary of the invention

[0010] Technical issues

[0011] The present invention relates to an organic light emitting device having improved driving voltage, efficiency and lifespan.

[0012] Solution to the problem

[0013] The present invention provides the following organic light-emitting device:

[0014] Including: anode;

[0015] cathode;

[0016] A light-emitting layer between the anode and the cathode;

[0017] a hole blocking layer between the cathode and the light-emitting layer; and

[0018] an electron transport layer, an electron injection layer, or an electron transport and injection layer between the hole blocking layer and the cathode,

[0019] The hole blocking layer includes a first compound represented by the following chemical formula 1:

[0020] The electron transport layer, the electron injection layer, or the electron transport and injection layer comprises a second compound represented by the following Chemical Formula 2:

[0021] The values ​​of the dipole moment of the first compound represented by the above Chemical Formula 1 and the dipole moment of the second compound represented by the above Chemical Formula 2 satisfy the following Formula 1:

[0022] [Chemical formula 1]

[0023]

[0024] In the above chemical formula 1,

[0025] X is O or S,

[0026] R 1 At least one of them is represented by the following chemical formula A, and the others are each independently hydrogen; deuterium; substituted or unsubstituted C 1-60 Alkyl; substituted or unsubstituted C 6-60 Aryl; and substituted or unsubstituted C containing any one or more heteroatoms selected from N, O, S and Si 2-60 Heteroaryl, or two adjacent R 1 Combined with each other to form a substituted or unsubstituted aromatic ring,

[0027] [Chemical formula A]

[0028]

[0029] In the above chemical formula A,

[0030] X 1 Each independently is N or CR 2 , and X 1 At least one of them is N,

[0031] R 2 is hydrogen or deuterium, or is adjacent to a substituent -(L2-- ) l2 -Ar 2 or -(L 3 ) l3 -Ar 3 Combined to form a substituted or unsubstituted aromatic ring,

[0032] L 1 To L 3 are each independently a single bond; substituted or unsubstituted C 6-60 Arylene; or a substituted or unsubstituted C containing any one or more heteroatoms selected from N, O, S and Si 2-60 Heteroarylene,

[0033] Ar 2 and Ar 3 are each independently substituted or unsubstituted C 1-60 Alkyl; substituted or unsubstituted C 1-60 Alkoxy; substituted or unsubstituted C 6-60 Aryl; substituted or unsubstituted C containing any one or more heteroatoms selected from N, O, S and Si 2-60 heteroaryl; or -Si(Z 1 )(Z 2 )(Z 3 ),

[0034] Among them, Z 1 To Z 3 are each independently substituted or unsubstituted C 1-60 Alkyl, or substituted or unsubstituted C 6-60 Aryl,

[0035] l 1 To 3 are each independently an integer from 1 to 3,

[0036] The above 1 When it is 2 or more, two or more L 1 Same or different from each other,

[0037] The above 2 When it is 2 or more, two or more L 2 Same or different from each other,

[0038] The above 3 When it is 2 or more, two or more L 3 Same or different from each other,

[0039] [Chemical formula 2]

[0040]

[0041] In the above chemical formula 2,

[0042] X 2 Each independently is N or CR 3 , and X 2 At least two of them are N,

[0043] X 3 Each independently is N or CR 4 , and X 3 At least two of them are N,

[0044] R 3 and R 4 are each independently hydrogen, deuterium, substituted or unsubstituted C 1-60 Alkyl, or substituted or unsubstituted C 6-60 Aryl, or two adjacent R 3 or R 4 Combined with each other to form a substituted or unsubstituted aromatic ring,

[0045] L 4 and L 5 are each independently a single bond, or a substituted or unsubstituted C 6-60 Arylene,

[0046] Ar 4 is phenylene or biphenyl diyl,

[0047] The above Ar 4 unsubstituted or substituted with one or more deuterium,

[0048] R 3 , R 4 and Ar 4 At least one of them is substituted by a cyano group,

[0049] But, L 4 and L 5 When Ar is a single bond, 4 is unsubstituted or deuterium-substituted phenylene or biphenyldiyl,

[0050] [Formula 1]

[0051] P EI >P EB +2

[0052] In the above formula 1,

[0053] P EI represents the dipole moment value of the compound represented by Chemical Formula 2,

[0054] P EB represents the dipole moment value of the compound represented by Chemical Formula 1.

[0055] Effects of the Invention

[0056] The above-mentioned organic light emitting device is excellent in driving voltage, efficiency and lifespan. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 The figure shows an example of an organic light-emitting device composed of a substrate 1 , an anode 2 , a light-emitting layer 3 , and a cathode 4 .

[0058] Figure 2 An example of an organic light-emitting device composed of a substrate 1 , an anode 2 , a hole injection layer 5 , a hole transport layer 6 , a light-emitting layer 3 , a hole blocking layer 7 , an electron transport and injection layer 8 , and a cathode 4 is shown. DETAILED DESCRIPTION

[0059] In the following, the present invention will be described in more detail to help understanding the present invention.

[0060] In this manual, It represents the bond to other substituents.

[0061] In the present specification, the term "substituted or unsubstituted" refers to a group selected from deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthio group Arylthio Alkylsulfonyl Arylsulfonyl Silyl; boryl; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; aralkenyl; alkylaryl; alkylamino; aralkylamino; heteroarylamino; arylamino; arylphosphino; or substituted or unsubstituted with one or more substituents in a heterocyclic group containing one or more N, O and S atoms, or substituted or unsubstituted with a substituent formed by connecting two or more substituents among the substituents exemplified above. For example, "a substituent formed by connecting two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may also be interpreted as a substituent formed by connecting two phenyl groups.

[0062] In the present specification, the number of carbon atoms in the carbonyl group is not particularly limited, but preferably the number of carbon atoms is 1 to 40. Specifically, the substituent may be a substituent of the following structure, but the substituent is not limited thereto.

[0063]

[0064] In the present specification, in the ester group, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, the substituents may be of the following structural formulas, but are not limited thereto.

