KR20210015643A - Organic electric device - Google Patents

Abstract

Embodiments of the present invention relate to an organic electric element capable of improving high light emitting efficiency, low driving voltage, high heat resistance, color purity, or lifespan. To this end, the organic electric element comprises a first electrode, a second electrode, and an organic material layer.

Description

Organic electric device{ORGANIC ELECTRIC DEVICE}

Embodiments of the present invention relate to an organic electric device.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using organic materials. An organic electric device using an organic light emission phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer may have a multilayer structure made of different materials in order to increase the efficiency and stability of the organic electric device.

Currently, the portable display market is increasing in size as a large-area display. Since the portable display has a battery, which is a limited power supply, more efficient power consumption than the power consumption required in the existing portable display is required. In addition, in addition to efficient power consumption, the problem of luminous efficiency and lifespan must be solved.

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

Efficiency, lifespan, and driving voltage are related to each other. As the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, the crystallization of organic materials caused by Joule heating during driving decreases. It shows a tendency to increase the lifespan. However, simply improving organic materials cannot maximize efficiency. This is because the long life and high efficiency can be achieved at the same time when the energy level and T1 value between each organic material and the intrinsic properties of the material (mobility, interfacial properties, etc.) are optimally combined. Therefore, there is a need to develop a material that has high thermal stability and can efficiently achieve charge balance in the light emitting layer.

In particular, in a tandem organic electric device, the efficiency, life, and driving voltage of the organic electric device may vary depending on which organic material is used in combination with which layer.

Embodiments of the present invention can provide an organic electric device having a low driving voltage, high efficiency, color purity, and long life.

In one aspect, an organic electric device according to embodiments of the present invention includes a first electrode, a second electrode, and an organic material layer.

The organic material layer is positioned between the first electrode and the second electrode, and includes a first stack, a second stack, and a third stack.

The first stack includes a first hole transport region, a first emission layer, and a first electron transport region.

The first hole transport region includes a first hole transport layer and a first light emission auxiliary layer.

The first hole transport layer or the first light emission auxiliary layer includes a first compound represented by Formula 1 below.

<Formula 1>

According to embodiments of the present invention, it is possible to provide an organic electric device having high luminous efficiency, low driving voltage, high heat resistance, and greatly improved color purity and lifetime.

1 is a schematic diagram of an organic electric device according to embodiments of the present invention.
2 is a diagram schematically illustrating a first hole transport layer of an organic electric device according to embodiments of the present invention.
3 and 4 are diagrams schematically showing organic electric devices according to embodiments of the present invention.
5 is a schematic view showing a stack of organic electric devices according to embodiments of the present invention.

Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings.

In adding reference numerals to elements of each drawing, the same elements may have the same numerals as possible even if they are indicated on different drawings. In addition, in describing the present invention, when it is determined that a detailed description of a related known configuration or function may obscure the subject matter of the present invention, a detailed description thereof may be omitted. When "include", "have", "consists of" and the like mentioned in the present specification are used, other parts may be added unless "only" is used. In the case of expressing the constituent elements in the singular, the case including plural may be included unless there is a specific explicit description.

In addition, in describing the constituent elements of the present invention, terms such as first, second, A, B, (a) and (b) may be used. These terms are only for distinguishing the component from other components, and the nature, order, order, or number of the component is not limited by the term.

In the description of the positional relationship of the components, when two or more components are described as being "connected", "coupled" or "connected", the two or more components are directly "connected", "coupled" or "connected" "It may be, but it should be understood that two or more components and other components may be further "interposed" to be "connected", "coupled" or "connected". Here, the other components may be included in one or more of two or more components "connected", "coupled" or "connected" to each other.

In addition, when a component such as a layer, film, region, or plate is said to be "on" or "on" another component, it is not only "directly over" another component, as well as another component in the middle. It should be understood that cases may also be included. Conversely, it should be understood that when an element is "directly above" another part, it means that there is no other part in the middle.

In the description of the temporal flow relationship related to the components, the operation method or the manufacturing method, for example, the temporal predecessor relationship such as "after", "after", "after", "before", etc. Alternatively, a case where a flow forward and backward relationship is described may also include a case that is not continuous unless "direct" or "direct" is used.

On the other hand, when a numerical value for a component or its corresponding information is mentioned, the numerical value or its corresponding information may be caused by various factors (e.g., process factors, internal or external shock, noise, etc.) It can be interpreted as including a possible error range.

The term "halo" or "halogen" as used in the present application includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), unless otherwise specified.

The term "alkyl" or "alkyl group" as used in the present application has 1 to 60 carbons connected by a single bond unless otherwise specified, and a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted It may mean a radical of a saturated aliphatic functional group including a cycloalkyl group and a cycloalkyl-substituted alkyl group.

The terms "haloalkyl group" or "halogenalkyl group" as used in the present application may mean an alkyl group in which halogen is substituted unless otherwise specified.

The terms "alkenyl" or "alkynyl" used in the present application each have a double bond or a triple bond, unless otherwise specified, include a straight or branched chain group, and may have 2 to 60 carbon atoms.

The term "cycloalkyl" used in the present application may mean an alkyl forming a ring having 3 to 60 carbon atoms unless otherwise specified.

The term "alkoxy group" or "alkyloxy group" used in the present application refers to an alkyl group to which an oxygen radical is bonded, and may have 1 to 60 carbon atoms unless otherwise specified.

The terms "alkenyl group", "alkenoxy group", "alkenyloxy group", or "alkenyloxy group" as used in the present application mean an alkenyl group to which an oxygen radical is attached, and unless otherwise specified, 2 to 60 May have carbon number of.

The terms "aryl group" and "arylene group" as used in the present application each have 6 to 60 carbon atoms, but are not limited thereto. In the present application, the aryl group or the arylene group may include a monocyclic type, a ring aggregate, a conjugated multiple ring system, a spiro compound, and the like. For example, the aryl group includes, but is limited to, phenyl group, biphenyl, naphthyl, anthryl, indenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like. It is not. The naphthyl includes 1-naphthyl and 2-naphthyl, and the anthryl may include 1-anthryl, 2-anthryl, and 9-anthryl.

In the present application, the terms "fluorenyl group" or "fluorenylene group" may each mean a monovalent or divalent functional group of fluorene unless otherwise specified. In addition, the "fluorenyl group" or "fluorenylene group" may mean a substituted fluorenyl group or a substituted fluorenylene group. "Substituted fluorenyl group" or "substituted fluorenylene group" may mean a monovalent or divalent functional group of substituted fluorene. "Substituted fluorene" may mean that at least one of the following substituents R, R', R" and R'" is a functional group other than hydrogen. It may include the case where R and R'are bonded to each other to form a spy compound with the carbon to which they are bonded.

The term "spyro compound" as used in the present application has a'spiro union', and the spiro linkage refers to a connection made by two rings sharing only one atom. At this time, the atoms shared in the two rings are referred to as'spiro atoms', and these are respectively referred to as'monospiro-','dispiro-', and'trispyro-' depending on the number of spiro atoms in a compound. 'It can be called a compound.

The term "heterocyclic group" as used in the present application includes not only an aromatic ring such as a "heteroaryl group" or a "heteroarylene group", but also a non-aromatic ring, and unless otherwise stated, the number of carbon atoms each containing one or more heteroatoms It means a ring of 2 to 60, but is not limited thereto. The term "heteroatom" as used in the present application represents N, O, S, P, or Si unless otherwise specified, and the heterocyclic group is a monocyclic type including a heteroatom, a ring aggregate, a conjugated ring system, spy It may mean a compound or the like.

In addition, the "heterocyclic group" may also include a ring including SO ₂ instead of carbon forming a ring. For example, the "heterocyclic group" may include the following compounds.

The term “ring” used in the present application includes monocyclic and polycyclic rings, and includes a heterocycle including at least one heteroatom as well as a hydrocarbon ring, and may include aromatic and non-aromatic rings.

The term "polycyclic" as used in the present application includes ring assemblies, fused ring systems and spiro compounds, and includes not only aromatic but also non-aromatic, hydrocarbon rings as well as at least one hetero It may contain a heterocycle containing an atom.

The term “aliphatic ring group” used in this application refers to cyclic hydrocarbons excluding aromatic hydrocarbons, and includes monocyclic types, cyclic aggregates, conjugated cyclic systems, spiro compounds, etc., unless otherwise stated, It may mean 3 to 60 rings. For example, benzene as an aromatic ring and cyclohexane, a non-aromatic ring, are fused to an aliphatic ring.

The term "ring assemblies" as used in this application means that two or more ring systems (single ring or fused ring system) are directly connected to each other through a single bond or a double bond. For example, in the case of an aryl group, it may be a biphenyl group, a terphenyl group, or the like, but is not limited thereto.

The term "conjugated multiple ring systems" as used in the present application refers to a fused ring type that shares at least two atoms. For example, the aryl group may be a naphthalenyl group, a phenanthrenyl group, or a fluorenyl group, but is not limited thereto.

In addition, when the prefixes are named consecutively, it may mean that the substituents are listed in the order described first. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxycarbonyl group, it means a carbonyl group substituted with an alkoxy group, and in the case of an arylcarbonylalkenyl group, it may mean an alkenyl group substituted with an arylcarbonyl group. have. Here, the arylcarbonyl group may be a carbonyl group substituted with an aryl group.

In addition, unless expressly stated, the term "substituted or unsubstituted" used in the present application "substituted" refers to deuterium, halogen, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₁ -C ₂₀ alkylamine group, C ₁ -C ₂₀ alkylthiophene group, C ₆ -C ₂₀ arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl group of, C ₆ -C ₂₅ aryl group, of a C ₆ -C ₂₅ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron It means substituted with one or more substituents selected from the group consisting of a C ₂ -C ₂₀ heterocyclic group including a group, a germanium group, and at least one heteroatom selected from the group consisting of O, N, S, Si and P It can be, but is not limited to these substituents.

In the present application, the'functional group name' corresponding to the aryl group, arylene group, heterocyclic group, etc. exemplified as examples of each symbol and its substituent may describe the'name of the functional group reflecting the number', but it is described as the'parent compound name' You may. For example, in the case of'phenanthrene,' a kind of aryl group, the monovalent'group' is'phenanthryl (group)', and the divalent group is labeled with the name of the group by dividing the valence such as'phenanthrylene (group)'. Although it can be done, it can also be described as'phenanthrene', which is the name of the parent compound regardless of the valence. Similarly, in the case of pyrimidine, it is described as'pyrimidine' regardless of the valence, or in the case of monovalent, the'group' of the corresponding valency, such as pyrimidinyl (group), in the case of divalent, pyrimidinylene (group), etc. You can also write it as'name'. Therefore, when the type of the substituent is described as the parent compound name in the present application, it may mean an n-valent'group' formed by desorbing a carbon atom and/or a hydrogen atom bonded to a heteroatom of the parent compound.

In addition, unless there is an explicit description, the formula used in this application may be applied in the same manner as the definition of the substituent 　 in the index definition of the following formula.

Here, when a is 0, the substituent R ¹ means that the substituent R ¹ is absent, which means that all hydrogens are bonded to the carbon forming the benzene ring, and at this time, the indication of hydrogen bonded to the carbon is omitted and the formula or compound Can be described. In addition, when a is 1, one substituent R ¹ is bonded to any one of the carbons forming a benzene ring, and when a is 2 or 3, each can be bonded as follows, and a is 4 to 6 In the case of an integer, it is bonded to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R ¹ may be the same or different from each other.

In the present application, that substituents are bonded to each other to form a ring means that adjacent groups are bonded to each other to form a single ring or multiple conjugated rings, and the single ring and the formed conjugated multiple rings are hydrocarbon rings as well as at least one hetero It includes a heterocycle containing an atom, and may include aromatic and non-aromatic rings.

In the present application, the organic electric device may mean a component(s) between an anode and a cathode, or an organic light emitting diode including an anode and a cathode, and component(s) positioned therebetween.

In addition, in some cases, the organic electric device in the present application may refer to an organic light-emitting diode and a panel including the same, or may refer to an electronic device including a panel and a circuit. Here, for example, the electronic device is a display device, a lighting device, a solar cell, a portable or mobile terminal (eg, a smart phone, a tablet, a PDA, an electronic dictionary, a PMP, etc.), a navigation terminal, a game machine, various TVs, and various computers. Any type of device may be included as long as it includes all of the monitors and the like, but is not limited thereto.

1 is a schematic diagram of an organic electric device according to embodiments of the present invention.

The organic electric device 100 according to the embodiments of the present application is positioned between the first electrode 110, the second electrode 130, the first electrode 110 and the second electrode 130, and It includes an organic material layer 120 including a stack 141, a second stack 142 and a third stack 143.

In FIG. 1, embodiments in which the second stack 142 is positioned on the first stack 141 and the third stack 143 are positioned on the second stack 142 are illustrated. However, embodiments of the present application It is not limited.

The first electrode 110 may be, for example, an anode electrode, and the second electrode 130 may be a cathode electrode. The organic material layer 120 is a layer including an organic material while being positioned between the first electrode 110 and the second electrode 130 and may be formed of a plurality of layers.

For example, the first electrode 110 may be a transparent electrode, and the second electrode 130 may be a reflective electrode. In another example, the first electrode 110 may be a reflective electrode, and the second electrode 130 may be a transparent electrode.

Since the organic material layer 120 includes at least three stacks, for example, the organic electric device according to the embodiments of the present application may be a tandem organic electric device including a plurality of stacks. In this case, the organic material layer may be stacked by repeating the same stack three or more times, and three or more different stacks may be stacked.

The three or more stacks described above may include a first stack 141, a second stack 142, and a third stack 143.

The first stack 141 includes a first hole transport region 1411, a first emission layer 1412, and a first electron transport region 1413.

The first emission layer 1412 is a layer in which energy generated by meeting electrons and holes is emitted as light, and may include, for example, a host material and a dopant.

The first hole transport region 1411 is positioned between, for example, the first electrode 110, which is an anode electrode, and the first emission layer 1412 to transfer holes supplied from the first electrode 110 to the first emission layer 1412. ) May be a transport area. The first electron transport region 1413 is, for example, a region located between the second electrode 130 that is a cathode electrode and the first emission layer 1412 to transport electrons supplied from the second electrode 130 to the emission layer Can be

The first hole transport region 1411 may include a P-type dopant, and the first electron transport region 1413 may include an N-type dopant. Here, the P-doped layer refers to a layer having a more positive (hole) property than before by adding a P-type dopant. On the contrary, the N-doped layer is more negative (electron) than before by adding an N-type dopant. It refers to a layer having one property.

