WO2025080064A1 - Organic electric element comprising compound for organic electric element, and electronic device comprising same - Google Patents

Abstract

The present invention provides a tandem composition comprising a novel compound capable of improving the luminous efficiency, stability, and lifespan of an element, an organic electric element using the same, and an electronic device comprising same.

Description

Organic electric device comprising compound for organic electric device and electronic device thereof

The present invention relates to an organic electric device using a compound for an organic electric device and an electronic device thereof.

In general, the organic luminescence phenomenon refers to the phenomenon of converting electrical energy into light energy using organic materials. Organic electric devices utilizing the organic luminescence phenomenon usually have a structure including an anode and a cathode and an organic layer between them. Here, the organic layer can be formed into a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic electric device.

The current portable display market is trending toward increasing in size with large-area displays. Since portable displays have batteries with limited power supply, more efficient power consumption is required than the power consumption required by existing portable displays. In addition to efficient power consumption, luminous efficiency and lifespan issues must also be resolved.

In order to solve the problems of power consumption, luminous efficiency, and lifespan, research is being conducted on tandem organic electric devices including two or more stacks (or luminous units) in which each organic layer includes a luminous layer. In particular, research is being conducted to improve the power consumption, luminous efficiency, and lifespan of organic electric devices by improving the organic materials included in the stack.

Efficiency, lifespan, and driving voltage are interrelated. As efficiency increases, the driving voltage relatively decreases. As the driving voltage decreases, the crystallization of organic materials due to Joule heating generated during operation decreases, which tends to increase the lifespan. However, efficiency cannot be maximized simply by improving organic materials. This is because long lifespan and high efficiency can be achieved simultaneously when the energy level and T1 value of each organic material, and the inherent characteristics of the material (mobility, interfacial characteristics, etc.) are optimally combined. Therefore, it is necessary to develop a material that has high thermal stability and can efficiently achieve charge balance within the light-emitting layer.

In addition, in tandem organic devices, a charge generation layer is required between two or more stacks (or light-emitting units) to increase the current efficiency generated in the light-emitting layer and to facilitate charge distribution. Depending on how smoothly the charge distribution is facilitated in the charge generation layer, it affects the driving voltage of the entire device, and depending on the energy level difference between the n-type charge generation layer and the p-type charge generation layer, the concentration of the doping material doped in the charge generation layer, etc., it also affects the charge injection characteristics and the lifespan of the device.

That is, in tandem organic electric devices, the efficiency, lifespan, and operating voltage of the organic electric device can vary depending on which organic material is combined and used in which layer, and the development of stable and efficient organic layer materials for organic electric devices has not yet been sufficiently accomplished. Therefore, the development of new materials continues to be required.

The present invention aims to provide a composition including a compound capable of lowering the driving voltage of a device and improving the luminous efficiency, color purity, stability and lifespan of the device, an organic electric device and an electronic device thereof.

The present invention provides a tandem composition comprising a compound represented by the following chemical formula 1.

<Chemical Formula 1>

In another aspect, the present invention provides an organic electric device including a first electrode; a second electrode; and an organic layer formed between the first electrode and the second electrode, wherein the organic layer includes n stacks including a hole transport region, a light-emitting layer, and an electron transport region, wherein n is an integer from 2 to 5, and the hole transport regions of the n stacks include the tandem composition.

In another aspect, the present invention provides an electronic device including the organic electric element.

By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and the color purity and lifespan of the device can be greatly improved.

Figure 1 is an exemplary diagram of an organic electroluminescent device according to the present invention.

300: Organic electric element 110: First electrode

170: Second electrode 180: Light efficiency improvement layer

320: 1st hole injection layer 330: 1st hole transport layer

340: First light-emitting layer 350: First electron transport layer

360: n-type charge generation layer 361: p-type charge generation layer

420: Second hole injection layer 430: Second hole transport layer

440: Second light-emitting layer 450: Second electron transport layer

CGL: Charge generation layer ST1: 1st stack

ST2: Second Stack

Hereinafter, the present invention will be described in detail with reference to embodiments. In describing the present invention, if it is judged 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.

Also, in 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.

As used in this specification and the appended claims, unless otherwise stated, the following terms have the following meanings:

The term "halo" or "halogen" as used herein, unless otherwise stated, means fluorine (F), bromine (Br), chlorine (Cl), or iodine (I).

The term "alkyl" or "alkyl group" as used in the present invention, unless otherwise stated, means a radical of a saturated aliphatic functional group having a single bond of 1 to 60 carbon atoms, 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 18 carbon atoms or 1 to 12 carbon atoms, including a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cycloalkyl group or a cycloalkyl-substituted alkyl group.

The term "alkenyl group", "alkenyl group" or "alkynyl group" as used in the present invention, unless otherwise stated, includes a straight-chain or branched-chain group having a double bond or a triple bond, each having 2 to 60 carbon atoms, 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 18 carbon atoms or 2 to 12 carbon atoms, but is not limited thereto.

The term "cycloalkyl" or "cycloalkyl" as used in the present invention, unless otherwise stated, means alkyl forming a ring having 3 to 60 carbon atoms, 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 18 carbon atoms or 3 to 12 carbon atoms, but is not limited thereto.

The term “alkoxyl group,” “alkoxy group,” or “alkyloxy group” as used in the present invention means an alkyl group having an oxygen radical attached thereto, and unless otherwise specified, has, but is not limited to, 1 to 60 carbon atoms, 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 18 carbon atoms, or 1 to 12 carbon atoms.

The term "aryloxyl group" or "aryloxy group" as used in the present invention means an aryl group having an oxygen radical attached thereto, and unless otherwise specified, has, but is not limited to, 6 to 60 carbon atoms, 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms.

The terms "aryl group" and "arylene group" used in the present invention, unless otherwise stated, have, but are not limited to, 6 to 60 carbon atoms, 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 18 carbon atoms or 6 to 12 carbon atoms, respectively. In the present invention, the aryl group or arylene group means a single ring or multi-ring aromatic group, and includes an aromatic ring formed by the participation of adjacent substituents in a bond or reaction. For example, the aryl group can be a phenyl group, a biphenyl group, a fluorene group, or a spirofluorene group.

The prefix "aryl" or "ar" refers to a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and the aryl substituted radical has the carbon numbers described herein.

Also, when prefixes are named consecutively, it means that the substituents are listed in the order they were first described. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxylcarbonyl group, it means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, it means an alkenyl group substituted with an arylcarbonyl group, where the arylcarbonyl group is a carbonyl group substituted with an aryl group.

The term "heterocyclic group" as used in the present invention, unless otherwise stated, contains one or more heteroatoms, has 2 to 60 carbon atoms, 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 18 carbon atoms or 2 to 12 carbon atoms, includes at least one of a single ring and a multiple ring, and includes a heteroaliphatic ring and a heteroaromatic ring. It may also be formed by bonding adjacent functional groups.

The term "heteroatom" as used herein, unless otherwise stated, represents N, O, S, P or Si.

In addition, the "heterocyclic group" means a single ring, a ring aggregate, a fused multiple ring system, a spiro compound, etc., which contain a heteroatom. In addition, a compound which contains a heteroatom group such as SO ₂ , P = O, etc. instead of carbon forming a ring, such as the following compounds, can also be included in the heterocyclic group. For example, the "heterocyclic group" includes the following compounds.

The term "aliphatic ring" used in the present invention means a cyclic hydrocarbon excluding an aromatic hydrocarbon, and includes a single ring, a ring aggregate, a fused multiple ring system, a spiro compound, etc., and unless otherwise specified, means a ring having 3 to 60 carbon atoms, a ring having 3 to 30 carbon atoms, a ring having 3 to 25 carbon atoms, a ring having 3 to 18 carbon atoms, or a ring having 3 to 12 carbon atoms, but is not limited thereto. For example, even if an aromatic ring, benzene, and a non-aromatic ring, cyclohexane, are fused, it is also considered an aliphatic ring.

The terms "fluorenyl group", "fluorenylene group" or "fluorene triyl group" used in the present invention, unless otherwise stated, mean a monovalent, divalent or trivalent functional group wherein R, R' and R" in the structures below are all hydrogen, and a "substituted fluorenyl group", "substituted fluorenylene group" or "substituted fluorene triyl group" means that at least one of the substituents R, R', R" is a substituent other than hydrogen, and includes a case where R and R' are bonded to each other to form a spiro compound together with the carbon to which they are bonded. In the present specification, regardless of valence, a fluorenyl group, a fluorenylene group and a fluorene triyl group may all be referred to as a fluorene group.

The term "spiro compound" used in the present invention has a 'spiro union', and a spiro union means a connection formed by two rings sharing only one atom. At this time, the atom shared between the two rings is called a 'spiro atom', and depending on the number of spiro atoms contained in a compound, they are called 'monospiro-', 'dicepiro-', and 'trispiro-' compounds, respectively.

Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 18 carbon atoms or 1 to 12 carbon atoms, and "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms, 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 18 carbon atoms or 3 to 12 carbon atoms.

Unless otherwise stated, the term "ring" as used in the present invention means an aliphatic ring having 3 to 60 carbon atoms, 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 18 carbon atoms or 3 to 12 carbon atoms; or an aromatic ring having 6 to 60 carbon atoms, 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 18 carbon atoms or 6 to 12 carbon atoms; or a heterocycle having 2 to 60 carbon atoms, 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 18 carbon atoms or 2 to 12 carbon atoms; or a fused ring composed of a combination thereof, including a saturated or unsaturated ring.

Other heterocyclic compounds or heteroradicals other than the aforementioned heterocyclic compounds contain one or more heteroatoms, but are not limited thereto.

In addition, unless explicitly stated otherwise, "substituted" in the term "substituted or unsubstituted" used in the present invention means a deuterium, a halogen, an amino group, a nitrile group, a nitro group, a C ₁ to C ₂₀ alkyl group, a C ₁ to C ₂₀ alkoxyl group, a C ₁ to C ₂₀ alkylamine group, a C ₁ to C ₂₀ alkylthiophene group, a C ₆ to C ₂₀ arylthiophene group, a C ₂ to C ₂₀ alkenyl group, a C ₂ to C ₂₀ alkynyl group, a C ₃ to C ₂₀ cycloalkyl group, a C ₆ to C ₂₀ aryl group, a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₈ to C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, and a C ₂ to C It means being substituted with one or more substituents selected from the group consisting of ₂₀ heterocyclic groups, but is not limited to these substituents.

In this specification, the 'group name' corresponding to the aryl group, arylene group, heterocyclic group, etc., which are exemplified as examples of each symbol and its substituent, may be described as the 'group name reflecting the valence', or may be described as the 'parent compound name'. For example, in the case of 'phenanthrene', which is a type of aryl group, the name of the group may be described by distinguishing the valence, such as 'phenanthryl' for the monovalent 'group' and 'phenantrylene' for the divalent group, or it may be described as the parent compound name 'phenanthrene' regardless of the valence. Similarly, in the case of pyrimidine, it may be described as 'pyrimidine' regardless of the valence, or it may be described as the 'group name' of the corresponding valence, such as pyrimidinyl group for monovalent and pyrimidinylene for divalent. In addition, in this specification, numbers or alphabets indicating positions may be omitted when describing the compound name or substituent name. For example, pyrido[4,3-d]pyrimidine can be written as pyridopyrimidine, benzofuro[2,3-d]pyrimidine can be written as benzofuropyrimidine, 9,9-dimethyl-9H-fluorene can be written as dimethylfluorene, etc. Accordingly, both benzo[g]quinoxaline and benzo[f]quinoxaline can be written as benzoquinoxaline.