[0065]

[0066] In the present specification, the number of carbon atoms in the imide group is not particularly limited, but the number of carbon atoms is preferably 1 to 25. Specifically, the substituent may be a substituent of the following structure, but the substituent is not limited thereto.

[0067]

[0068] In the present specification, specific examples of the silyl group include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, and phenylsilyl, but are not limited thereto.

[0069] In the present specification, specific examples of the boryl group include trimethylboryl, triethylboryl, tert-butyldimethylboryl, triphenylboryl, and phenylboryl, but the present invention is not limited thereto.

[0070] In the present specification, as examples of the halogen group, there are fluorine, chlorine, bromine or iodine.

[0071] In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 10. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 6. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, and 5-methylhexyl.

[0072] In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms of the alkenyl group is 2 to 20. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 10. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 6. As specific examples, there are vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthalene-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbene, styryl, etc., but are not limited thereto.

[0073] In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are not limited thereto.

[0074] In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. Regarding the aryl group, as a monocyclic aryl group, it may be phenyl, biphenyl, terphenyl, etc., but it is not limited thereto. As the polycyclic aryl group, it may be naphthyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, yl, fluorenyl, etc., but are not limited to these.

[0075] In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure. etc. However, the present invention is not limited thereto.

[0076] In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si and S as hetero elements, and the number of carbon atoms is not particularly limited, but preferably the number of carbon atoms is 2 to 60. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, Azolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzo oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophenyl, dibenzothiophenyl, benzofuranyl, phenanthroline, isothiophene oxazolyl, thiadiazolyl, phenothiazinyl and dibenzofuranyl, but are not limited thereto.

[0077] In this specification, an aromatic ring refers to a fused monocyclic ring or fused polycyclic ring containing only carbon atoms as ring atoms and having aromaticity as a whole molecule. The number of carbon atoms in the aromatic ring is 6 to 60, or 6 to 30, or 6 to 20, but is not limited thereto. In addition, the aromatic ring may be a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, etc., but is not limited thereto.

[0078] In the present specification, the aryl group in aralkyl, aralkenyl, alkylaryl, and arylamine is the same as the examples of the aryl group described above. In the present specification, the alkyl group in aralkyl, alkylaryl, and alkylamine is the same as the examples of the alkyl group described above. In the present specification, the heteroaryl group in heteroarylamine can be applied to the above-mentioned description of the heterocyclic group. In the present specification, the alkenyl group in aralkenyl is the same as the examples of the alkenyl group described above. In the present specification, the arylene group is a divalent group, and the above-mentioned description of the aryl group can be applied. In the present specification, the heteroarylene group is a divalent group, and the above-mentioned description of the heterocyclic group can be applied. In the present specification, the hydrocarbon ring is not a monovalent group, but two substituents are combined, and the above-mentioned description of the aryl group or cycloalkyl group can be applied. In the present specification, the heterocycle is not a monovalent group, but two substituents are combined, and the above-mentioned description of the heterocyclic group can be applied.

[0079] On the other hand, in order to improve the efficiency of organic light-emitting devices, as the electron transport layer material located in the electron transport region between the cathode and the light-emitting layer, a compound with a high dipole moment, that is, a compound with a high intramolecular polarity is used. However, when the electron transport layer containing such a compound with a high dipole moment is in contact with the light-emitting layer, the excitons generated at the interface are lost, which may cause the problem of reduced efficiency of the organic light-emitting device.

[0080] Therefore, the organic light-emitting device according to the present invention further includes a hole blocking layer between the light-emitting layer and the electron transport layer, wherein the hole blocking layer contains a compound having a smaller dipole moment value than the compound contained in the above-mentioned electron transport layer, thereby preventing excitons from being lost in the interface between the light-emitting layer and the electron transport layer.

[0081] Specifically, the dipole moment values ​​of the first compound contained in the hole blocking layer and the second compound contained in the electron transporting layer satisfy the following [Formula 1].

[0082] [Formula 1]

[0083] P EI >P EB +2

[0084] In the above formula 1,

[0085] P EI represents the dipole moment value of the compound represented by Chemical Formula 2,

[0086] P EB represents the dipole moment value of the compound represented by Chemical Formula 1.

[0087] As shown in Formula 1 above, when the difference between the dipole moment value of the second compound contained in the electron transport layer and the dipole moment value of the first compound contained in the hole blocking layer is greater than 2, the loss of excitons in the interface of the light-emitting layer is prevented, and the life of the organic light-emitting device can be improved.

[0088] For example, the dipole moment value of the first compound may be a value that is greater than +2, greater than +2.1, greater than +2.2, greater than +2.3, greater than +2.4, or greater than +2.5 of the dipole moment value of the second compound.

[0089] In addition, the more similar parts the first compound contained in the hole blocking layer and the second compound contained in the electron transport layer have, the smoother the migration of electrons along the cathode-electron transport layer-hole blocking layer-light-emitting layer can be formed. Therefore, it is required that the substances contained in the hole blocking layer and the electron transport layer have similar parts and have a dipole moment within the above range. In order to achieve the above requirements, the organic light-emitting device of the present invention contains the first compound represented by the above chemical formula 1 that does not contain a cyano group in the hole blocking layer as described below, and contains the second compound represented by the above chemical formula 2 that must contain a cyano group in the electron transport layer.

[0090] Therefore, the above-mentioned organic light-emitting device exhibits a hole blocking layer with a low dipole moment value due to the lack of cyano group, thereby preventing the loss of excitons in the light-emitting layer. At the same time, due to the compound substituted by cyano group, the density of the electron transport layer becomes higher, thereby showing high efficiency and increased life compared with an organic light-emitting device having a hole blocking layer containing a compound substituted by cyano group and an electron transport layer not containing a compound substituted by cyano group.

[0091] On the other hand, the dipole moment in the present invention is a physical quantity showing the degree of polarity, and can be calculated by the following mathematical formula 1, with the unit being "Debye (D)".