The thickness of the first hole transport region 1411 may be 10 nm to 100 nm. The lower limit of the thickness of the first hole transport region 1411 may be, for example, 15 nm or more or 20 nm or more. The upper limit of the thickness of the first hole transport region 1411 may be, for example, 90 nm or less or 80 nm or less. When the thickness of the first hole transport region 1411 is within the above range, the organic electric device may have high luminous efficiency, low driving voltage, and long life.

The organic material layer 120 may include one or more charge generation layers 150 positioned between stacks. The charge generation layer 150 refers to a layer in which holes and electrons are generated when a voltage is applied. When there are three or more stacks, the charge generation layer 150 may be positioned between the stacks. In this case, the plurality of charge generation layers 150 may be identical to each other and may be different from each other. Since the charge generation layer 150 is disposed between the stacks, current efficiency can be increased in each stack, and charges can be smoothly distributed.

Specifically, the charge generation layer 150 is provided between two adjacent stacks and can serve to drive the tandem organic light emitting device with only a pair of anodes and cathodes without a separate internal electrode positioned between the stacks. have.

The charge generation layer 150 may include, for example, an N-type charge generation layer 151 and a P-type charge generation layer 152. The N-type charge generation layer 151 may be located adjacent to the first electrode 110, which is an anode electrode, for example, and the P-type charge generation layer 152 is located on the second electrode 130, which is a cathode electrode. They can be located adjacent to each other.

A capping layer 160 may be positioned on the second electrode 130. When the capping layer 160 is formed, the light efficiency of the organic electronic device may be improved.

In the case of a top emission organic electronic device, the capping layer 160 may reduce optical energy loss due to surface plasmon polaritons (SPPs) in the second electrode 130. In the case of a bottom emission organic electric device, the capping layer 160 may function as a buffer for the second electrode 130.

The first hole transport region 1411 includes a first hole transport layer 1411a and a first light emission auxiliary layer 1411b. The first light emission auxiliary layer 1411b may be positioned between, for example, the first light emission layer 1412 and the first hole transport layer 1411a.

The electron transport region 143 may include an electron transport layer (not shown).

2 is a diagram schematically illustrating a first hole transport layer 1411a of an organic electric device according to embodiments of the present invention.

Referring to FIG. 2, the thickness Tt of the first hole transport layer 1411a may be defined as a distance between H1 and H3. H1 may be an interface between the first hole transport layer 1411a and an arbitrary layer positioned under the first hole transport layer, for example, the first electrode. H3 may be an interface between the first hole transport layer 1411a and an arbitrary layer positioned above the first hole transport layer, for example, the first light emission auxiliary layer 1411b.

The thickness Tt of the first hole transport layer 1411a may be 250 Å to 700 Å. The lower limit of the thickness Tt of the first hole transport layer 1411a may be, for example, 260 Å or more or 270 Å or more. The upper limit of the thickness Tt of the first hole transport layer 1411a may be, for example, 650 Å or less or 600 Å or less.

When the thickness of the first hole transport layer 1411a satisfies the above-described range, the first hole transport layer 1411a may contain sufficient hole transport material to have excellent hole injection and hole transport functions, and the charge is excessive. By preventing the injection, it is possible to provide an organic electric device having excellent driving voltage, efficiency, or life and having a thin thickness.

In the first hole transport layer 1411a, 10% to 50% of the thickness Tt of the first transport layer may be doped with a first doping material. A portion of the first hole transport layer 1411a doped with a first doping material may be referred to as a first doping material doping layer 1411aa, and the first hole transport layer 1411a is a first doped doped with a first doping material. A material doped layer 1411aa and a first doped material undoped layer 1411ab in which the first doped material is not doped may be included. The first doped material undoped layer 1411ab may be positioned between the first doped material doped layer 1411aa and the first emission layer.

For example, the first hole transport layer 1411a may include a hole transport material, and the first doping material doping layer 1411aa may be a layer including the hole transport material and a first doping material. The hole transport material is not particularly limited as long as it is a material having hole transport properties, but may be, for example, at least one of a first compound and a fourth compound.

The thickness T ₁ of the first doping material doping layer 1411aa may be 10% to 50% of the thickness of the first hole transport layer 1411a. The thickness T ₁ of the first doping material doping layer 1411aa may be defined as a distance between H1 and H2. H2 may be an interface between the first doped material doped layer 1411aa and the first doped material undoped layer 1411ab.

The lower limit of the ratio of the thickness T ₁ of the first doping material doping layer 1411aa to the thickness of the first hole transport layer 1411a may be, for example, 12% or more or 15% or more. The upper limit of the ratio of the thickness T ₁ of the first doping material doping layer 1411aa to the thickness Tt of the first hole transport layer may be, for example, 40% or less or 30% or less.

The thickness T ₁ of the first doping material doping layer 1411aa may be, for example, 30 Å to 300 Å while satisfying the ratio range with respect to the above-described first hole transport layer thickness Tt. The lower limit of the thickness T ₁ of the first doping material doping layer 1411aa may be, for example, 60 Å or more or 80 Å or more. The upper limit of the thickness T ₁ of the first doping material doping layer 1411aa may be, for example, 200 Å or less or 150 Å or less.

When the thickness T ₁ of the first doping material doping layer 1411a satisfies the above-described ratio range and thickness range, the generation of holes and charges in the first hole transport layer 1411a is promoted to the first emission layer 1412. Hole injection is smoothly made to provide an organic electric device having excellent life or efficiency, preventing a short circuit problem of the device, and preventing an increase in manufacturing cost due to excessive use of a doping material.

The first doping material doping layer includes the first compound, and may include 5 parts by weight to 15 parts by weight of the first doping material relative to 100 parts by weight of the first compound.

The first doping material doping layer includes at least one of the first compound and the fourth compound, and may include 5 parts by weight to 15 parts by weight of the first doping material based on 100 parts by weight of the total of the first compound and the fourth compound. . The lower limit of the doping ratio of the first doping material may be, for example, 7 parts by weight or more or 9 parts by weight or more. The upper limit of the doping ratio of the first doping material may be, for example, 13 parts by weight or less or 11 parts by weight or less. The lower limit of the doping ratio of the first doping material may be, for example, 7 parts by weight or more or 9 parts by weight or more. The upper limit of the doping ratio of the first doping material may be, for example, 13 parts by weight or less or 11 parts by weight or less.

When the doping ratio of the first doping material satisfies the above range, the generation of holes and charges in the first hole transport layer is promoted to facilitate the injection of holes into the first emission layer, thereby providing an organic electronic device having excellent lifespan or efficiency. In addition, it is possible to prevent a short circuit problem of the device, and to prevent an increase in manufacturing cost due to excessive use of a doping material.

For the second stack 142 and the third stack 143, the same as described above for the first stack 141 may be applied, unless otherwise specifically described.

The second stack 142 may include a second hole transport region, a second emission layer, and a second electron transport region. For the second hole transport region, the second emission layer, and the second electron transport region, the first hole transport region 1411, the first emission layer 1412, and the first electron transport region 1413 are previously described unless otherwise specified. The same can be applied to what has been described.

The second hole transport region may include a second hole transport layer and a second light emission auxiliary layer. For the second hole transport layer and the second light emission auxiliary layer, the same as described above for the first hole transport layer 1411a and the first light emission auxiliary layer 1411b may be applied, unless otherwise specified.

As for the thickness of the second hole transport layer and the doping of the second hole transport layer, what has been described about the thickness of the first hole transport layer 1411a and the doping of the first hole transport layer 1411a may be applied.

The thickness of the second hole transport layer may be 250Å to 700Å. The lower limit of the thickness of the second hole transport layer may be, for example, 260 Å or more or 270 Å or more. The upper limit of the thickness of the second hole transport layer may be, for example, 650 Å or less or 600 Å or less.

When the thickness of the second hole transport layer satisfies the above-described range, the second hole transport layer may contain sufficient hole transport material to have excellent hole injection and hole transport functions, and is driven by preventing excessive injection of charges. It is possible to provide an organic electric device having excellent voltage, efficiency, or life and having a thin thickness.

In the second hole transport layer, 10% to 50% of the thickness of the second forward transport layer may be doped with a second doping material. A portion of the second hole transport layer doped with a second doping material may be referred to as a second doping material doping layer, and the second hole transport layer includes a second doping material doping layer and a second doping material doped with a second doping material. It may include an undoped second doped material undoped layer. The second doped material undoped layer may be positioned between the second doped material doped layer and the second emission layer.

For example, the second hole transport layer may include a hole transport material, and the second doping material doping layer may be a layer including the hole transport material and a second doping material. The hole transport material is not particularly limited as long as it is a material having hole transport properties, but may be, for example, a second compound.

The thickness of the doping layer of the second doping material may be 10% to 50% of the thickness of the second hole transport layer. The lower limit of the ratio of the thickness of the doping layer of the second doping material to the thickness of the second hole transport layer may be, for example, 12% or more or 15% or more. The upper limit of the ratio of the thickness of the second doping material doping layer to the thickness of the second hole transport layer may be, for example, 40% or less or 30% or less.

The thickness of the doping layer of the second doping material may be, for example, 30 Å to 300 Å, while satisfying the ratio range to the thickness of the second hole transport layer described above. The lower limit of the thickness of the second doping material doping layer may be, for example, 60 Å or more or 80 Å or more. The upper limit of the thickness of the second doping material doping layer may be, for example, 200 Å or less or 150 Å or less.

When the thickness of the second doping material-doped layer satisfies the above-described ratio range and thickness range, the generation of holes and charges in the second hole transport layer is promoted to facilitate the injection of holes into the second emission layer, thereby providing excellent lifespan or efficiency. An electric device may be provided, a short circuit problem of the device may be prevented, and an increase in manufacturing cost due to excessive use of a doping material may be prevented.

The second doping material doping layer may include a second compound, and may include 5 parts by weight to 15 parts by weight of a second doping material based on 100 parts by weight of the second compound.

The second doping material doping layer may include a second compound, and may include 5 parts by weight to 15 parts by weight of a second doping material based on 100 parts by weight of the second compound. The lower limit of the doping ratio of the second doping material may be, for example, 7 parts by weight or more or 9 parts by weight or more. The upper limit of the doping ratio of the second doping material may be, for example, 13 parts by weight or less or 11 parts by weight or less. The lower limit of the doping ratio of the second doping material may be, for example, 7 parts by weight or more or 9 parts by weight or more. The upper limit of the doping ratio of the second doping material may be, for example, 13 parts by weight or less or 11 parts by weight or less.

When the doping ratio of the second doping material satisfies the above range, the generation of holes and charges in the second hole transport layer is promoted to facilitate hole injection into the second emission layer, thereby providing an organic electronic device having excellent lifespan or efficiency. In addition, it is possible to prevent a short circuit problem of the device, and to prevent an increase in manufacturing cost due to excessive use of a doping material.

The third stack 143 may include a third hole transport region, a third emission layer, and a third electron transport region. For the third hole transport region, the third light emitting layer, and the third electron transport region, the first hole transport region 1411, the first light emitting layer 1412, and the first electron transport region 1413 are previously described unless otherwise specified. The same can be applied to what has been described.

The third hole transport region may include a third hole transport layer and a third light emission auxiliary layer. For the third hole transport layer and the third light emission auxiliary layer, the same as described above for the first hole transport layer 1411a and the first light emission auxiliary layer 1411b may be applied, unless otherwise specified.

As for the thickness of the third hole transport layer and the doping of the third hole transport layer, what has been described about the thickness of the first hole transport layer 1411a and the doping of the first hole transport layer 1411a may be applied.

The thickness of the third hole transport layer may be 250 Å to 700 Å. The lower limit of the thickness of the third hole transport layer may be, for example, 260 Å or more or 270 Å or more. The upper limit of the thickness of the third hole transport layer may be, for example, 650 Å or less or 600 Å or less.

When the thickness of the third hole transport layer satisfies the above-described range, the third hole transport layer may contain sufficient hole transport material to have excellent hole injection and hole transport functions, and is driven by preventing excessive injection of charges. It is possible to provide an organic electric device having excellent voltage, efficiency, or life and having a thin thickness.

In the third hole transport layer, 10% to 50% of the thickness of the third forward transport layer may be doped with a third doping material. A portion of the third hole transport layer doped with a third doping material may be referred to as a third doping material doping layer, and the third hole transport layer includes a third doping material doping layer and a third doping material doped with a third doping material. It may include an undoped third doped material undoped layer. The third doped material undoped layer may be positioned between the third doped material doped layer and the third emission layer.

For example, the third hole transport layer may include a hole transport material, and the third doping material doping layer may be a layer including the hole transport material and a third doping material. The hole transport material is not particularly limited as long as it is a material having hole transport properties, but may be, for example, at least one of a first compound and a fourth compound.

The thickness of the doping layer of the third doping material may be 10% to 50% of the thickness of the third hole transport layer. The lower limit of the ratio of the thickness of the doping layer of the third doping material to the thickness of the third hole transport layer may be, for example, 12% or more or 15% or more. The upper limit of the ratio of the thickness of the doping layer of the third doping material to the thickness of the third hole transport layer may be, for example, 40% or less or 30% or less.

The thickness of the doping layer of the third doping material may be, for example, 30 Å to 300 Å, while satisfying the ratio range to the thickness of the third hole transport layer described above. The lower limit of the thickness of the doping layer of the third doping material may be, for example, 60 Å or more or 80 Å or more. The upper limit of the thickness of the doping layer of the third doping material may be, for example, 200 Å or less or 150 Å or less.

When the thickness of the doping layer of the third doping material satisfies the above-described ratio range and thickness range, the generation of holes and charges is promoted in the third hole transport layer, thereby smoothly injecting holes into the third light-emitting layer, resulting in excellent lifespan or efficiency. An electric device may be provided, a short circuit problem of the device may be prevented, and an increase in manufacturing cost due to excessive use of a doping material may be prevented.

The third doping material doping layer may include a third compound, and may include 5 parts by weight to 15 parts by weight of a third doping material based on 100 parts by weight of the third compound.