Additionally, unless explicitly stated otherwise, the chemical formulas used in the present invention are applied in the same manner as the substituent definitions by the index definitions of the chemical formulas below.

Here, when a is an integer of 0, the substituent R ¹ is absent, and when a is an integer of 1, one substituent R ¹ is bonded to any one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, they are bonded as follows, wherein R ¹ may be the same or different, and when a is an integer of 4 to 6, they are bonded to the carbon of the benzene ring in a similar manner, and meanwhile, the indication of the hydrogen bonded to the carbon forming the benzene ring is omitted.

In addition, unless explicitly stated, the terms "ortho", "meta", and "para" used in the present invention mean all substitution positions of substituents, and the ortho position refers to a compound where the positions of the substituents are immediately adjacent, for example, in the case of benzene, it refers to the 1st and 2nd positions, the meta position refers to the substitution position next to the immediately adjacent substitution position, and refers to the 1st and 3rd positions when benzene is an example, and the para position refers to the substitution position next to the meta position, and refers to the 1st and 4th positions when benzene is an example. A more detailed description of examples of substitution positions is as follows, and it can be confirmed that the ortho- and meta- positions are substituted in a non-linear type, and the para- position is substituted in a linear type.

[Example of ortho-position]

[Example of meta-position]

[Example of para-location]

The term "composition" as used in the present invention is intended to be broadly interpreted to include not only compounds but also solutions, dispersions, liquids and solid mixtures (mixtures, admixtures). The composition of the present invention may contain the compound of the present invention alone, or may contain two or more different combinations of the compounds, or may contain the compound with two or more other compounds in combination. In other words, the composition may contain the compound corresponding to the chemical formula 1 alone, may contain a mixture of two or more compounds of the chemical formula 1, or may contain a mixture of the compound of the chemical formula 1 and a compound not corresponding to the present invention. Here, the compound not corresponding to the present invention may be a single compound or may be two or more compounds. In this case, when the compound is contained in a combination of two or more other compounds, the other compounds may be compounds already known in each organic layer, or compounds to be developed in the future. In this case, the compound contained in the organic layer may be composed solely of the same compound, or may be a mixture of two or more heterogeneous compounds represented by the chemical formula 1.

The term "tandem" used in the present invention means two pairs or more devices mechanically coupled in parallel, and the tandem device structure means a structure in which two or more independent organic electric elements are connected in series. In other words, the tandem organic electric element means an organic electric element in which two or more sets of stacks of multilayer organic layers are formed between a first electrode and a second electrode, and a charge generation layer may be formed between the stacks of organic layers. Here, each stack may be an organic layer having the same stacked structure, but may also be an organic layer having different stacked structures.

Reorganization Energy (RE) refers to the energy lost due to changes in molecular structure arrangement when charges (electrons, holes) move. It depends on molecular geometry and has the characteristic that its value decreases as the difference between the neutral potential energy surface (PES) and the charged PES decreases. The RE value can be obtained by the following calculation formula.

Each argument can be defined as follows:

NONE: Neutral geometry of a neutral molecule (hereinafter, NO opt.)

NOAE: Anion geometry of neutral molecules

NOCE: Cation geometry of a neutral molecule

AONE: Neutral geometry of anion molecules

AOAE: Anion geometry of anion molecules (hereinafter, AO opt.)

CONE: Neutral geometry of cation molecules

COCE: Cation geometry of cation molecules (hereinafter, CO opt.)

The reorganization energy value and mobility are inversely proportional, and under the condition of having the same r and T values, the RE value of each material directly affects the mobility. The relationship between the RE value and mobility is expressed as follows.

Each argument can be defined as follows:

λ : Reorganization energy, μ : mobility, r: dimer displacement, t: intermolecular charge transfer matrix element.

From the above equation, we can see that the lower the RE value, the faster the mobility.

Reorganization energy values require a simulation tool that can calculate potential energy according to molecular structure, and we used Gaussian09 (hereinafter, G09) and Jaguar (hereinafter, JG) modules from Schrodinger Materials Science. Both G09 and JG are tools that analyze the properties of molecules through quantum mechanical (QM) calculations, and have the function of optimizing molecular structures or calculating energy for a given molecular structure (Single-point energy).

The process of performing QM calculations on molecular structures requires large computational resources, and we use two cluster servers for these calculations. Each cluster server consists of four node workstations and one master workstation, and each node uses a CPU with 36 or more cores to perform molecular QM calculations using parallel computing through symmetric multiprocessing (SMP).

Using G09, the molecular structures optimized in neutral/charge states and their potential energies (NONE/COCE) required for rearrangement energy are calculated. By changing only the charge of the two optimized structures, the charge state potential energy (NOCE) of the structure optimized in neutral state and the neutral state potential energy (CONE) of the structure optimized in charge state are calculated. After that, the rearrangement energy is calculated according to the following relationship.

Since Schrödinger provides a function to automatically perform this type of calculation process, the potential energy for each state was sequentially calculated and the RE value was calculated through the JG module simply by providing the molecular structure (NO) of the basic state.

Hereinafter, the laminated structure of an organic electric device including the compound of the present invention will be described with reference to Fig. 1.

When adding reference signs to components of each drawing, it should be noted that identical components are given the same signs as much as possible even if they are shown on different drawings. In addition, when describing the present invention, if it is determined that a specific description of a related known configuration or function may obscure the gist of the present invention, the detailed description is omitted.

Figure 1 is an exemplary diagram of an organic electric device according to an embodiment of the present invention.

Referring to FIG. 1, an organic electric element (300) according to an embodiment of the present invention may have two or more sets of stacks (ST1, ST2) of organic layers formed in multiple layers formed between a first electrode (110) and a second electrode (170), and a charge generation layer (CGL) may be formed between the stacks of organic layers.

Specifically, an organic electric device according to one embodiment of the present invention may include a first electrode (110), a first stack (ST1), a charge generation layer (CGL: Charge Generation Layer), a second stack (ST2), a second electrode (170), and a light efficiency improvement layer (180).

The first stack (ST1) is an organic layer formed on the first electrode (110), which may include a first hole injection layer (320), a first hole transport layer (330), a first light-emitting layer (340), and a first electron transport layer (350), and the second stack (ST2) may include a second hole injection layer (420), a second hole transport layer (430), a second light-emitting layer (440), and a second electron transport layer (450), and the second hole injection layer (420) of the second stack (ST2) may be omitted as needed. In this way, the first stack and the second stack may be organic layers having the same stacked structure, but may also be organic layers having different stacked structures.

A charge generation layer (CGL) may be formed between the first stack (ST1) and the second stack (ST2). The charge generation layer (CGL) may include an n-type charge generation layer (360) adjacent to the first electron transport layer (350) of the first stack (ST1) and a p-type charge generation layer (361) adjacent to the second hole injection layer (420) of the second stack (ST2). This charge generation layer (CGL) is formed between the first light-emitting layer (340) and the second light-emitting layer (440) to increase the current efficiency generated in each light-emitting layer and to smoothly distribute charges. In the case of a top emission organic light emitting device, the formation of a light efficiency improvement layer (180) can reduce optical energy loss due to SPPs (surface plasmon polaritons) in the second electrode (170), and in the case of a bottom emission organic light emitting device, the light efficiency improvement layer (180) can perform a buffering role for the second electrode (170).

When a plurality of light-emitting layers are formed by a multilayer stack structure as in Fig. 1, not only can an organic light-emitting device be manufactured that emits white light by the mixing effect of the light emitted from each light-emitting layer, but an organic light-emitting device that emits light of various colors can also be manufactured. Although not shown in Fig. 1, a buffer layer and a light-emitting auxiliary layer may be further formed between the hole transport layer and the light-emitting layer of each stack, and an electron transport auxiliary layer may be further formed between the light-emitting layer and the electron transport layer.

Although FIG. 1 describes a tandem device having two stacks, the organic electric device according to the present invention may be a tandem device having two or more stacks (e.g., a tandem device having three stacks, a tandem device having four stacks).

Preferably, the compounds represented by chemical formulas 1 and 2 of the present invention can be used as a charge generation layer (CGL), and more preferably, the compound represented by chemical formula 1 can be used as a p-type charge generation layer, and the compound represented by chemical formula 2 can be used as an n-type charge generation layer.

Even if the core is identical or similar, the band gap, electrical properties, interfacial properties, etc. can vary depending on which substituent is bonded at which position. Therefore, research is needed on the selection of the core and the combination of sub-substituents bonded to it. In particular, when the energy level and T1 value between each organic layer, and the intrinsic properties of the material (mobility, interfacial properties, etc.) are optimally combined, long life and high efficiency can be achieved at the same time.

An organic light-emitting device according to one embodiment of the present invention may be manufactured using various deposition methods. It can be manufactured using a deposition method such as PVD or CVD, for example, a metal or a conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode (110), and a first stack (ST1) sequentially including a first hole injection layer (320), a first hole transport layer (330), a first light-emitting layer (340), and a first electron transport layer (350) is formed thereon, and then a charge generation layer (CGL) sequentially including an n-type charge generation layer (360) and a p-type charge generation layer (361) for connecting two stacks is formed thereon, and then a second stack (ST2) sequentially including a second hole injection layer (420), a second hole transport layer (430), a second light-emitting layer (440), and a second electron transport layer (450) is formed thereon. It can be manufactured by forming an electron injection layer and depositing a material that can be used as a cathode (170) thereon. In addition, a buffer layer (not shown) and a light-emitting auxiliary layer (not shown) may be further formed between the hole transport layer and the light-emitting layer of each stack, and an electron transport auxiliary layer (not shown) may be further formed between the light-emitting layer and the electron transport layer, or two or more stack structures may be formed as described above.

In addition, the organic layer can be manufactured with a smaller number of layers by using various polymer materials, rather than a deposition method, such as a solution process or a solvent process, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, a roll-to-roll process, a doctor blading process, a screen printing process, or a thermal transfer method. Since the organic layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the formation method.

In addition, the organic electric device according to one embodiment of the present invention may be selected from the group consisting of an organic light-emitting device, an organic solar cell, an organic photoconductor, an organic transistor, a monochrome lighting device, and a quantum dot display device.

Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. At this time, the electronic device may be a current or future wired or wireless communication terminal, and includes all 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.

Hereinafter, a composition according to one aspect of the present invention and an organic electric device comprising the same will be described.

The present invention provides a tandem composition comprising a compound represented by the following chemical formula 1.

