Organic light-emitting device

Abstract

The present invention relates to a tandem organic light-emitting device comprising a plurality of light-emitting layers and, more specifically, to an organic light-emitting device comprising a novel charge generation layer (CGL). The CGL according to the present invention has a first compound having 4,5-diazaspirobifluorene as the core thereof, which is applied as an electron transport material of an N-type CGL. In addition, a second compound having at least one tertiary amine as the core thereof is applied as a hole transport material of a P-type CGL, and the combination of the first compound and the second compound lowers the driving voltage of the device and further improves the efficiency and lifespan thereof. Furthermore, the organic light-emitting device of the present invention can achieve further improved device performance through a CGL comprising the first compound, lithium or ytterbium, the second compound and a third compound at the same time.

Description

organic light-emitting diode

[0001] The present invention relates to a tandem type organic light emitting device including a plurality of light emitting layers, and more specifically, to an organic light emitting device including a novel charge generation layer (CGL).

[0002] The technology of organic light emitting devices (OLEDs), one of the currently widely used flat panel display devices, is developing rapidly.

[0003] In general, an organic light-emitting device has an organic thin film layer including a light-emitting layer formed between an anode (hole injection electrode) and a cathode (electron injection electrode), and has a principle of emitting light when holes injected from the anode and electrons injected from the cathode pair up in the light-emitting layer and then disappear.

[0004] More specifically, the organic light-emitting device is configured to include an organic thin film layer formed between an anode and a cathode, and the organic thin film layer may be configured to include a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer sequentially laminated on the anode, and holes injected from the anode and electrons injected from the cathode combine in the light-emitting layer to form excitons, which enter an unstable energy state (excited state) and then return to a stable ground state to emit light.

[0005] In the development of organic light-emitting devices, high efficiency, long lifespan, color purity, color stability according to changes in current and voltage, and ease of device manufacturing are important, so research and development are in progress according to each method. The structure of organic light-emitting devices can be broadly divided into a single-layer light-emitting structure with one light-emitting layer and a multilayer light-emitting structure with two or more light-emitting layers. Among these, a tandem structure of a multilayer light-emitting structure that stacks two or more light-emitting layers is mainly adopted for organic light-emitting devices with long lifespan.

[0006] Meanwhile, an organic light-emitting device having a tandem structure such as this is provided with a charge generation layer (CGL) between the light-emitting layers to double the current efficiency generated in the light-emitting layer and to facilitate charge distribution. This charge generation layer is a layer that generates charges, that is, electrons and holes, and performs the role of preventing an increase in the driving voltage by doubling the current efficiency generated in the light-emitting layer and facilitating charge distribution. This charge generation layer is generally composed of a P-type charge generation layer and an N-type charge generation layer.

[0007] If charge transport is disrupted or current leakage occurs due to differences in energy levels in these charge-generation layers, the amount of electrons transported to other light-emitting layers decreases, leading to a gradual increase in operating voltage and a negative impact on lifespan. Therefore, with the growing demand for high-performance devices, the development of charge-generation layers is also becoming increasingly necessary.

[0008] The purpose of the present invention is to lower the driving voltage and improve the efficiency and lifespan by introducing a novel charge generation layer (CGL) into a tandem organic light-emitting device including a plurality of light-emitting layers.

[0009] The present invention relates to a tandem organic light-emitting device, comprising: a first electrode and a second electrode; a plurality of light-emitting portions positioned between the first electrode and the second electrode; and a charge generation layer positioned at at least one position between two adjacent light-emitting portions; wherein at least one of the charge generation layers includes an N-type charge generation layer and a P-type charge generation layer, and the N-type charge generation layer includes a first compound represented by the following chemical formula 1.

[0010]

[0011] In the above chemical formula 1,

[0012] L1 to L4 are each independently a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,

[0013] Ar1 to Ar4 are each independently selected from the group consisting of deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted sulfide group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryloxy group, substituted or unsubstituted thio group, substituted or unsubstituted amine group, substituted or unsubstituted silyl group, and substituted or unsubstituted phosphine oxide group,

[0014] m and p are each independently integers from 0 to 4,

[0015] n and o are each independently integers from 0 to 3,

[0016] However, m+n+o+p is greater than or equal to 1.

[0017] The present invention introduces a novel charge generation layer (CGL) into a tandem organic light-emitting device comprising a plurality of light-emitting layers, thereby enabling the implementation of low voltage, high efficiency, and long lifespan. More specifically, by applying a 4,5-diazaspirobifluorene compound to the N-type charge generation layer and introducing a charge generation layer comprising a compound containing one or more tertiary amines to the P-type charge generation layer, the present invention has the effects of lowering the driving voltage and improving efficiency and lifespan.

[0018] FIG. 1 is a schematic diagram showing a tandem organic light-emitting device according to an embodiment of the present invention.

[0019] In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted.

[0020] In this specification, when a part is said to 'include' a certain component, this does not mean that other components are excluded, but rather that other components may be included, unless otherwise specifically stated.

[0021] In this specification, when it is said that a member is located 'on' another member, this includes not only cases where a member is in contact with another member, but also cases where another member exists between the two members.

[0022] When describing components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only intended to distinguish the components from other components, and the nature, order, or sequence of the components are not limited by the terms. When it is described that a component is "connected," "coupled," or "connected" to another component, it should be understood that the component may be directly connected or connected to the other component, but another component may also be "connected," "coupled," or "connected" between each component.

[0023] In this specification, examples of substituents are described below, but are not limited thereto.

[0024] As used herein, the term "substitution" refers to the replacement of a hydrogen atom bonded to a carbon atom of a compound with another substituent. The position of substitution is not particularly limited as long as it is a position where substitution is possible, and when substitution is made with two or more substituents, the substituents may be the same or different.

[0025] In this specification, the term 'substituted or unsubstituted' means that it is substituted with one or more substituents selected from the group consisting of deuterium, halogen, cyano, nitro, nitrile, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, alkoxy, sulfide, aryloxy, heteroaryloxy, thio, amine, silyl, phosphine oxide, aryl, and heteroaryl groups, or is substituted with a substituent in which two or more substituents selected from the above group are connected, or has no substituents, and the selected substituents may or may not form a ring by combining with each other. An example of a substituent in which two or more substituents are connected is a biphenyl group. That is, a biphenyl group may correspond to an aryl group and at the same time correspond to a substituent having two phenyl groups connected, and at the same time correspond to an aryl group having one phenyl group substituted.

[0026] In the present specification, the alkyl group may be a straight or branched chain having 1 to 60 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 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-ethylpropyl, Examples thereof include, but are not limited to, 1,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl. Specifically, the alkyl group may have 1 to 30 carbon atoms, and more specifically, 1 to 20 carbon atoms.

[0027] In the present specification, the alkenyl group may be a straight or branched chain having 2 to 60 carbon atoms, and specific examples thereof include, but are not limited to, a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 3-methyl-1-butenyl group, a 1,3-butadienyl group, an allyl group, a 1-phenylvinyl-1-yl group, a 2-phenylvinyl-1-yl group, a 2,2-diphenylvinyl-1-yl group, a 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, a 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, a stilbenyl group, and a styrenyl group. Specifically, the number of carbon atoms in the alkenyl group may be 2 to 30, and more specifically, 2 to 20.

[0028] In the present specification, the alkynyl group may be a straight or branched chain having 2 to 60 carbon atoms. Specifically, the alkynyl group may have 2 to 30 carbon atoms, and more specifically, 2 to 20 carbon atoms.

[0029] In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain having 1 to 60 carbon atoms, and specific examples thereof include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. Specifically, the alkoxy group may have 1 to 30 carbon atoms, and more specifically, 1 to 20 carbon atoms.

[0030] In the present specification, the cycloalkyl group may be monocyclic or polycyclic having 3 to 60 carbon atoms, and specific examples thereof include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl. Specifically, the cycloalkyl group may have 3 to 30 carbon atoms, and more specifically, 3 to 20 carbon atoms.

[0031] In the present specification, a heterocycloalkyl group is a group that contains at least one non-carbon atom, i.e., a heteroatom, and specifically, may be a cycloalkyl group that contains at least one heteroatom selected from the group consisting of O, N, S, Se, etc., and may be a monocyclic or polycyclic group having 2 to 60 carbon atoms. Specifically, the heterocycloalkyl group may have 2 to 30 carbon atoms, and more specifically, may have 2 to 20 carbon atoms.

[0032] In the present specification, a sulfide group includes S and may have 1 to 60 carbon atoms. Specific examples include, but are not limited to, an alkyl sulfide group such as a dimethyl sulfide group, an aryl sulfide group such as diphenyl sulfide, and a heteroaryl sulfide group substituted with a heteroaryl group. Specifically, the sulfide group may have 1 to 30 carbon atoms, and more specifically, 1 to 20 carbon atoms.

[0033] In the present specification, the aryloxy group may be a substituent that contains O, and the O atom may be directly connected as a radical, and may have 6 to 60 carbon atoms. Specific examples include phenoxy groups, naphthoxy groups, biphenoxy groups, etc., which are oxy groups substituted with aryl groups, but are not limited thereto. The heteroaryloxy group is an oxy group substituted with heteroaryl groups, and may have 2 to 60 carbon atoms. Specifically, the aryloxy group may have 6 to 30 carbon atoms, and more specifically, may have 6 to 20 carbon atoms.

[0034] In the present specification, the thio group includes S and may have 1 to 60 carbon atoms. Specific examples include, but are not limited to, alkylthio groups such as methylthio, ethylthio, butylthio, pentylthio, and hexylthio, arylthio groups such as phenylthio, and naphthylthio, and heteroarylthio groups substituted with heteroaryl groups. Specifically, the thio group may have 1 to 30 carbon atoms, and more specifically, 1 to 20 carbon atoms.

[0035] In the present specification, the silyl group may be a substituent containing Si, and the Si atom may be directly connected as a radical, and may have 1 to 60 carbon atoms. Specific examples thereof include, but are not limited to, alkylsilyl groups such as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, and propyldimethylsilyl groups, arylsilyl groups such as triphenylsilyl, diphenylsilyl, and phenylsilyl groups, and heteroarylsilyl groups substituted with heteroaryl groups. Specifically, the silyl group may have 1 to 30 carbon atoms, and more specifically, 1 to 20 carbon atoms.

[0036] In the present specification, the phosphine oxide group includes P=O and may have 1 to 60 carbon atoms. Specific examples include, but are not limited to, an alkylphosphine oxide group such as a dimethylphosphine oxide group, an arylphosphine oxide group such as a diphenylphosphine oxide group and a dinaphthylphosphine oxide group, and a heteroarylphosphine oxide group substituted with a heteroaryl group. Specifically, the phosphine oxide group may have 1 to 30 carbon atoms, and more specifically, 1 to 20 carbon atoms.