The third doping material doping layer may include a third compound, and may include 5 parts by weight to 15 parts by weight of a third doping material based on 100 parts by weight of the third compound. The lower limit of the doping ratio of the third doping material may be, for example, 7 parts by weight or more or 9 parts by weight or more. The upper limit of the doping ratio of the third doping material may be, for example, 13 parts by weight or less or 11 parts by weight or less. The lower limit of the doping ratio of the third doping material may be, for example, 7 parts by weight or more or 9 parts by weight or more. The upper limit of the doping ratio of the third doping material may be, for example, 13 parts by weight or less or 11 parts by weight or less.

When the doping ratio of the third doping material satisfies the above range, the generation of holes and charges in the third hole transport layer is promoted to facilitate injection of holes into the third emission layer, thereby providing an organic electronic device having excellent lifespan or efficiency. In addition, it is possible to prevent a short circuit problem of the device, and to prevent an increase in manufacturing cost due to excessive use of a doping material.

3 is a schematic diagram of an organic electric device according to embodiments of the present invention.

Referring to FIG. 3, the organic material layer of the organic electric device according to embodiments of the present invention may further include a fourth stack 144.

For the fourth stack 144, the same as described above for the first stack 141 may be applied, unless otherwise specifically described.

In the embodiment shown in FIG. 3, the first electrode 110, the first stack 141, the second stack 142, the third stack 143, the fourth stack 144, and the second electrode 120 are in the order of However, the embodiments of the present invention are not limited to these organic electric devices. As long as the first to fourth stacks 141 to 144 are positioned between the first electrode 110 and the second electrode 120, the upper and lower relations of each other may be different from that shown in FIG. 3.

The fourth stack 144 may include a fourth hole transport region 1441, a fourth emission layer 1442, and a fourth electron transport region 1443. For the fourth hole transport region 1441, the fourth emission layer 144, and the fourth electron transport region, the first hole transport region 1411, the first emission layer 1412, and the first electrons are previously described unless otherwise specified. What has been described for the transport area 1413 may be equally applied.

The fourth hole transport region 1441 may include a fourth hole transport layer 1441a and a fourth light emission auxiliary layer 1441b. For the fourth hole transport layer 1441a and the fourth light emission auxiliary layer 1441b, the same as described above for the first hole transport layer 1411a and the first light emission auxiliary layer 1411b can be applied unless otherwise specified. have.

As for the thickness of the fourth hole transport layer 1441a and the doping of the fourth hole transport layer 1441a, the thickness of the first hole transport layer 1411a and the doping of the first hole transport layer 1411a may be applied.

The thickness of the fourth hole transport layer 1441a may be 250Å to 700Å. The lower limit of the thickness of the fourth hole transport layer 1441a may be, for example, 260 Å or more or 270 Å or more. The upper limit of the thickness of the fourth hole transport layer 1441a may be, for example, 650 Å or less or 600 Å or less.

When the thickness of the fourth hole transport layer 1441a satisfies the above-described range, the fourth hole transport layer 1441a may contain sufficient hole transport material to have excellent hole injection and hole transport functions, and the charge is excessive. By preventing the injection, it is possible to provide an organic electric device having excellent driving voltage, efficiency, or life and having a thin thickness.

In the fourth hole transport layer 1441a, 10% to 50% of the thickness of the fourth forward transport layer 1441a may be doped with a fourth doping material. A portion of the fourth hole transport layer 1441a doped with a fourth doping material may be referred to as a fourth doping material doping layer, and the fourth hole transport layer 1441a is a fourth doping material doped layer doped with a fourth doping material. And a fourth doped material undoped layer to which the fourth doping material is not doped. The fourth doped material undoped layer may be positioned between the fourth doped material doped layer and the fourth emission layer.

For example, the fourth hole transport layer 1441a may include a hole transport material, and the fourth doping material doping layer may be a layer including the hole transport material and a fourth doping material. The hole transport material is not particularly limited as long as it is a material having hole transport properties, but may be, for example, at least one of a fifth compound and a sixth compound.

The thickness of the fourth doping material doping layer may be 10% to 50% of the thickness of the fourth hole transport layer 1441a. The lower limit of the ratio of the thickness of the fourth doping material doping layer to the thickness of the fourth hole transport layer 1441a may be, for example, 12% or more or 15% or more. The upper limit of the ratio of the thickness of the fourth doping material doping layer to the thickness of the fourth hole transport layer 1441a may be, for example, 40% or less or 30% or less.

The thickness of the doping layer of the fourth doping material may be, for example, 30 Å to 300 Å, while satisfying the ratio of the thickness of the fourth hole transport layer 1441a. The lower limit of the thickness of the fourth doping material doping layer may be, for example, 60 Å or more or 80 Å or more. The upper limit of the thickness of the fourth doping material doping layer may be, for example, 200 Å or less or 150 Å or less.

When the thickness of the fourth doping material doping layer satisfies the above-described ratio range and thickness range, the generation of holes and electric charges in the fourth hole transport layer 1441a is promoted, so that the injection of holes into the fourth emission layer 1442 is made smoothly. It is possible to provide an organic electric device having excellent lifespan or efficiency, prevent a short circuit problem of the device, and prevent an increase in manufacturing cost due to excessive use of a doping material.

4 is a schematic diagram of an organic electric device according to embodiments of the present invention.

The organic electric device 200 according to the embodiments of the present application is positioned between the first electrode 210, the second electrode 230, and the first electrode 210 and the second electrode 230, and at least two And an organic material layer 220 including stacks 240.

The first electrode 210 may be, for example, an anode electrode, and the second electrode 230 may be a cathode electrode. The organic material layer 220 is a layer including an organic material while being positioned between the first electrode 210 and the second electrode 230 and may be formed of a plurality of layers.

For example, the first electrode 210 may be a transparent electrode, and the second electrode 230 may be a reflective electrode. In another example, the first electrode 210 may be a reflective electrode, and the second electrode 230 may be a transparent electrode.

Since the organic material layer 220 includes at least two stacks 240, for example, the organic electric device according to the exemplary embodiments of the present application may be a tandem organic electric device including a plurality of stacks. In this case, the organic material layer may be stacked by repeating the same stack two or more times, and two or more different stacks may be stacked.

The above-described stack 240 includes a hole transport region 241, a light emitting layer 242 and an electron transport region 243, respectively. The hole transport region 241 is, for example, a region positioned between the first electrode 210 as an anode electrode and the light emitting layer 242 to transport holes supplied from the first electrode 210 to the light emitting layer 242 I can. The electron transport region 243 may be, for example, a region positioned between the second electrode 230 as a cathode electrode and the emission layer 242 to transport electrons supplied from the second electrode 230 to the emission layer.

The emission layer 242 is a layer in which energy generated by meeting electrons and holes is emitted as light, and may include, for example, a host material and a dopant.

The thickness of the hole transport region may be 10 nm to 100 nm. The lower limit of the thickness of the hole transport region may be, for example, 15 nm or more or 20 nm or more. The upper limit of the thickness of the hole transport region may be, for example, 80 nm or less or 60 nm or less. When the thickness of the hole transport region is within the above range, the organic electric device may have high luminous efficiency, low driving voltage, and long life.

The organic material layer 220 may include one or more charge generation layers 250 positioned between the stacks 240. When there are three or more stacks 240, a charge generation layer 250 may be positioned between the stacks 240. In this case, the plurality of charge generation layers 250 may be the same and may be different from each other. Since the charge generation layer 250 is disposed between the stacks, current efficiency can be increased in each stack, and charges can be smoothly distributed.

The charge generation layer 250 may include, for example, an N-type charge generation layer 251 and a P-type charge generation layer 252. The N-type charge generation layer 251 may be located adjacent to the first electrode 210 as an anode electrode, and the P-type charge generation layer 252 is on the second electrode 230 as a cathode They can be located adjacent to each other.

The charge generation layer 250 and the stack 240 may be repeatedly positioned n times, which is a positive integer. For example, n may be an integer of 1 to 5. For example, when n is 2, the organic material layer may include three stacks and two charge generation layers.

A capping layer 260 may be positioned on the second electrode 230. When the capping layer 260 is formed, light efficiency of the organic electric device may be improved.

In the case of a top emission organic electronic device, the capping layer 260 may reduce optical energy loss due to surface plasmon polaritons (SPPs) in the second electrode 230. In the case of a bottom emission organic electric device, the capping layer 260 may serve as a buffer for the second electrode 230.

In the hole transport regions 241 included in the plurality of stacks 240, at least one hole transport region 241 includes a first hole transport layer and a second hole transport layer. For example, when the organic material layer includes two stacks, one of the two hole transport regions included in the two stacks may include a first hole transport layer and a second hole transport layer, and two Each of the hole transport regions may include a first hole transport layer and a second hole transport layer.

5 is a diagram schematically illustrating a stack 240 according to embodiments of the present invention.

Referring to FIG. 5, at least one hole transport region 241 may include a first hole transport layer 244 and a second hole transport layer 245. For example, the first hole transport layer 244 and the second hole transport layer 245 are located in the hole transport region 241, but the first hole transport layer 244 is the first electrode than the second hole transport layer 245 ( It is positioned adjacent to 210, and the second hole transport layer 245 may be positioned adjacent to the second electrode 230 rather than the first hole transport layer 244. In addition, the second hole transport layer 245 may be positioned closer to the light emitting layer 242 than the first hole transport layer 244.

Although not shown in FIG. 5, the hole transport region 241 may further include a third hole transport layer (not shown). The third hole transport layer may be positioned between, for example, the first hole transport layer 244 and the second hole transport layer 245. In the above example, the first hole transport layer 244 is located closer to the first electrode 210 than the second hole transport layer 245, and the second hole transport layer 245 is more than the first hole transport layer 244, the light emitting layer 242 ), and the third hole transport layer may be positioned between the first hole transport layer 244 and the second hole transport layer 245.

The electron transport region 243 may include an electron transport layer 248.

The above-described first hole transport layer may include a seventh compound. The seventh compound described above includes a radical of a compound represented by Formula A to be described later, and may be represented by Formula C to be described later or Formula D to be described later. The second hole transport layer described above may include the eighth compound. The eighth compound described above includes a radical of a compound represented by Formula A to be described later or Formula B to be described later, and may be represented by Formula C or Formula D to be described later.

Since the first hole transport layer includes the seventh compound and the second hole transport layer includes the eighth compound, the luminous efficiency, lifespan, driving voltage, and color purity of the organic electronic device may be further improved.

The above-described third hole transport layer may include a ninth compound. The above-described ninth compound includes a radical of a compound represented by Formula A to be described later or Formula B to be described later, and is represented by Formula C to be described later or Formula D to be described later. In addition, the ninth compound described above is different from the eighth compound. When the hole transport region 241 further includes the aforementioned third hole transport layer, the luminous efficiency, lifespan, driving voltage, and color purity of the organic electric device may be further improved.

When the first hole transport layer includes the seventh compound, it may mean that it includes at least one seventh compound. For example, the first hole transport layer may include two seventh compounds different from each other.

That the second hole transport layer includes the eighth compound may mean that it contains one or more eighth compounds. For example, the second hole transport layer may include two different types of eighth compounds.

When the third hole transport layer includes the ninth compound, it may mean that it includes at least one ninth compound. For example, the third hole transport layer may include two different types of ninth compounds.

The organic electric device according to the embodiments of the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

WOLED (White Organic Light Emitting Device) is easy to realize high resolution and excellent processability, while there is an advantage that can be manufactured using the existing color filter technology of LCD. Various structures for white organic electric devices mainly used as backlight devices have been proposed and patented. Typically, R(Red), G(Green), B(Blue) light emitting parts are arranged side-by-side in a mutually planar way, and R, G, B light emitting layers are stacked up and down. In addition, there is a color conversion material (CCM) method that uses electroluminescence by the blue (B) organic light-emitting layer and photo-luminescence of an inorganic phosphor using light therefrom. May be applied to such WOLED.

The first hole transport layer 1411a or the first light emission auxiliary layer 1411b may include a first compound represented by Formula 1 below. In another example, the first hole transport layer 1411a and the first emission auxiliary layer 1411b may include a first compound represented by Formula 1 below.

<Formula 1>

Hereinafter, the formula 1 will be described.

m and n are each independently 0 or 1, and m+n is 1.

Ar ¹ and Ar ² are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60.

Ar ¹ and Ar ² are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; And O, N, S, Si, and a C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; It may be selected from the group consisting of.

When Ar ¹ and Ar ² are any one of the date aryl, any of the aryl groups Ar ¹ and Ar ² are, for example, an aryl group of C ₆ -C ₆₀ aryl group, C ₆ -C ₄₀ of, C ₆ - It may be a C ₂₅ aryl group, or a C ₆ -C ₁₀ aryl group.

If any of the heterocyclic date of Ar ¹ and Ar ^2, any of the heterocyclic group Ar ¹ and Ar ² are, for example, O, N, S, Si and C containing at least one hetero atom of the P ₂ -C ₄₀ heterocyclic group, a C ₂ -C ₂₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P, or at least one of O, N, S, Si and P It may be a C ₂ -C ₁₀ heterocyclic group including a hetero atom of.

Ar ³ and Ar ⁴ are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60.

Ar ³ and Ar ⁴ may each independently be an aryl group of C ₆ ~ C ₆₀ .

Ar ³ and Ar ^4, if either the date of aryl, any of the aryl groups Ar ³ and Ar ⁴ is, for example, an aryl group of C ₆ -C ₆₀ aryl group, C ₆ -C ₄₀ of, C ₆ - It may be a C ₂₅ aryl group, or a C ₆ -C ₁₀ aryl group.

L ¹ to L ⁶ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60.

L ¹ to L ⁶ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; And O, N, S, Si, and a C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; It may be selected from the group consisting of.

L ¹ to L ^6, if any of the arylene group, the arylene group L ¹ to L ^6, any one of, for example, C ₆ -C ₆₀ aryl group, C ₆ -C ₄₀ aryl group, C _{It may be a 6} -C ₂₅ arylene group, or a C ₆ -C ₁₀ arylene group.

Any of L ¹ to L ⁶ is the case the heterocyclic group, any of the heterocyclic group L ¹ to L ⁶ is, for example, O, N, S, Si and C containing at least one hetero atom of the P ₂ -C ₄₀ heterocyclic group, a C ₂ -C ₂₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P, or at least one of O, N, S, Si and P It may be a C ₂ -C ₁₀ heterocyclic group including a hetero atom of.

X is hydrogen; heavy hydrogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; And C ₂ -C ₂₀ alkynyl group; is selected from the group consisting of.