<Chemical Formula 1>

In the above chemical formula 1, each symbol can be defined as follows.

R ¹ , R ² and R ³ are each the same or different from each other and are independently selected from the group consisting of hydrogen; deuterium; halogen; cyano group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ cycloalkyl group; fused ring group of _{C 3} ~ C ₆₀ aliphatic ring and _{C 6} ~ C ₆₀ aromatic ring; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C 20 alkynyl group; C 1 ~ C ₃₀ alkoxyl group; and C ₆ ~ C ₃₀ aryloxy group;

The above R ¹ , R ² and R ³ may be, when they are aryl groups, preferably C ₆ to C ₃₀ aryl groups, more preferably C ₆ to C ₂₅ , C ₆ to C ₁₈ or C ₆ to C ₁₂ aryl groups, such as phenyl, biphenyl, terphenyl, naphthalene, phenanthrene, chrysene and the like.

The above R ¹ , R ² and R ³ may be a heterocyclic group, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₂₅ , C ₂ to C ₁₈ or C ₂ to C ₁₂ heterocyclic group, and examples thereof include pyrazine, thiophene, pyridine, pyrimidine, quinoline, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, quinoxaline, benzoquinazoline, carbazole, dibenzoquinazoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, benzothiophenopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, naphthobenzofuran, It could be naphthobenzothiophene, etc.

When the above R ¹ , R ² and R ³ are a cycloalkyl group, they may preferably be a C ₃ to C ₃₀ cycloalkyl group, more preferably a C ₃ to C ₂₅ , C ₃ to C ₁₈ or C ₃ to C ₁₂ cycloalkyl group, and specifically, they may be cyclobutane, cyclopentane, cyclohexane, bicycloheptane, adamantyl, etc.

When the above R ¹ , R ² and R ³ are a fused ring group, they may preferably be a fused ring group of an aliphatic ring of C ₃ to C ₃₀ and an aromatic ring of C ₆ to C ₃₀ , and more preferably a fused ring group of an aliphatic ring of C ₃ to C ₂₅ and an aromatic ring of C ₆ to C ₂₅ .

When the above R ¹ , R ² and R ³ are alkyl groups, they may preferably be C ₁ to C ₃₀ alkyl groups, more preferably C ₁ to C ₂₅ , C ₁ to C ₁₈ or C ₁ to C ₁₂ alkyl groups, and for example, may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, etc.

When the above R ¹ , R ² and R ³ are alkoxyl groups, they may preferably be alkoxyl groups of C ₁ to C ₂₅ , C ₁ to C ₁₈ or C ₁ to C ₁₂ .

When the above R ¹ , R ² and R ³ are aryloxy groups, they may preferably be aryloxy groups of C ₆ to C ₂₅ , C ₆ to C ₁₈ or C ₆ to C ₁₂ .

Ar ¹ and Ar ² are independently selected from the group consisting of a C ₆ to C ₆₀ aryl group; a fluorenyl group; and a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P;

The above Ar ¹ and Ar ² may be, when they are aryl groups, preferably C ₆ to C ₃₀ aryl groups, more preferably C ₆ to C ₂₅ , C ₆ to C ₁₈ or C ₆ to C ₁₂ aryl groups, such as phenyl, biphenyl, terphenyl, naphthalene, phenanthrene, chrysene, etc.

The above Ar ¹ and Ar ² , when a heterocyclic group, may be preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₂₅ , C ₂ to C ₁₈ or C ₂ to C ₁₂ heterocyclic group, and examples thereof may include pyrazine, thiophene, pyridine, pyrimidine, quinoline, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, quinoxaline, benzoquinazoline, carbazole, dibenzoquinazoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, benzothioenopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, naphthobenzofuran, naphthobenzothiophene, etc. there is.

X ¹ is O or S,

a and c are independently integers from 0 to 4, b is an integer from 0 to 3,

Here, the aryl group, the heterocyclic group, the fluorenyl group, the fused ring group, the cycloalkyl group, the alkyl group, the alkenyl group, the alkynyl group, the alkoxy group and the aryloxy group are each independently selected from deuterium; halogen; a silane group; a siloxane group; a boron group; a germanium group; a cyano group; a nitro group; a C ₁ to C ₂₀ alkylthio group; _{a C 1 to} C ₂₀ alkoxyl group; a C ₁ to C ₂₀ alkyl group; a C ₂ to C ₂₀ alkenyl group; a C 2 to C 20 alkynyl group; a _{C 6} to C ₂₀ aryl group; a C ₆ to C ₂₀ aryl group substituted with deuterium; a fluorenyl group; a C ₂ to C ₂₀ heterocyclic group; a C ₃ to C ₂₀ cycloalkyl group; C ₇ to C ₂₀ arylalkyl group; and C ₈ to C ₂₀ arylalkenyl group; may be further substituted with one or more substituents selected from the group consisting of, and further, hydrogen of these substituents may be further substituted with one or more deuteriums, and further, these substituents may be combined with each other to form a ring, wherein the 'ring' refers to a fused ring formed of a C ₃ to C ₆₀ aliphatic ring, a C ₆ to C ₆₀ aromatic ring, a C ₂ to C ₆₀ heterocycle, or a combination thereof, and includes a saturated or unsaturated ring.

In addition, the present invention provides a tandem composition in which the chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-3.

<Chemical Formula 1-1> <Chemical Formula 1-2>

<Chemical Formula 1-3>

{In the above chemical formulas 1-1 to 1-3, R ¹ , R ² , R ³ , Ar ¹ , Ar ² , X ¹ , a, b and c are the same as defined in the above chemical formula 1.}

In addition, the present invention provides a tandem composition in which at least one of Ar ¹ and Ar ² is represented by the following chemical formula A-1 or chemical formula A-2.

<Chemical Formula A-1> <Chemical Formula A-2>

In the above chemical formulas A-1 and A-2, each symbol can be defined as follows.

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each the same or different and independently hydrogen; deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C ₁ to C ₂₀ alkylthio group; C ₁ to C ₂₀ alkoxyl group; C ₁ to C ₂₀ alkyl group; C ₂ to C ₂₀ alkenyl group; C ₂ to C ₂₀ alkynyl group; C ₆ to C ₂₀ aryl group; fluorenyl group; C ₂ to C ₂₀ heterocyclic group; C ₃ to C ₂₀ cycloalkyl group; C ₇ to C ₂₀ arylalkyl group; and is selected from the group consisting of an arylalkenyl group having C ₈ to C ₂₀ ;

X ² is O, S or NR',

The above R' is selected from the group consisting of a C ₆ ~ C ₂₀ aryl group; a fluorenyl group; a C ₂ ~ C ₂₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P; a fused ring group of a C ₃ ~ C ₂₀ aliphatic ring and a C ₆ ~ C ₂₀ aromatic ring; a C ₁ ~ C ₂₀ alkyl group; a C ₂ ~ C ₂₀ alkenyl group; and a C ₂ ~ C ₂₀ alkynyl group;

d, f, h and i are independently integers from 0 to 4, e is an integer from 0 to 3, g is an integer from 0 to 5,

* indicates the position of joining,

Here, the aryl group, heterocyclic group, fluorenyl group, alkyl group, alkenyl group, alkynyl group, alkoxy group, arylalkyl group, arylalkenyl group, alkylthio group and cycloalkyl group may be further substituted with one or more substituents selected from the group consisting of deuterium; a C ₁ to C ₂₀ alkyl group; _{a C 2 to} C ₂₀ alkenyl group; a C ₂ to C ₂₀ alkynyl group; a C ₆ to C ₂₀ aryl group; a fluorenyl group; and a _C 2 to C 20 heterocyclic group.

The above chemical formula A-1 can be represented by any one of the following chemical formulas A-1-1 to A-1-4.

<Chemical Formula A-1-1> <Chemical Formula A-1-2>

<Chemical Formula A-1-3> <Chemical Formula A-1-4>

{In the above chemical formulas A-1-1 to A-1-4, X ² , R ⁴ , R ⁵ , d, e and * are the same as defined in the above chemical formula A-1.}

The above chemical formula A-2 can be represented by any one of the following chemical formulas A-2-1 to A-2-3.

<Chemical Formula A-2-1> <Chemical Formula A-2-2>

<Chemical Formula A-2-3>

{In the above chemical formulas A-2-1 to A-2-3, R ⁶ , R ⁷ , R ⁸ , R ⁹ , f, g, h, i and * are the same as defined in the above chemical formula A-1.}

Specifically, the compound of the above chemical formula 1 may be any one of the following compounds P-1 to P-112, but is not limited thereto.

In addition, in another aspect, the present invention provides an organic electric device including a first electrode; a second electrode; and an organic layer formed between the first electrode and the second electrode, wherein the organic layer includes n stacks including a hole transport region, a light-emitting layer, and an electron transport region, wherein n is an integer from 2 to 5, and the hole transport region of at least one stack among the n stacks includes a tandem composition including a compound represented by the chemical formula 1.

In addition, the present invention provides an organic electric device including a hole transport region, a hole transport layer, and a light-emitting auxiliary layer formed on the hole transport layer. In addition, the present invention provides an organic electric device including a tandem composition including a compound represented by the chemical formula 1 in the light-emitting auxiliary layer.

In addition, the organic electric device according to the present invention may further include a light efficiency improvement layer formed on at least one surface of the first electrode and the second electrode, which is opposite to the organic layer.

In another aspect, the present invention provides an electronic device including a display device including the organic electric element; and a control unit for driving the display device. At this time, the organic electric element may be at least one of an organic light-emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochrome or white lighting element. At this time, the electronic device may be a current or future wired or wireless communication terminal, and includes all 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.

Hereinafter, examples of synthesis of a compound represented by chemical formula 1 according to the present invention and examples of manufacturing an organic electric device will be described in detail by way of examples, but the present invention is not limited to the following examples.

[Synthesis method]

The compound represented by chemical formula 1 according to the present invention (Final Product) can be synthesized by a reaction as in the following reaction scheme 1, but is not limited thereto.

<Reaction Formula 1>

{In the above reaction scheme 1, Hal ¹ is I, Br or Cl.}

I. Synthesis of sub 1

Sub 1 of the above reaction scheme 1 can be synthesized by the reaction path of the following reaction scheme 2, but is not limited thereto.

<Reaction Formula 2>

{In the above reaction scheme 2, Hal ¹ and Hal ² are I, Br or Cl.}

1. sub 1-1 synthesis example

2-bromodibenzo[b,d]furan (30 g, 121.41 mmol) and (4-chlorophenyl)boronic acid (18.99 g, 121.41 mmol) were dissolved in 400 mL of THF in a round-bottomed flask, and Pd(pph ₃ ) ₄ (4.21 g, 3.64 mmol) and K ₂ CO ₃ (33.5 g, 242.84 mmol) dissolved in 100 mL of water were added, and the mixture was stirred at 80°C. Upon completion of the reaction, the mixture was extracted with THF and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain 25.7 g (yield: 76%) of the product sub 1-1 .