[0092] [Mathematical formula 1]

[0093]

[0094] ·ρ(r 0 ): molecular density

[0095] V: volume

[0096] r: the point of observation

[0097] ·d B r 0 : per unit volume (an elementary volume)

[0098] In the above mathematical formula 1, the value of the dipole moment can be obtained by calculating the molecular density. For example, the charge (Charge) and dipole (Dipole) of each atom can be obtained using the Hirshfeld Charge Analysis method, and the molecular density can be obtained by calculation according to the following formula, and the calculation result can be substituted into the above mathematical formula 1 to obtain the dipole moment.

[0099] Weight Function

[0100]

[0101] ·ρ α (rR α ): spherically averaged ground-state amomic density

[0102] · Promolecule density

[0103] Defomation Density

[0104]

[0105] ρ(r): molecular density

[0106] ·ρ a (rR a ): located at coordinate R a The density of the free atom αlocated at coordinates R a )

[0107] Atomic Charge

[0108] q(α)=-∫ρ d (r)W α (r)d 3 r

[0109] ·W α (r): Weight Function

[0110] In addition, in order to obtain an organic light-emitting device that can be driven at low voltage and has high efficiency, the holes and electrons injected into the organic light-emitting device should be smoothly transferred to the light-emitting layer, and the injected holes and electrons should not escape outside the light-emitting layer. To this end, a material with a suitable HOMO (Highest occupied molecular orbital) energy level, LUMO (Lowest Unoccupied Molecular Orbital) energy level and bandgap should be used. In particular, the LUMO energy level of the host material used for the light-emitting layer and the material used for the electron transport layer is important in adjusting the charge balance of the entire device.

[0111] At this time, the term "LUMO energy level" used in this specification refers to the distance from the vacuum energy level to the lowest unoccupied molecular orbital, and the "HOMO energy level" refers to the distance from the vacuum energy level to the highest occupied molecular orbital. Therefore, even when the energy level is expressed in the negative (-) direction from the vacuum energy level, it is interpreted that the energy level refers to the absolute value of the corresponding energy value.

[0112] Such LUMO energy level can be obtained after measuring the HOMO energy level, but the above HOMO energy level can be experimentally obtained by detecting the electrons knocked out when UV is irradiated on the surface of the film to measure the ionization potential (IP) of the substance by ultraviolet photoemission spectroscopy (UPS). At this time, the HOMO energy level and the LUMO energy level can be calculated as shown in the following mathematical formula 1,

[0113] [Mathematical formula 1]

[0114] HOMO(eV)=IP

[0115] LUMO (eV) = HOMO - optical gap

[0116] Alternatively, the HOMO level and the LUMO level can be measured using oxidation potential and reduction potential obtained by dissolving a target substance for measurement together with an electrolyte in a solvent and then performing a voltage sweep.

[0117] Specifically, the HOMO energy level can be determined by measuring the onset potential (E 开始 ), and the potential of ferrocene (E 1 / 2(Fc) ), and then the potential of ferrocene is set to 4.8 eV relative to the vacuum level, and the following mathematical formula 2 is used for calculation.

[0118] [Mathematical formula 2]

[0119] HOMO(eV)=4.8+(E 开始 -E 1 / 2(Fc) )

[0120] Furthermore, the LUMO energy level can be converted to the absorption edge wavelength (λ 边 ) is converted into a band gap and converted into energy units, and then calculated using the following mathematical formula 3. In this case, the band gap refers to the difference between the LUMO energy level and the HOMO energy level.

[0121] [Mathematical formula 3]

[0122] Bandgap (eV) = 1240 / λ 边

[0123] LUMO(eV)=HOMO(eV)-bandgap(eV)

[0124] On the other hand, the organic light-emitting device according to the present invention contains substances with specific LUMO energy levels in the hole blocking layer and the electron transport layer, the electron injection layer, or the electron transport and injection layer, respectively. The electrons injected from the cathode are smoothly transferred to the light-emitting layer, and the transferred electrons and holes are effectively recombined, thereby showing low driving voltage and high efficiency.

[0125] Specifically, the LUMO energy level of the first compound of the organic light-emitting device is 2.6eV to 2.85eV, and the LUMO energy level of the second compound is 2.85eV to 3.2eV. The hole blocking substance is a xanthene compound having a structure represented by the above chemical formula 1, and the electron transport and / or injection substance is an azine compound having a structure represented by the above chemical formula 2 containing at least one cyano group. When the LUMO energy level of the hole blocking substance exceeds the above range, it may cause the outflow of holes from the light-emitting layer to the adjacent layer. When the LUMO energy level of the electron transport and / or injection substance exceeds the above range, it may reduce the electron migration from the electron transport layer to the light-emitting layer. Therefore, according to the hole blocking layer and the electron transport layer of the present invention, the LUMO energy level of the molecules in which electrons can flow is appropriately arranged, so that the characteristics of the organic light-emitting device can be improved.

[0126] Hereinafter, the present invention will be described in detail according to each configuration.

[0127] Anode and cathode

[0128] The anode and cathode used in the present invention refer to electrodes used in an organic light emitting device.

[0129] As the above-mentioned anode material, in order to enable holes to be smoothly injected into the organic layer, it is preferred to use a material with a large work function. Specific examples of the above-mentioned anode material include metals such as vanadium, chromium, copper, zinc, gold, or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO:Al or SnO 2 : Combinations of metals such as Sb and oxides; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, etc., but are not limited to these.

[0130] The cathode material is preferably a material with a small work function in order to facilitate electron injection into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; LiF / Al or LiO 2 / Al and other multi-layer structure materials, but not limited to these.

[0131] Luminescent layer

[0132] The light-emitting substance contained in the light-emitting layer is a substance that can receive holes and electrons from the hole transport layer and the electron transport layer, respectively, and combine them to emit light in the visible light region, and is preferably a substance with high quantum efficiency for fluorescence or phosphorescence.

[0133] As a specific example, there is 8-hydroxy-quinoline aluminum complex (Alq 3); carbazole compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzo Compounds of the oxazole, benzothiazole and benzimidazole series; poly(p-phenylene vinylene) (PPV) series polymers; spiro compounds; polyfluorene, rubrene, etc., but are not limited to these.