X is hydrogen; heavy hydrogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; And a C ₁ -C ₃₀ alkyl group; It may be selected from the group consisting of.

When X is an aryl group, the aryl group X is, for example, a C ₆ -C ₆₀ aryl group, a C ₆ -C ₄₀ aryl group, a C ₆ -C ₂₅ aryl group, or a C ₆ -C ₁₀ aryl It can be a flag.

When X is a heterocyclic group, the heterocyclic group X is, for example, a C ₂ -C ₄₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P, O, N, S , C ₂ -C ₂₀ heterocyclic group including at least one heteroatom of Si and P, or C ₂ -C ₁₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P It can be a flag.

Y is i) hydrogen when n is 0; heavy hydrogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; And C ₂ -C ₂₀ alkynyl group; is selected from the group consisting of, ii) when n is 1, C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And fused ring groups of the aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; is selected from the group consisting of.

When n is 0, Y is hydrogen; heavy hydrogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; And C ₁ -C ₃₀ Alkyl group; may be selected from the group consisting of.

When n is 1, Y is a C ₆ ~ C ₆₀ arylene group; Fluorenylene group; And O, N, S, Si, and a C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; It may be selected from the group consisting of.

When Y is an aryl group, the aryl group Y is, for example, a C ₆ -C ₆₀ aryl group, a C ₆ -C ₄₀ aryl group, a C ₆ -C ₂₅ aryl group, or a C ₆ -C ₁₀ aryl It can be a flag.

When Y is an arylene group, the arylene group Y is, for example, a C ₆ -C ₆₀ arylene group, a C ₆ -C ₄₀ arylene group, a C ₆ -C ₂₅ arylene group, or a C ₆ -C ₁₀ It may be an arylene group of.

When Y is a heterocyclic group, the heterocyclic group Y is, for example, a C ₂ -C ₄₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P, O, N, S , C ₂ -C ₂₀ heterocyclic group including at least one heteroatom of Si and P, or C ₂ -C ₁₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P It can be a flag.

X and Y can combine with each other to form a spy compound.

Ring A and Ring B are each independently a C ₆ -C ₁₀ aryl group.

R ¹ and R ² are each independently deuterium; halogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ ~ C ₃₀ aryloxy group; is selected from the group consisting of.

R ¹ and R ² are each independently deuterium; C ₆ -C ₃₀ aryl group; Fluorenyl group; And a C ₂ -C ₃₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P; it may be selected from the group consisting of.

If R ¹ and R ² either is an aryl date of, any of the aryl groups R ¹ and R ² is, for example, an aryl group of C ₆ -C ₆₀ aryl group, C ₆ -C ₄₀ of, C ₆ - It may be a C ₂₅ aryl group, or a C ₆ -C ₁₀ aryl group.

R cases ¹ and R ² either is a heterocyclic date of, the heterocyclic group R ¹ and R ^2, any one of, for example, O, N, S, Si and C containing at least one hetero atom of the P ₂ -C ₄₀ heterocyclic group, a C ₂ -C ₂₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P, or at least one of O, N, S, Si and P It may be a C ₂ -C ₁₀ heterocyclic group including a hetero atom of.

a is an integer of 0 to 7, and b is an integer of 0 to 8.

In Formula 1, the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group and fluorenylene group, respectively, are deuterium; Halogen group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₆ ~ C ₂₅ aryl group; C ₆ ~ C ₂₅ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; And C ₃ ~ C ₂₀ cycloalkyl group; one or more substituents selected from the group consisting of may be further substituted,

Each of the additionally substituted substituents is deuterium; Halogen group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₆ ~ C ₂₅ aryl group; C ₆ ~ C ₂₅ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; And C ₃ ~ C ₂₀ cycloalkyl group; one or more substituents selected from the group consisting of may be further substituted, and these substituents may be bonded to each other to form a ring.

The first compound may be represented by any one of Formulas 2 to 5 below.

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

Hereinafter, the above Chemical Formulas 2 to 5 will be described.

c and d are each independently an integer of 0 to 4, and e is an integer of 0 to 5.

R ³ , R ⁴ and R ⁶ are, i) each independently, deuterium; halogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ ~ C ₃₀ aryloxy group; is selected from the group consisting of, and ii) a plurality of R ⁴ and a plurality of R ⁶ may be bonded to each other to form a ring.

R ³ , R ⁴ and R ⁶ are each independently deuterium; C ₆ -C ₃₀ aryl group; And a C ₂ -C ₃₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P; it may be selected from the group consisting of.

R ⁵ is hydrogen; heavy hydrogen; halogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ ~ C ₃₀ aryloxy group; may be selected from the group consisting of.

R ⁵ is hydrogen; heavy hydrogen; C ₆ -C ₃₀ aryl group; And a C ₂ -C ₃₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P; it may be selected from the group consisting of.

R ³ to R ^6, when either one of the aryl group, the aryl group R ³ to R ⁶ is any one of, for example, an aryl group of C ₆ -C ₆₀ aryl group, C ₆ -C ₄₀ of, C ₆ - It may be a C ₂₅ aryl group, or a C ₆ -C ₁₀ aryl group.

R ³ to R, if any one of ^hexavalent heterocyclic group, any of the heterocyclic group R ³ to R ⁶ are, for example, O, N, S, Si and C containing at least one hetero atom of the P ₂ -C ₄₀ heterocyclic group, a C ₂ -C ₂₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P, or at least one of O, N, S, Si and P It may be a C ₂ -C ₁₀ heterocyclic group including a hetero atom of.

Ar ¹ to Ar ⁴ , L ¹ to L ⁶ , R ¹ , R ² , a and b are Ar ¹ to Ar ⁴ , L ¹ to L ⁶ , R ¹ , R ² , a and Same as b.

The first compound may be represented by any one of Formulas 6 to 9 below.

<Formula 6>

<Formula 7>

<Formula 8>

<Formula 9>

Hereinafter, the above Chemical Formulas 6 to 9 will be described.

Z is O, S, NR' or CR'R".

R'and R" are each independently a C ₁ -C ₃₀ alkyl group; C ₆ -C ₃₀ aryl group; And O, N, S, Si, and C ₃ -including at least one heteroatom of P C ₃₀ heterocyclic group; or selected from the group consisting of, these may be combined with each other to form a spy compound.

When any one of R'and R" is an aryl group, R'and R" which are aryl groups Any one of them may be, for example, a C ₆ -C ₆₀ aryl group, a C ₆ -C ₄₀ aryl group, a C ₆ -C ₂₅ aryl group, or a C ₆ -C ₁₀ aryl group.

When any one of R'and R" is a heterocyclic group, R'and R" which are heterocyclic groups Any one of, for example, a C ₂ -C ₄₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P, at least one of O, N, S, Si and P It may be a C ₂ -C ₂₀ heterocyclic group including a heteroatom, or a C ₂ -C ₁₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P.

R ⁷ and R ⁸ are, i) each independently, deuterium; halogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ ~ C ₃₀ aryloxy group; is selected from the group consisting of, and ii) a plurality of R ⁷ and a plurality of R ⁸ may be bonded to each other to form a ring.

R ⁷ and R ⁸ are, i) each independently, deuterium; C ₆ -C ₃₀ aryl group; And a C ₂ -C ₃₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P; and ii) a plurality of R ⁷ and a plurality of R ⁸ Can be combined to form a ring.

R ⁷ and R ⁸ each case one of the date is aryl, aryl group R ⁷ and R ⁸ is any one of, for example, an aryl group of C ₆ -C ₆₀ aryl group, C ₆ -C ₄₀ of, C ₆ - It may be a C ₂₅ aryl group, or a C ₆ -C ₁₀ aryl group.

R ⁷ and R ⁸ in either the case the heterocyclic group, the heterocyclic group R ⁷ and R ⁸ any one of, for example, O, N, S, Si and C containing at least one hetero atom of the P ₂ -C ₄₀ heterocyclic group, a C ₂ -C ₂₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P, or at least one of O, N, S, Si and P It may be a C ₂ -C ₁₀ heterocyclic group including a hetero atom of.

f is an integer from 0 to 4, and g is an integer from 0 to 3.

Ar ² , L ¹ to L ³ , A ring, B ring, X, Y, R ¹ , R ² , a and b are Ar ² , L ¹ to L ³ , ring A, as defined in the foregoing description of Formula 1, It is the same as ring B, X, Y, R ¹ , R ² , a and b.

The first compound is an organic electric device represented by any one of the following Formulas 10 to 12:

<Formula 10>

<Formula 11>

<Formula 12>

Hereinafter, the above Chemical Formulas 10 to 12 will be described.

R ⁹ is, i) each independently, deuterium; halogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ ~ C ₃₀ aryloxy group; is selected from the group consisting of, ii) a plurality of R ⁹ may be bonded to each other to form a ring.

R ⁹ is, i) each independently, deuterium; halogen; C ₆ -C ₃₀ aryl group; And a C ₂ -C ₃₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P; It is selected from the group consisting of, and ii) a plurality of R ⁹ may be bonded to each other to form a ring.

When R ⁹ is an aryl group, the aryl group R ⁹ is, for example, a C ₆ -C ₆₀ aryl group, a C ₆ -C ₄₀ aryl group, a C ₆ -C ₂₅ aryl group, or a C ₆ -C ₁₀ It may be an aryl group of.

When R ⁹ is a heterocyclic group, the heterocyclic group R ⁹ is, for example, a C ₂ -C ₄₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P, O, N , C ₂ -C ₂₀ heterocyclic group including at least one heteroatom of S, Si and P, or C ₂ -C ₁₀ including at least one heteroatom of O, N, S, Si and P It may be a heterocyclic group.

Ar ¹ , Ar ³ , L ¹ , L ⁴ , A ring, B ring, X, Y, R ¹ , R ² , a and b are Ar ¹ , Ar ³ , L ¹ , which were previously defined while describing Formula 1 It is the same as L ⁴ , A ring, B ring, X, Y, R ¹ , R ² , a and b.

The first compound may be one or more of the following compounds.

When the first hole transport layer 1411a or the first light emission auxiliary layer 1411b contains the above-described first compound, and the first hole transport layer 1411a satisfies the above-described conditions for thickness and doping, efficiency or lifespan is reduced. It is possible to provide an excellent organic electric device.

The second hole transport layer or the second light emission auxiliary layer may include a second compound represented by Formula 1 above. In another example, the second hole transport layer and the second light emission auxiliary layer may include the second compound represented by Formula 1 above.

When the second hole transport layer or the second light emission auxiliary layer contains the above-described second compound, and the second hole transport layer satisfies the above-described conditions for thickness and doping, an organic electric device having excellent efficiency or lifetime can be provided. .

The third hole transport layer or the third light emission auxiliary layer may include a third compound represented by Formula 1 above. In another example, the third hole transport layer and the third light emission auxiliary layer may include the third compound represented by Formula 1 above.

When the third hole transport layer or the third light emission auxiliary layer contains the above-described third compound, and the third hole transport layer satisfies the above-described conditions for thickness and doping, an organic electric device having excellent efficiency or lifetime can be provided. .

The fourth hole transport layer 1441a or the fourth light emission auxiliary layer 1441b may include a fifth compound represented by Formula 1 above. In another example, the fourth hole transport layer 1441a and the fourth light emission auxiliary layer 1414b may include the fifth compound represented by Formula 1 above.

When the fourth hole transport layer or the fourth light emission auxiliary layer contains the above-described fifth compound, and the fourth hole transport layer satisfies the above-described conditions for thickness and doping, an organic electric device having excellent efficiency or lifetime can be provided. .

For the second compound, the third compound, and the fifth compound, the same as described for the first compound may be applied as described above, unless otherwise specifically described with respect to the first compound.

In another example, the first hole transport layer 1411a or the first light emission auxiliary layer 1411b may include at least one of the first compound and the fourth compound. In another example, the first hole transport layer 1411a and the first emission auxiliary layer 1411b may include at least one of the first compound and the fourth compound.

When the first hole transport layer 1411a or the first light emission auxiliary layer 1411b contains at least one of a first compound and a fourth compound, and the first hole transport layer 1411a satisfies the above-described conditions for thickness and doping , It is possible to provide an organic electric device excellent in efficiency or life.

In another example, the fourth hole transport layer 1441a or the fourth light emission auxiliary layer 1441b may include at least one of the fifth compound and the sixth compound. In another example, the fourth hole transport layer 1441a and the fourth light emission auxiliary layer 1441b may include at least one of the fifth compound and the sixth compound.

The fourth hole transport layer (1441a) or the fourth light emission auxiliary layer (1441b) contains at least one of the fifth compound and the sixth compound, and the fourth hole transport layer (1441a) satisfies the above-described conditions for thickness and doping. In this case, it is possible to provide an organic electric device having excellent efficiency or lifetime.

The fourth compound includes a radical of a compound represented by the following formula A or the following formula B, and may be represented by at least one of the compounds represented by the following formula C or the following formula D.

In the embodiments of the present invention, it means that an arbitrary compound "includes a radical of a compound represented by Formula A or Formula B, and is represented by Formula C or Formula D", means that any compound is represented by Formula C or Formula D. It has a structure represented by, but at least one of the substituents and linking groups contained in the formula (C) or (D) may mean that n of the compound represented by the formula (A) or (B) is a radical (where n is an integer of 1 or more) ). However, an arbitrary compound "includes a radical of a compound represented by Formula A or Formula B, and is represented by Formula C or Formula D" means that any compound is a radical of a compound represented by Formula A or Formula B. It may mean that n is not included in a radical form, but is included in a state in which the radical of the compound represented by Formula A or Formula B is covalently bonded with any element of the compound represented by Formula C or Formula D. .

Hereinafter, the formula A will be described.

a and b are each independently an integer of 0-4.

X is O, S, CR'R'' or NL ₁ -Ar ₁ .

R ₁ and R ₂ are each independently deuterium; Tritium; halogen; Cyano group; Nitro group; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And a C ₆ -C ₃₀ aryloxy group, and R ¹ and R ² may each be bonded to each other to form a ring.

When R ₁ or R ₂ is an aryl group, for example, it may be a C ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₄₀ aryl group, a C ₆ ~ C ₂₅ aryl group, a C ₆ ~ C ₁₀ aryl group have.

When R ₁ or R ₂ is a heterocyclic group, for example, it may be a C ₂ ~ C ₆₀ heterocyclic group, a C ₂ ~ C ₄₀ heterocyclic group, or a C ₂ ~ C ₂₀ heterocyclic group.