2. Synthesis example of sub 1-12

2-bromodibenzo[b,d]furan (30 g, 121.41 mmol) and (3-chloro-[1,1'-biphenyl]-2-yl)boronic acid (28.24 g, 121.41 mmol) were dissolved in 400 mL of THF in a round-bottomed flask, and Pd(pph ₃ ) ₄ (4.21 g, 3.64 mmol) and K ₂ CO ₃ (33.5 g, 242.84 mmol) dissolved in 100 mL of water were added, and the mixture was stirred at 80°C. Upon completion of the reaction, the mixture was extracted with THF and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain 35.76 g (yield: 83%) of the product sub 1-12 .

3. sub 1-34 synthesis example

2-Bromo-8-fluorodibenzo[b,d]furan (20 g, 75.45 mmol) and (3-chlorophenyl)boronic acid (11.80 g, 75.45 mmol) were dissolved in 300 mL of THF in a round-bottomed flask, and Pd(pph ₃ ) ₄ (2.62 g, 2.26 mmol) and K ₂ CO ₃ (20.82 g, 150.90 mmol) dissolved in 80 mL of water were added, and the mixture was stirred at 80°C. Upon completion of the reaction, the mixture was extracted with THF and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain 17.91 g (yield: 80%) of the product sub 1-34 .

Meanwhile, compounds belonging to sub 1 may be, but are not limited to, the compounds below, and Table 1 below shows the FD-MS (Field Desorption-Mass Spectrometry) values of compounds belonging to sub 1.

compound FD-MS compound FD-MS sub 1-1 m/z=278.05 (C ₁₈ H ₁₁ ClO=278.74) sub 1-2 m/z=278.05 (C ₁₈ H ₁₁ ClO=278.74) sub 1-3 m/z=278.05 (C ₁₈ H ₁₁ ClO=278.74) sub 1-4 m/z=354.08 (C ₂₄ H ₁₅ ClO=354.83) sub 1-5 m/z=354.08 (C ₂₄ H ₁₅ ClO=354.83) sub 1-6 m/z=292.07 (C ₁₉ H ₁₃ ClO=292.76) sub 1-7 m/z=334.11 (C ₂₂ H ₁₉ ClO=334.84) sub 1-8 m/z=294.80 (C ₁₈ H ₁₁ ClS=294.80) sub 1-9 m/z=292.07 (C ₁₉ H ₁₃ ClO=292.76) sub 1-10 m/z=354.08 (C ₂₄ H ₄₂ ClO=354.83) sub 1-11 m/z=334.11 (C ₂₂ H ₁₉ ClO=334.84) sub 1-12 m/z=354.08 (C ₂₄ H ₁₅ ClO=354.83) sub 1-13 m/z=294.03 (C ₁₈ H ₁₁ ClS=294.80) sub 1-14 m/z=354.08 (C ₂₄ H ₁₅ ClO=354.83) sub 1-15 m/z=292.07 (C ₁₉ H ₁₃ ClO=292.76) sub 1-16 m/z=354.08 (C ₂₄ H ₁₅ ClO=354.83) sub 1-17 m/z=334.11 (C ₂₂ H ₁₆ ClO=334.84) sub 1-18 m/z=444.09 (C ₃₀ H ₁₇ ClO ₂ =444.91) sub 1-19 m/z=460.07 (C ₃₀ H ₁₇ ClOS=460.98) sub 1-20 m/z=444.09 (C ₃₀ H ₁₇ ClO ₂ =444.91) sub 1-21 m/z=460.07 (C ₃₀ H ₁₇ ClOS=460.98) sub 1-22 m/z=354.08 (C ₂₄ H ₁₅ ClO=354.83) sub 1-23 m/z=354.08 (C ₂₄ H ₁₅ ClO=354.83) sub 1-24 m/z=285.09 (C ₁₈ H ₄ D7ClO=285.78) sub 1-25 m/z=282.07 (C ₁₈ H ₇ D4ClO=282.76) sub 1-26 m/z=289.12 (C ₁₈ D ₁₁ ClO=289.80) sub 1-27 m/z=282.07 (C ₁₈ H ₇ D4ClO=282.76) sub 1-28 m/z=282.07 (C ₁₈ H ₇ D4ClO=282.76) sub 1-29 m/z=289.12 (C ₁₈ D ₁₁ ClO=289.80) sub 1-30 m/z=305.10 (C ₁₈ D ₁₁ ClS=305.86) sub 1-31 m/z=305.10 (C ₁₈ D ₁₁ ClS=305.86) sub 1-32 m/z=358.11 (C ₂₄ H ₁₁ D4ClO=358.86) sub 1-33 m/z=365.15 (C ₂₄ H ₄ D ₁₁ ClO=365.90) sub 1-34 m/z=296.04 (C ₁₈ H ₁₀ ClFO=296.73) sub 1-35 m/z=312.02 (C ₁₈ H ₁₀ ClFS=312.79) sub 1-36 m/z=296.04 (C ₁₈ H ₁₀ ClFO=296.73) sub 1-37 m/z=360.13 (C ₂₄ H ₂₁ ClO=360.88) sub 1-38 m/z=354.08 (C ₂₄ H ₁₅ ClO=354.83) sub 1-39 m/z=354.08 (C ₂₄ H ₁₅ ClO=354.83) sub 1-40 m/z=360.13 (C ₂₄ H ₂₁ ClO=360.88) sub 1-41 m/z=370.06 (C ₂₄ H ₁₅ ClS=370.89) sub 1-42 m/z=303.05 (C ₁₉ H ₁₀ ClNO=303.75) sub 1-43 m/z=379.08 (C ₂₅ H ₁₅ ClNO=379.84) sub 1-44 m/z=395.05 (C ₂₅ H ₁₄ ClNS=395.90)

II. Synthesis of sub 2

Sub 2 of the above reaction scheme 1 can be synthesized by the reaction path of the following reaction scheme 3, but is not limited thereto.

<Reaction Formula 3>

{In the above reaction scheme 3, Hal ³ is I, Br or Cl.}

1. sub 2-1 synthesis example

dibenzo[b,d]furan-1-amine (20 g, 109.16 mmol) and 1-bromodibenzo[b,d]furan (26.97 g, 109.16 mmol) was dissolved in 300 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (3.0 g, 3.28 mmol), P(t-bu) ₃ (1.33 g, 6.55 mmol), t-BuONa (20.98 g, 218.33 mmol) were added and stirred at 40°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column and recrystallized to obtain 34.33 g (yield: 90%) of the product sub 2-1 .

2. sub 2-11 synthesis example

Dibenzo[b,d]furan-1-amine (20 g, 109.16 mmol) and 9-(3-bromophenyl)-9-phenyl-9H-fluorene (43.37 g, 109.16 mmol) were dissolved in 300 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (3.0 g, 3.28 mmol), P(t-bu) ₃ (1.33 g, 6.55 mmol), and t-BuONa (20.98 g, 218.33 mmol) were added and stirred at 40°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain 49.09 g (yield: 90%) of the product sub 2-11 .

3. sub 2-25 synthesis example

9,9-dimethyl-9H-fluoren-4-amine (20 g, 95.56 mmol) and 2-bromo-9-phenyl-9H-carbazole (30.79 g, 95.56 mmol) were dissolved in 300 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (2.63 g, 2.87 mmol), P(t-bu) ₃ (1.16 g, 5.73 mmol), and t-BuONa (18.36 g, 191.12 mmol) were added and stirred at 40°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column and recrystallized to obtain 40.91 g (yield: 95%) of the product sub 2-25.

Meanwhile, compounds belonging to sub 2 may be compounds as follows, but are not limited thereto, and Table 2 below shows the FD-MS values of compounds belonging to sub 2.

compound FD-MS compound FD-MS sub 2-1 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.39) sub 2-2 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.39) sub 2-3 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.39) sub 2-4 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.39) sub 2-5 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) sub 2-6 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) sub 2-7 m/z=424.16 (C ₃₀ H ₂₀ N ₂ O=424.50) sub 2-8 m/z=375.16 (C ₂₇ H ₂₁ NO=375.47) sub 2-9 m/z=335.13 (C ₂₄ H ₁₇ NO=335.41) sub 2-10 m/z=341.18 (C ₂₄ H ₂₃ NO=341.45) sub 2-11 m/z=499.19 (C ₃₇ H ₂₅ NO=499.61) sub 2-12 m/z=499.19 (C ₃₇ H ₂₅ NO=499.61) sub 2-13 m/z=499.19 (C ₃₇ H ₂₅ NO=499.61) sub 2-14 m/z=499.19 (C ₃₇ H ₂₅ NO=499.61) sub 2-15 m/z=525.69 (C ₄₀ H ₃₁ N=525.69) sub 2-16 m/z=525.69 (C ₄₀ H ₃₁ N=525.69) sub 2-17 m/z=485.21 (C ₃₇ H ₂₇ N=485.63) sub 2-18 m/z=559.23 (C ₄₃ H ₂₉ N=559.71) sub 2-19 m/z=423.20 (C ₃₂ H ₂₅ N=423.56) sub 2-20 m/z=465.25 (C ₃₅ H ₃₁ N=465.64) sub 2-21 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) sub 2-22 m/z=251.17 (C ₁₈ H ₂₁ N=251.37) sub 2-23 m/z=361.18 (C ₂₇ H ₂₃ N=361.49) sub 2-24 m/z=401.21 (C ₃₀ H ₂₇ N=401.55) sub 2-25 m/z=450.21 (C ₃₃ H ₂₆ N ₂ =450.59) sub 2-26 m/z=499.20 (C ₃₆ H ₂₅ N ₃ =499.62) sub 2-27 m/z=575.22 (C ₄₃ H ₂₉ NO=575.71) sub 2-28 m/z=575.22 (C ₄₃ H ₂₉ NO=575.71) sub 2-29 m/z=477.25 (C ₃₆ H ₃₁ N=477.65) sub 2-30 m/z=526.24 (C ₃₉ H ₃₀ N ₂ =526.68) sub 2-31 m/z=356.15 (C ₂₄ H ₈ D ₇ NO ₂ =356.43) sub 2-32 m/z=363.20 (C ₂₄ HD ₁₄ NO ₂ =363.47) sub 2-33 m/z=506.24 (C ₃₇ H ₁₈ D ₇ NO=506.66) sub 2-34 m/z=516.30 (C ₃₇ H ₈ D ₁₇ NO=516.72) sub 2-35 m/z=250.15 (C ₁₈ H ₁₀ D ₅ N=250.3.6) sub 2-36 m/z=522.35 (C ₃₆ H ₂ D ₂₃ N ₃ =522.76) sub 2-37 m/z=603.40 (C ₄₃ HD ₂₈ NO=403.88) sub 2-38 m/z=501.31 (C ₃₇ H ₁₁ D ₁₆ N=501.73) sub 2-39 m/z=506.24 (C ₃₇ H ₁₈ D ₇ NO=506.66) sub 2-40 m/z=361.18 (C ₂₇ H ₂₃ N=361.49) sub 2-41 m/z=485.21 (C ₃₇ H ₂₇ N=485.63) sub 2-42 m/z=321.15 (C ₂₄ H ₁₉ N=321.42) sub 2-43 m/z=393.15 (C ₂₇ H ₂₀ NFO=393.16) sub 2-44 m/z=353.12 (C ₂₄ H ₁₆ FNO=353.40) sub 2-45 m/z=367.10 (C ₂₄ H ₁₄ FNO ₂ =367.38) sub 2-46 m/z=346.15 (C ₂₅ H ₁₈ N ₂ =346.43) sub 2-47 m/z=437.21 (C ₃₃ H ₂₇ N=437.59) sub 2-48 m/z=361.18 (C ₂₇ H ₂₃ N=361.49) sub 2-49 m/z=411.16 (C ₃₀ H ₂₁ NO=411.50) sub 2-50 m/z=485.21 (C ₃₇ H ₂₇ N=485.63) sub 2-51 m/z=485.21 (C ₃₇ H ₂₇ N=485.63) sub 2-52 m/z=367.22 (C ₂₇ H ₁₇ D ₆ N=367.52) sub 2-53 m/z=407.25 (C ₃₀ H ₂₁ D ₆ N=407.59) sub 2-54 m/z=381.20 (C ₂₇ H ₁₅ D ₆ NO=381.51) sub 2-55 m/z=531.28 (C ₄₀ H ₂₀ D ₆ N=531.73)