[0134] The above-mentioned light-emitting layer may include a host material and a dopant material. The host material includes an aromatic fused ring derivative or a heterocyclic compound. Specifically, as an aromatic fused ring derivative, there are anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., as heterocyclic compounds, there are carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, etc. Pyrimidine derivatives, etc., but are not limited to these.

[0135] On the other hand, the dopant material is not particularly limited as long as it is a substance used in an organic light-emitting device. As an example, there are aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, etc. Specifically, the aromatic amine derivative is an aromatic condensed ring derivative having a substituted or unsubstituted arylamino group, and there are pyrene, anthracene, The styrylamine compound is a compound in which at least one arylvinyl group is substituted on a substituted or unsubstituted arylamine, and is substituted or unsubstituted with one or more substituents selected from aryl, silyl, alkyl, cycloalkyl and arylamino. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetramine, etc., but not limited thereto. In addition, as metal complexes, there are iridium complexes, platinum complexes, etc., but not limited thereto.

[0136] Hole transport layer

[0137] The organic light emitting device according to the present invention may include a hole transport layer between the above-mentioned light emitting layer and the anode.

[0138] The hole transport layer is a layer that can receive holes from the hole injection layer and transport the holes to the light-emitting layer. The hole transport material is a material that can receive holes from the anode or the hole injection layer and transfer them to the light-emitting layer. Materials with high hole mobility are suitable.

[0139] Specific examples of the hole transport material include arylamine-based organic substances, conductive polymers, and block copolymers having both a conjugated portion and a non-conjugated portion, but are not limited thereto.

[0140] Hole injection layer

[0141] The organic light emitting device according to the present invention may further include a hole injection layer between the anode and the hole transport layer as required.

[0142] The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material is preferably a compound that has the ability to transport holes, has the effect of injecting holes from the anode, has an excellent hole injection effect for the light-emitting layer or the light-emitting material, prevents the excitons generated in the light-emitting layer from migrating to the electron injection layer or the electron injection material, and has excellent thin film forming ability. In addition, it is preferred that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer.

[0143] Specific examples of hole injection materials include metal porphyrin, oligothiophene, aromatic amine organic matter, hexanitrile hexaazatriphenylene organic matter, quinacridone organic matter, perylene organic matter, anthraquinone, polyaniline and polythiophene conductive polymers, but are not limited to these.

[0144] Hole blocking layer

[0145] The hole blocking layer is formed on the light-emitting layer. Specifically, the hole blocking layer refers to a layer that is disposed in contact with the light-emitting layer and improves the probability of combining holes and electrons by preventing excessive migration of holes, thereby improving the efficiency of the organic light-emitting device. In particular, in the present invention, as a material for the hole blocking layer, the first compound represented by the above chemical formula 1 can be used.

[0146] Preferably, R 1 At least one of them is represented by the above chemical formula A, and the others are independently hydrogen, deuterium, methyl, n-propyl, n-butyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, dimethylfluorenyl or triphenylene, or two adjacent R 1 They are combined with each other to form a benzene ring which is unsubstituted or substituted with deuterium, wherein the phenyl group is unsubstituted or substituted with one or more deuterium, methyl or tert-butyl groups.

[0147] Preferably, R 1 One or both of are represented by the above chemical formula A.

[0148] Preferably, X 1 At least two of them are N.

[0149] Preferably, R -2 is hydrogen or deuterium, or is adjacent to a substituent -(L 2-- ) l2 -Ar 2 or -(L3 ) l3 -Ar 3 Combine to form unsubstituted or deuterium substituted benzene ring.

[0150] Preferably, 1 is 1 or 2,

[0151] L 1 Each of them is independently a single bond, phenylene, biphenyldiyl, naphthalenediyl, dibenzothiophenylene, dibenzofuranylene, dimethylfluorenylene, furanylene, thienylene, carbazol-9-ylene, pyridylene, indole dimethylfluorenylene, 9-phenylcarbazolylene, dimethylsilylfluorenylene, phenanthene Thiol, phenoxy Oxazine, 9-phenylbenzocarbazolyl, or 9-benzocarbazolyl, wherein the above L 1 Unsubstituted or substituted with one or more deuterium, methyl, phenyl or dimethylphenyl groups.

[0152] More preferably, the phenylene group is unsubstituted or substituted with one or more deuterium or methyl groups, and the 9-phenylcarbazolylene and 9-phenylbenzocarbazolylene groups are unsubstituted or substituted with one or more deuterium, methyl, phenyl or dimethylphenyl groups.

[0153] Preferably, 2 and l 3 Each independently is 1 or 2, L 2 and L 3 Each of them is independently a single bond, a phenylene group, a biphenyldiyl group, a dibenzothienyl group, a dibenzofuranyl group, a carbazole-9-yl group, or a 9-phenylcarbazole-9-yl group, wherein the above L 2 and L 3 When L is phenylene, biphenyldiyl, dibenzothienyl, dibenzofuranyl, carbazole-9-yl and 9-phenylcarbazolyl, 2 and L 3 It may be unsubstituted or substituted with any one or more substituents selected from one or more deuterium, methyl, phenyl and tolyl.

[0154] Preferably, Ar 2 and Ar 3 Each of them is independently phenyl, biphenyl, naphthyl, terphenyl, triphenylene, phenanthrenyl, dimethylfluorenyl, phenanthryl, fluoranthenyl, carbazole-9-yl, 9-phenylcarbazolyl, dibenzothiophene, phenanthrenyl, Azinyl, phenylene Thiol, phenothiazinyl, benzocarbazolyl, dibenzofuranyl, pyridyl, indole dimethyl fluorenyl, phenyl indole dimethyl fluorenyl, dimethyl silyl fluorenyl, triphenylsilyl, dimethyl acridinyl, or quinolyl, wherein the above Ar 2 and Ar3 Unsubstituted or substituted with any one or more substituents selected from the group consisting of deuterium, cyano, methyl, trifluoromethyl, trifluoromethoxy, phenyl substituted with cyano, trimethylsilyl, triphenylsilyl, carbazole-9-yl, dibenzothienyl and dibenzofuranyl.