R'and R'' are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ is selected from the group consisting of a fused ring of an aromatic ring of C ₆₀ of aliphatic rings and C ₆ ~ C _60, R 'and R''may bond to one another to form a ring.

When R'or R'' is an aryl group, for example, an aryl group of C ₆ to C _60, an aryl group of C ₆ to C _40, an aryl group of C ₆ to C _25, an aryl group of C ₆ to C ₁₀ I can.

When R'or R'' is a heterocyclic group, for example, it may be a C ₂ ~ C ₆₀ heterocyclic group, a C ₂ ~ C ₄₀ heterocyclic group, or a C ₂ ~ C ₂₀ heterocyclic group.

L ₁ is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60.

When L ₁ is an arylene group, for example, it may be a C ₆ ~ C ₆₀ arylene group, a C ₆ ~ C ₄₀ arylene group, a C ₆ ~ C ₂₅ arylene group, or a C ₆ ~ C ₁₀ arylene group. .

When L ₁ is a heterocyclic group, for example, it may be a C ₂ ~ C ₆₀ heterocyclic group, a C ₂ ~ C ₄₀ heterocyclic group, or a C ₂ ~ C ₂₀ heterocyclic group.

Ar ₁ is a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60.

When Ar ₁ is an aryl group, for example, it may be a C ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₄₀ aryl group, a C ₆ ~ C ₂₅ aryl group, a C ₆ ~ C ₁₀ aryl group.

When Ar ₁ is a heterocyclic group, for example, it may be a C ₂ to C ₆₀ heterocyclic group, a C ₂ to C ₄₀ heterocyclic group, or a C ₂ to C ₂₀ heterocyclic group.

Hereinafter, the formula B will be described.

l is an integer from 0 to 5.

m is an integer from 0 to 4.

y and z are integers from 0 to 4, and y+z is not 0.

R _a and R _b are each independently deuterium; Tritium; halogen; Cyano group; Nitro group; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And a C ₆ -C ₃₀ aryloxy group, and R _a and R _b may each be bonded to each other to form a ring.

When R _a or R _b is an aryl group, for example, it may be a C ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₄₀ aryl group, a C ₆ ~ C ₂₅ aryl group, a C ₆ ~ C ₁₀ aryl group have.

When R _a or R _b is a heterocyclic group, for example, it may be a C ₂ ~ C ₆₀ heterocyclic group, a C ₂ ~ C ₄₀ heterocyclic group, or a C ₂ ~ C ₂₀ heterocyclic group.

Hereinafter, the formula (C) will be described.

n is 1 or 2.

Ar ₂ is a radical of a compound represented by Formula A or a radical of a compound represented by Formula B.

Ar ₃ and Ar ₄ are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60.

When Ar ₃ or Ar ₄ is an aryl group, for example, it may be a C ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₄₀ aryl group, a C ₆ ~ C ₂₅ aryl group, a C ₆ ~ C ₁₀ aryl group have.

When Ar ₃ or Ar ₄ is a heterocyclic group, for example, it may be a C ₂ ~ C ₆₀ heterocyclic group, a C ₂ ~ C ₄₀ heterocyclic group, or a C ₂ ~ C ₂₀ heterocyclic group.

L ₂ to L ₄ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; And O, N, S, Si and P is selected from the group consisting of a C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom.

When any one of L ₂ to L ₄ is an arylene group, for example, an arylene group of C ₆ to C _60, an arylene group of C ₆ to C _40, an arylene group of C ₆ to C ₂₅ , or C ₆ to C ₁₀ It may be an arylene group of.

When any one of L ₂ to L ₄ is a heterocyclic group, for example, it may be a C ₂ to C ₆₀ heterocyclic group, a C ₂ to C ₄₀ heterocyclic group, or a C ₂ to C ₂₀ heterocyclic group .

Hereinafter, formula D will be described.

o is an integer from 1 to 4.

Ar ₅ to Ar ₈ are each independently a C ₆ to C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60.

When any one of Ar ₅ to Ar ₈ is an aryl group, for example, C ₆ to C ₆₀ aryl group, C ₆ to C ₄₀ aryl group, C ₆ to C ₂₅ aryl group, C ₆ to C ₁₀ It may be an aryl group.

When any one of Ar ₅ to Ar ₈ is a heterocyclic group, for example, it may be a C ₂ to C ₆₀ heterocyclic group, a C ₂ to C ₄₀ heterocyclic group, or a C ₂ to C ₂₀ heterocyclic group .

L ₅ to L ₉ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C doedoe of ₆₀ alicyclic and C ₆ ~ C ₆₀ selected from the group consisting of a fused ring of an aromatic ring, L ₉ is a radical of a compound represented by the radical or the formula (B) of the compound of the formula A Can be

When any one of L ₅ to L ₉ is an arylene group, for example, an arylene group of C ₆ to C _60, an arylene group of C ₆ to C _40, an arylene group of C ₆ to C ₂₅ , or C ₆ to C ₁₀ It may be an arylene group of.

When any one of L ₅ to L ₉ is a heterocyclic group, for example, it may be a C ₂ to C ₆₀ heterocyclic group, a C ₂ to C ₄₀ heterocyclic group, or a C ₂ to C ₂₀ heterocyclic group. .

In Formulas A to D, the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group and fluorenylene group are each deuterium; Nitro group; Nitrile group; Halogen group; Amino group; C ₁ ~ C ₂₀ alkylthio group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₆ ~ C ₂₅ aryl group; C ₆ ~ C ₂₅ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; A C ₃ ~C ₂₀ cycloalkyl group; One or more substituents selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group and C ₈ ~ C ₂₀ arylalkenyl group may be further substituted, and the additionally substituted substituents may be bonded to each other to form a ring. And the additionally substituted substituents are each deuterium; Nitro group; Nitrile group; Halogen group; Amino group; C ₁ ~ C ₂₀ alkylthio group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₆ ~ C ₂₅ aryl group; C ₆ ~ C ₂₅ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; A C ₃ ~C ₂₀ cycloalkyl group; C ₇ ~ C ₂₀ arylalkyl group; And one or more substituents selected from the group consisting of C ₈ ~ C ₂₀ arylalkenyl group may be further substituted, and these substituents may be bonded to each other to form a ring.

The fourth compound includes a radical of the compound represented by Formula A, represented by Formula C, and may be represented by any one of Formulas H-1 to H-5 below.

Formula H-1 Formula H-2

Formula H-3 Formula H-4 Formula H-5

In Formulas H-1 to H-5, a, b, n, R ₁ , R ₂ , R', R'', Ar ₁ , Ar ₃ , Ar ₄ and L ₁ to L ₄ are, Formula A to It is the same as a, b, R ₁ , R ₂ , R', R'', Ar ₁ , Ar ₃ , Ar ₄ and L ₁ to L ₄ defined while describing the formula D.

The fourth compound includes a radical of the compound represented by Formula A, represented by Formula D, and may be represented by any one of Formulas I-1 to I-3 below.

In Formulas I-1 to I-3, a, b, R ₁ , R ₂ , R', R'', Ar ₅ to Ar ₈ and L ₅ to L ₉ are described with respect to Formulas A to D It is the same as defined a, b, R ₁ , R ₂ , R', R'', Ar ₅ to Ar ₈ and L ₅ to L ₉ .

The fourth compound includes a radical of the compound represented by Formula A, represented by Formula D, and may be represented by any one of Formulas I-4 to I-6 below.

In Formulas I-4 to I-6, a, b, R ₁ , R ₂ , R', R'', Ar ₅ to Ar ₈ and L ₅ to L ₉ are described for Formulas A to D It is the same as a, b, R ₁ , R ₂ , R', R'', Ar ₅ to Ar ₈ and L ₅ to L ₉ as defined.

The fourth compound includes a radical of the compound represented by Formula B, is represented by Formula C or Formula D, and may be represented by any one of Formulas J-1 to J-3 below.

In Formulas J-1 to J-3, l, m, n, y, z, R _a , R _b , Ar ₃ to Ar ₈ and L ₅ to L ₉ are L ₉ is for Formulas A to D It is the same as l, m, n, R _a , R _b , Ar ₃ to Ar ₈ and L ₅ to L ₉ defined while describing.

The formula H-1 may be represented by the following formula H-1-A or H-1-B.

In Formula H-1-A and Formula H-1-B, a, b, R ₁ , R ₂ , Ar ₁ , Ar ₃ , Ar ₄ and L ₁ to L ₄ are described with respect to Formulas A to D It is the same as defined a, b, R ₁ , R ₂ , Ar ₁ , Ar ₃ , Ar ₄ , Ar _a , Ar _b and L ₁ to L ₄ .

The L ₁ to L ₈ may each independently be represented by any one of the following Formulas b-1 to b-13.

Hereinafter, the formulas b-1 to b-13 will be described.

Y is each independently NL ⁶ -Ar ⁹ , O, S or CR ^d R ^e .

L ⁶ is the same as L ₁ defined while describing the formulas A to D.

Ar ⁹ is the same as Ar ₁ defined while describing the formulas A to D.

R ^d and R ^e are the same as R'and R'' defined while describing the formulas A to D.

a'', c'', d'' and e'' are each independently an integer of 0 to 4, and b'' is each independently an integer of 0 to 6.

f'' and g'' are each independently an integer of 0 to 3, h'' is an integer of 0 to 2, and i'' is an integer of 0 or 1.

R ⁸ to R ¹⁰ are each independently hydrogen; heavy hydrogen; Tritium; halogen; Cyano group; Nitro group; C ₆ -C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; C ₆ -C ₃₀ aryloxy group and -L ^a -N (R ^d ) (R ^e ) is selected from the group consisting of, R ⁸ to R ¹⁰ may be bonded to each other to form a ring.

L ^a is a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene group; A C ₂ -C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And C ₃ -C ₆₀ is selected from the group consisting of an aliphatic hydrocarbon group.

R ^d and R ^e are each independently a C ₆ -C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₆₀ heterocyclic group containing at least one hetero atom selected from the group consisting of P; And a fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ .

Z ⁴⁹ , Z ⁵⁰ , Z ⁵¹ are each independently CR ^f or N, and at least one of Z ⁴⁹ , Z ⁵⁰ , and Z ⁵¹ is N.

R ^f is hydrogen; heavy hydrogen; Tritium; halogen; Cyano group; Nitro group; C ₆ -C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And a C ₆ -C ₃₀ aryloxy group, and neighboring R ⁸ and R ^f may be bonded to each other to form a ring.

The fourth compound includes a radical of the compound represented by Formula A, represented by Formula C, and may be at least one of Compounds 1-1 to 6-35 below.

The fourth compound includes a radical of the compound represented by Formula A, represented by Formula D, and may be one or more of Compounds 7-1 to 10-189 below.

The fourth compound includes a radical of the compound represented by Formula B, is represented by Formula C or Formula D, and may be at least one of Formulas 11-1 to 12-71 below.

For the sixth compound, the description for the fourth compound may be the same as that described for the fourth compound, unless otherwise specifically described.

The first doping material may be a P-type dopant. P-type dopants, for example, quinodimethane compounds, azaindenofluorenedions, azaphenalenes, azatriphenylenes, I2, metal halides, transition metal halides, metal oxides, In complexes of metal from main group 3 or metal oxides containing at least one transition metal, transition metal complexes, and ligands containing at least one oxygen atom as a bonding site and Cu, Co, Ni, Pd and Pt Can be chosen. In another example, the P-type dopants may be selected from oxides of rhenium, molybdenum and tungsten, for example, Re2O7, MoO3, WO3 and ReO3.

In another example, the first doping material may be represented by Formula E below.

<Formula E>

Hereinafter, the formula E will be described.

R _p1 to R _p6 are each independently hydrogen; Halogen group; Nitrile group; Nitro group; -SO ₂ R; -SOR; -SO ₂ NR ₂ ; -SO ₃ R; Trifluoromethyl group; -COOR; -CONHR; -CONRR'; An alkoxyl group of C ₁ -C ₃₀ ; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; Fluorenyl group; C ₆ -C ₃₀ aryl group; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; And -NRR'; may be selected from the group consisting of.

Each of R and R'is a C ₁ -C ₃₀ alkyl group; Fluorenyl group; C ₆ -C ₃₀ aryl group; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; And a C ₂ -C ₃₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P; it may be selected from the group consisting of.

Following Formula E, the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group and alkoxyl group, respectively, are deuterium; Halogen group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₆ ~ C ₂₅ aryl group; C ₆ ~ C ₂₅ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; And C ₃ ~ C ₂₀ cycloalkyl group; one or more substituents selected from the group consisting of may be substituted.

In another example, the first doping material may be selected from E-1 to E-4 below.

In another example, the first doping material may be selected from E-5 to E-8 below.

For the second doping material to the fourth doping material, the same as described for the first doping material may be applied, unless otherwise specifically described with respect to the first doping material.

In some embodiments of the present invention, the organic material layer 130 includes a first stack 141, a second stack 142, and a third stack 143, and the first stack 141 is a first hole transport region. 1411, a first emission layer 1412, and a first electron transport region 1413 may be included. In these embodiments, the first hole transport region 1411 includes the first hole transport layer 1411a and the first light emission auxiliary layer 1411b, and the first hole transport layer 1411a or the first light emission auxiliary layer 1411b ) Contains the first compound represented by Formula 1, the thickness of the first hole transport layer 1411a is 250Å to 700Å, and the first hole transport layer 1411a is 10% of the thickness of the first hole transport layer 1411a To 50% may be doped with the first doping material.

In some embodiments of the present invention, the organic material layer 130 includes a first stack 141, a second stack 142, and a third stack 143, and the first stack 141 is a first hole transport region. 1411, a first emission layer 1412, and a first electron transport region 1413 may be included. In these embodiments, the first hole transport region 1411 includes the first hole transport layer 1411a and the first light emission auxiliary layer 1411b, and the first hole transport layer 1411a or the first light emission auxiliary layer 1411b ) Contains the first compound represented by Formula 1, the thickness of the first hole transport layer 1411a is 250Å to 700Å, and the first hole transport layer 1411a is 10% of the thickness of the first hole transport layer 1411a To 50% may be doped with the first doping material. In these embodiments, the second stack 142 may include a second hole transport region 1421, a second emission layer 1422, and a second electron transport region 1423. In these embodiments, the second hole transport region 1421 includes the second hole transport layer 1421a and the second light emission auxiliary layer 1421b, and the second hole transport layer 1421a or the second light emission auxiliary layer 1421b ) Contains the second compound represented by Formula 1, the thickness of the second hole transport layer 1421a is 250Å to 700Å, and the second hole transport layer 1421a is 10% to 10% of the thickness of the second hole transport layer 1421a 50% may be doped with the second doping material. In these embodiments, the third stack 143 may include a third hole transport region 1431, a third emission layer 1432, and a third electron transport region 1433. In these embodiments, the third hole transport region 1431 includes a third hole transport layer 1431a and a third light emission auxiliary layer 1431b, and the third hole transport layer 1431a or the third light emission auxiliary layer 1431b ) Contains the third compound represented by Formula 1, the thickness of the third hole transport layer 1431a is 250Å to 700Å, and the third hole transport layer 1431a is 10% to 10% of the thickness of the third hole transport layer 1431a 50% may be doped with a third doping material.