III. Synthesis of Final Product

1. P-1 Synthesis Example

Sub 1-1 (20 g, 71.75 mmol) and sub 2-1 (25.07 g, 71.75 mmol) were dissolved in 200 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (1.97 g, 2.15 mmol), P (t-bu) ₃ (0.87 g, 4.31 mmol), and t-BuONa (13.79 g, 143.50 mmol) were added and stirred at 120°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column and recrystallized to obtain 39.48 g of the product P-1 (yield: 93%).

2. P-19 Synthetic Example

Sub 1-11 (20 g, 59.73 mmol) and sub 2-4 (20.87 g, 59.73 mmol) were dissolved in 200 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (1.64 g, 1.79 mmol), P (t-bu) ₃ (0.72 g, 3.58 mmol), and t-BuONa (11.48 g, 119.46 mmol) were added and stirred at 120°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain 37.14 g of the product P-19 (yield: 96%).

3. P-21 Synthetic Example

Sub 1-1 (20 g, 71.75 mmol) and sub 2-11 (35.85 g, 71.75 mmol) were dissolved in 200 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (1.97 g, 2.15 mmol), P (t-bu) ₃ (0.87 g, 4.31 mmol), and t-BuONa (13.79 g, 143.50 mmol) were added and stirred at 120°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column and recrystallized to obtain 49.51 g of the product P-21 (yield: 93%).

4. P-33 Synthetic Example

Sub 1-14 (20 g, 56.37 mmol) and sub 2-15 (29.63 g, 56.37 mmol) were dissolved in 200 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (1.55 g, 1.69 mmol), P (t-bu) ₃ (0.68 g, 3.38 mmol), and t-BuONa (10.83 g, 112.73 mmol) were added and stirred at 120°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column and recrystallized to obtain 42.34 g (yield: 89%) of the product P-33 .

5. P-42 Synthetic Example

Sub 1-2 (20 g, 71.75 mmol) and sub 2-21 (17.60 g, 71.75 mmol) were dissolved in 200 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (1.97 g, 2.15 mmol), P (t-bu) ₃ (0.87 g, 4.31 mmol), and t-BuONa (13.79 g, 143.50 mmol) were added and stirred at 120°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain 33.24 g of the product P-42 (yield: 95%).

6. P-50 Synthetic Example

Sub 1-19 (30 g, 65.08 mmol) and sub 2-2 (22.74 g, 65.08 mmol) were dissolved in 200 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (1.79 g, 1.95 mmol), P (t-bu) ₃ (0.79 g, 3.90 mmol), and t-BuONa (12.51 g, 130.16 mmol) were added and stirred at 120°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column and recrystallized to obtain 45.83 g of the product P-50 (yield: 91%).

7. P-65 Synthetic Example

Sub 1-24 (20 g, 69.98 mmol) and sub 2-11 (34.96 g, 69.98 mmol) were dissolved in 200 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (1.92 g, 2.10 mmol), P (t-bu) ₃ (0.85 g, 4.20 mmol), and t-BuONa (13.45 g, 139.97 mmol) were added and stirred at 120°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain 47.70 g of the product P-65 (yield: 91%).

8. P-74 Synthetic Example

Sub 1-12 (20 g, 56.37 mmol) and sub 2-32 (20.49 g, 56.37 mmol) were dissolved in 200 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (1.55 g, 1.69 mmol), P (t-bu) ₃ (0.68 g, 3.38 mmol), and t-BuONa (10.83 g, 112.73 mmol) were added and stirred at 120°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column and recrystallized to obtain 33.82 g (yield: 88%) of the product P-74 .

9. P-89 Synthetic Example

Sub 1-2 (20 g, 71.75 mmol) and sub 2-43 (28.23 g, 71.75 mmol) were dissolved in 200 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (1.97 g, 2.15 mmol), P (t-bu) ₃ (0.87 g, 4.31 mmol), and t-BuONa (13.79 g, 143.50 mmol) were added and stirred at 120°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column and recrystallized to obtain 38.77 g of the product P-89 (yield: 85%).

10. P-100 Synthetic Example

Sub 1-14 (20 g, 56.37 mmol) and sub 2-40 (20.37 g, 56.37 mmol) were dissolved in 200 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (1.55 g, 1.69 mmol), P (t-bu) ₃ (0.68 g, 3.38 mmol), and t-BuONa (10.83 g, 112.73 mmol) were added and stirred at 120°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain 36.40 g (yield: 95%) of the product P-100 .

11. P-106 Synthetic Example

Sub 1-40 (20 g, 55.42 mmol) and sub 2-4 (19.36 g, 55.42 mmol) were dissolved in 200 mL of toluene in a round-bottomed flask, and Pd ₂ (dba) ₃ (1.52 g, 1.66 mmol), P (t-bu) ₃ (0.67 g, 3.33 mmol), and t-BuONa (10.65 g, 110.84 mmol) were added and stirred at 120°C. When the reaction was completed, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column and recrystallized to obtain 34.36 g of the product P-106 (yield: 92%).

Meanwhile, the FD-MS values of compounds P-1 to P-112 of the present invention manufactured according to the above-described synthetic examples are as shown in Table 3 below.