[0037] In the present specification, the aryl group may be monocyclic or polycyclic and have 6 to 60 carbon atoms. In the case of a monocyclic aryl group, specific examples thereof include a phenyl group, a biphenyl group, a terphenyl group, etc., but are not limited thereto. In the case of a polycyclic aryl group, specific examples thereof include a naphthyl group, anthracenyl group, a phenanthrenyl group, a triphenylenyl group, a pyrenyl group, a fluorenyl group, etc., but are not limited thereto. Specifically, the aryl group may have 6 to 50 carbon atoms, and more specifically, 6 to 30 carbon atoms.

[0038] In the present specification, a heteroaryl group includes at least one non-carbon atom, i.e., a heteroatom, and may specifically include at least one heteroatom selected from the group consisting of O, N, S, and Se, and may be a monocyclic or polycyclic group having 2 to 60 carbon atoms. Specific examples include a thiophenyl group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridinyl group, a bipyridinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrazinyl group, a quinolinyl group, a quinazolyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyrazinyl group, a pyrazinopyrazinyl group, a pyridoindolyl group, a benzothienopyrimidyl group, an indenocarbazolyl group, an isoquinolinyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a benzothiophenyl group, Examples thereof include, but are not limited to, a dibenzothiophenyl group, a benzofuranyl group, a phenanthridinyl group, a phenanthrolinyl group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group. Specifically, the heteroaryl group may have 2 to 50 carbon atoms, and more specifically, 2 to 30 carbon atoms.

[0039] In the present specification, the amine group may be selected from the group consisting of -NH2, an alkylamine group, an N-alkylarylamine group, an arylamine group, an N-arylheteroarylamine group, an N-alkylheteroarylamine group, and a heteroarylamine group.

[0040] In this specification, an arylene group refers to a divalent aryl group having two bonding positions to an aryl group, and a heteroarylene group also refers to a divalent heteroaryl group having two bonding positions to a heteroaryl group. The descriptions of the aryl group and heteroaryl group described above can be applied to these groups, except that they are each divalent groups.

[0041] In the chemical formula or structural formula in this specification, * or indicates the binding position.

[0042] In this specification, diazaspirobifluorene means a structure in which nitrogen (N) is substituted at two carbon positions of spirobifluorene, and 4,5-diazaspirobifluorene means a structure in which nitrogen (N) is substituted at the carbon positions at positions 4 and 5 based on the spirobifluorene diagram shown below.

[0043]

[0044] The present invention relates to a tandem organic light-emitting device, and relates to a tandem organic light-emitting device that can be included in a display device applied to various electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation systems, game consoles, various TVs, and various computers.

[0045] The present invention will be described in detail below.

[0046] The present invention relates to a tandem organic light-emitting device comprising a first electrode, a second electrode, a plurality of light-emitting portions positioned between the first electrode and the second electrode, and a charge generation layer positioned at at least one position between two adjacent light-emitting portions, wherein at least one of the charge generation layers comprises a first compound represented by the following chemical formula 1.

[0047] According to one embodiment of the present invention, a plurality of light-emitting units means two or more light-emitting units, and since the charge generation layer is respectively positioned at one or more locations between two adjacent light-emitting units, when there are two light-emitting units, there is one charge generation layer, when there are three light-emitting units, there are two charge generation layers, and when there are four light-emitting units, there can be three charge generation layers. That is, when the number of light-emitting units is n, the number of charge generation layers can be n-1 (n is 2 or more), and at least one of the n-1 charge generation layers can include the first compound represented by Chemical Formula 1.

[0048] Hereinafter, the tandem organic light-emitting device according to the present invention will be described in more detail.

[0049] FIG. 1 is a schematic diagram showing an organic light-emitting device according to one embodiment of the present invention, and specifically, a schematic diagram showing a tandem organic light-emitting device having two light-emitting parts.

[0050] As illustrated in FIG. 1, an organic light-emitting device (1000) according to an embodiment of the present invention may be configured to include a first electrode (100), a second electrode (200), and an organic layer (300) positioned between the first electrode and the second electrode.

[0051] According to one embodiment, the first electrode (100) may be an anode electrode and the second electrode (200) may be a cathode electrode, or vice versa. Also, according to one embodiment, the first electrode (100) may be a transparent electrode and the second electrode (200) may be a reflective electrode, or vice versa.

[0052] The organic layer (300) is a layer positioned between the first electrode (100) and the second electrode (200) and includes one or more organic layers, and may be composed of two or more layers.

[0053] Specifically, the organic layer (300) may be configured to include a first light-emitting portion (310), a second light-emitting portion (320), and a charge generation layer (330) positioned between the first light-emitting portion (310) and the second light-emitting portion (320).

[0054] The first light-emitting portion (310) includes a first light-emitting layer (311). According to one embodiment, the first light-emitting layer (311) may include a host material and a dopant material.

[0055] In addition, the first light-emitting portion (310) may additionally include a first hole transport region (312) that transports holes to the first light-emitting layer (311) and a second electron transport region (313) that transports electrons to the first light-emitting layer (311).

[0056] The above first hole transport region (312) may be configured to include at least one of a hole injection layer, a hole transport layer, a hole functional layer, and an electron blocking layer. Here, the hole functional layer refers to a layer that simultaneously injects and transports holes. In addition, one or more auxiliary layers may be additionally included.

[0057] The above first electron transport region (313) may be configured to include one or more of an electron injection layer, an electron transport layer, an electron functional layer, and a hole blocking layer. Here, the electron functional layer refers to a layer that simultaneously injects and transports electrons. In addition, one or more auxiliary layers may be additionally included.

[0058] Meanwhile, the second light-emitting portion (320) also includes a second light-emitting layer (321) like the first light-emitting portion (310). According to one embodiment, the second light-emitting layer (321) may include a host material and a dopant material.

[0059] This second light-emitting portion (320) may also additionally include a second hole transport region (322) that transports holes to the second light-emitting layer (321) and a second electron transport region (323) that transports electrons to the second light-emitting layer (321).

[0060] The second hole transport region (322) may be configured to include at least one of a hole injection layer, a hole transport layer, a hole functional layer, and an electron blocking layer. The hole functional layer is omitted as it is the same as described above.

[0061] The second electron transport region (323) may be configured to include at least one of an electron injection layer, an electron transport layer, an electron functional layer, and a hole blocking layer. The electron functional layer is the same as described above and is therefore omitted.

[0062] Of course, both the second hole transport region (322) and the second electron transport region (323) may additionally include one or more auxiliary layers in addition to the aforementioned layers.

[0063] The tandem organic light-emitting device according to the present invention has a first light-emitting part (310) and a second light-emitting part (320) configured as described above, so that holes and electrons transferred from the first electrode (100) and the second electrode (200) meet in the first light-emitting layer (311) and the second light-emitting layer (321) to emit light.

[0064] Meanwhile, the charge generation layer (330) is positioned between two adjacent light-emitting parts (310, 320) and serves to increase the current efficiency of the light-emitting layer by smoothly distributing charges. Specifically, the charge generation layer (330) may be configured to include a P-type charge generation layer and an N-type charge generation layer to smoothly distribute charges. When the first electrode (100) is an anode electrode and the second electrode (200) is a cathode electrode, the layer (331) positioned close to the anode electrode becomes an N-type charge generation layer, and the layer (332) positioned close to the cathode electrode becomes a P-type charge generation layer.

[0065] Such an N-type charge generation layer and a P-type charge generation layer may be laminated in direct contact as shown in FIG. 1, or may be laminated with one or more layers between the N-type charge generation layer and the P-type charge generation layer. That is, although not shown in FIG. 1, the charge generation layer (330) may further include one or more layers positioned between the two layers (331, 332). According to one embodiment, a layer including a metal may be positioned between the N-type charge generation layer and the P-type charge generation layer.

[0066] Meanwhile, FIG. 1 illustrates a tandem organic light-emitting device having two light-emitting parts, but the embodiments of the present invention are not limited to a tandem organic light-emitting device including two light-emitting parts, and it is natural that a tandem organic light-emitting device including three, four, five or more light-emitting parts is also included in the embodiments of the present invention.

[0067] According to one embodiment, when the organic light-emitting device of the present invention includes three light-emitting parts, which are referred to as a first light-emitting part, a second light-emitting part, and a third light-emitting part, the charge generation layer may include a first charge generation layer positioned between the first light-emitting part and the second light-emitting part, and a second charge generation layer positioned between the second light-emitting part and the third light-emitting part. In addition, the first charge generation layer and the second charge generation layer may include an N-type charge generation layer and a P-type charge generation layer, respectively.

[0068] According to an embodiment, two or more light-emitting units or two or more charge-generation layers may be configured with the same structure or different structures. In addition, they may be configured with the same material or different materials. According to an embodiment, when a tandem organic light-emitting device includes three light-emitting layers and two charge-generation layers, the three light-emitting layers may be the same or different in structure or material, and the two charge-generation layers may also be the same or different in structure or material.

[0069] Meanwhile, although not illustrated in FIG. 1, the tandem organic light-emitting device of the present invention may additionally include a capping layer (also referred to as a light efficiency improvement layer) formed on the outer side of at least one of the first electrode (100) and the second electrode (200). Here, the outer side of the electrode means the outer side, not between the two electrodes, when the place where the organic layer exists between the two electrodes is referred to as the inner side of the electrode. According to one embodiment, it may mean the upper side of the second electrode (200) based on FIG. 1.

[0070] Meanwhile, in the tandem organic light-emitting device of the present invention, the first electrode, the second electrode, the light-emitting layer, the hole injection layer, the hole transport layer, the hole functional layer, the electron blocking layer, the electron injection layer, the electron transport layer, the electron functional layer, the hole blocking layer, and other auxiliary layers or capping layers are not particularly limited, and those known in the art can be used according to the role of each layer.

[0071] According to one embodiment of the present invention, at least one of the N-type charge generation layers has electron transport capability and includes a first compound represented by the following chemical formula 1.

[0072]

[0073] In the above chemical formula 1,

[0074] L1 to L4 are each independently a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,

[0075] Ar1 to Ar4 are each independently selected from the group consisting of deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted sulfide group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryloxy group, substituted or unsubstituted thio group, substituted or unsubstituted amine group, substituted or unsubstituted silyl group, and substituted or unsubstituted phosphine oxide group,

[0076] m and p are each independently integers from 0 to 4,

[0077] n and o are each independently integers from 0 to 3,

[0078] However, m+n+o+p is greater than or equal to 1.

[0079] The 4,5-diazaspirobifluorene core of the first compound represented by the above chemical formula 1 prevents an increase in conjugation length by introducing an SP3 hybrid orbital carbon to the 1,10-phenanthroline core, which is widely used as an existing N-type charge generation layer, thereby reducing electron absorption and improving electron mobility, resulting in an increase in device efficiency and a decrease in operating voltage, and thus has characteristics more suitable for an N-type charge generation layer.

[0080] The N-type charge generation layer including the first compound has the effect of facilitating electron injection, thereby increasing electron injection into the electron transport layer and achieving a balance with the large amount of holes injected from the cathode.

[0081] Additionally, it has the effect of lowering the driving voltage of the device by lowering the energy barrier felt by electrons.