In the above embodiments, the thickness of the first hole transport layer 1411a is 400 Å to 500 Å, the thickness of the second hole transport layer 1421a is 500 Å to 650 Å, and the thickness of the third hole transport layer 1431a is It may be 450 Å to 560 Å. For example, a first electrode 110, a first stack 141, a second stack 142, a third stack 143, and a second electrode 120 are sequentially stacked, and the first emission layer 1412, The second emission layer 1422 and the third emission layer 1432 each include a blue host and a blue dopant, and the first hole transport layer 1411a, the second hole transport layer 1421a, and the third hole transport layer 1431a are described above. While satisfying the thickness range, the first hole transport layer 1411a or the first light emission auxiliary layer 1411b contains the first compound, and the second hole transport layer 1421a or the second light emission auxiliary layer 1421b is a second compound Including, and when the third hole transport layer (1431a) or the third light emission auxiliary layer (1431b) contains the third compound, it is possible to provide an organic electric device having excellent efficiency or lifetime.

In the above embodiments, the first hole transport layer 1411a includes a first doped material doped layer 1411aa doped with a first doping material and a first doped material non-doped layer 1411ab doped with a first doping material. Including, the first doping material doping layer 1411aa includes a first compound, and may include 5 parts by weight to 15 parts by weight of the first doping material based on 100 parts by weight of the first compound. The second hole transport layer includes a second doping material doped layer doped with a second doping material and a second doping material undoped layer not doped with the second doping material, and the second doping material doped layer contains a second compound. And 5 parts by weight to 15 parts by weight of a second doping material relative to 100 parts by weight of the second compound. The third hole transport layer includes a third doping material doped layer doped with a third doping material and a third doping material undoped layer not doped with the third doping material, and the third doping material doped layer contains a third compound. And 5 parts by weight to 15 parts by weight of a third doping material relative to 100 parts by weight of the third compound.

In the above embodiments, the first compound, the second compound, and the third compound may be the same compound.

In some embodiments of the present invention, the organic material layer 130 includes a first stack 141, a second stack 142, and a third stack 143, and the first stack 141 is a first hole transport region. 1411, a first emission layer 1412, and a first electron transport region 1413 may be included. In these embodiments, the first hole transport region 1411 includes the first hole transport layer 1411a and the first light emission auxiliary layer 1411b, and the first hole transport layer 1411a or the first light emission auxiliary layer 1411b ) Includes at least one of the first compound and the fourth compound represented by Formula 1, the thickness of the first hole transport layer 1411a is 250Å to 700Å, and the first hole transport layer 1411a is the first hole 10% to 50% of the thickness of the transport layer 1411a may be doped with the first doping material.

In some embodiments of the present invention, the organic material layer 130 includes a first stack 141, a second stack 142, a third stack 143, and a fourth stack 144, and the first stack 141 ) May include a first hole transport region 1411, a first emission layer 1412, and a first electron transport region 1413. In these embodiments, the first hole transport region 1411 includes the first hole transport layer 1411a and the first light emission auxiliary layer 1411b, and the first hole transport layer 1411a or the first light emission auxiliary layer 1411b ) Contains the first compound represented by Formula 1, the thickness of the first hole transport layer 1411a is 250Å to 700Å, and the first hole transport layer 1411a is 10% of the thickness of the first hole transport layer 1411a To 50% may be doped with the first doping material. In these embodiments, the fourth stack 144 may include a fourth hole transport region 1441, a fourth emission layer 1442, and a fourth electron transport region 1443. In these embodiments, the fourth hole transport region 1441 includes the fourth hole transport layer 1441a and the fourth light emission auxiliary layer 1441b, and the fourth hole transport layer 1441a or the fourth light emission auxiliary layer 1441b ) Includes at least one of the fifth compound and the sixth compound represented by Formula 1, the thickness of the fourth hole transport layer 1441a is 250Å to 700Å, and the fourth hole transport layer 1441a is the first 4 10% to 50% of the thickness of the hole transport layer 1441a may be doped with the fourth doping material.

In embodiments of the present invention, at least one of the first emission layer 1412, the second emission layer 1422, and the third emission layer 1432 may be an emission layer emitting blue light. At least one of the first to third light-emitting layers is a light-emitting layer that emits green light, and the first hole transport layer 1411a or the first light-emitting auxiliary layer 1411b contains the first compound, When the conditions are satisfied, it is possible to provide an organic electric device having excellent efficiency, lifetime, or color purity.

In the present application, the light-emitting layer emitting blue light may mean a light-emitting layer that emits light having a wavelength of about 450 nm to 495 nm when electrons and holes meet and are excited in the light-emitting layer.

In embodiments of the present invention, the first emission layer 1412, the second emission layer 1422, and the third emission layer 1432 may emit blue light. When the first to third light-emitting layers are light-emitting layers that emit green light and the first hole transport layer 1411a or the first light-emitting auxiliary layer 1411b contains the first compound and satisfies the above-described conditions for thickness and doping, It is possible to provide an organic electric device having excellent efficiency, lifetime or color purity.

In embodiments of the present invention, one to two of the first emission layer 1412, the second emission layer 1422, and the third emission layer 1432 are emission layers that emit blue light, and one or two of the emission layers emit green light. It may be a light emitting layer. One to two of the first light-emitting layer 1412, the second light-emitting layer 1422, and the third light-emitting layer 1432 are light-emitting layers that emit blue light, and one to two are light-emitting layers that emit green light and a first hole transport layer 1411a. ) Or, when the first light emission auxiliary layer 1411b includes the first compound and satisfies the above-described conditions for thickness and doping, an organic electric device having excellent efficiency, lifetime, or color purity may be provided.

In the present application, the emission layer emitting green light may mean an emission layer emitting light having a wavelength of about 495 nm to 570 nm when electrons and holes meet and are excited in the emission layer.

In embodiments of the present invention, two of the first emission layer 1412, the second emission layer 1422, and the third emission layer 1432 are emission layers that emit blue light, and the other emission layer emits green light. It may be a light emitting layer. Two of the first emission layer 1412, the second emission layer 1422, and the third emission layer 1432 are emission layers that emit blue light, and the other emission layer is a emission layer that emits green light, and the first hole transport layer 1411a ) Or when the first light-emitting auxiliary layer 1411b contains the first compound and satisfies the above-described conditions for thickness and doping, an organic electric device having excellent efficiency, lifetime, or color purity may be provided.

In embodiments of the present invention, two of the first emission layer 1412, the second emission layer 1422, and the third emission layer 1432 are emission layers that emit blue light, and the other emission layer emits green light. In the case of an emission layer, the emission layer emitting green light may be positioned between two emission layers emitting blue light. When the first to third light-emitting layers satisfy the above-described conditions, and the first hole transport layer 1411a or the first light-emitting auxiliary layer 1411b contains the first compound and satisfies the aforementioned conditions for thickness and doping, It is possible to provide an organic electric device having excellent efficiency, lifetime or color purity.

In embodiments of the present invention, at least one of the first emission layer 1412, the second emission layer 1422, and the third emission layer 1432 may be a multi emission layer emitting green light and blue light.

In the present application, the multi-light emitting layer in which the light emitting layer emits green light and blue light may mean a light emitting layer that emits light having a wavelength of about 450 nm to 570 nm when electrons and holes meet and are excited in the light emitting layer.

At least one of the first light-emitting layer 1412, the second light-emitting layer 1422, and the third light-emitting layer 1432 is a multi-light-emitting layer that emits green light and blue light, and the first hole transport layer 1411a or the first light-emitting auxiliary layer 1411b ) Contains the first compound and satisfies the above-described conditions for thickness and doping, it is possible to provide an organic electric device having excellent efficiency, lifetime, or color purity.

In embodiments of the present invention, two of the first emission layers 1412 to 4442 are emitting layers that emit blue light, and the other emitting layer different from the two emitting layers is a emitting layer that emits green light. Can be Two of the first light-emitting layers 1412 to 4442 are light-emitting layers that emit blue light, and the other one is a light-emitting layer that emits green light, and a fourth hole transport layer 1441a or a fourth light-emitting auxiliary layer When (1441b) includes at least one of the fifth compound and the sixth compound and satisfies the above-described conditions for thickness and doping, an organic electric device having excellent efficiency, lifetime, or color purity may be provided.

In embodiments of the present invention, three of the first to fourth emission layers 1412 to 1442 may be emission layers that emit blue light, and the other emission layer may be a emission layer that emits green light. Three of the first to fourth light emitting layers 1412 to 1442 are light emitting layers that emit blue light, and the other light emitting layer is a light emitting layer that emits green light, and a fourth hole transport layer 1441a or a fourth light emitting auxiliary layer When (1441b) includes at least one of the fifth compound and the sixth compound and satisfies the above-described conditions for thickness and doping, an organic electric device having excellent efficiency, lifetime, or color purity may be provided.

Hereinafter, examples for synthesizing the hole transport layer compound and an organic electric device according to the present invention will be described in detail, but the present invention is not limited to the following examples.

[Synthesis Example]

Compounds (e.g., the above-described fourth compound, sixth compound, seventh compound, and eighth compound) containing a radical of a compound represented by Formula A or Formula B according to the present invention and represented by Formula C As shown in Scheme 1, any one of Sub 1-A to Sub 1-C is prepared by reacting with Sub 2, but is not limited thereto.

<Reaction Scheme 1>

In more detail, Scheme 1 may be represented as in Scheme 2 to Scheme 4 below, but is not limited thereto.

<Reaction Scheme 2>

<Reaction Scheme 3>

<Reaction Scheme 4>

Sub 1-A synthesis

Sub 1A of Scheme 1 may be synthesized by the reaction route of Scheme 5 below, but is not limited thereto.

<Reaction Scheme 5>

Sub 1-B synthesis

Sub 1B of Scheme 2 may be synthesized by the reaction route of Scheme 6 below, but is not limited thereto.

<Reaction Scheme 6>

Sub 1-C synthesis

Sub 1C of Scheme 3 may be synthesized by the reaction route of Scheme 6 below, but is not limited thereto.

<Reaction Scheme 7>

Synthesis example of Sub 1-A-3

9-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (29.5 g, 80 mmol), THF 360 mL, 1-bromo-4 -iodobenzene (23.8 g, 84 mmol), Pd(PPh ₃ ) ₄ (2.8 g, 2.4mmol), NaOH (9.6 g, 240mmol), 180 mL of water were added, and the mixture was stirred to reflux. When the reaction was completed, the product was extracted with ether and water, and the organic layer was dried with MgSO ₄ and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 22.9 g (72%) of the product.

Synthesis example of Sub 1-A-5

Dissolve 9-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (73.92 g, 200.2 mmol) in 880 mL of THF in a round bottom flask. Afterwards, 1-bromo-2-iodobenzene (85.0 g, 300.3 mmol), Pd(PPh ₃ ) ₄ (11.6 g, 10 mmol), K ₂ CO ₃ (83 g, 600.6 mmol), and 440 mL of water were added to the Sub 1 Proceeding in the same manner as in the experimental method of -A-3, the product 55.8g (yield: 70%) was obtained.

Synthesis Example of Sub 1-B-2

After dissolving 9H-carbazole (12 g, 71.8 mmol) with nitrobenzene (450ml) in a round bottom flask, 4-bromo-4'-iodo-1,1'-biphenyl (38.65 g, 107.6 mmol), Na ₂ SO ₄ (10.19 g, 71.8 mmol), K ₂ CO ₃ (9.92 g, 71.8 mmol), Cu (1.37 g, 21.5 mmol) were added and stirred at 200 °C. When the reaction was completed, nitrobenzene was removed through distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 21.15 g (yield: 74%) of the product.

Sub 2 synthesis example

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 8 below, but is not limited thereto.

<Reaction Scheme 8>

Synthesis of Sub 2-1

Add bromobenzene (37.1 g, 236.2 mmol) to a round-bottom flask, dissolve with toluene (2200 mL), aniline (20 g, 214.8 mmol), Pd ₂ (dba) ₃ (9.83 g, 10.7 mmol), P( t -Bu ) ₃ (4.34 g, 21.5 mmol), NaO t -Bu (62 g, 644.3 mmol) were added in order and stirred at 100 °C. When the reaction was completed, the product was extracted with ether and water, and the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 28 g (yield: 77%) of the product.

Synthesis of Sub 2-80

In a round bottom flask, [1,1'-biphenyl]-4-amine (15 g, 88.64 mmol), 2-bromodibenzo[b,d]thiophene (23.32 g, 88.64 mmol), Pd ₂ (dba) ₃ (2.43 g) , 2.66 mmol), P(t-Bu) ₃ (17.93 g, 88.64 mmol), NaOt-Bu (17.04 g, 177.27 mmol), toluene (886 mL) were tested in the same manner as in Sub 2-1, and the product was 24.61. g obtained. (Yield: 79%)

Synthesis of Sub 2-134

[1,1'-biphenyl]-4-amine (15 g, 88.6 mmol), 2-(4-bromophenyl)-9,9-diphenyl-9H-fluorene (46.2 g, 97.5 mmol), Pd in a round bottom flask ₂ (dba) ₃ (4.06 g, 4.43 mmol), P(t-Bu) ₃ (1.8 g, 8.86 mmol), NaOt-Bu (28.1 g, 292.5 mmol), toluene (931 mL) was added to the Sub 2-1 The experiment was carried out in the same manner as to obtain 34.9 g of the product. (Yield: 70%)

Synthesis example of Sub 2-222

In a round bottom flask, 3-bromonaphtho[2,3-b]benzofuran (15 g, 50.48 mmol), [1,1'-biphenyl]-4-amine (8.54 g, 50.48 mmol), Pd ₂ (dba) ₃ ( 1.39 g, 1.51 mmol), P(t-Bu) ₃ (10.21 g, 50.48 mmol), NaOt-Bu (9.70 g, 100.96 mmol), toluene (505 mL) were tested in the same manner as in Sub 2-1. 13.82 g of the product was obtained. (Yield: 71%)

Examples of Sub 2 are as follows, but are not limited thereto.