compound FD-MS compound FD-MS P-1 m/z=591.18 (C ₄₂ H ₂₅ NO ₃ =591.67) P-2 m/z=591.18 (C ₄₂ H ₂₅ NO ₃ =591.67) P-3 m/z=591.18 (C ₄₂ H ₂₅ NO ₃ =591.67) P-4 m/z=591.18 (C ₄₂ H ₂₅ NO ₃ =591.67) P-5 m/z=667.21 (C ₄₈ H ₂₉ NO ₃ =667.76) P-6 m/z=667.21 (C ₄₈ H ₂₉ NO ₃ =667.76) P-7 m/z=605.20 (C ₄₃ H ₂₇ NO ₃ =605.69) P-8 m/z=647.25 (C ₄₆ H ₃₃ NO ₃ =647.77) P-9 m/z=607.16 (C ₄₂ H ₂₅ NO ₂ =607.73) P-10 m/z=607.16 (C ₄₂ H ₂₅ NO ₂ =607.73) P-11 m/z=607.16 (C ₄₂ H ₂₅ NO ₂ =607.73) P-12 m/z=623.14 (C ₄₂ H ₂₅ NOS ₂ =623.79) P-13 m/z=666.23 (C ₄₈ H ₃₀ N ₂ O ₂ =666.78) P-14 m/z=617.24 (C ₄₅ H ₃₁ NO ₂ =617.75) P-15 m/z=577.20 (C ₄₂ H ₂₇ NO ₂ =577.68) P-16 m/z=583.25 (C ₄₂ H ₃₃ NO ₂ =583.73) P-17 m/z=605.20 (C ₄₃ H ₂₇ NO ₃ =605.69) P-18 m/z=667.21 (C ₄₈ H ₂₉ NO ₃ =667.76) P-19 m/z=647.25 (C ₄₆ H ₃₃ NO ₃ =647.77) P-20 m/z=667.21 (C ₄₈ H ₂₉ NO ₃ =667.76) P-21 m/z=741.27 (C ₅₅ H ₃₅ NO ₂ =741.89) P-22 m/z=741.27 (C ₅₅ H ₃₅ NO ₂ =741.89) P-23 m/z=741.27 (C ₅₅ H ₃₅ NO ₂ =741.89) P-24 m/z=741.27 (C ₅₅ H ₃₅ NO ₂ =741.89) P-25 m/z=767.32 (C ₅₈ H ₄₁ NO=767.97) P-26 m/z=767.32 (C ₅₈ H ₄₁ NO=767.97) P-27 m/z=767.32 (C ₅₈ H ₄₁ NO=767.97) P-28 m/z=767.32 (C ₅₈ H ₄₁ NO=767.97) P-29 m/z=783.30 (C ₅₈ H ₄₁ NS=784.03) P-30 m/z=783.30 (C ₅₈ H ₄₁ NS=784.03) P-31 m/z=757.24 (C ₅₅ H ₃₅ NOS=757.95) P-32 m/z=757.24 (C ₅₅ H ₃₅ NOS=757.95) P-33 m/z=843.35 (C ₆₄ H ₄₅ NO=844.07) P-34 m/z=781.33 (C ₅₉ H ₄₃ NO=782.00) P-35 m/z=817.30 (C ₆₁ H ₃₉ NO ₂ =817.99) P-36 m/z=797.33 (C ₅₉ H ₄₃ NO ₂ =798.00) P-37 m/z=801.30 (C ₆₁ H ₃₉ NO=801.99) P-38 m/z=877.33 (C ₆₇ H ₄₃ NO=878.09) P-39 m/z=681.25 (C ₅₀ H ₃₅ NS=681.90) P-40 m/z=723.30 (C ₅₃ H ₄₁ NS=723.98) P-41 m/z=487.19 (C ₃₆ H ₂₅ NO=487.60) P-42 m/z=487.19 (C ₃₆ H ₂₅ NO=487.60) P-43 m/z=487.19 (C ₃₆ H ₂₅ NO=487.60) P-44 m/z=493.24 (C ₃₆ H ₃₁ NO=493.65) P-45 m/z=603.26 (C ₄₅ H ₃₃ NO=603.76) P-46 m/z=643.29 (C ₄₈ H ₃₇ NO=643.83) P-47 m/z=692.28 (C ₅₁ H ₃₆ N ₂ O=692.86) P-48 m/z=741.28 (C ₅₄ H ₃₅ N ₃ O=741.89) P-49 m/z=757.23 (C ₅₄ H ₃₁ NO ₄ =757.84) P-50 m/z=773.20 (C ₅₄ H ₃₁ NO ₃ S=773.91) P-51 m/z=757.23 (C ₅₄ H ₃₁ NO ₄ =757.84) P-52 m/z=773.20 (C ₅₄ H ₃₁ NO ₃ S=773.91) P-53 m/z=591.18 (C ₄₂ H ₂₅ NO ₃ =591.67) P-54 m/z=591.18 (C ₄₂ H ₂₅ NO ₃ =591.67) P-55 m/z=843.35 (C ₆₄ H ₄₅ NO=844.07) P-56 m/z=843.35 (C ₆₄ H ₄₅ NO=844.07) P-57 m/z=833.28 (C ₆₁ H ₃₉ NOS=834.05) P-58 m/z=833.28 (C ₆₁ H ₃₉ NOS=834.05) P-59 m/z=719.32 (C ₅₄ H ₄₁ NO=719.93) P-60 m/z=768.31 (C ₅₇ H ₄₀ N ₂ O=768.96) P-61 m/z=598.23 (C ₄₂ H ₁₈ D ₇ NO ₃ =598.71) P-62 m/z=598.23 (C ₄₂ H ₁₈ D ₇ NO ₃ =598.71) P-63 m/z=595.21 (C ₄₂ H ₂₁ D ₄ NO ₃ =595.69) P-64 m/z=616.34 (C ₄₂ D ₂₅ NO ₃ =616.82) P-65 m/z=748.31 (C ₅₅ H ₂₈ D ₇ NO ₂ =748.93) P-66 m/z=748.31 (C ₅₅ H ₂₈ D ₇ NO ₂ =748.93) P-67 m/z=758.37 (C ₅₅ H ₁₈ D ₁₇ NO ₂ =758.99) P-68 m/z=745.29 (C ₅₅ H ₃₁ D ₄ NO ₂ =745.91) P-69 m/z=492.22 (C ₃₆ H ₂₀ D ₅ NO=492.63) P-70 m/z=491.22 (C ₃₆ H ₂₁ D ₄ NO=491.63) P-71 m/z=703.35 (C ₅₁ H ₂₅ D ₁₁ N2O=703.93) P-72 m/z=764.42 (C ₅₄ H ₁₂ D ₂₃ N ₃ O=765.03) P-73 m/z=654.29 (C ₄₆ H ₂₆ D ₇ NO ₃ =654.82) P-74 m/z=681.30 (C ₄₈ H ₁₅ D ₁₄ NO ₃ =681.85) P-75 m/z=844.34 (C ₆₁ H ₂₈ D ₁₁ NOS=845.12) P-76 m/z=872.52 (C ₆₁ D ₃₉ NOS=873.29) P-77 m/z=835.40 (C ₆₁ H ₂₅ D ₁₆ NS=836.16) P-78 m/z=840.32 (C ₆₁ H ₃₂ D ₇ NOS=841.09) P-79 m/z=683.89 (C ₅₁ H ₃₃ D ₄ NO=683.89) P-80 m/z=690.36 (C ₅₁ H ₂₆ D ₁₁ NO=690.93) P-81 m/z=745.28 (C ₅₅ H ₃₆ FNO=745.90) P-82 m/z=801.29 (C ₅₈ H ₄₀ FNS=802.02) P-83 m/z=817.30 (C ₆₁ H ₃₉ NO ₂ =817.99) P-84 m/z=803.32 (C ₆₁ H ₄₁ NO=804.00) P-85 m/z=819.30 (C ₆₁ H ₄₁ NS=820.07) P-86 m/z=833.28 (C ₆₁ H ₃₉ NOS=834.05) P-87 m/z=639.26 (C ₄₈ H ₃₃ NO=639.80) P-88 m/z=655.23 (C ₄₈ H ₃₃ NS=655.86) P-89 m/z=635.23 (C ₄₅ H ₃₀ FNO ₂ =635.74) P-90 m/z=595.19 (C ₄₂ H ₂₆ FNO ₂ =595.67) P-91 m/z=609.17 (C ₄₂ H ₂₄ FNO ₃ =609.66) P-92 m/z=609.17 (C ₄₂ H ₂₄ FNO ₃ =609.66) P-93 m/z=792.31 (C ₅₉ H ₄₀ N ₂ O=792.98) P-94 m/z=842.29 (C ₆₂ H ₃₈ N ₂ O ₂ =843.00) P-95 m/z=664.25 (C ₄₉ H ₃₂ N ₂ O=664.81) P-96 m/z=680.23 (C ₄₉ H ₃₂ N ₂ S=680.87) P-97 m/z=679.29 (C ₅₁ H ₃₇ NO=679.86) P-98 m/z=679.29 (C ₅₁ H ₃₇ NO=679.86) P-99 m/z=679.29 (C ₅₁ H ₃₇ NO=679.86) P-100 m/z=679.29 (C ₅₁ H ₃₇ NO=679.86) P-101 m/z=849.40 (C ₆₄ H ₅₁ NO=850.12) P-102 m/z=679.29 (C ₅₁ H ₃₇ NO=679.86) P-103 m/z=563.22 (C ₄₂ H ₂₉ NO=563.70) P-104 m/z=653.24 (C ₄₈ H ₃₁ NO ₂ =653.78) P-105 m/z=667.21 (C ₄₈ H ₂₉ NO ₃ =667.76) P-106 m/z=673.26 (C ₄₈ H ₃₅ NO ₃ =673.81) P-107 m/z=803.32 (C ₆₁ H ₄₁ NO=804.00) P-108 m/z=803.32 (C ₆₁ H ₄₁ NO=804.00) P-109 m/z=609.29 (C ₄₅ H ₂₇ D ₆ NO=609.80) P-110 m/z=649.33 (C ₄₈ H _31- D ₆ NO=649.87) P-111 m/z=623.27 (C ₄₅ H ₂₅ D ₆ NO ₂ =623.78) P-112 m/z=773.36 (C ₅₈ H ₃₅ D ₆ NO=774.01)

Meanwhile, although the exemplary synthetic examples of the present invention represented by Chemical Formula 1 have been described above, they are all based on the Buchwald-Hartwig cross coupling reaction, the Miyaura boration reaction, the Suzuki cross-coupling reaction, the Intramolecular acid-induced cyclization reaction ( J. Mater. Chem . 1999, 9, 2095), the Pd(II)-catalyzed oxidative cyclization reaction ( Org. Lett. 2011, 13, 5504), and the PPh ₃ -mediated reductive cyclization reaction ( J. Org. Chem. 2005, 70, 5014), and it will be easily understood by those skilled in the art that the above reaction proceeds even if a substituent other than the substituent specified in the specific synthetic examples is combined.

Manufacturing and Evaluation of Organic Electronics

When the organic electroluminescent device according to the present specification is a front-emitting type and the first electrode is formed on the substrate before the formation of the organic layer and the second electrode, not only a transparent material but also an opaque material with excellent light reflectivity can be used as the first electrode material.

If the organic electroluminescent device according to the present specification is a back-emitting type and the first electrode is formed on the substrate before the formation of the organic layer and the second electrode, a transparent material should be used as the first electrode material, or an opaque material should be formed into a thin film that becomes transparent.

In this embodiment, a front-emitting tandem organic electroluminescent device is fabricated and the following examples are presented, but the embodiments of the present invention are not limited thereto. A tandem organic electroluminescent device according to one embodiment of the present invention is fabricated by connecting a plurality of stacks through charge generation layers.

A tandem organic electroluminescent device according to one embodiment of the present invention uses the same compound in each of the light-emitting layers of two to four stacks, but is not limited thereto.

[Example 1] Tandem organic electric device with two stacks connected

A tandem organic electroluminescent device having two stacks connected was simply fabricated with a structure of first electrode/first hole transport layer/first light-emitting auxiliary layer/first light-emitting layer/first electron transport layer/n-type first charge generation layer/p-type first charge generation layer/second hole transport layer/second light-emitting auxiliary layer/second light-emitting layer/second electron transport layer/electron injection layer/second electrode.

Specifically, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine (hereinafter referred to as BCFN) and 1,4,5,8,9,11-Hexaazatriphenylenehexacarbonitrile (hereinafter referred to as HATCN) were doped in a weight ratio of 90:10 on an ITO layer (first electrode) formed on a glass substrate to form a hole injection layer having a thickness of 10 nm. BCFN was vacuum-deposited to a thickness of 15 nm on the hole injection layer to form a first hole transport layer. Subsequently, compound P-1 represented by chemical formula 1 of the present invention was vacuum-deposited to a thickness of 5 nm on the first hole transport layer to form a first light-emitting auxiliary layer. A first light-emitting auxiliary layer was deposited with a thickness of 30 nm by doping 4,4'-N,N'-dicarbazole-biphenyl (hereinafter referred to as CBP) as a host for the first light-emitting layer and [tris(2-phenylpyridine)-iridium] (hereinafter referred to as Ir(ppy) ₃ ) as a dopant material at a weight ratio of 90:10. Subsequently, Tris(8-hydroxyquinolinato)aluminium (hereinafter referred to as Alq ₃ ) was vacuum-deposited with a thickness of 30 nm to form a first electron transport layer. Next, Li was doped into 2% Bathophenanthroline (hereinafter referred to as Bphen) on the first electron transport layer to form an n-type first charge-generation layer with a thickness of 7.5 nm, and BCFN and HATCN were doped on the n-type first charge-generation layer at a weight ratio of 90:10 to form a p-type first charge-generation layer with a thickness of 10 nm. Thereafter, the second stack (the second hole transport layer, the second light emitting layer, the second electron transport layer) was formed by sequentially depositing the same configuration as the first hole transport layer, the first light emitting layer, and the first electron transport layer as described above. However, C-1 was used as the second light emitting auxiliary layer. Thereafter, 8-Quinolinolato lithium (hereinafter, Liq) was deposited to a thickness of 1.5 nm as an electron injection layer to form an electron injection layer, and then Ag and Mg were deposited at a weight ratio of 9:1 to a thickness of 150 nm on the electron injection layer to form a cathode, thereby manufacturing an organic light emitting device.

[Example 2] to [Example 21]

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compound of the present invention described in Table 4 below was used instead of the compound P-1 of the present invention as a light-emitting auxiliary layer material.

[Comparative Example 1] to [Comparative Example 3]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that comparative compound A was used instead of compound P-1 of the present invention as a light-emitting auxiliary layer material.

[Compound A] [Compound C-1]

[Example 22] Tandem organic electric element with three stacks connected

A tandem organic electroluminescent device with three stacks connected was simply fabricated with a structure of first electrode/first hole transport layer/first light-emitting auxiliary layer/first light-emitting layer/first electron transport layer/n-type first charge generation layer/p-type first charge generation layer/second hole transport layer/second light-emitting auxiliary layer/second light-emitting layer/second electron transport layer/n-type second charge generation layer/p-type second charge generation layer/third hole transport layer/third light-emitting auxiliary layer/third light-emitting layer/third electron transport layer/electron injection layer/second electrode.