[0082] In addition, it is possible to implement an organic light-emitting device with excellent luminous efficiency and a lower operating voltage by maximizing the tunneling effect in the junction region of electrons and holes, thereby improving the efficiency of the light-emitting layer.

[0083] In addition, since smooth interaction with dopants such as metals is possible, charge generation and mobility can be further improved, and by effectively preventing the dopant from diffusing from the N-type charge generation layer to other layers such as the P-type charge generation layer, problems such as a decrease in lifespan due to diffused dopants can be solved. Here, interaction with a dopant may mean bonding with a dopant, and the first compound according to the present invention is particularly effective in improving the lifespan of a device by bonding with a dopant to form a stable and smooth gap state.

[0084] The above L1 to L4 may each independently be a direct bond, a substituted or unsubstituted C6~C30 arylene group, or a substituted or unsubstituted C2~C30 heteroarylene group, and more specifically, may be a direct bond, a substituted or unsubstituted C6~C20 arylene group, or a substituted or unsubstituted C2~C20 heteroarylene group. L1 to L4 may each be the same or different, and L1, L2, L3, or L4 may also be the same or different.

[0085] The above Ar1 to Ar4 may each independently be a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C3~C30 cycloalkyl group, a substituted or unsubstituted C2~C30 heterocycloalkyl group, a substituted or unsubstituted C6~C30 aryl group, or a substituted or unsubstituted C2~C30 heteroaryl group, and more specifically, may be a substituted or unsubstituted C6~C30 aryl group, or a substituted or unsubstituted C2~C30 heteroaryl group. Even more specifically, may be a substituted or unsubstituted C6~C20 aryl group, or a substituted or unsubstituted C2~C20 heteroaryl group. Ar1 to Ar4 may each be the same as or different from each other, and Ar1, Ar2, Ar3, or Ar4 may also be the same as or different from each other.

[0086] The substituents that can be substituted on the above L1 to L4 and Ar1 to Ar4 may be at least one selected from among deuterium, a halogen group, a cyano group, a nitro group, a nitrile group, a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group, a C6 to C20 aryl group, a C6 to C20 aryl group substituted with deuterium, a C6 to C20 fused ring group in which an aryl group and a cycloalkyl group are fused, a C2 to C20 heteroaryl group, and a C2 to C20 heteroaryl group substituted with deuterium, and more specifically, deuterium, a halogen group, a cyano group, a nitro group, a nitrile group, a C1 to C10 alkyl group, a C3 to C10 cycloalkyl group, a C6 to C10 aryl group, a C6 to C10 aryl group substituted with deuterium, and a C6 to C10 aryl group fused with an aryl group and a cycloalkyl group. It may be at least one selected from a C6~C10 fused ring group, a C2~C10 heteroaryl group, and a C2~C10 heteroaryl group substituted with deuterium. According to one embodiment, examples thereof include, but are not particularly limited to, deuterium, a fluorine group (-F), a cyano group (-CN), a methyl group, an ethyl group, a t-butyl group, an adamantyl group, a phenyl group, a phenyl group substituted with deuterium, a biphenyl group, a naphthyl group, a deuterium-substituted naphthyl group, a pyridine group, a pyrimidine group, a quinoline group, an isoquinoline group, a dibenzofuran group, a dibenzothiophene group, a benzoxazole group, or a benzothiazole group.

[0087] The above m, p, n and o can each independently be an integer from 0 to 2, and specifically, can be 0 or 1. Therefore, m+n+o+p can be an integer from 1 to 4.

[0088] According to the above, the chemical formula 1 may be represented by one of the following chemical formulas 2 to 10. According to one embodiment of the present invention, it may be chemical formula 2 or chemical formula 3.

[0089]

[0090]

[0091] In the above chemical formulas 2 to 10, L1 to L4 and Ar1 to Ar4 have the same definitions as in the above chemical formula 1.

[0092] According to one embodiment of the present invention, chemical formula 2 or chemical formula 3, in which m+n+o+p is 1 or 2, may be preferred. Specifically, chemical formula 2 may be represented by one of chemical formulas 2-1 to 2-4 below, chemical formula 3 may be represented by one of chemical formulas 3-1 to 3-3 below, chemical formula 5 may be represented by chemical formula 5-1 below, chemical formula 6 may be represented by chemical formula 6-1 below, and chemical formula 7 may be represented by chemical formula 7-1 below. That is, when m+n+o+p is 2, one substituent may be fixed as a phenyl group.

[0093]

[0094]

[0095]

[0096] In the above chemical formulas 2-1 to 2-4, 3-1 to 3-3, 5-1, 6-1 and 7-1, L1, L3, Ar1 and Ar3 are the same as defined in the above chemical formula 1.

[0097] Among the above chemical formulas, chemical formula 3-1, which has one substituent and is bonded to position 6, which is right next to nitrogen (N) of 4,5-diazaspirobifluorene, may be preferable for application to the N-type charge generation layer.

[0098] According to one embodiment of the present invention, Ar1, Ar2, Ar3 or Ar4 are each independently a phenyl group, a naphthyl group, anthracene group, a phenanthrene group, a pyrene group, a benzophenanthrene group, a benzoanthracene group, a chrysene group, a triphenylene group, a spirobifluorene group, a fluoranthene group, a dimethylfluorene group, a diphenylfluorene group, a dibenzofuran group, a dibenzothiophene group, a benzofuropyridine group, a benzothienopyridine group, a benzofuropyrimidine group, a benzothienopyrimidine group, a furodipyridine group, a thienodipyridine group, a benzoxazole group, a benzothiazole group, a naphthooxazole group, a naphthothiazole group, a phenanthrooxazole group, a phenanthrothiazole group, a benznaphthooxazole group, which are unsubstituted or substituted with one or more substituents, which are the same or different. It may be any one of a benznaphthothiazole group, a carbazole group, a carboline group, a diazacabazole group, a benzocarbazole group, a benzoimidazole group, a naphthoimidazole group, a pyridine group, a pyrimidine group, a pyridazine group, a pyrazine group, a triazine group, a quinoline group, an isoquinoline group, a quinazoline group, a quinoxaline group, a phthalazine group, a cinnoline group, a 1,5-naphthyridine group, a 1,6-naphthyridine group, a 1,7-naphthyridine group, a 1,8-naphthyridine group, a 2,7-naphthyridine group, a benzoquinoline group, a benzoquinazoline group, a 1,4-phenanthroline group, a 1,10-phenanthroline group, or a triphenylsilane group.

[0099] The substituents that can be substituted for Ar1, Ar2, Ar3 or Ar4 include deuterium, a halogen group, a cyano group, a C1 to C10 alkyl group, a C3 to C10 cycloalkyl group, a C6 to C10 aryl group, a C6 to C10 aryl group substituted with deuterium, a C2 to C10 heteroaryl group, a C2 to C10 heteroaryl group substituted with deuterium, and according to one embodiment, deuterium, a fluorine group (-F), a cyano group (-CN), a methyl group, an ethyl group, a t-butyl group, a phenyl group, a phenyl group substituted with deuterium, a biphenyl group, a naphthyl group, a pyridine group, a pyrimidine group, a quinoline group, an isoquinoline group, a dibenzofuran group, a dibenzothiophene group, a benzoxazole group or a benzothiazole group. However, it is not limited to this.

[0100] More specifically, Ar1, Ar2, Ar3 or Ar4 may be a phenyl group, a naphthyl group, anthracene group, a phenanthrene group, a pyrene group, a benzophenanthrene group, a benzoanthracene group, a chrysene group, a triphenylene group, a spirobifluorene group, a fluoranthene group, a dimethylfluorene group, a diphenylfluorene group, a dibenzofuran group, a dibenzothiophene group, a benzoxazole group, a benzothiazole group, a benzimidazole group, a naphthoxazole group, a naphthothiazole, a naphthoimidazole, a pyridine group, a pyrimidine group, a triazine group, a quinoline group, an isoquinoline group, a quinazoline group, a 1,5-naphthyridine or a 1,10-phenanthroline group, which is substituted or unsubstituted with one or more substituents that are the same or different, and the substituents that may be substituted therewith are a phenyl group, a deuterium substituted A phenyl group, a pyridine group, or a pyrimidine group may be selected, and when such a substituent is substituted, one or two may be substituted. In one embodiment, when two substituents are substituted, the two substituents may have a meta bonding position to each other as in the example below. The example below shows a case where Ar1, Ar2, Ar3, or Ar4 is a triazine group, and two phenyl groups are substituted in a meta bonding position.

[0101]

[0102] In one embodiment, when Ar1, Ar2, Ar3 or Ar4 is a substituted or unsubstituted aryl group, it may be specifically a substituted or unsubstituted C10 or higher condensed aryl group, more specifically a substituted or unsubstituted C10 or higher condensed aryl group, and even more specifically one selected from a substituted or unsubstituted phenanthrene group, a pyrene group, a benzophenanthrene group, a benzoanthracene group, a chrysene group, a triphenylene group, a spirobifluorene group and a fluoranthene group.

[0103] According to one embodiment of the present invention, each of L1, L2, L3 or L4 may independently be a direct bond, or may be one of the structural formulae L-1 to L-30, or may be formed by combining two or more thereof. In the present specification, the meaning of forming a combination of two or more thereof means combining two or more of the same or different structural formulae, and in one embodiment, the case of combining three structural formulae L-1, a case of combining structural formulae L-1 and L-2, a case of combining two structural formulae L-1 and one structural formula L-2, etc. may be included. In this case, the order of combination is not particularly determined, and combinations in all possible cases are possible.

[0104]

[0105] More specifically, L1, L2, L3 or L4 may each independently be a direct bond, or a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene or a substituted or unsubstituted pyridine group, and when substituted, the substituent may be a phenyl group, a pyridine group or a pyrimidine group. Even more specifically, L1, L2, L3 or L4 may each independently be a direct bond, or one of phenylene, pyridine or naphthylene, or a combination of two or more thereof. According to one embodiment, it may be a combination of any one or two or more of the structural formulae below. In this case, the order of combination is not particularly determined, and combinations in all possible cases are possible.

[0106]

[0107] According to one embodiment of the present invention, the first compound represented by Chemical Formula 1 may be selected from, but is not limited to, compounds 1-1 to 1-160, compounds 2-1 to 2-180, compounds 3-1 to 3-228, and compounds 4-1 to 4-208.

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144] Meanwhile, the N-type charge generation layer according to an embodiment of the present invention may further include one or more of a metal, a metal compound, and an organic complexing agent of a metal. According to an embodiment, the metal compound may include, but is not limited to, a metal oxide, a metal fluoride, etc. Specifically, the N-type charge generation layer may further include one or more of an alkali metal, an alkaline earth metal, an alkali metal compound, an alkaline earth metal compound, an organic complexing agent of an alkali metal, and an organic complexing agent of an alkaline earth metal. According to one embodiment, the composition may further include one or more metals, metal compounds and organic complexes of metals selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), ytterbium (Yb), samarium (Sm), tin (Sn), copper (Cu), titanium (Ti), cadmium (Cd), mercury (Hg), lead (Pb), bismuth (Bi), zinc (Zn), iron (Fe), cobalt (Co), nickel (Ni), indium (In), gallium (Ga), thorium (Th), uranium (U), silver (Ag), aluminum (Al), gold (Au), molybdenum (Mo), niobium (Nb), palladium (Pd), platinum (Pt) and europium (Eu). In one embodiment, the metal may be selected from lithium (Li) or ytterbium (Yb).