Final products 1 synthesis example

Synthesis of 1-54

1) Synthesis of Inter_A-1

N-phenyl-[1,1'-biphenyl]-4-amine (11.6g, 47.3 mmol), toluene (500 mL), 2-(3,5-dibromophenyl)-9-phenyl-9H-carbazole (24.8g , 52.0 mmol), Pd ₂ (dba) ₃ (2.4 g, 2.6 mmol), P( t -Bu) ₃ (1.05 g, 5.2 mmol), NaO t -Bu (13.6 g, 141.8 mmol) was added and 100 Stir at °C. When the reaction was completed, CH ₂ Cl ₂ and water were extracted, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 22.8 g (yield: 75%) of Inter_A-1.

2) Synthesis of 1-54

N-phenyldibenzo[b,d]thiophen-2-amine (8 g, 29.05 mmol), Inter_A-1 (20.5 g, 32 mmol), toluene (305 mL), Pd ₂ (dba) ₃ (1.5 g, 1.6 mmol) ), P( t- Bu) ₃ (0.65 g, 3.2 mmol), NaO t -Bu (8.4 g, 87.2 mmol) were performed in the same manner as in the experimental method of Inter_A-1, and product 1-54 was 18g (yield: 74%).

Synthesis of 2-9

After dissolving Sub 2-26 (7 g, 21.8 mmol) in a round bottom flask with toluene (230ml), Sub 1-2 (9.54 g, 24 mmol), Pd ₂ (dba) ₃ (1 g, 1.1 mmol), 50% P( t -Bu) ₃ (1.1ml, 2.2 mmol), NaO t -Bu (6.91 g, 71.9 mmol) was added and stirred at 100 °C. When the reaction was completed, the product was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 11.69 g (yield: 84%) of the product.

Synthesis of 3-52

2-bromonaphtho[2,3-b]benzofuran (10 g, 33.65 mmol), N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]thiophen-2-amine (11.83 g, 33.65 mmol), Pd ₂ (dba) ₃ (0.92 g, 1.01 mmol), P(t-Bu) ₃ (6.81 g, 33.65 mmol), NaOt-Bu (6.47 g, 67.31 mmol), toluene (337 mL) The experiment was carried out in the same manner as in 2-9 to obtain 15.28 g of the product. (Yield: 80%)

Synthesis of 6-12

2-bromo-11,11-dimethyl-11H-benzo[b]fluorene (10 g, 30.94 mmol), N-([1,1'-biphenyl]-4-yl)naphtho[2,3-b]benzofuran -3-amine (11.93 g, 30.94 mmol), Pd ₂ (dba) ₃ (0.85 g, 0.93 mmol), P(t-Bu) ₃ (6.26 g, 30.94 mmol), NaOt-Bu (5.95 g, 61.88 mmol) ), toluene (309 mL) was tested in the same manner as in 2-9 to obtain 15.15 g of the product. (Yield: 78%)

Synthesis of 11-4

1-(4-bromophenyl)naphthalene (10 g, 35.3 mmol), bis(4-(naphthalen-1-yl)phenyl)amine (14.8 g, 35.31 mmol), Pd ₂ (dba) ₃ (0.97 g, 1.06 mmol) ), P(t-Bu) ₃ (7.14 g, 35.31 mmol), NaOt-Bu (6.79 g, 70.63 mmol), and toluene (353 mL) were tested in the same manner as in 2-9 to obtain 16.9 g of the product. (Yield: 78%)

[Synthesis Example 2]

A compound represented by the formula (D) containing a radical of a compound represented by Formula A or Formula B according to the present invention (e.g., the above-described fourth compound, sixth compound, seventh compound, and eighth compound) is As shown in Scheme 9, Sub 3-A to Sub 3-D are prepared by reacting with Sub 4, but are not limited thereto.

<Reaction Scheme 9>

In more detail, Scheme 8 may be represented as in Scheme 10 to Scheme 13 below, but is not limited thereto.

<Reaction Scheme 10>

<Reaction Scheme 11>

<Reaction Scheme 12>

<Reaction Scheme 13>

Sub 3-A and Sub 3-B synthesis

Sub 3-A and Sub 3-B in Scheme 10 and Scheme 11 may be synthesized by the reaction routes of Scheme 14 and Scheme 15 below, but are not limited thereto.

<Reaction Scheme 14>

<Reaction Scheme 15>

Sub 3-C and Sub 3-D synthesis

Sub 3-C and Sub 3-D in Scheme 12 and Scheme 13 may be synthesized by the reaction routes of Scheme 16 and Scheme 17 below, but are not limited thereto.

<Reaction Scheme 16>

<Scheme 17>

1. Sub 3-1 synthesis example

After dissolving the starting material Dphenylamine (15.22 g, 89.94 mmol) with Toluene (750ml) in a round bottom flask, Sub 3-1-st (CAS Registry Number: 669773-34-6) (46.14 g, 134.91 mmol), Pd ₂ (dba) ₃ (2.47 g, 2.70 mmol), P( t -Bu) ₃ (1.82 g, 8.99 mmol), NaO t -Bu (25.93 g, 269.81 mmol) were added and stirred at 80 °C. When the reaction was completed, the product was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 23.61 g (yield: 61%) of the product.

2. Sub 3-63 Synthesis Example

Sub 3-63-st (10 g, 42.18 mmol), Pd ₂ (dba) ₃ (1.16 g, 1.27 mmol) in the starting material N-phenyldibenzo[b,d]furan-4-amine (10.94 g, 42.18 mmol) ) P( t- Bu) ₃ (8.53 g, 42.18 mmol), NaO t- Bu (8.11 g, 84.36 mmol), Toluene (422ml) was added and the product 13 g (yield: 67%).

3. Sub 3-157 synthesis example

Sub 3-157-st (16.08 g, 95 mmol), Pd ₂ (dba) ₃ (2.61 g, 2.85 mmol) P( t -Bu) ₃ (19.22 g, in starting material Dphenylamine (25 g, 95 mmol) 95 mmol), NaO t -Bu (18.26 g, 190 mmol), and Toluene (950ml) were added, and the product 24.45 g (yield: 65%) was obtained using the above Sub 3-1 synthesis method.

Examples of Sub 3-A to Sub 3-D are as follows, but are not limited thereto.

Sub 4 synthesis example

The synthesis method of Sub 4 in Scheme 8 is the same as the synthesis method of Sub 2, but is not limited thereto. The compound belonging to Sub 4 is the same as Sub 2, but is not limited thereto.

Final Product 2 synthesis

After dissolving Sub 3 (1 equivalent) with Toluene in a round bottom flask, Sub 4 (1 equivalent), Pd ₂ (dba) ₃ (0.03 equivalent), ( t -Bu) ₃ P (0.1 equivalent), NaO t -Bu (3 equivalents) was stirred at 100 °C. When the reaction was completed, CH ₂ Cl _{2 was} extracted with water and the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized in a silicagel column to obtain a final product 2.

Some of the compounds of the present invention are prepared by the synthesis method disclosed in the applicant's Korean Patent No. 1 0-1668448 (registered on October 17, 2016) and Korean Patent No. 1 0-1789998 (registered on October 19, 2017). Became.

1. 10-37 Synthesis Example

N,N-diphenyldibenzo[b,d]thiophen-3-amine (5.29 g, 12.29 mmol) obtained in the above synthesis N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]thiophen -2-amine (4.32 g, 12.29 mmol), Pd ₂ (dba) ₃ (0.34 g, 0.37 mmol) P( t -Bu) ₃ (0.25 g, 1.23 mmol), NaO t -Bu (3.54 g, 36.87 mmol) ), Toluene (125ml) was added, and 6.81 g (yield: 79%) of the product was obtained using the above synthesis method.

2. 7-8 Synthesis Example

In 7-bromo-9,9-dimethyl-N,N-diphenyl-9H-fluoren-2-amine (8 g, 18.2 mmol) obtained in the above synthesis, N-phenyldibenzo[b,d]thiophen-2-amine (5 g, 18.2 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.55 mmol) P( t -Bu) ₃ (0.23 g, 1.1 mmol), NaO t -Bu (5.3 g, 54.6 mmol), Toluene (100ml) Was added, and 8.9 g (yield: 76%) of the product was obtained using the above 10-37 synthesis method.

3. 10-176 Synthesis Example

9-chloro-N-(dibenzo[b,d]thiophen-3-yl)-N-phenyl-[2,4'-bidibenzo[b,d]thiophen]-1'-amine obtained in the above synthesis (25 g , 37.08 mmol) in diphenylamine (6.27 g, 37.08 mmol), Pd ₂ (dba) ₃ (1.02 g, 1.11 mmol) P( t -Bu) ₃ (7.50 g, 37.08 mmol), NaO t -Bu (7.13 g, 74.15 mmol) and Toluene (371ml) were added, and 8.9 g of the product (yield: 72%) was obtained using the above 10-37 synthesis method.

4. 12-1 Synthesis Example

Diphenylamine (9.39 g, 55.51 mmol) in N-(4'-bromo-[1,1'-biphenyl]-4-yl)-N-phenylnaphthalen-1-amine (25 g, 55.51 mmol) obtained in the above synthesis, Pd ₂ (dba) ₃ (1.52 g, 1.67 mmol) P( t -Bu) ₃ (11.23 g, 55.51 mmol), NaO t -Bu (10.67 g, 111.02 mmol), Toluene (555ml) was added and the above 10- 37 Synthesis was used to give 21.77 g (yield: 81%) of the product.

Meanwhile, FD-MS values of compounds 7-1 to 12-63 of the present invention prepared according to the synthesis example as described above are shown in Table 5 below.

Manufacturing evaluation of organic electric devices

When the organic electric device according to the present specification is a top emission type, and the anode is formed on the substrate before the organic material layer and the cathode are formed, not only a transparent material but also an opaque material having excellent light reflectance may be used as the anode material.

When the organic electric device according to the present specification is of a back-emission type, and the anode is formed on the substrate before the organic material layer and the cathode are formed, a transparent material is used as the anode material, or the opaque material must be formed in a thin film so as to become transparent. .

In this embodiment, a front light-emitting tandem organic electric device is manufactured and the following embodiments are presented, but embodiments of the present invention are not limited thereto. The tendem organic electric device according to an embodiment of the present invention is manufactured by connecting a plurality of stacks through a charge generation layer.

[Examples 1 to 45] Tandem organic electric device with two stacks connected

The tandem organic electric device in which the two stacks are connected was manufactured in a structure of an anode/hole transport region/light emitting layer/electron transport region/charge generation layer/hole transport region/light emitting layer/electron transport region/electron injection layer/cathode. Specifically, as a hole injection layer on the anode formed on the glass substrate, N,N'-Bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine ( Hereinafter abbreviated as NPB), a 10% HATCN-doped film was deposited to have a thickness of 10 nm. Subsequently, as the hole transport layer Ⅰ, a compound I (the first hole transport material) represented by the formula C or the formula D was deposited to a thickness of 15 nm, including the radical of the compound represented by the formula A, and the hole transport layer Ⅱ was formed with the formula A Alternatively, a compound (second hole transport material) Ⅱ containing a radical of a compound represented by Formula B and represented by Formula C or Formula D was deposited to a thickness of 5 nm. DPVBi was used as a host on the hole transport layer, and a light emitting layer having a thickness of 20 nm was deposited by doping BCzVBi with 5% weight as a dopant. A film was formed to a thickness of 30 nm using Alq3 as an electron transport layer. Next, to connect the two stacks, Bphen was doped with 2% Li to form an N-type charge generation layer, and NPB was doped with HATCN by 10% to deposit a P-type charge generation layer to form a charge generation layer. Thereafter, as described above, a second stack was formed by sequentially depositing a hole transport region, a light emitting layer, and an electron transport region. Thereafter, Liq was deposited to a thickness of 1.5 nm as an electron injection layer, and then Ag:Mg was deposited to a thickness of 150 nm and used as a cathode, thereby manufacturing a tandem organic electric device.

The electroluminescence (EL) characteristics were measured with a PR-650 of photoresearch company by applying a forward bias DC voltage to the organic electroluminescent devices of the Examples and Comparative Examples thus prepared, and the result of the measurement was at 1500 cd/m2 standard luminance. The T95 life was measured through a life measurement equipment manufactured by McScience. The following table shows the results of device fabrication and evaluation.

[Comparative Example 1] and [Comparative Example 2]

A tandem organic electric device was manufactured in the same manner as in Example, except that NPB and Compound 4-21 of the present invention were used as the first hole transport material, respectively, and the hole transport layer II was not used.

[Comparative Example 3]

A tandem organic electric device was manufactured in the same manner as in the above Example, except that NPB was used as the first hole transport material and Compound 6-30 of the present invention was used as the second hole transport material.

[Example 46] to [Example 90] Tandem organic electric device with three stacks connected

A tandem organic electric element was manufactured in the same manner as in Examples 1 to 45, except that three stacks were connected to manufacture a tandem organic electric element.

[Comparative Example 4] and [Comparative Example 5]

A tandem organic electric device was manufactured in the same manner as in Example 46, except that NPB and Compound 4-21 of the present invention were used as the first hole transport material, respectively, and the hole transport layer II was not used.

[Comparative Example 6]

A tandem organic electric device was manufactured in the same manner as in Example 46, except that NPB was used as the first hole transport material and Compound 6-30 of the present invention was used as the second hole transport material.

[Examples 91 to 135] Tandem organic electric device with four stacks connected

A tandem organic electric element was manufactured in the same manner as in Examples 1 to 45, except that four stacks were connected to manufacture a tandem organic electric element.

[Comparative Example 7] and [Comparative Example 8]

A tandem organic electric device was manufactured in the same manner as in Example 91, except that NPB and Compound 4-21 of the present invention were used as the first hole transport material, respectively, and the hole transport layer II was not used.

[Comparative Example 9]

A tandem organic electric device was manufactured in the same manner as in Example 91, except that NPB was used as the first hole transport material and Compound 6-30 of the present invention was used as the second hole transport material.