[0155] Representative examples of the first compound represented by the above Chemical Formula 1 are shown below:

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294] On the other hand, R in the first compound represented by the above Chemical Formula 1 1 When any one of them is represented by the above chemical formula A and the rest are hydrogen, as an example, it can be produced by the production method shown in the following reaction formula 1, and the remaining compounds can also be produced by a similar method.

[0295] [Reaction 1]

[0296]

[0297] In the above reaction formula 1, except for Z, the rest are the same as the above definitions, and Z is a halogen, preferably bromine or chlorine.

[0298] The above reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactive group used in the above reaction can be changed according to the technique known in the art. The above production method can be further embodied in the production examples described below.

[0299] Electron transport layer, electron injection layer, or electron transport and injection layer

[0300] The organic light emitting device according to the present invention may include an electron transport layer, an electron injection layer, or an electron transport and injection layer between the above-mentioned light emitting layer and the cathode.

[0301] The electron transport layer is a layer that receives electrons from the cathode or the electron injection layer formed on the cathode and transports the electrons to the light-emitting layer, and inhibits the transfer of holes from the light-emitting layer. The electron transport substance is a substance that can well receive electrons from the cathode and transfer them to the light-emitting layer. It is suitable for substances with high electron mobility. In the present invention, it may include a compound represented by the above chemical formula 2.

[0302] The electron injection layer is a layer for injecting electrons from the electrode, and preferably uses the following compounds: compounds that have the ability to transport electrons, have the effect of injecting electrons from the cathode, have an excellent electron injection effect on the light-emitting layer or the light-emitting material, prevent the excitons generated in the light-emitting layer from migrating to the hole injection layer, and have excellent thin film forming ability. In the present invention, the compound represented by the above chemical formula 2 may be included.

[0303] The electron transport and injection layer is a layer that simultaneously transports and injects electrons, and may include the second compound represented by Chemical Formula 2.

[0304] Preferably, R 3 and R 4 are independently hydrogen, deuterium, methyl, isopropyl, phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenylnaphthylphenyl or pyridyl, or are combined with each other to form an unsubstituted or deuterium-substituted benzene ring, wherein the above R 3 and R 4 It is unsubstituted or substituted with any one or more substituents selected from methyl, tert-butyl, cyclohexyl and cyano.

[0305] Preferably, L 4 and L 5 Each is independently a phenylene group, a biphenylene group or a naphthylene group.

[0306] As an example, the above substituent -L 4 -Ar 4 -L 5 - may be any one selected from the group consisting of the following substituents:

[0307]

[0308] In the above group,

[0309] a is an integer from 0 to 4,

[0310] b is an integer from 0 to 3,

[0311] c is an integer from 0 to 6.

[0312] Representative examples of the second compound represented by the above Chemical Formula 2 are shown below:

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368] On the other hand, as an example, the second compound represented by the above Chemical Formula 2 can be produced by the production method shown in the following Reaction Formula 2, and the remaining compounds can also be produced by a similar method.

[0369] [Reaction 2]

[0370]

[0371] In the above reaction formula 2, except for Z, the rest are the same as the above definitions, and Z is a halogen, preferably bromine or chlorine.

[0372] The above reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactive group used in the above reaction can be changed according to the techniques known in the art. The above production method can be further embodied in the production examples described below.

[0373] The electron transport layer may further include a metal coordination compound. Specific examples of the metal coordination compound include an Al complex of 8-hydroxyquinoline, an Alq 3 The electron transport layer can be used together with any desired cathode material as used in the prior art. In particular, examples of suitable cathode materials are conventional materials with a low work function and accompanied by an aluminum layer or a silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in each case accompanied by an aluminum layer or a silver layer.

[0374] Specific examples of the substance that can be used as the electron injection layer include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azoles, Examples include, but are not limited to, diazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylene methane, anthrone, and derivatives thereof, metal coordination compounds, and nitrogen-containing five-membered ring derivatives.

[0375] Examples of the metal coordination compounds include, but are not limited to, 8-hydroxyquinoline lithium, bis(8-hydroxyquinoline) zinc, bis(8-hydroxyquinoline) copper, bis(8-hydroxyquinoline) manganese, tris(8-hydroxyquinoline) aluminum, tris(2-methyl-8-hydroxyquinoline) aluminum, tris(8-hydroxyquinoline) gallium, bis(10-hydroxybenzo[h]quinoline) beryllium, bis(10-hydroxybenzo[h]quinoline) zinc, bis(2-methyl-8-hydroxyquinoline) gallium chloride, bis(2-methyl-8-hydroxyquinoline)(o-cresol) gallium, bis(2-methyl-8-hydroxyquinoline)(1-naphthol) aluminum, and bis(2-methyl-8-hydroxyquinoline)(2-naphthol) gallium.

[0376] Organic light-emitting devices

[0377] The structure of the organic light emitting device according to the present invention is shown in Figure 1 . Figure 1 The figure shows an example of an organic light-emitting device composed of a substrate 1 , an anode 2 , a light-emitting layer 3 , and a cathode 4 . Figure 2 An example of an organic light-emitting device composed of a substrate 1 , an anode 2 , a hole injection layer 5 , a hole transport layer 6 , a light-emitting layer 3 , a hole blocking layer 7 , an electron transport and injection layer 8 , and a cathode 4 is shown.

[0378] The organic light-emitting device according to the present invention can be manufactured by stacking the above-mentioned structures in sequence. In this case, it can be manufactured as follows: a metal or a conductive metal oxide or an alloy thereof is evaporated on a substrate to form an anode using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation, and then the above-mentioned layers are formed on the anode, and then a substance that can be used as a cathode is evaporated thereon to manufacture. In addition to this method, an organic light-emitting device can also be manufactured by evaporating from a cathode material to an anode material in the reverse order of the above-mentioned structure on a substrate (WO 2003 / 012890). In addition, the main body and the dopant can be formed into a light-emitting layer not only by vacuum evaporation method, but also by solution coating method. Here, the so-called solution coating method refers to spin coating method, dip coating method, blade coating method, inkjet printing method, screen printing method, spray method, roller coating method, etc., but is not limited to this.