[0145] Such a metal, metal compound or organic complex of a metal may be included in the form of being doped into the first compound represented by Chemical Formula 1, may be included in the form of a layer, or may be included in both the form of being doped and the form of a layer. When included in the form of doping, it may be doped in an amount of 0.1 to 20 wt% based on the first compound according to Chemical Formula 1, specifically, may be doped in an amount of 0.5 to 15 wt%, and this may vary depending on the type of metal. In one embodiment, in the case of lithium, the doping amount may be 0.5 to 5 wt%, and in the case of ytterbium, the doping amount may be 5 to 5 wt%. Meanwhile, when included in the form of a layer, it may be located between the layer made of the first compound represented by Chemical Formula 1 and the P-type charge generation layer.

[0146] Meanwhile, at least one of the P-type charge generation layers of the organic light-emitting device according to one embodiment of the present invention has a hole transport capability and may include a second compound represented by the following chemical formula 11.

[0147]

[0148] In the above chemical formula 11,

[0149] L5 to L7 are each independently a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,

[0150] Ar5 to Ar7 are each independently selected from the group consisting of a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted amine group, and a substituted or unsubstituted fused ring group.

[0151] Including the above, throughout the present specification, the fused ring group includes a fused ring group in which an aryl group and a cycloalkyl group are fused, a fused ring group in which a heteroaryl group and a cycloalkyl group are fused, a fused ring group in which an aryl group and a heterocycloalkyl group are fused, or a fused ring group in which a heteroaryl group and a heterocycloalkyl group are fused. According to one embodiment, the tetralin group represented by the structural formula below may correspond to one of the fused ring groups in which an aryl group and a cycloalkyl group are fused, and benzo-1,4-dioxane may correspond to one of the fused ring groups in which an aryl group and a heterocycloalkyl group are fused.

[0152]

[0153] Specifically, L5 to L7 may each independently be a direct bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroarylene group, and more specifically, may be a direct bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heteroarylene group. L5 to L7 may each be the same or different, and L5, L6, or L7 may also be the same or different.

[0154] In one embodiment, L5 to L7 may each independently be a direct bond, or a substituted or unsubstituted phenylene, or a substituted or unsubstituted naphthylene, and more specifically, may be a direct bond, or one of phenylene and naphthylene, or a combination of two or more thereof. In one embodiment, it may be one or a combination of two or more of the structural formulae below. In one embodiment, it may be a direct bond, phenylene, or biphenylene.

[0155]

[0156] Specifically, Ar5 to Ar7 may each independently be a substituted or unsubstituted C3~C30 cycloalkyl group, a substituted or unsubstituted C2~C30 heterocycloalkyl group, a substituted or unsubstituted C6~C30 aryl group, a substituted or unsubstituted C2~C30 heteroaryl group, a substituted or unsubstituted C2~C30 amine group, or a substituted or unsubstituted C6~C30 fused ring group. Ar5 to Ar7 may each be the same or different, and Ar5, Ar6, or Ar7 may also be the same or different.

[0157] According to one embodiment, Ar5 to Ar7 may be, but are not particularly limited to, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a carbazole group, an adamantyl group, a norbornene group, a cyclohexyl group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a benzodimethylfluorene group, a benzodiphenylfluorene group, or a benzospirobifluorene group, each independently substituted or unsubstituted with one or more substituents, which are the same or different.

[0158] The substituents that can be substituted on each of the above L5 to L7 and Ar5 to Ar7 may be at least one selected from among deuterium, a halogen group, a cyano group, a nitro group, a nitrile group, a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group, a C6 to C20 aryl group, a C6 to C20 aryl group substituted with deuterium, a C6 to C20 fused ring group, a C2 to C20 heteroaryl group, a C2 to C20 heteroaryl group substituted with deuterium, a C2 to C20 arylamine group, a C2 to C20 heteroarylamine group, and a C3 to C20 arylsilyl group, and according to one embodiment, deuterium, a methyl group, an ethyl group, a t-butyl group, a phenyl group, a biphenyl group, a phenyl group substituted with one or more deuterium, a biphenyl group substituted with one or more deuterium, Examples thereof include, but are not limited to, an adamantyl group, a norbornene group, a cyclohexyl group, a tetralin group, a tetralin group substituted with one or more methyl groups, and a benzo-1,4-dioxane group.

[0159] According to one embodiment of the present invention, at least one of Ar5 to Ar7 may be a substituted or unsubstituted carbazole group, or a substituted or unsubstituted fluorene group. According to the above, the chemical formula 11 may be represented by one of the following chemical formulas 12 to 14.

[0160]

[0161] In the above chemical formula 12, L5 to L7, Ar5 and Ar6 are the same as defined in the above chemical formula 11,

[0162] R1 is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted fused ring group,

[0163] R2 and R3 are each independently selected from the group consisting of deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted sulfide group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted fused ring group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryloxy group, substituted or unsubstituted thio group, substituted or unsubstituted amine group, substituted or unsubstituted silyl group, and substituted or unsubstituted phosphine oxide group, and adjacent R2s or adjacent R3s may or may not combine with each other to form a ring,

[0164] a is an integer from 0 to 3, and b is an integer from 0 to 4.

[0165] Specifically, the R1 may be a substituted or unsubstituted C6~C30 aryl group, or a substituted or unsubstituted C2~C30 heteroaryl group, and more specifically, may be a substituted or unsubstituted C6~C20 aryl group, or a substituted or unsubstituted C2~C20 heteroaryl group, and according to one embodiment, may be a phenyl group, a biphenyl group, a naphthyl group, a phenyl group substituted with one or more deuterium atoms, a biphenyl group substituted with one or more deuterium atoms, or a naphthyl group substituted with one or more deuterium atoms, but is not particularly limited thereto.

[0166] Specifically, R2 and R3 may each independently be deuterium, halogen, cyano, nitro, nitrile, a substituted or unsubstituted C1~C20 alkyl, a substituted or unsubstituted C6~C20 aryl, a substituted or unsubstituted C2~C20 heteroaryl, or a substituted or unsubstituted C6~C20 fused ring group, and according to one embodiment, may include deuterium, a methyl group, an ethyl group, a t-butyl group, a phenyl group, a biphenyl group, a phenyl group substituted with one or more deuteriums, a biphenyl group substituted with one or more deuteriums, an adamantyl group, a norbornene group, a cyclohexyl group, a tetralin group, a tetralin group substituted with one or more methyl groups, a benzo-1,4-dioxane group, and the like, but are not particularly limited thereto.

[0167] Specifically, a is an integer from 0 to 2, and more specifically, can be 0 or 1.

[0168] Specifically, b is an integer from 0 to 3, more specifically an integer from 0 to 2, and even more specifically can be 0 or 1.

[0169] <Chemical Formula 13>

[0170]

[0171] In the above chemical formula 13, L5 to L7, Ar5 and Ar6 are the same as defined in the above chemical formula 11,

[0172] R4 and R5 are each independently selected from the group consisting of deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted sulfide group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted fused ring group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryloxy group, substituted or unsubstituted thio group, substituted or unsubstituted amine group, substituted or unsubstituted silyl group, and substituted or unsubstituted phosphine oxide group, and adjacent R4s or adjacent R5s may or may not combine with each other to form a ring,

[0173] c and d are each independently integers from 0 to 4.

[0174] Specifically, R4 and R5 may each independently be deuterium, halogen, cyano, nitro, nitrile, a substituted or unsubstituted C1~C20 alkyl, a substituted or unsubstituted C6~C20 aryl, a substituted or unsubstituted C2~C20 heteroaryl, or a substituted or unsubstituted C6~C20 fused ring group, and according to one embodiment, may include, but is not particularly limited to, a methyl group, an ethyl group, a t-butyl group, a phenyl group, a biphenyl group, a phenyl group substituted with one or more deuteriums, a biphenyl group substituted with one or more deuteriums, an adamantyl group, a norbornene group, a cyclohexyl group, a tetralin group, a tetralin group substituted with one or more methyl groups, a benzo-1,4-dioxane group, and the like.

[0175]

[0176] In the above chemical formula 14, L5 to L7, Ar5 and Ar6 are the same as defined in the above chemical formula 11,

[0177] R8 and R9 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, which may or may not be combined with each other to form a ring,

[0178] R6 and R7 are each independently selected from the group consisting of deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted sulfide group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted fused ring group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryloxy group, substituted or unsubstituted thio group, substituted or unsubstituted amine group, substituted or unsubstituted silyl group, and substituted or unsubstituted phosphine oxide group, and adjacent R6 or adjacent R7 may or may not combine with each other to form a ring,

[0179] e is an integer from 0 to 3, and f is an integer from 0 to 4.

[0180] Specifically, R6 and R7 may each independently be deuterium, halogen, cyano, nitro, nitrile, a substituted or unsubstituted C1~C20 alkyl, a substituted or unsubstituted C6~C20 aryl, a substituted or unsubstituted C2~C20 heteroaryl, or a substituted or unsubstituted C6~C20 fused ring group, and in one embodiment, may be deuterium, a methyl group, an ethyl group, a t-butyl group, a phenyl group, a biphenyl group, a phenyl group substituted with one or more deuteriums, a biphenyl group substituted with one or more deuteriums, an adamantyl group, a norbornene group, a cyclohexyl group, a tetralin group, a tetralin group substituted with one or more methyl groups, a benzo-1,4-dioxane group, and the like, but are not particularly limited thereto.

[0181] Specifically, R8 and R9 may each independently be a substituted or unsubstituted C1~C20 alkyl group, a substituted or unsubstituted C6~C20 aryl group, or a substituted or unsubstituted C2~C20 heteroaryl group, and in one embodiment, may be a methyl group or a phenyl group, or may be combined with each other to form a ring. In one embodiment, when R8 and R9 are combined with each other to form a ring, thereby forming spirobifluorene, Chemical Formula 14 may be represented by Chemical Formula 15 below.

[0182]

[0183] In the above chemical formula 15, L5 to L7, Ar5 and Ar6 are the same as defined in the above chemical formula 11, R6, R7, e and f are the same as defined in the above chemical formula 14, R10 and R11 are the same as defined in the above chemical formula 14, and g and h are the same as defined in the above chemical formula 14, and therefore are omitted.

[0184] Meanwhile, according to one embodiment of the present invention, one of Ar5 to Ar7 may be a carbazole group and the other may be a fluorene group. According to the above, chemical formula 11 may be represented by chemical formula 16 or chemical formula 17 below.