Specifically, a hole injection layer having a thickness of 10 nm was formed on an ITO layer (first electrode) formed on a glass substrate by doping BCFN and HATCN in a weight ratio of 90:10. BCFN was vacuum-deposited on the hole injection layer to a thickness of 15 nm to form a first hole transport layer. Subsequently, a compound P-1 represented by the chemical formula 1 of the present invention was vacuum-deposited on the first hole transport layer to a thickness of 5 nm to form a first light-emitting auxiliary layer. CBP as a host of the first light-emitting layer and Ir(ppy) ₃ as a dopant material were doped on the first light-emitting auxiliary layer at a weight ratio of 90:10 to deposit a first light-emitting layer having a thickness of 30 nm. Subsequently, Alq ₃ was vacuum-deposited to a thickness of 30 nm to form a first electron transport layer. Next, a 7.5 nm thick n-type first charge generation layer was formed on the first electron transport layer by doping 2% Li into Bphen, and a 10 nm thick p-type first charge generation layer was formed on the n-type first charge generation layer by doping BCFN and HATCN in a weight ratio of 90:10. Thereafter, as described above, the first hole transport layer, the first light-emitting layer, and the first electron transport layer were sequentially deposited to form a second stack (second hole transport layer, second light-emitting layer, second electron transport layer). However, C-1 was used as the second light-emitting auxiliary layer. An n-type second charge generation layer and a p-type second charge generation layer were sequentially formed on the second electron transport layer with the same configuration as the n-type first charge generation layer and the p-type first charge generation layer, and a third stack (a third hole transport layer, a third light-emitting layer, a third electron transport layer) was formed by sequentially depositing the same configuration as the first hole transport layer, the first light-emitting layer, and the first electron transport layer. However, C-1 was used as the third light-emitting auxiliary layer. Thereafter, Liq was deposited to a thickness of 1.5 nm as an electron injection layer to form an electron injection layer, and then Ag and Mg were deposited on the electron injection layer at a weight ratio of 9:1 to a thickness of 150 nm to form a cathode, thereby manufacturing an organic light-emitting device.

[Example 23] to [Example 42]

An organic light-emitting device was manufactured in the same manner as in Example 22, except that the compound of the present invention described in Table 5 below was used instead of the compound P-1 of the present invention as a light-emitting auxiliary layer material.

[Example 43] Tandem organic electric element with four stacks connected

A tandem organic electroluminescent device having three stacks connected was briefly fabricated with a structure of first electrode/first hole transport layer/first light-emitting auxiliary layer/first light-emitting layer/first electron transport layer/n-type first charge generation layer/p-type first charge generation layer/second hole transport layer/second light-emitting auxiliary layer/second light-emitting layer/second electron transport layer/n-type second charge generation layer/p-type second charge generation layer/third hole transport layer/third light-emitting auxiliary layer/third light-emitting layer/third electron transport layer/n-type third charge generation layer/p-type third charge generation layer/fourth hole transport layer/fourth light-emitting auxiliary layer/fourth light-emitting layer/fourth electron transport layer/electron injection layer/second electrode.

Specifically, a hole injection layer having a thickness of 10 nm was formed on an ITO layer (first electrode) formed on a glass substrate by doping BCFN and HATCN in a weight ratio of 90:10. BCFN was vacuum-deposited on the hole injection layer to a thickness of 15 nm to form a first hole transport layer. Subsequently, a compound P-1 represented by the chemical formula 1 of the present invention was vacuum-deposited on the first hole transport layer to a thickness of 5 nm to form a first light-emitting auxiliary layer. CBP as a host of the first light-emitting layer and Ir(ppy) ₃ as a dopant material were doped on the first light-emitting auxiliary layer at a weight ratio of 90:10 to deposit a first light-emitting layer having a thickness of 30 nm. Subsequently, Alq ₃ was vacuum-deposited to a thickness of 30 nm to form a first electron transport layer. Next, a 7.5 nm thick n-type first charge-generation layer was formed on the first electron-transport layer by doping 2% Li into Bphen, and a 10 nm thick p-type first charge-generation layer was formed on the n-type first charge-generation layer by doping BCFN and HATCN in a weight ratio of 90:10. Thereafter, as described above, the first hole-transport layer, the first light-emitting layer, and the first electron-transport layer were sequentially deposited to form a second stack (second hole-transport layer, second light-emitting layer, second electron-transport layer). However, C-1 was used as the second light-emitting auxiliary layer. An n-type second charge generation layer and a p-type second charge generation layer were sequentially formed on the second electron transport layer with the same configuration as the n-type first charge generation layer and the p-type first charge generation layer, and a third stack (third hole transport layer, third emission layer, third electron transport layer) was formed by sequentially depositing the same configuration as the first hole transport layer, first emission layer, and first electron transport layer. However, C-1 was used as the third emission auxiliary layer. An n-type third charge generation layer and a p-type third charge generation layer were sequentially formed on the third electron transport layer with the same configuration as the n-type first charge generation layer and the p-type first charge generation layer, and the fourth stack (fourth hole transport layer, fourth emission layer, fourth electron transport layer) was formed by sequentially depositing the same configuration as the first hole transport layer, the first emission layer, and the first electron transport layer. However, C-1 was used as the fourth emission auxiliary layer. Thereafter, Liq was deposited to a thickness of 1.5 nm as an electron injection layer to form an electron injection layer, and then Ag and Mg were deposited on the electron injection layer at a weight ratio of 9:1 to a thickness of 150 nm to form a cathode, thereby manufacturing an organic light emitting device.

[Example 44] to [Example 70]

An organic light-emitting device was manufactured in the same manner as in Example 43, except that the compound of the present invention described in Table 6 below was used instead of the compound P-1 of the present invention as a light-emitting auxiliary layer material.

The electroluminescence (EL) characteristics were measured using PR-650 of Photoresearch by applying a forward bias DC voltage to the organic electroluminescence devices manufactured in this manner and the comparative examples, and the T95 lifespan was measured using a lifespan measuring device manufactured by Maxscience at a standard luminance of 5000 cd/m ² . Tables 4 to 6 below show the results of device fabrication and evaluation.

This measuring device allows the performance of new materials to be evaluated against reference compounds under identical conditions, without being affected by possible daily variations in deposition rate, vacuum quality or other parameters.

Since, during the evaluation, one batch contains four identically prepared OLEDs including a comparison compound, and the performance of a total of 12 OLEDs is evaluated in three batches, the values of the experimental results obtained in this way exhibit statistical significance.

First light-emitting auxiliary layer Second light-emitting auxiliary layer Driving voltage
(V) electric current
(mA/cm ² ) Efficiency
(cd/A) T(95) Comparative example (1) Comparative compound A C-1 12.2 10.0 50.1 175.2 Comparative example (2) C-1 Comparative compound A 11.1 9.3 53.5 186.9 Comparative example (3) Comparative compound A Comparative compound A 10.4 9.1 54.7 190.2 Example (1) P-1 C-1 9.1 7.1 70.2 239.0 Example (2) P-15 C-1 8.7 6.8 73.1 237.2 Example (3) P-21 C-1 8.9 7.0 71.8 234.8 Example (4) P-37 C-1 9.2 7.2 69.9 224.6 Example (5) P-45 C-1 8.3 6.5 77.4 225.3 Example (6) P-77 C-1 8.4 6.6 76.0 230.7 Example (7) P-104 C-1 8.6 6.7 74.3 232.3 Example (8) C-1 P-1 8.9 6.9 72.4 241.9 Example (9) C-1 P-15 8.6 6.6 75.4 240.1 Example (10) C-1 P-21 8.7 6.8 74.0 237.6 Example (11) C-1 P-37 9.0 6.9 72.1 227.3 Example (12) C-1 P-45 8.2 6.3 79.8 228.0 Example (13) C-1 P-77 8.2 6.4 78.3 233.5 Example (14) C-1 P-104 8.4 6.5 76.6 235.1 Example (15) P-1 P-1 8.8 6.8 73.1 244.5 Example (16) P-15 P-15 8.5 6.6 76.2 242.7 Example (17) P-21 P-21 8.7 6.7 74.8 240.2 Example (18) P-37 P-37 8.9 6.9 72.9 229.8 Example (19) P-45 P-45 8.1 6.2 80.6 230.5 Example (20) P-77 P-77 8.1 6.3 79.1 236.0 Example (21) P-104 P-104 8.3 6.5 77.4 237.6

First light-emitting auxiliary layer Second light-emitting auxiliary layer Third light-emitting auxiliary layer Driving voltage (V) electric current
(mA/cm ² ) Efficiency
(cd/A) T(95) Example (22) P-1 C-1 C-1 12.7 5.5 91.3 295.1 Example (23) P-15 C-1 C-1 12.2 5.3 95.1 292.8 Example (24) P-21 C-1 C-1 12.5 5.4 93.4 289.8 Example (25) P-37 C-1 C-1 12.8 5.5 90.9 277.3 Example (26) P-45 C-1 C-1 11.7 5.0 100.6 278.1 Example (27) P-77 C-1 C-1 11.7 5.1 98.8 284.8 Example (28) P-104 C-1 C-1 12.0 5.2 96.6 286.7 Example (29) C-1 P-1 C-1 12.4 5.3 94.2 298.9 Example (30) C-1 P-15 C-1 11.9 5.1 98.2 296.7 Example (31) C-1 P-21 C-1 12.2 5.2 96.4 293.6 Example (32) C-1 P-37 C-1 12.6 5.4 93.3 280.3 Example (33) C-1 P-45 C-1 11.4 4.8 103.8 281.7 Example (34) C-1 P-77 C-1 11.5 4.9 102.0 288.5 Example (35) C-1 P-104 C-1 11.8 5.0 99.7 290.5 Example (36) C-1 C-1 P-1 12.3 5.3 95.2 302.8 Example (37) C-1 C-1 P-15 11.8 5.0 99.2 300.5 Example (38) C-1 C-1 P-21 12.1 5.1 97.4 297.3 Example (39) C-1 C-1 P-37 12.4 5.3 94.7 283.6 Example (40) C-1 C-1 P-45 11.3 4.8 104.9 285.3 Example (41) C-1 C-1 P-77 11.3 4.9 103.0 292.2 Example (42) C-1 C-1 P-104 11.6 5.0 100.8 294.2