[0379] In addition to this method, an organic light emitting device can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003 / 012890). However, the manufacturing method is not limited to this.

[0380] On the other hand, the organic light-emitting device according to the present invention may be a bottom emission device, a top emission device, or a bidirectional light-emitting device, and in particular, may be a bottom emission device requiring relatively high light-emitting efficiency.

[0381] Below, preferred embodiments are presented to help understand the present invention. However, the following embodiments are provided only to make the present invention easier to understand, and the content of the present invention is not limited thereto.

[0382] [Manufacturing example]

[0383] Preparation Example 1: Preparation of Compound H1

[0384]

[0385] Under nitrogen atmosphere, H1-A (20 g, 43.6 mmol) and H1-B (16.9 g, 43.6 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. Then, potassium carbonate (18.1 g, 130.9 mmol) was dissolved in 18 ml of water and added. After sufficient stirring, tetrakis(triphenylphosphine)palladium (1.5 g, 1.3 mmol) was added. After reacting for 2 hours, the organic layer and the aqueous layer were separated after cooling to room temperature, and the organic layer was distilled. It was put into 557 ml of chloroform again and dissolved, washed with water twice, and then the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound H1 (16.4 g, 59%).

[0386] MS:[M+H] + =639

[0387] Preparation Example 2: Preparation of Compound H2

[0388]

[0389] The compound H2 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0390] MS:[M+H] + =537

[0391] Preparation Example 3: Preparation of Compound H3

[0392]

[0393] The compound H3 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0394] MS:[M+H] + =728

[0395] Preparation Example 4: Preparation of Compound H4

[0396]

[0397] Under nitrogen atmosphere, H4-A (20 g, 34.2 mmol) and H4-B (9.2 g, 34.2 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. Then, potassium carbonate (14.2 g, 102.7 mmol) was dissolved in 14 ml of water and added. After sufficient stirring, tetrakis(triphenylphosphine)palladium (1.2 g, 1 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was again added to 544 ml of chloroform and dissolved, washed with water twice, and the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound H4 (19 g, 70%).

[0398] MS:[M+H] + =795

[0399] Preparation Example 5: Preparation of Compound H5

[0400]

[0401] The compound H5 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0402] MS:[M+H] + =762

[0403] Preparation Example 6: Preparation of Compound H6

[0404]

[0405] The compound H6 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0406] MS:[M+H] + =640

[0407] Preparation Example 7: Preparation of Compound H7

[0408]

[0409] The compound H7 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0410] MS:[M+H] + =640

[0411] Preparation Example 8: Preparation of Compound H8

[0412]

[0413] The compound H8 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0414] MS:[M+H] + =690

[0415] Preparation Example 9: Preparation of Compound H9

[0416]

[0417] The compound H9 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0418] MS:[M+H] + =746

[0419] Preparation Example 10: Preparation of Compound H10

[0420]

[0421] The compound H10 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0422] MS:[M+H] + =792

[0423] Preparation Example 11: Preparation of Compound E1

[0424]

[0425] Under nitrogen atmosphere, E1-A (20 g, 76.7 mmol) and E1-B (66.8 g, 153.4 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. Then, potassium carbonate (31.8 g, 230 mmol) was dissolved in 32 ml of water and added. After sufficient stirring, tetrakis(triphenylphosphine)palladium (2.7 g, 2.3 mmol) was added. After reacting for 1 hour, the organic layer and the aqueous layer were separated after cooling to room temperature, and the organic layer was distilled. It was put into 1100 ml of chloroform again and dissolved, washed with water twice, and then the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was filtered after stirring. The filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to produce a white solid compound E1 (27.5 g, 50%).

[0426] MS:[M+H] + =718

[0427] Preparation Example 12: Preparation of Compound E2

[0428]

[0429] The compound E2 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0430] MS:[M+H] + =718

[0431] Preparation Example 13: Preparation of Compound E3

[0432]

[0433] The compound E3 was produced by the same method as in Synthesis Example 11 except that the starting materials were used as in the above reaction formula.

[0434] MS:[M+H] + =744

[0435] Preparation Example 14: Preparation of Compound E4

[0436]

[0437] The compound E4 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0438] MS:[M+H] + =594

[0439] Preparation Example 15: Preparation of Compound E5

[0440]

[0441] The compound E5 was produced by the same method as in Synthesis Example 11 except that the starting materials were used as in the above reaction formula.

[0442] MS:[M+H] + =794

[0443] Preparation Example 16: Preparation of Compound E6

[0444]

[0445] The compound E6 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0446] MS:[M+H] + =794

[0447] Preparation Example 17: Preparation of Compound E7

[0448]

[0449] The compound E7 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0450] MS:[M+H] + =718

[0451] Preparation Example 18: Preparation of Compound E8

[0452]

[0453] The compound E8 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0454] MS:[M+H] + =794

[0455] Preparation Example 19: Preparation of Compound E9

[0456]

[0457] The compound E9 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0458] MS:[M+H] + =799

[0459] Preparation Example 20: Preparation of Compound E10

[0460]

[0461] The compound E10 was produced by the same method as in Synthesis Example 1 except that the starting materials were used as in the above reaction formula.