[0185]

[0186] Additionally, according to one embodiment of the present invention, two of Ar5 to Ar7 may be fluorene groups. According to the above, chemical formula 11 may be represented by the following chemical formula 18.

[0187]

[0188] In the above chemical formulas 16 to 18, each symbol is the same as that explained above and is therefore omitted. In the above chemical formula 18, R6, R7, R8, or R9 may be the same or different from each other.

[0189] As in the above chemical formulas 16 to 18, the second compound may be an amine compound containing at least one fluorene group, and more specifically, may be an amine compound containing a carbazole group and a fluorene group, as in chemical formula 16 or 17, or may be an amine compound containing two fluorene groups, as in chemical formula 18.

[0190] In the above chemical formulas 16 to 18, Ar5 may be formed by combining one or two or more of a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a dibenzofuran group, a dibenzothiophene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a cyclohexyl group, a norbornene group, an adamantyl group, a tetralin group, a 1,1,4,4-tetramethyltetralin group, and a benzo-1,4-dioxane group, which are unsubstituted or substituted with one or more substituents according to one embodiment, but is not particularly limited thereto. Here, examples of substituents that may be substituted for Ar5 include, but are not particularly limited to, deuterium, a methyl group, a t-butyl group, a phenyl group, and the like.

[0191] Meanwhile, according to one embodiment, the second compound may be a compound exhibiting low refractive index characteristics, and for this purpose, may structurally include an ortho bond. Specifically, L5, L6, or L7 may be a linking group having an ortho bond, such as 1,2-phenylene. According to one embodiment, in Chemical Formulas 16 to 18, *-L5-Ar5 may be a substituent including 1,2-phenylene.

[0192] According to one embodiment of the present invention, the second compound may be an amine compound comprising one or more tertiary amines, and more specifically, may be an amine compound comprising one tertiary amine. More specifically, the second compound according to the present invention may be an amine compound comprising one or more fluorene groups and one tertiary amine.

[0193] According to one embodiment of the present invention, the second compound represented by chemical formula 11 may be selected from, but is not limited to, compounds 5-1 to 5-92 below.

[0194]

[0195]

[0196]

[0197]

[0198]

[0199] Meanwhile, the P-type charge generation layer according to one embodiment of the present invention may further include a third compound having at least one cyano group (-CN) substituted. More specifically, the third compound may be a compound having at least four cyano groups (-CN) substituted, and even more specifically, may be a compound containing from four to eight cyano groups (-CN). This third compound acts as a dopant and may be included in the P-type charge generation layer in a doped form.

[0200] More specifically, the third compound has a structure in which a core composed of at least one of a C6~C30 aryl group, a C3~C30 cycloalkyl group, a C3~C30 cycloalkenyl group, and a C2~C30 heteroaryl group is substituted with at least one substituent, which is the same or different, wherein the substituent is hydrogen; a halogen group; -F; -Cl; -CF3; -CN; -NC; -NO2; -OCF3; -SCN; -OCN; -SF5; -OC(CH3)3; a C1~C12 alkyl group substituted with at least one of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5, and -OC(CH3)3; A C1~C12 alkoxy group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5, and -OC(CH3)3; A C6~C12 aryl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5, and -OC(CH3)3; and a C2~C12 heteroaryl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5, and -OC(CH3)3; provided that the third compound contains four or more cyano groups (-CN).

[0201] According to one embodiment of the present invention, the third compound may be represented by the following chemical formula A.

[0202]

[0203] In the above chemical formula A,

[0204] Ring A is one of a substituted or unsubstituted C6~C30 aryl group, a substituted or unsubstituted C3~C30 cycloalkyl group, a substituted or unsubstituted C3~C30 cycloalkenyl group, and a substituted or unsubstituted C2~C30 heteroaryl group,

[0205] R12 and R13 are each independently a halogen group; -F; -Cl; -CF3; -CN; -NC; -NO2; -OCF3; -SCN; -OCN; -SF5; -OC(CH3)3; a C1~C12 alkyl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5 and -OC(CH3)3; a C1~C12 alkoxy group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5 and -OC(CH3)3; A C6~C12 aryl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5 and -OC(CH3)3; and a C2~C12 heteroaryl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5 and -OC(CH3)3;

[0206] i can be an integer from 0 to 3,

[0207] However, the chemical formula A contains four or more cyano groups (-CN).

[0208] The above R12 and R13 may be the same or different, and R12 or R13 may also be the same or different.

[0209] According to one embodiment, the substituents that can be substituted on the A ring include hydrogen; a halogen group; -F; -Cl; -CF3; -CN; -NC; -NO2; -OCF3; -SCN; -OCN; -SF5; -OC(CH3)3; a C1 to C12 alkyl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5, and -OC(CH3)3; a C1 to C12 alkoxy group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5, and -OC(CH3)3; A C6~C12 aryl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5, and -OC(CH3)3; and a C2~C12 heteroaryl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5, and -OC(CH3)3.

[0210] In one embodiment, i may be an integer from 1 to 3, and more specifically 2 or 3.

[0211] According to one embodiment of the present invention, the chemical formula A may be represented by one of the following chemical formulas 19 to 27.

[0212]

[0213] In the above chemical formulas 19 to 27, R is each independently hydrogen; a halogen group; -F; -Cl; -CF3; -CN; -NC; -NO2; -OCF3; -SCN; -OCN; -SF5; -OC(CH3)3; a C1 to C12 alkyl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5, and -OC(CH3)3; a C1 to C12 alkoxy group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5, and -OC(CH3)3; A C6~C12 aryl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5 and -OC(CH3)3; and a C2~C12 heteroaryl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5 and -OC(CH3)3; wherein each chemical formula includes at least four -CN. Naturally, R in each chemical formula may be the same or different. In one embodiment, the C6~C12 aryl group may be a phenyl group, and the C2~C12 heteroaryl group may be a pyridine group.

[0214] According to one embodiment of the present invention, the third compound may be selected from compounds 6-1 to 6-36 below, but is not limited thereto.

[0215]

[0216]

[0217]

[0218] A novel charge generation layer of a tandem organic light-emitting device according to the present invention applies a first compound having 4,5-diazaspirobifluorene as a core as an electron transport material of an N-type charge generation layer, and applies a second compound having one or more tertiary amines as a core as a hole transport material of a P-type charge generation layer, and through the combination of the first compound and the second compound, transport of charges is facilitated and current leakage to the side is prevented, thereby resulting in the effect of lowering the driving voltage of the device and improving the efficiency and lifespan. Furthermore, the organic light-emitting device of the present invention can exhibit low voltage, high efficiency, and long lifespan through the charge generation layer that simultaneously includes the first compound, lithium or ytterbium, the second compound, and the third compound.

[0219] Hereinafter, the present invention will be described in more detail with synthetic examples, practical examples, and experimental examples. However, the following contents do not limit the scope of the present invention.

[0220] Synthetic example

[0221] Synthesis of the first compound

[0222] Synthesis of 2'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene]

[0223]

[0224] In a 500-mL round-bottom flask, completely dissolve 4-bromo-2-iodo-1,1'-biphenyl (20 g, 55.8 mmol) in 100 mL of THF, cool to -78°C, and stir. Slowly add n-BuLi (1.6 M in hexane, 41.9 mL). When the addition is complete, stir at -78°C for 2 hours. Dissolve 4,5-diazafluorene-9-one (12.2 g, 67.1 mmol) in 50 mL of THF and add dropwise to the reaction solution. When the addition is complete, raise the temperature to room temperature and stir for 1 hour. When the reaction is complete, add water, stir, and extract using dichloromethane. Dry the organic layer with MgSO4, and concentrate under reduced pressure. Add 100 mL of acetic acid and stir under reflux for 2 hours. Cool to room temperature and filter. The solid was purified by column chromatography to obtain the target compound 2'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] (16.4 g, 74%).

[0225] Synthesis Example 1: Compound 1-13

[0226]

[0227] In a 500 mL round-bottomed flask, completely dissolve previously synthesized 2'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] (10.0 g, 25.2 mmol), 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (12.1 g, 27.7 mmol), and tetrakis(triphenylphophine)palladium (1.5 g, 1.3 mmol) in 80 mL of THF. Add potassium carbonate (10.5 g, 75.6 mmol) dissolved in 80 mL of H2O, and stir under reflux for 8 hours. When the reaction is complete, raise the temperature to room temperature and concentrate under reduced pressure to obtain a filtrate. The resulting filtrate was extracted with dichloromethane and water. The organic layer was dehydrated with MgSO4 and concentrated under reduced pressure. The resulting filtrate was purified by column chromatography to obtain the target compound, compound 1-13 (12.3 g, 78%). LC-MS m / z = 626 (M+H)

[0228] Synthetic Example 2: Synthesis of Compound 1-21

[0229]

[0230] In a 500 mL round-bottomed flask, add previously synthesized 2'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] (10.0 g, 25.2 mmol), 22,4-bis(phenyl-d5)-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (12.3 g, 27.7 mmol), and tetrakis(triphenylphophine)palladium (1.5 g, 1.3 mmol) to 80 mL of THF and stir. Then, add potassium carbonate (10.5 g, 75.6 mmol) dissolved in 80 mL of H2O and stir under reflux for 8 hours. When the reaction was complete, the mixture was warmed to room temperature and concentrated under reduced pressure to obtain a filtrate. The resulting filtrate was extracted with dichloromethane and water. The organic layer was dehydrated with MgSO4 and concentrated under reduced pressure. The resulting filtrate was purified by column chromatography to obtain the target compound, compound 1-21 (13.5 g, 84%). LC-MS m / z = 636 (M+H)

[0231] Synthesis Example 3: Compound 1-42

[0232]

[0233] In a 500 mL round-bottomed flask, completely dissolve 2'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] (10.0 g, 25.2 mmol), 2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[d]oxazole (8.9 g, 27.7 mmol), and tetrakis(triphenylphophine)palladium (1.5 g, 1.3 mmol) in 80 mL of THF. Add potassium carbonate (10.5 g, 75.6 mmol) dissolved in 80 mL of H2O, and stir under reflux for 8 hours. When the reaction is complete, raise the temperature to room temperature and concentrate under reduced pressure to obtain a filtrate. Extract the obtained filtrate using dichloromethane and water. The organic layer was dehydrated with MgSO4 and concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain the target compound, compound 1-42 (10.6 g, 82%). LC-MS m / z = 512 (M+H)

[0234] Synthesis of 4'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene]

[0235]

[0236] In a 1 L round-bottom flask, completely dissolve 2-bromo-2'-iodo-1,1'-biphenyl (30.0 g, 107.1 mmol) in 192 mL of THF, cool to -78°C, and stir. Slowly add n-BuLi (1.6 M in hexane, 62.9 mL). When the addition is complete, stir at -78°C for 2 hours. Dissolve 2-bromo-5H-cyclopenta[2,1-b:3,4-b']dipyridin-5-one (33.6 g, 128.6 mmol) in 96 mL of THF and add dropwise to the reaction solution. When the addition is complete, raise the temperature to room temperature and stir for 1 hour. When the reaction is complete, add water, stir, and extract using dichloromethane. Dry the organic layer with MgSO4 and concentrate under reduced pressure. Add 195 mL of acetic acid and reflux for 2 hours. Cool to room temperature and filter. The solid was purified by column chromatography to obtain the target compound 4'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] (26.8 g, 63%).