First light-emitting auxiliary layer Second light-emitting auxiliary layer Third light-emitting auxiliary layer 4th light-emitting auxiliary layer Driving voltage (V) electric current
(mA/cm ² ) Efficiency
(cd/A) T(95) Example (43) P-1 C-1 C-1 C-1 16.1 4.4 113.2 356.2 Example (44) P-15 C-1 C-1 C-1 15.5 4.2 118.0 353.5 Example (45) P-21 C-1 C-1 C-1 15.8 4.3 115.8 349.8 Example (46) P-37 C-1 C-1 C-1 16.3 4.4 112.7 334.7 Example (47) P-45 C-1 C-1 C-1 14.8 4.0 124.7 335.7 Example (48) P-77 C-1 C-1 C-1 14.9 4.1 122.5 343.8 Example (49) P-104 C-1 C-1 C-1 15.2 4.2 119.8 346.1 Example (50) C-1 P-1 C-1 C-1 15.7 4.3 116.0 360.8 Example (51) C-1 P-15 C-1 C-1 15.1 4.1 120.9 358.1 Example (52) C-1 P-21 C-1 C-1 15.4 4.2 118.7 354.3 Example (53) C-1 P-37 C-1 C-1 15.9 4.3 115.2 339.0 Example (54) C-1 P-45 C-1 C-1 14.4 3.9 127.9 340.1 Example (55) C-1 P-77 C-1 C-1 14.5 4.0 125.6 348.2 Example (56) C-1 P-104 C-1 C-1 14.9 4.1 122.8 350.6 Example (57) C-1 C-1 P-1 C-1 15.6 4.2 118.2 362.0 Example (58) C-1 C-1 P-15 C-1 15.0 4.1 123.1 359.2 Example (59) C-1 C-1 P-21 C-1 15.3 4.1 120.9 355.5 Example (60) C-1 C-1 P-37 C-1 15.8 4.2 117.7 340.4 Example (61) C-1 C-1 P-45 C-1 14.3 3.8 130.2 341.2 Example (62) C-1 C-1 P-77 C-1 14.4 3.9 127.9 349.4 Example (63) C-1 C-1 P-104 C-1 14.8 4.0 125.0 351.7 Example (64) C-1 C-1 C-1 P-1 15.3 4.2 119.2 367.2 Example (65) C-1 C-1 C-1 P-15 14.7 4.0 124.2 364.5 Example (66) C-1 C-1 C-1 P-21 15.0 4.1 121.9 360.6 Example (67) C-1 C-1 C-1 P-37 15.6 4.2 118.7 345.1 Example (68) C-1 C-1 C-1 P-45 14.0 3.8 131.4 346.1 Example (69) C-1 C-1 C-1 P-77 14.1 3.9 129.0 354.4 Example (70) C-1 C-1 C-1 P-104 14.5 4.0 126.1 356.8

As can be seen from Tables 4 to 6 above, when a green organic electroluminescence device is manufactured using the material for a tandem organic electroluminescence device of the present invention as a light-emitting auxiliary layer, it can be confirmed that the compound of the present invention affects the overall performance improvement of the device compared to the comparative example.

First, when comparing Comparative Compound A with the compound of the present invention, Comparative Compound A has 4-dibenzofuran bonded, whereas the compound of the present invention has 2-dibenzofuran or dibenzothiophene substituted including a phenyl linker. This difference in substituents significantly affects the physical properties of the compounds, which in turn affects the device performance.

The HOMO in Table 7 below is data measured using the DFT Method (B3LYP/6-31g(D)) of the Gaussian program for the comparative compound A and the compound P-37 of the present invention. (HOMO is expressed as an absolute value.)

Additionally, the RE values in Table 7 below describe the calculated Reorganization Energy values of comparative compounds A and P-37.

The RE values listed in Table 7 below represent the values calculated for the RE _hole .

　 Comparative compound A P-37 HOMO (eV) 4.871 4.836 RE (eV) 0.171 0.147

When the above Table 7 is explained in detail, it can be seen that the HOMO value of the compound P-37 of the present invention is shallower than that of the comparative compound A. This means that holes are more easily injected from the anode or the charge generation layer. Therefore, the holes can be smoothly transferred to the host. Similarly, in the case of the RE value, it can be seen that the P-37 is lower than that of the comparative compound A, which also means that the hole mobility is faster. In other words, this means that the driving voltage becomes faster and the efficiency of the entire device increases due to this difference. In addition, it seems that the stability of the compound also increases as the HOMO and RE values decrease.

As can be seen in Tables 4 to 6 above, as the number of stacks increases, the distance through which holes and electrons move increases, which increases the driving voltage. However, contrary to the decrease in the driving voltage, the number of points at which light can be emitted increases, which results in increased efficiency and increased lifespan. Additionally, although the present invention did not conduct experiments by adjusting the thickness differently for each stack, if the thickness is adjusted with constructive interference in mind, the efficiency increases due to constructive interference in the light-emitting area, and in particular, the lifespan can be increased dramatically. Therefore, it can be seen that it is very suitable for a display that requires long-life characteristics.

In addition, in the case of the compound of the present invention, if it is formed in a stack close to the cathode as a material with excellent hole mobility, it shows even better effects. This is because holes and electrons are generated in the charge generation layer and are injected into the two emitting layers, respectively, but the charge may be weaker than that of the electrode. Therefore, if a material with fast hole mobility is introduced after the charge generation layer, it seems to show excellent characteristics in the overall performance of the device.

In addition, the evaluation results of the aforementioned device fabrication explained the device characteristics when the compound of the present invention was applied only to the light-emitting auxiliary layer, but the compound of the present invention can be used by applying it to the hole transport layer or by applying it to both the hole transport layer and the light-emitting auxiliary layer.

The above description is merely an example of the present invention, and those skilled in the art will appreciate that various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in this specification are not intended to limit the present invention, but rather to explain it, and the spirit and scope of the present invention are not limited by these embodiments.

The scope of protection of the present invention should be interpreted by the claims below, and all technologies within a scope equivalent thereto should be interpreted as being included in the scope of the rights of the present invention.

According to the present invention, an organic device having excellent device characteristics such as high brightness, high luminescence, and long lifespan can be manufactured, and thus has industrial applicability.

Claims (10)

A tandem composition comprising a compound represented by the following chemical formula 1 <Chemical formula 1>

{In the above chemical formula 1, R ¹ , R ² and R ³ are each the same or different from each other and are independently selected from the group consisting of hydrogen; deuterium; halogen; cyano group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ cycloalkyl group; fused ring group of _{C 3} ~ C ₆₀ aliphatic ring and _{C 6} ~ C ₆₀ aromatic ring; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C 20 alkynyl group; C 1 ~ C ₃₀ alkoxyl group; and C ₆ ~ C ₃₀ aryloxy group; Ar ¹ and Ar ² are independently selected from the group consisting of a C ₆ to C ₆₀ aryl group; a fluorenyl group; and a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; X ¹ is O or S, a and c are independently integers from 0 to 4, b is an integer from 0 to 3, Here, the aryl group, the heterocyclic group, the fluorenyl group, the fused ring group, the cycloalkyl group, the alkyl group, the alkenyl group, the alkynyl group, the alkoxy group and the aryloxy group are each independently selected from deuterium; halogen; a silane group; a siloxane group; a boron group; a germanium group; a cyano group; a nitro group; a C ₁ to C ₂₀ alkylthio group; _{a C 1 to} C ₂₀ alkoxyl group; a C ₁ to C ₂₀ alkyl group; a C ₂ to C ₂₀ alkenyl group; a C 2 to C 20 alkynyl group; a _{C 6} to C ₂₀ aryl group; a C ₆ to C ₂₀ aryl group substituted with deuterium; a fluorenyl group; a C ₂ to C ₂₀ heterocyclic group; a C ₃ to C ₂₀ cycloalkyl group; C ₇ ~ C ₂₀ arylalkyl group; and C ₈ ~ C ₂₀ arylalkenyl group; may be further substituted with one or more substituents selected from the group consisting of, and further, the hydrogen of these substituents may be further substituted with one or more deuteriums, and further, these substituents may be combined with each other to form a ring, wherein the 'ring' refers to a fused ring formed by a C ₃ ~ C ₆₀ aliphatic ring, a C ₆ ~ C ₆₀ aromatic ring, a C ₂ ~ C ₆₀ heterocycle, or a combination thereof, and includes a saturated or unsaturated ring. In claim 1, a tandem composition characterized in that the chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-3. <Chemical Formula 1-1> <Chemical Formula 1-2>

<Chemical Formula 1-3>

{In the above chemical formulas 1-1 to 1-3, R ¹ , R ² , R ³ , Ar ¹ , Ar ² , X ¹ , a, b and c are the same as defined in claim 1.} In claim 1, a tandem composition characterized in that at least one of Ar ¹ and Ar ² is represented by the following chemical formula A-1 or chemical formula A-2. <Chemical Formula A-1> <Chemical Formula A-2>

{In the above chemical formulas A-1 and A-2, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each the same or different and independently hydrogen; deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C ₁ to C ₂₀ alkylthio group; C ₁ to C ₂₀ alkoxyl group; C ₁ to C ₂₀ alkyl group; C ₂ to C ₂₀ alkenyl group; C ₂ to C ₂₀ alkynyl group; C ₆ to C ₂₀ aryl group; fluorenyl group; C ₂ to C ₂₀ heterocyclic group; C ₃ to C ₂₀ cycloalkyl group; C ₇ to C ₂₀ arylalkyl group; and is selected from the group consisting of an arylalkenyl group having C ₈ to C ₂₀ ; X ² is O, S or NR', The above R' is selected from the group consisting of a C ₆ ~ C ₂₀ aryl group; a fluorenyl group; a C ₂ ~ C ₂₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P; a fused ring group of a C ₃ ~ C ₂₀ aliphatic ring and a C ₆ ~ C ₂₀ aromatic ring; a C ₁ ~ C ₂₀ alkyl group; a C ₂ ~ C ₂₀ alkenyl group; and a C ₂ ~ C ₂₀ alkynyl group; d, f, h and i are independently integers from 0 to 4, e is an integer from 0 to 3, g is an integer from 0 to 5, * indicates the position of joining, Here, the aryl group, heterocyclic group, fluorenyl group, alkyl group, alkenyl group, alkynyl group, alkoxy group, arylalkyl group, arylalkenyl group, alkylthio group and cycloalkyl group may be further substituted with one or more substituents selected from the group consisting of deuterium; a C ₁ to C ₂₀ alkyl group; _{a C 2 to} C ₂₀ alkenyl group; a C ₂ to C ₂₀ alkynyl group; a C ₆ to C ₂₀ aryl group; a fluorenyl group _; and a C 2 to C 20 heterocyclic group. In claim 1, a tandem composition characterized in that the compound represented by the chemical formula 1 is any one of the following compounds P-1 to P-112

In an organic electric device comprising a first electrode; a second electrode; and an organic layer formed between the first electrode and the second electrode; The above organic layer comprises n stacks including a hole transport region, an emission layer, and an electron transport region, The above n is an integer from 2 to 5, An organic electric device characterized in that the hole transport region of at least one stack among the above n stacks comprises a tandem composition according to claim 1. In the fifth paragraph, an organic electric device characterized in that the hole transport region includes a hole transport layer and a light-emitting auxiliary layer formed on the hole transport layer. In claim 6, the light-emitting auxiliary layer is characterized in that it includes a tandem composition containing a compound represented by the chemical formula 1 according to claim 1. In the fifth paragraph, an organic electric device further comprising a light efficiency improvement layer formed on at least one surface of the first electrode and the second electrode, the surface being opposite to the organic layer. An electronic device comprising a display device including an organic electric element of clause 5; and a control unit for driving the display device; In claim 9, the organic electric element is an electronic device characterized in that it is at least one of an organic light-emitting element, an organic solar cell, an organic photoconductor, an organic transistor, and a monochrome or white lighting element.

Images