[0462] MS:[M+H] + =691

[0463] [Example]

[0464] Embodiment 1: Device Example

[0465] ITO (indium tin oxide) is used The glass substrate coated with a film of a thickness of 10000 mm was placed in distilled water dissolved with a detergent and washed with ultrasonic waves. At this time, the detergent used a product of Fischer Co., and the distilled water used distilled water filtered twice by a filter manufactured by Millipore Co. After ITO was washed for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes. After the distilled water washing was completed, ultrasonic washing was carried out with a solvent of isopropanol, acetone, and methanol and dried, and then transported to a plasma cleaning machine. In addition, after the above-mentioned substrate was cleaned for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

[0466] On the ITO transparent electrode prepared in this way, the following HI-A compound was applied as The following HAT compounds were sequentially vacuum-deposited on the hole injection layer: and the following HT-A compound Then, on the second hole transport layer, a film thickness of The following BH compound and compound BD were vacuum deposited at a weight ratio of 50:1 to form a light-emitting layer. On the light-emitting layer, compound H1 prepared in the above-mentioned preparation example 1 was deposited at a weight ratio of 50:1. The hole blocking layer was formed by vacuum evaporation at a thickness of 1:1, and the compound E1 prepared in the above-mentioned Preparation Example 11 and the following LiQ compound were vacuum evaporated at a weight ratio of 1:1, so as to form a hole blocking layer. On the electron transport and injection layer, lithium fluoride (LiF) is sequentially The thickness of the aluminum A cathode is formed by evaporation with a thickness of .

[0467] In the above process, the evaporation rate of organic matter is maintained to Lithium fluoride at cathode maintains The evaporation speed of aluminum is maintained The evaporation speed is 1*10 -7 Up to 5*10 -5 A support is provided to manufacture an organic light-emitting device.

[0468]

[0469] Examples 2 to 100

[0470] An organic light-emitting device was manufactured by the same method as in Example 1-1, except that the compounds described in Table 1 below were used instead of the compounds H1 and E1 in Example 1-1.

[0471] Comparative Examples 1 to 100

[0472] An organic light-emitting device was manufactured by the same method as in Example 1, except that the compounds listed in Table 1 below were used instead of the compounds H1 and E1 in Example 1.

[0473]

[0474] Experimental Example 1: Device Characteristics Evaluation

[0475] For the organic light emitting devices manufactured in the above Examples 1 to 100 and Comparative Examples 1 to 100, the 2 The driving voltage and luminous efficiency were measured at a current density of 20 mA / cm 2 The time (T90) until the initial luminance reaches 90% was measured at a current density of 1.3 Å, and the results are shown in Table 1 below. In addition, the LUMO level value of each compound is shown in Table 1 below.

[0476] On the other hand, the calculation of the above-mentioned LUMO energy level (eV) can be performed using the quantum chemical calculation program DMol3 manufactured by Biovia. For the structure optimized using density functional theory (DFT) using Bpw91 as a functional and dnd as a basis function, the calculated value of the dipole moment is obtained by time-dependent density functional theory (TD-DFT).

[0477]

Table 1

[0478]

[0479]

[0480]

[0481]

[0482]

[0483]

[0484]

[0485]

[0486]

[0487]

[0488]

[0489]

[0490]

[0491] As shown in Table 1, it is confirmed that the organic light-emitting device in which the compound represented by Chemical Formula 1 is used in the hole blocking layer and the compound represented by Chemical Formula 2 is used in the electron transporting region shows significant effects in terms of driving voltage, efficiency and lifespan.

[0492] By comparing Examples 1 to 100 of Table 1 above with Comparative Examples 21 to 40 and devices in which the compound represented by Chemical Formula 1 is used for the hole blocking layer and ET-5 or ET-6 is used for the electron transport layer (Comparative Examples 45, 46, 51, 52, 57, 58, 63, 64, 69, 70, 75, 76, 81, 82, 87, 88, 93, 94, 99 and 100), it can be confirmed that the organic light-emitting device according to the present invention shows significantly excellent characteristics in terms of lifespan.

[0493] Experimental Example 2

[0494] The dipole moment (Debye) values ​​of chemical formulas H1 to H10, E1 to E10, HB-1 to HB-2, and ET-1 to ET-6 according to one embodiment of the present specification and whether Formula 1 is satisfied in the organic light-emitting devices of Examples 1 to 100 and Comparative Examples 1 to 101 are shown in Table 2 below.

[0495]

Table 2

[0496]

[0497]

[0498]

[0499]

[0500]

[0501]

[0502]

[0503]

[0504]

[0505]

[0506]

[0507]

[0508]

[0509] The above-mentioned calculation of the dipole moment (Debye) was performed using Gaussian 03, a quantum chemical calculation program manufactured by Gaussian Corporation of the United States. The structure was optimized using density functional theory (DFT) with B3LYP as the functional and 6-31G* as the basis function, and the calculated value of the dipole moment was obtained using time-dependent density functional theory (TD-DFT).

[0510] [Explanation of symbols]

[0511] 1: Substrate 2: Anode

[0512] 3: Light-emitting layer 4: Cathode

[0513] 5: Hole injection layer 6: Hole transport layer

[0514] 7: Hole blocking layer 8: Electron transport and injection layer.