[0237] Synthetic Example 4: Synthesis of Compound 1-97

[0238]

[0239] In a 500 mL round-bottomed flask, add previously synthesized 4'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] (10.0 g, 25.2 mmol), 2-(4-(benzo[c]phenanthren-5-yl)naphthalen-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (13.3 g, 27.7 mmol), and tetrakis(triphenylphophine)palladium (1.5 g, 1.3 mmol) to 80 mL of THF and stir. Then, add potassium carbonate (10.5 g, 75.6 mmol) dissolved in 80 mL of H2O and stir under reflux for 8 hours. When the reaction was complete, the mixture was warmed to room temperature and concentrated under reduced pressure to obtain a filtrate. The resulting filtrate was extracted with dichloromethane and water. The organic layer was dehydrated with MgSO4 and concentrated under reduced pressure. The resulting filtrate was purified by column chromatography to obtain the target compound, compound 1-97 (13.7 g, 81%). LC-MS m / z = 671 (M+H)

[0240] Synthetic Example 5: Synthesis of Compound 1-131

[0241]

[0242] Compound 1-131 (11.2 g, 85%) was obtained by proceeding in the same manner as in Synthesis Example 4, except that 3'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] (11.2 g, 25.2 mmol) was used instead of 4'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] and 2-(6-chloropyridin-2-yl)quinoline (6.7 g, 27.7 mmol) was used instead of 2-(4-(benzo[c]phenanthren-5-yl)naphthalen-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. Obtained.

[0243] Synthetic Example 6: Synthesis of Compound 2-17

[0244]

[0245] Compound 2-17 (20.2 g, 86%) was obtained in the same manner as in Synthesis Example 4, except that 2-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] was used instead of 4'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] and 4,4,5,5-tetramethyl-2-(4-(phenanthren-9-yl)naphthalen-1-yl)-1,3,2-dioxaborolane (18.1 g, 23.2 mmol) was used instead of 2-(4-(benzo[c]phenanthren-5-yl)naphthalen-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. LC-MS m / z = 621 (M+H), Tg = 206C

[0246] Synthesis Example 7: Compound 2-71

[0247]

[0248] Compound 2-71 (20.2 g, 84%) was obtained by proceeding in the same manner as in Synthesis Example 6, except that 1-phenyl-3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzofuro[2,3-c]pyridine (18.6 g, 41.5 mmol) was used instead of 4,4,5,5-tetramethyl-2-(4-(phenanthren-9-yl)naphthalen-1-yl)-1,3,2-dioxaborolane. LC-MS m / z = 638 (M+H)

[0249] Synthesis Example 8: Compound 2-82

[0250]

[0251] Compound 2-82 (18.4 g, 78%) was obtained by proceeding in the same manner as in Synthesis Example 6, except that 4,6-diphenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrimidine (18 g, 41.5 mmol) was used instead of 4,4,5,5-tetramethyl-2-(4-(phenanthren-9-yl)naphthalen-1-yl)-1,3,2-dioxaborolane. LC-MS m / z = 625 (M+H)

[0252] Synthetic Example 9: Synthesis of Compound 2-86

[0253]

[0254] Compound 2-86 (17.9 g, 76%) was obtained by proceeding in the same manner as in Synthesis Example 6, except that 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (18.1 g, 23.2 mmol) was used instead of 4,4,5,5-tetramethyl-2-(4-(phenanthren-9-yl)naphthalen-1-yl)-1,3,2-dioxaborolane. LC-MS m / z = 626 (M+H), Tg = 166C

[0255] Synthesis of 2-bromo-8-phenylspiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene]

[0256]

[0257] In a round-bottomed flask, completely dissolve 2-iodo-1,1'-biphenyl (20 g, 71.4 mmol) in 100 mL of THF, cool to -78°C, and stir. Slowly add n-BuLi (1.6 M in hexane, 41.9 mL). Once the addition is complete, stir at -78°C for 2 hours. To this, dissolve 2-bromo-8-phenyl-5H-cyclopenta[2,1-b:3,4-b']dipyridin-5-one (17.3 g, 85.7 mmol) in 50 mL of THF and add dropwise to the reaction solution. Once the addition is complete, raise the temperature to room temperature and stir for 1 hour. When the reaction is complete, add water, stir, and extract using dichloromethane. Dry the organic layer with MgSO4 and concentrate under reduced pressure. Add 100 mL of acetic acid and stir under reflux for 2 hours. After cooling to room temperature, filter. The solid was purified by column chromatography to obtain the target compound (20.5 g, 71%).

[0258] Synthesis Example 10: Compound 3-76

[0259]

[0260] In a round-bottomed flask, add previously synthesized 2-bromo-8-phenylspiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] (10.0 g, 21.1 mmol), 9-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-pyrido[2,3-b]indole (18.1 g, 23.2 mmol), and tetrakis(triphenylphophine)palladium (1.2 g, 1.1 mmol) to 80 mL of THF and stir. Then, add potassium carbonate (8.8 g, 63.4 mmol) dissolved in 80 mL of H2O and stir under reflux for 8 hours. When the reaction is complete, raise the temperature to room temperature and concentrate under reduced pressure to obtain a filtrate. The obtained filtrate was extracted using dichloromethane and water. The organic layer was dehydrated with MgSO4 and concentrated under reduced pressure, and the obtained filtrate was purified by column chromatography to obtain compound 3-76 (10.3 g, 77%).

[0261] Synthesis Example 11: Compound 3-87

[0262]

[0263] Compound 3-87 (12.3 g, 83%) was obtained in the same manner as in Synthetic Example 10, except that 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrimidine (18.1 g, 23.2 mmol) was used instead of 9-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-pyrido[2,3-b]indole.

[0264] Synthesis Example 12: Compound 3-103

[0265]

[0266] Compound 3-103 (10.8 g, 79%) was obtained in the same manner as in Synthetic Example 10, except that 2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,10-phenanthroline (18.1 g, 23.2 mmol) was used instead of 9-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-pyrido[2,3-b]indole.

[0267] Synthesis of 2-phenyl-5H-cyclopenta[2,1-b:3,4-b']dipyridin-5-one

[0268]

[0269] In a 1000 mL round-bottomed flask, add 2-bromo-5H-cyclopenta[2,1-b:3,4-b']dipyridin-5-one (30.0 g, 115.0 mmol), phenylboronic acid (16.8 g, 137.9 mmol), and tetrakis(triphenylphophine)palladium (6.7 g, 5.7 mmol) to 300 mL of THF and stir. Add potassium carbonate (39.7 g, 345 mmol) dissolved in 150 mL of H2O and stir under reflux for 8 hours. When the reaction is complete, raise the temperature to room temperature and concentrate under reduced pressure to obtain a filtrate. Extract the obtained filtrate with dichloromethane and water. Remove moisture from the organic layer with MgSO4 and concentrate under reduced pressure. The obtained filtrate was purified by column chromatography to obtain the target compound (21.4, 72%).

[0270] Synthesis of 2'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene]

[0271]

[0272] In a 500 mL round-bottomed flask, completely dissolve 4-bromo-2-iodo-1,1'-biphenyl (27.3 g, 76.2 mmol) in 150 mL of THF, cool to -78 °C, and stir. Slowly add n-BuLi (1.6 M in hexane, 47.6 mL) dropwise. When the addition is complete, stir at -78 °C for 2 hours. Dissolve 2-phenyl-5H-cyclopenta[2,1-b:3,4-b']dipyridin-5-one (19.7 g, 76.2 mmol) in 100 mL of THF and add dropwise to the reaction solution. When the addition is complete, raise the temperature to room temperature and stir for 1 hour. When the reaction is complete, add water, stir, and extract using dichloromethane. Dry the organic layer with MgSO4 and concentrate under reduced pressure. Add 100 mL of acetic acid and reflux for 2 hours. Cool to room temperature and filter. The solid was purified by column chromatography to obtain the target compound (22.3 g, 74%).

[0273] Synthesis Example 13: Compound 4-3

[0274]

[0275] In a 500 mL round-bottomed flask, add 2'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] (10.0 g, 21.2 mmol), 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidine (8.4 g, 23.3 mmol), and tetrakis(triphenylphophine)palladium (1.4 g, 1.2 mmol) to 100 mL of 1,4-dioxane and stir. To this, potassium carbonate (8.8 g, 63.6 mmol) dissolved in 50 mL of H2O is added dropwise, and the mixture is refluxed and stirred for 8 hours. When the reaction is complete, the temperature is raised to room temperature and the mixture is concentrated under reduced pressure to obtain a filtrate. The obtained filtrate is extracted using dichloromethane and water. The organic layer was dehydrated with MgSO4 and concentrated under reduced pressure, and the resulting filtrate was purified by column chromatography to obtain compound 4-3 (9.9 g, 75%). LC-MS m / z = 625 (M+H)

[0276] Synthesis Example 14: Compound 4-46

[0277]

[0278] Compound 4-46 (10.6 g, 69%) was obtained by proceeding in the same manner as in Synthesis Example 1, except that 3'-bromo-2-phenylspiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] (10.0 g, 21.2 mmol) was used instead of 2'-bromospiro[cyclopenta[2,1-b:3,4-b']dipyridine-5,9'-fluorene] and 4-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[h]quinazoline (10.7 g, 23.3 mmol) was used instead of 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidine. Obtained. LC-MS m / z = 725 (M+H)

[0279] Synthesis of the second compound

[0280] Synthetic Example 15: Synthesis of Compound 5-1

[0281]

[0282] In a round-bottomed flask, add 9-(4'-chloro-[1,1'-biphenyl]-4-yl)-9H-carbazole (7 g, 20 mmol), toluene 200 mL, di([1,1'-biphenyl]-4-yl)amine (6.7 g, 21 mmol), Pd2(dba)3 (0.5 g, 0.6 mmol), P(t-Bu)3 (0.24 g, 1.2 mmol), and NaOt-Bu (3.8 g, 40 mmol) and reflux. When the reaction was complete, extract using dichloromethane and water. The organic layer was dried with MgSO4 and concentrated under reduced pressure, and the obtained filtrate was purified by column chromatography to obtain the target compound 5-1 (11.2 g, 88%). LC-MS m / z = 639 (M+H)

[0283] Synthetic Example 16: Synthesis of Compound 5-21

[0284]

[0285] Compound 5-21 (9.2 g, 82%) was obtained by proceeding in the same manner as in Synthetic Example 15, except that 3-(4-chlorophenyl)-9-phenyl-9H-carbazole (7.1 g, 20 mmol) was used instead of 9-(4'-chloro-[1,1'-biphenyl]-4-yl)-9H-carbazole and N-phenyl-[1,1'-biphenyl]-4-amine (5.2 g, 21 mmol) was used instead of di([1,1'-biphenyl]-4-yl)amine. LC-MS m / z = 563 (M+H)

[0286] Synthetic Example 17: Synthesis of Compound 5-26

[0287]

[0288] Compound 5-26 (9.5 g, 79%) was obtained in the same manner as in Synthetic Example 15, except that 2-bromo-9-phenyl-9H-carbazole (6.4 g, 20 mmol) was used instead of 9-(4'-chloro-[1,1'-biphenyl]-4-yl)-9H-carbazole and N-([1,1'-biphenyl]-2-yl)-9,9-dimethyl-9H-fluoren-2-amine (7.6 g, 21 mmol) was used instead of di([1,1'-biphenyl]-4-yl)amine. LC-MS m / z = 603 (M+H)

[0289] Synthetic Example 18: Synthesis of Compound 5-86

[0290]

[0291] Compound 5-86 (9.3 g, 77%) was obtained by proceeding in the same manner as in Synthetic Example 15, except that 4'-chloro-N,N-diphenyl-[1,1'-biphenyl]-4-amine (7.1 g, 20 mmol) was used instead of 9-(4'-chloro-[1,1'-biphenyl]-4-yl)-9H-carbazole and 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (6 g, 21 mmol) was used instead of di([1,1'-biphenyl]-4-yl)amine. LC-MS m / z = 605 (M+H)

[0292] Although synthetic examples have been described above, it is possible to synthesize compounds of the present invention by methods other than those specified, such as Buchwald-Hartwig coupling reaction (Chemical Reviews, 2016, 116, 12564-12649), Miyaura boration reaction (J. Am. Chem. Soc. 2002, 124, 27, 8001-8006), Suzuki cross-coupling reaction (J. Org. Chem. 1996, 61, 15, 5169-5171), and oxidative cyclization reaction.

[0293] Fabrication and Evaluation of Organic Light-Emitting Devices (1)

[0294] Comparative Example 1

[0295] After patterning the ITO substrate to be the anode so that the light-emitting area is 2 mm × 2 mm, it is cleaned with isopropyl alcohol and UV ozone, respectively. After that, the ITO substrate is mounted on the substrate holder of the vacuum deposition device and the vacuum level is 1 × 10 -7The pressure was set to 10 torr. Afterwards, plasma treatment was performed for 3 minutes under a N2 atmosphere. First, HAT-CN was vacuum-deposited to form a first hole injection layer with a thickness of 5 nm. On top of this, NPB material was vacuum-deposited to form a first hole transport layer with a thickness of 20 nm. Afterwards, GH-1 material was used as a host and GD-1 material was used as a dopant to form a 20 nm thick first green light-emitting layer by co-depositing at a mass ratio of approximately 10%. TmPyPb compound was vacuum-deposited on this first light-emitting layer to form a 20 nm thick first electron transport layer. Afterwards, Comparative Compound 1 was used as a host material and Li was used as a dopant to form a 2% mass ratio to form a 10 nm thick N-type charge generation layer. Afterwards, NPB was used as a host material and compounds 6-7 were used as dopant materials and co-deposited at a mass ratio of 10% to form a 5 nm thick P-type charge generation layer. This P-type charge generation layer can also be utilized as a second hole injection layer. On top of this, NPB material was vacuum-deposited to form a 50 nm thick second hole transport layer. Afterwards, GH-1 material was used as a host and GD-1 material was used as a dopant and co-deposited at a mass ratio of approximately 10% to form a 20 nm thick green second emitting layer. On this second emitting layer, TmPyPb compound was used as a host and Liq compound was used as a dopant and co-deposited at a mass ratio of approximately 33% to form a 20 nm thick second electron transport layer. After this, LiF material was vacuum-deposited to form an electron injection layer with a thickness of 1 nm. Finally, Al was deposited to form a 50 nm thick cathode, thereby fabricating the final tandem organic light-emitting device. The structures of the previously used HAT-CN, NPB, GH-1, GD-1, TmPyPb, and Liq materials are shown in Table 1 below.

[0296] Table 1

[0297]

[0298] Comparison Example 2

[0299] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the previously synthesized compound 5-1 was used as a P-type charge generation layer host.

[0300] Comparative Example 3

[0301] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that Comparative Compound 2 was used as an N-type charge generation layer host and Compound 5-1, previously synthesized, was used as a P-type charge generation layer host.

[0302] Comparative Example 4

[0303] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that Comparative Compound 3 was used as an N-type charge generation layer host and Compound 5-1, previously synthesized, was used as a P-type charge generation layer host.

[0304] Example 1

[0305] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the previously synthesized compound 1-97 was used as the N-type charge generation layer host, and the previously synthesized compound 5-1 was used as the P-type charge generation layer host.

[0306] Example 2

[0307] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the previously synthesized compound 2-17 was used as the N-type charge generation layer host, and the previously synthesized compound 5-1 was used as the P-type charge generation layer host.

[0308] Example 3

[0309] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the previously synthesized compound 2-86 was used as the N-type charge generation layer host, and the previously synthesized compound 5-1 was used as the P-type charge generation layer host.

[0310] Example 4

[0311] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the previously synthesized compound 1-97 was used as the N-type charge generation layer host, and the previously synthesized compound 5-26 was used as the P-type charge generation layer host.

[0312] Example 5

[0313] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the previously synthesized compound 2-17 was used as the N-type charge generation layer host, and the previously synthesized compound 5-26 was used as the P-type charge generation layer host.

[0314] Example 6

[0315] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the previously synthesized compound 2-86 was used as the N-type charge generation layer host, and the previously synthesized compound 5-26 was used as the P-type charge generation layer host.

[0316] The charge generation layers according to the previously produced comparative examples 1 to 4 and examples 1 to 6 are organized as shown in Table 2 below, and the structures of the compounds used in each are shown in detail in Table 3.

[0317] Table 2

[0318]

[0319] Table 3

[0320]

[0321] The driving voltage, current efficiency, and lifespan of the organic light-emitting devices fabricated in this manner were evaluated. The results are shown in Table 4 below.

[0322] Table 4

[0323]

[0324] As shown in Table 4 above, the embodiments according to the present invention generally exhibited lower operating voltages and higher efficiency and lifespans than the comparative examples. This will be described in more detail below.

[0325] Comparative Examples 2 to 4 and Examples 1 to 3 only changed the N-type charge generation layer host, and Examples 1 to 3 showed lower voltage, higher efficiency, and longer lifespan than Comparative Examples 2 to 4. Specifically, Comparative Example 2 used a phenanthroline compound (Comparative Compound 1) as the N-type charge generation layer host, Comparative Example 3 used an azaspirobifluorene compound (Comparative Compound 2) having one nitrogen (N), and Comparative Example 4 used a 3,7-diazaspirobifluorene compound (Comparative Compound 3) having two nitrogens (N) applied to the 3 and 7 positions. Compared to these, Examples 1 to 3 using a 4,5-diazaspirobifluorene compound having two nitrogens (N) applied to the 4 and 5 positions showed lower voltage, higher efficiency, and longer lifespan. Through this, it can be seen that the compound according to the chemical formula 1 of the present invention having 4,5-diazaspirobifluorene as a core is more preferable for application as an N-type charge generation layer host, and that the combination with an amine compound used as a P-type charge generation layer host is also better.

[0326] Meanwhile, Examples 4 to 6 are the same as Examples 1 to 3, except that the P-type charge generation layer host was changed from Compound 5-1 to Compound 5-26. When Examples 1 and 4, Examples 2 and 5, and Examples 3 and 6 were compared with each other, Examples 4 to 6 showed relatively low voltage, high efficiency, and long lifespan. Through this, it can be seen that when the compound according to Chemical Formula 1 of the present invention is used as an N-type charge generation layer host, a P-type charge generation layer host that forms a more preferable combination therewith is an amine compound containing a fluorene group.

[0327] Fabrication and Evaluation of Organic Light-Emitting Devices (2)

[0328] Comparative Example 5

[0329] After patterning the ITO substrate to be the anode so that the light-emitting area is 2 mm × 2 mm, it is cleaned with isopropyl alcohol and UV ozone, respectively. After that, the ITO substrate is mounted on the substrate holder of the vacuum deposition device and the vacuum level is 1 × 10 -7The pressure was set to 10 torr. Afterwards, plasma treatment was performed for 3 minutes under a N2 atmosphere. First, HAT-CN was vacuum-deposited to form a first hole injection layer with a thickness of 5 nm. On top of this, NPB material was vacuum-deposited to form a first hole transport layer with a thickness of 20 nm. Afterwards, GH-1 material was used as a host and GD-1 material was used as a dopant and co-deposited to a mass ratio of approximately 10% to form a green first light-emitting layer with a thickness of 20 nm. TmPyPb compound was vacuum-deposited on this first light-emitting layer to form a first electron transport layer with a thickness of 20 nm. Afterwards, Comparative Compound 1 was used as a host material and Yb was used as a dopant and co-deposited to a mass ratio of 5% to form a 10 nm thick N-type charge generation layer. Afterwards, NPB was used as a host material and compound 6-35 was used as a dopant material and co-deposited at a mass ratio of 10% to form a 5 nm thick P-type charge generation layer. This P-type charge generation layer can also be utilized as a second hole injection layer. On top of this, NPB material was vacuum-deposited to form a 50 nm thick second hole transport layer. Afterwards, GH-1 material was used as a host and GD-1 material was used as a dopant and co-deposited at a mass ratio of approximately 10% to form a 20 nm thick green second emitting layer. On this second emitting layer, TmPyPb compound was used as a host and Liq compound was used as a dopant and co-deposited at a mass ratio of approximately 33% to form a 20 nm thick second electron transport layer. After this, LiF material was vacuum-deposited to form an electron injection layer with a thickness of 1 nm. Finally, Al was deposited to form a 50 nm thick cathode, thereby fabricating the final tandem organic light-emitting device. The structures of the previously used HAT-CN, NPB, GH-1, GD-1, TmPyPb, and Liq materials are each identical to Table 1 above.

[0330] Comparative Example 6

[0331] An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that the previously synthesized compound 5-21 was used as a P-type charge generation layer host.

[0332] Comparative Example 7

[0333] An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that Comparative Compound 2 was used as an N-type charge generation layer host and Compound 5-21, previously synthesized, was used as a P-type charge generation layer host.

[0334] Comparative Example 8

[0335] An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that Comparative Compound 3 was used as an N-type charge generation layer host and Compound 5-21, previously synthesized, was used as a P-type charge generation layer host.

[0336] Example 7

[0337] An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that the previously synthesized compound 1-21 was used as the N-type charge generation layer host, and the previously synthesized compound 5-21 was used as the P-type charge generation layer host.

[0338] Example 8

[0339] An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that the previously synthesized compound 1-131 was used as the N-type charge generation layer host, and the previously synthesized compound 5-21 was used as the P-type charge generation layer host.