Claims

1. An organic light-emitting device, comprising: anode; cathode; A light-emitting layer between the anode and the cathode; A hole blocking layer between the cathode and the light-emitting layer; as well as an electron transport layer, an electron injection layer, or an electron transport and injection layer between the hole blocking layer and the cathode, The hole blocking layer includes a first compound represented by the following Chemical Formula 1, The electron transport layer, the electron injection layer, or the electron transport and injection layer includes a second compound represented by the following Chemical Formula 2, The dipole moment of the first compound represented by the chemical formula 1 and the dipole moment of the second compound represented by the chemical formula 2 satisfy the following formula 1: [Chemical formula 1] In the chemical formula 1, X is O or S, At least one of R1 is represented by the following chemical formula A, and the others are independently hydrogen; deuterium; substituted or unsubstituted C 1-60 Alkyl; substituted or unsubstituted C 6-60 Aryl; and substituted or unsubstituted C containing any one or more heteroatoms selected from N, O, S and Si 2-60 heteroaryl, or two adjacent R1s are bonded to each other to form a substituted or unsubstituted aromatic ring, [Chemical formula A] In the chemical formula A, X1 is each independently N or CR2, and at least one of X1 is N, R2 is hydrogen or deuterium, or is in a state of being ... 2-- ) l2 -Ar2 or -(L3) l3 -Ar3 combines to form a substituted or unsubstituted aromatic ring, L1 to L3 are each independently a single bond; substituted or unsubstituted C 6-60 Arylene; or a substituted or unsubstituted C containing any one or more heteroatoms selected from N, O, S and Si 2-60 Heteroarylene, Ar2 and Ar3 are each independently substituted or unsubstituted C 1-60 Alkyl; substituted or unsubstituted C 1-60 Alkoxy; substituted or unsubstituted C 6-60 Aryl; substituted or unsubstituted C containing any one or more heteroatoms selected from N, O, S and Si 2-60 heteroaryl; or -Si(Z1)(Z2)(Z3), wherein Z1 to Z3 are each independently substituted or unsubstituted C 1-60 Alkyl, or substituted or unsubstituted C 6-60 Aryl, l1 to l3 are each independently an integer from 1 to 3, When the number of L1 is 2 or more, two or more L1 are the same or different from each other. When the L2 is 2 or more, two or more L2 are the same or different from each other. When the number of L3 is 2 or more, two or more L3 are the same or different from each other. [Chemical formula 2] In the chemical formula 2, X2 are each independently N or CR3, and at least two of X2 are N, X3 are each independently N or CR4, and at least two of X3 are N, R3 and R4 are each independently hydrogen, deuterium, substituted or unsubstituted C 1-60 Alkyl, or substituted or unsubstituted C 6-60 aryl, or two adjacent R3 or R4 are combined with each other to form a substituted or unsubstituted aromatic ring, L4 and L5 are each independently a single bond, or a substituted or unsubstituted C 6-60 Arylene, Ar4 is phenylene or biphenyl diyl, Ar4 is unsubstituted or substituted with one or more deuteriums, At least one of R3, R4 and Ar4 is substituted by a cyano group, However, when L4 and L5 are single bonds, Ar4 is an unsubstituted or deuterium-substituted phenylene or biphenyl diyl group, [Formula 1] P EI >P EB +2 In the formula 1, P EI represents the dipole moment value of the compound represented by Chemical Formula 2, P EB represents the dipole moment value of the compound represented by Chemical Formula 1.

2. The organic light emitting device according to claim 1, wherein: The LUMO energy level of the first compound is 2.6 eV to 2.85 eV, The second compound has a LUMO energy level of 2.85 eV to 3.2 eV.

3. The organic light emitting device according to claim 1, wherein: At least one of R1 is represented by the chemical formula A, and the others are independently hydrogen, deuterium, methyl, n-propyl, n-butyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, dimethylfluorenyl or triphenylene, or two adjacent R1 are combined to form an unsubstituted or deuterium-substituted benzene ring, The phenyl group is unsubstituted or substituted with one or more deuterium, methyl or tert-butyl groups.

4. The organic light emitting device according to claim 1, wherein: One or both of R1 are represented by the chemical formula A.

5. The organic light emitting device according to claim 1, wherein: At least two of X1 are N.

6. The organic light emitting device according to claim 1, wherein: R -2 is hydrogen or deuterium, or is adjacent to a substituent -(L 2-- ) l2 -Ar2 or -(L3) l3 -Ar3 combines to form an unsubstituted or deuterium-substituted benzene ring.

7. The organic light emitting device according to claim 1, wherein: l1 is 1 or 2, L1 is each independently a single bond, phenylene, biphenyldiyl, naphthalenediyl, dibenzothiophenylene, dibenzofuranyl, dimethylfluorenylene, furanylene, thienylene, carbazol-9-ylene, pyridylene, indole dimethylfluorenylene, 9-phenylcarbazolylene, dimethylsilylfluorenylene, phenanthene-9-ylene, Thiol, phenoxy Azine group, a 9-phenylbenzocarbazolyl group, or a 9-phenylbenzocarbazolyl group, Wherein, the L1 is unsubstituted or substituted with one or more deuterium, methyl, phenyl or dimethylphenyl.

8. The organic light emitting device according to claim 1, wherein: l2 and L3 are each independently 1 or 2, L2 and L3 are each independently a single bond, a phenylene group, a biphenyldiyl group, a dibenzothienyl group, a dibenzofuranyl group, a carbazol-9-yl group, or a 9-phenylcarbazolyl group, Wherein, when L2 and L3 are phenylene, biphenylene, dibenzothiophenylene, dibenzofuranene, carbazole-9-yl and 9-phenylcarbazole-9-yl, L2 and L3 are unsubstituted or substituted by any one or more substituents selected from one or more deuterium, methyl, phenyl and tolyl.

9. The organic light emitting device according to claim 1, wherein: Ar2 and Ar3 are each independently phenyl, biphenyl, naphthyl, terphenyl, triphenylene, phenanthrenyl, dimethylfluorenyl, phenanthrenyl, fluoranthenyl, carbazole-9-yl, 9-phenylcarbazolyl, dibenzothiophene, phenanthrenyl, Azinyl, phenylene thiol, phenothiazinyl, benzocarbazolyl, dibenzofuranyl, pyridyl, indolodimethylfluorenyl, phenylindolodimethylfluorenyl, dimethylsilylfluorenyl, triphenylsilyl, dimethylacridinyl or quinolyl, Wherein, Ar2 and Ar3 are unsubstituted or substituted by any one or more substituents selected from deuterium, cyano, methyl, trifluoromethyl, trifluoromethoxy, phenyl substituted by cyano, trimethylsilyl, triphenylsilyl, carbazole-9-yl, dibenzothienyl and dibenzofuranyl.

10. The organic light emitting device according to claim 1, wherein: The first compound represented by the chemical formula 1 is any one selected from the following compounds:

11. The organic light emitting device according to claim 1, wherein: R3 and R4 are each independently hydrogen, deuterium, methyl, isopropyl, phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenylnaphthylphenyl or pyridyl, or are combined with each other to form a benzene ring which is unsubstituted or substituted with deuterium, Wherein, R3 and R4 are unsubstituted or substituted by any one or more substituents selected from methyl, tert-butyl, cyclohexyl and cyano.

12. The organic light emitting device according to claim 1, wherein: L4 and L5 are each independently a phenylene group, a biphenyldiyl group or a naphthylene group.

13. The organic light emitting device according to claim 1, wherein: The second compound represented by the chemical formula 2 is any one selected from the following compounds:

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