[0340] Example 9

[0341] An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that the previously synthesized compound 1-21 was used as the N-type charge generation layer host, and the previously synthesized compound 5-86 was used as the P-type charge generation layer host.

[0342] Example 10

[0343] An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that the previously synthesized compound 1-131 was used as the N-type charge generation layer host, and the previously synthesized compound 5-86 was used as the P-type charge generation layer host.

[0344] The charge generation layers according to the previously produced comparative examples 5 to 8 and examples 7 to 10 are organized as shown in Table 5 below, and the structures of the compounds used in each are shown in detail in Table 6.

[0345] Table 5

[0346]

[0347] Table 6

[0348]

[0349] The driving voltage, current efficiency, and lifespan of the organic light-emitting device fabricated in this manner were evaluated. The results are shown in Table 7 below.

[0350] Table 7

[0351]

[0352] As shown in Table 7 above, the examples according to the present invention showed lower driving voltages and higher efficiency and lifespans than the comparative examples, similar to the previous experimental results. This shows that even if the type of dopant in the N-type charge generation layer or the type of dopant in the P-type charge generation layer changes, the compound according to the chemical formula 1 of the present invention, which has 4,5-diazaspirobifluorene as a core, plays a significant role in improving device performance.

[0353] Similar to the previous experimental results, Examples 7 and 8, in which only the N-type charge generation layer host used the compound according to the chemical formula 1 of the present invention, exhibited lower voltage, higher efficiency, and longer lifespan than Comparative Examples 6 to 8. In addition, similar to the previous experimental results, Examples 9 and 10, in which the P-type charge generation layer host used an amine compound containing a fluorene group, exhibited lower voltage, higher efficiency, and longer lifespan than Examples 7 and 8.

[0354] Fabrication and Evaluation of Organic Light-Emitting Devices (3)

[0355] Comparative Example 9

[0356] After patterning the ITO substrate to be the anode so that the light-emitting area is 2 mm × 2 mm, it is cleaned with isopropyl alcohol and UV ozone, respectively. After that, the ITO substrate is mounted on the substrate holder of the vacuum deposition device and the vacuum level is 1 × 10 -7The pressure was set to 10 torr. Afterwards, plasma treatment was performed for 3 minutes under a N2 atmosphere. First, the HAT-CN compound was vacuum-deposited to form a first hole injection layer with a thickness of 5 nm. On top of this, the NPB material was vacuum-deposited to form a first hole transport layer with a thickness of 20 nm. Then, the GH-1 material was used as a host and the GD-1 material was used as a dopant and co-deposited to have a mass ratio of about 10% to form a green first light-emitting layer with a thickness of 20 nm. The TmPyPb compound was vacuum-deposited on this first light-emitting layer to form a first electron transport layer with a thickness of 20 nm. Afterwards, the Li material as a dopant was co-deposited to the host, Comparative Compound 4, at a mass ratio of 2% to form an N-type charge generation layer with a thickness of 10 nm. Afterwards, the HAT-CN compound was vacuum-deposited to form a P-type charge generation layer with a thickness of 5 nm. This layer was also used as a second hole injection layer. On this, NPB material was vacuum-deposited to form a second hole transport layer with a thickness of 50 nm. Thereafter, GH-1 material was used as a host and GD-1 material was used as a dopant to co-deposit at a mass ratio of approximately 10% to form a green second light-emitting layer with a thickness of 20 nm. On this light-emitting layer, TmPyPb compound was used as a host and Liq compound was used as a dopant to co-deposit at a mass ratio of approximately 33% to form a second electron transport layer with a thickness of 20 nm. Thereafter, LiF material was vacuum-deposited to form an electron injection layer with a thickness of 1 nm. Finally, aluminum (Al) was deposited at a thickness of 50 nm to form a cathode, thereby fabricating the final tandem organic light-emitting device. The structures of the HAT-CN, NPB, GH-1, GD-1, TmPyPb, and Liq materials used previously are the same as in Table 1, and therefore are omitted.

[0357] Comparative Examples 10 and 11

[0358] An organic light-emitting device was manufactured in the same manner as in Comparative Example 9, except that Comparative Compounds 5 and 6 were used instead of Comparative Compound 4, which was used as the host material of the N-type charge generation layer. The structures of Comparative Compounds 4 to 6 are respectively shown in Table 8 below.

[0359] Table 8

[0360]

[0361] Examples 11 to 19

[0362] An organic light-emitting device was manufactured in the same manner as in Comparative Example 9, except that the previously synthesized compounds in Table 9 were used instead of Comparative Compound 4, which was used as a host material for the N-type charge generation layer.

[0363] Table 9

[0364]

[0365] The driving voltage, current efficiency, and lifespan of the organic light-emitting device fabricated in this manner were evaluated. The results are shown in Table 10 below.

[0366] Table 10

[0367]

[0368] As shown in Table 10, it was confirmed that the organic light-emitting devices of the examples had lower driving voltages and improved efficiency and lifespans than the comparative examples. Compared to Comparative Example 9 using a phenanthroline compound (Comparative Compound 4), Comparative Example 10 using an azaspirobifluorene compound having one nitrogen (N) substituted (Comparative Compound 5), and Comparative Example 11 using a diazaspirobifluorene compound having two nitrogen (N) substituted at different positions from the present invention (Comparative Compound 6), it was confirmed that the efficiency and lifespans of the examples using the 4,5-diazaspirobifluorene compound according to the present invention were greatly improved. Through this, it can be seen that the 4,5-diazaspirobifluorene compound according to the present invention is most suitable as an N-type charge generation layer host compound.

[0369] As described above, the novel charge generation layer of the tandem organic light-emitting device according to the present invention is characterized by including a first compound having 4,5-diazaspirobifluorene as a core as a host for the N-type charge generation layer, and exhibiting low voltage, high efficiency, and long lifespan. In addition, by including a second compound having one or more tertiary amines as a core as a host for the P-type charge generation layer, the combination of the first compound and the second compound facilitates charge transport and prevents current leakage to the side, thereby lowering the driving voltage of the device and further improving the efficiency and lifespan. Furthermore, the organic light-emitting device of the present invention can achieve further improved device performance through the charge generation layer including the first compound, lithium or ytterbium, the second compound, and the third compound simultaneously.

Claims

1. First electrode and second electrode; A plurality of light-emitting parts positioned between the first electrode and the second electrode; and A charge generation layer is included, each of which is positioned at least at one location between two adjacent light-emitting portions; At least one of the charge generation layers includes an N-type charge generation layer and a P-type charge generation layer, The N-type charge generation layer comprises a first compound represented by the following chemical formula 1. Tandem organic light emitting diode; In the above chemical formula 1, L1 to L4 are each independently a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group, Ar1 to Ar4 are each independently selected from the group consisting of deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted sulfide group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryloxy group, substituted or unsubstituted thio group, substituted or unsubstituted amine group, substituted or unsubstituted silyl group, and substituted or unsubstituted phosphine oxide group, m and p are each independently integers from 0 to 4, n and o are each independently integers from 0 to 3, However, m+n+o+p is greater than or equal to 1.

2. In paragraph 1, The above chemical formula 1 is a tandem organic light-emitting device, which is one of the following chemical formulas 2 to 10; In the above chemical formulas 2 to 10, L1 to L4 and Ar1 to Ar4 have the same definitions as in the above chemical formula 1.

3. In paragraph 1, The N-type charge generation layer further comprises at least one metal, metal compound and organic complex of metal selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), ytterbium (Yb), samarium (Sm), tin (Sn), copper (Cu), titanium (Ti), cadmium (Cd), mercury (Hg), lead (Pb), bismuth (Bi), zinc (Zn), iron (Fe), cobalt (Co), nickel (Ni), indium (In), gallium (Ga), thorium (Th), uranium (U), silver (Ag), aluminum (Al), gold (Au), molybdenum (Mo), niobium (Nb), palladium (Pd), platinum (Pt) and europium (Eu). Tandem organic light-emitting device.

4. In paragraph 1, The above P-type charge generation layer comprises a second compound represented by the following chemical formula 11. Tandem organic light emitting diode; In the above chemical formula 11, L5 to L7 are each independently a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group, Ar5 to Ar7 are each independently selected from the group consisting of a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted amine group, and a substituted or unsubstituted fused ring group.

5. In paragraph 4, The above chemical formula 11 is a tandem organic light-emitting device, which is one of the following chemical formulas 12 to 14; In the above chemical formulas 12 to 14, L5 to L7, Ar5 and Ar6 are the same as defined in the above chemical formula 11, R1 is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted fused ring group, R2 to R7 are each independently selected from the group consisting of deuterium, halogen, cyano group, nitro group, nitrile group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted sulfide group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted fused ring group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryloxy group, substituted or unsubstituted thio group, substituted or unsubstituted amine group, substituted or unsubstituted silyl group, and substituted or unsubstituted phosphine oxide group, and adjacent R2s, adjacent R3s, adjacent R4s, adjacent R5s, adjacent R6s, or adjacent R7s may or may not combine with each other to form a ring, R8 and R9 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, which may or may not be combined with each other to form a ring, a and e are each independently integers from 0 to 3, b to d and f are each independently integers from 0 to 4.

6. In paragraph 4, The above P-type charge generation layer further comprises a third compound containing at least one cyano group (-CN). Tandem organic light-emitting device.

7. In paragraph 6, The third compound is a tandem organic light-emitting device represented by the following chemical formula A; In the above chemical formula A, Ring A is one of a substituted or unsubstituted C6~C30 aryl group, a substituted or unsubstituted C3~C30 cycloalkyl group, a substituted or unsubstituted C3~C30 cycloalkenyl group, and a substituted or unsubstituted C2~C30 heteroaryl group, R12 and R13 are each independently a halogen group; -F; -Cl; -CF3; -CN; -NC; -NO2; -OCF3; -SCN; -OCN; -SF5; -OC(CH3)3; a C1~C12 alkyl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5 and -OC(CH3)3; a C1~C12 alkoxy group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5 and -OC(CH3)3; A C6~C12 aryl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5 and -OC(CH3)3; and a C2~C12 heteroaryl group substituted with one or more of hydrogen, a halogen group, -F, -Cl, -CF3, -CN, -NC, -NO2, -OCF3, -SCN, -OCN, -SF5 and -OC(CH3)3; i can be an integer from 0 to 3, However, the above chemical formula A must contain four or more cyano groups (-CN).

8. In paragraph 1, The above multiple light emitting units are each independently, luminescent layer; a hole transport region for transporting holes to the above-described light-emitting layer; and A tandem organic light-emitting device comprising an electron transport region for transporting electrons to the above-described light-emitting layer.

9. In paragraph 8, The above hole transport region includes at least one of a hole injection layer, a hole transport layer, a hole functional layer that simultaneously injects holes and transports holes, and an electron blocking layer. The above electron transport region includes at least one of an electron injection layer, an electron transport layer, an electron functional layer that simultaneously injects electrons and transports electrons, and a hole blocking layer. Tandem organic light-emitting device.

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