As can be seen from the results of Tables 6 to 8, when a hole transport region is formed using Compound I and Compound II of the present invention (Examples 1 to 135), only the first hole transport layer is NPB; Or in the case of using compound 4-21 of the present invention, which is the first compound represented by Formula C or Formula D, including a radical of the compound represented by Formula A (Comparative Examples 1,2,4,5,7,8) , NPB as the first hole transport material; And it can be seen that the electrical properties of the device are improved compared to the case of using the compound 6-30 of the present invention represented by Formula C or Formula D as the second hole transport material (Comparative Examples 3, 6, 9). In detail, the device characteristics of Comparative Examples 2, 5, and 8 using Compound 4-21 of the present invention were improved than Comparative Examples 1, 4, and 7 using NPB as the first hole transport material, and only the first hole transport material The device characteristics of Comparative Examples 3, 6, and 9 using NPB as the first hole transport material and Compound 6-30 as the second hole transport material were compared to Comparative Examples 1,2,4,5,7,8 used. Improved. And, rather than Comparative Examples 1 to 9, the radical of the compound represented by Formula A, and the first compound represented by Formula C or Formula D as the first hole transport material, the compound represented by Formula A or Formula B It can be seen that the driving voltage, efficiency, and lifespan characteristics of the devices of Examples 1 to 135, including radicals, and using the second compound represented by Formula C or Formula D as the second hole transport material, were improved.

This is because by using the compound of the present invention as a first hole transport material and a second hole transport material, an appropriate amount of holes in the light-emitting layer can be efficiently moved, thereby achieving charge balance between holes and electrons in the light-emitting layer, and interfacial degradation at the interface of the light-emitting layer It is judged that efficiency and lifespan increase by preventing

Meanwhile, referring to Examples 1 to 45, Examples 46 to 90, and Examples 91 to 135 of the present invention, it can be seen that as the number of stacks to be connected increases, efficiency and lifetime among the characteristics of the device are improved. In detail, the driving voltage of the devices of Examples 46 to 90 in which three stacks are connected was increased compared to Examples 1 to 45 in which the two stacks were connected, but efficiency and life were improved. In addition, it can be seen that the driving voltage of the devices of Examples 91 to 135 in which four stacks are connected was increased, but the efficiency and lifespan were improved than in Examples 46 to 90. It is believed that the efficiency and lifespan increase proportionally as the number of stacks increases due to the Multi Photon Emission structure in which excitons are formed in each stack to emit light energy.

In addition, looking at Examples 1 to 45, Examples 46 to 90, and 91 to 135 of the present invention, it can be seen that the value of the color coordinate (CIE x) gradually decreases as the number of connected stacks increases. . It is determined that color purity improves as the half-value width of the emission wavelength decreases as the number of stacks increases.

The compound (Final Product) represented by Formula 1 according to the present invention is synthesized as shown in Scheme 18 below, but is not limited thereto.

Hal is I or Br, Cl.

<Reaction Scheme 18>

I. Synthesis of Sub 1 of Scheme 18

Sub 1 of Scheme 18 is synthesized by the reaction route of Scheme 19 below, but is not limited thereto.

Hal ¹ is I, Br, Cl, -B(OH) ₂ and Hal is I or Br, Cl.

p and q are 0 and 1 respectively

When p and q are 0, Hal ¹ is I, Br, and Cl, and no separate reaction is required,

When p and q are 1, Hal ¹ is -B(OH) ₂ .

<Reaction Scheme 19>

1. Synthesis example of Sub 1-6

After adding (9,9-dimethyl-9H-fluoren-4-yl)boronic acid (50.0 g, 210.0 mmol) (50 g, 125.8 mmol) in a round bottom flask, 2-bromo-4'-chloro-1, 1'-biphenyl (56.2 g, 210.0 mmol), Pd(PPh ₃ ) ₄ (14.6 g, 12.6 mmol), NaOH (25.2 g, 630.0 mmol), and water (525 mL) were added, followed by reflux while stirring. When the reaction was completed, the product was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 65.0 g of a product. (Yield: 81.3%)

The compound belonging to Sub 1 of Scheme 18 may be a compound as follows, but is not limited thereto, and Table 9 shows the FD-MS (Field Desorption-Mass Spectrometry) value of the compound belonging to Sub 1.

II. Synthesis of Sub 2

Sub 2 of Scheme 18 is synthesized by the reaction route of Scheme 20 below, but is not limited thereto.

<Reaction Scheme 20>

1.Synthesis of Sub 2-73

Add bromobenzene (37.1 g, 236.2 mmol) to a round-bottom flask, dissolve with toluene (2200 mL), aniline (20 g, 214.8 mmol), Pd ₂ (dba) ₃ (9.83 g, 10.7 mmol), P( t -Bu ) ₃ (4.34 g, 21.5 mmol), NaO t -Bu (62 g, 644.3 mmol) were added in order and stirred at 100 °C. When the reaction was completed, the product was extracted with ether and water, and the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 28 g (yield: 77%) of the product.

2. Synthesis of Sub 2-111

In a round bottom flask, [1,1'-biphenyl]-4-amine (15 g, 88.64 mmol), 2-bromodibenzo[b,d]thiophene (23.32 g, 88.64 mmol), Pd ₂ (dba) ₃ (2.43 g) , 2.66 mmol), P(t-Bu) ₃ (17.93 g, 88.64 mmol), NaOt-Bu (17.04 g, 177.27 mmol), and toluene (886 mL) were tested in the same manner as in Sub 2-73, and the product 24.6 was conducted. g obtained. (Yield: 79%)

The compound belonging to Sub 2 of Scheme 18 may be the following compound, but is not limited thereto, and Table 10 shows the FD-MS (Field Desorption-Mass Spectrometry) value of the compound belonging to Sub 2.

III. Final Product Synthesis

1. Synthesis Example of P1-4

In a round bottom flask, Sub 1-2 (10.0 g, 43.7 mmol), Sub 2-3 (15.8 g, 43.7 mmol), Pd ₂ (dba) ₃ (1.2 g, 1.3 mmol), P(t-Bu) ₃ ( 0.5 g, 2.6 mmol), NaOt-Bu (8.4 g, 87.4 mmol), and toluene (219 mL) were tested in the same manner as in Sub 2-73 to obtain 17.4 g of the product. (Yield: 72%)

2. Synthesis Example of P2-13

In a round bottom flask, Sub 1-9 (10.0 g, 28.3 mmol), Sub 2-26 (9.5 g, 28.3 mmol), Pd ₂ (dba) ₃ (0.8 g, 0.9 mmol), P(t-Bu) ₃ ( 0.3 g, 1.7 mmol), NaOt-Bu (5.4 g, 56.7 mmol), and toluene (142 mL) were tested in the same manner as in Sub 2-73 to obtain 13.9 g of a product. (Yield: 75%)

3. Synthesis Example of P3-15

In a round bottom flask, Sub 1-31 (10.0 g, 23.4 mmol), Sub 2-82 (8.5 g, 23.4 mmol), Pd ₂ (dba) ₃ (0.6 g, 0.7 mmol), P(t-Bu) ₃ ( 0.3 g, 1.4 mmol), NaOt-Bu (4.5 g, 46.8 mmol), and toluene (117 mL) were tested in the same manner as in Sub 2-73 to obtain 12.2 g of a product. (Yield: 69%)

4. Synthesis Example of P4-21

In a round bottom flask, Sub 1-9 (10.0 g, 28.3 mmol), Sub 2-3 (10.2 g, 28.3 mmol), Pd ₂ (dba) ₃ (0.8 g, 0.9 mmol), P(t-Bu) ₃ ( 0.3 g, 1.7 mmol), NaOt-Bu (5.4 g, 56.7 mmol), and toluene (142 mL) were tested in the same manner as in Sub 2-73 to obtain 13.7 g of a product. (Yield: 72%)

5. Synthesis Example of P5-38

In a round bottom flask, Sub 1-63 (10.0 g, 24.9 mmol), Sub 2-112 (9.4 g, 24.9 mmol), Pd ₂ (dba) ₃ (0.7 g, 0.8 mmol), P(t-Bu) ₃ ( 0.3 g, 1.5 mmol), NaOt-Bu (4.8 g, 49.9 mmol), and toluene (125 mL) were tested in the same manner as in Sub 2-73 to obtain 13.1 g of a product. (Yield: 70%)

6. Synthesis Example of P6-9

In a round bottom flask, Sub 1-113 (10.0 g, 35.9 mmol), Sub 2-106 (12.0 g, 35.9 mmol), Pd ₂ (dba) ₃ (1.0 g, 1.1 mmol), P(t-Bu) ₃ ( 0.4 g, 2.2 mmol), NaOt-Bu (6.9 g, 71.7 mmol), and toluene (179 mL) were tested in the same manner as in Sub 2-73 to obtain 15.7 g of a product. (Yield: 76%)

Meanwhile, the FD-MS values of the compounds of the present invention prepared according to the synthesis example as described above are shown in Table 11 below.

Manufacturing evaluation of organic electric devices

When the organic electric device according to the present specification is a top emission type, and the anode is formed on the substrate before the organic material layer and the cathode are formed, not only a transparent material but also an opaque material having excellent light reflectance may be used as the anode material.

When the organic electric device according to the present specification is of a back-emission type, and the anode is formed on the substrate before the organic material layer and the cathode are formed, a transparent material is used as the anode material, or the opaque material must be formed in a thin film so as to become transparent. .

In this embodiment, a front light-emitting tandem organic electric device is manufactured and the following embodiments are presented, but embodiments of the present invention are not limited thereto. The tendem organic electric device according to an embodiment of the present invention is manufactured by connecting a plurality of stacks through a charge generation layer. In the tandem organic electric device according to an embodiment of the present invention, the same compound is used for the hole transport layer in each of the three stacks, but the present invention is not limited thereto.

[Example 136] Tandem organic electric device with three stacks connected

The tandem organic electronic device with three stacks connected is the first electrode (anode)/first hole transport region/first light emitting layer/first electron transport region/charge generation layer/second hole transport region/second light emitting layer/second electron A transport region/charge generation layer/third hole transport region/third light-emitting layer/third electron transport region/electron injection layer/second electrode (cathode) was prepared.

Specifically, 4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter, abbreviated as 2-TNATA) was vacuum deposited to a thickness of 60 nm on the anode formed on the glass substrate to form a hole injection layer. After formation, 11 nm (35% of the total thickness of 30 nm) by doping 10% of HATCN as a doping material to compound P1-4 (hereinafter, referred to as 1HTM) represented by the present invention as the first hole transport layer of the first stack. After forming, 19 nm of Formula P1-4 represented by Formula 1 of the present invention is formed thereon. Subsequently, DPVBi was used as a host on the first hole transport layer, and a first emission layer having a thickness of 20 nm was deposited by doping BCzVBi with 5% weight as a dopant. A film was formed to a thickness of 30 nm using Alq3 as an electron transport layer. Next, for connection with the second stack, a charge generation layer is formed by doping 2% of Li in Bphen, and the second hole transport layer of the second stack is compound P1-4 (hereinafter, referred to as 2HTM ) Is doped with 10% of HATCN as a doping material to form 14 nm (25% of the total thickness of 55 nm), and 41 nm of compound P1-4 represented by Formula 1 of the present invention is formed thereon. Thereafter, as described above, a second emission layer, a second electron transport region, and a charge generation layer were sequentially formed. Finally, 10 nm (20% of the total thickness of 50 nm) was doped with HATCN as a doping material in compound P1-4 (hereinafter, referred to as 3HTM) of the present invention as the third hole transport layer of the third stack. After formation, 40 nm of the compound P1-4 represented by Formula 1 of the present invention is formed thereon. Thereafter, as described above, a third light emitting layer and a third electron transport region are sequentially deposited, and then Liq is deposited to a thickness of 1.5 nm as an electron injection layer, and then Ag: Mg is deposited to a thickness of 150 nm to be used as a cathode. Was prepared.

The electroluminescence (EL) characteristics were measured with a PR-650 of photoresearch company by applying a forward bias DC voltage to the organic electroluminescent devices of the Examples and Comparative Examples thus prepared, and the result of the measurement was at 1500 cd/m2 standard luminance. The T95 life was measured through a life measurement equipment manufactured by McScience. The following table shows the results of device fabrication and evaluation.

[Example 137] to [Example 170]

An organic electroluminescent device was manufactured in the same manner as in Example 136, except that the compound shown in Table 4 below was used as a material for each of the first to third stacks.

[Comparative Example 10] and [Comparative Example 11]

A device was fabricated in the same manner as in the above embodiment, except that only the first stack was formed, and the following ref 1 and ref 2 were respectively used as the hole transport layer material.

ref 1 ref 2

As can be seen from the results of Table 12, when a three-stack tandem organic light-emitting device was fabricated using the compound represented by Formula 1 of the present invention as a hole transport layer material (Examples 136 to 170), ref 1 and It can be seen that the electrical properties of the device are improved compared to the case where the ref 2 compound is made of a one-stack organic light-emitting device as a material for each hole transport layer (Comparative Examples 10 and 11). In detail, Examples 136 to 170 and Comparative Examples 10 and 11 have the same thickness in which the material constituting the hole transport layer is doped with the doping material, but there is a difference in the number of connected stacks. As the number of stacks connected as in Examples 136 to 170 increased, it was confirmed that the efficiency and lifetime among the characteristics of the device were remarkably improved. It is believed that the efficiency and lifespan increase proportionally as the number of stacks increases due to the Multi Photon Emission structure in which excitons are formed in each stack to emit light energy.

In addition, it can be seen that the value of the color coordinate (CIE x) gradually decreases as it has a three-stack device structure as in the embodiment of the present invention. It is determined that color purity improves as the half-value width of the emission wavelength decreases as the number of stacks increases.

On the one hand, by using the compound represented by Formula 1 of the present invention as a material for the first hole transport layer, it can be determined that the device characteristics are further improved than when ref1 is used as the material for the first hole transport layer. By using as a hole transport material, it is judged that the efficiency and lifespan are increased by efficiently moving a suitable amount of holes in the emission layer, thereby achieving charge balance between holes and electrons in the emission layer and preventing interfacial deterioration at the interface of the emission layer. .

[Example 171] and [Example 174] Tandem organic electric device with three stacks connected

As shown in Table 13 below, compounds P1-17 and P3-8 were used as hole transport layer materials of each of the first to third stacks, and the thickness of each hole transport layer was doped with HATCN at a thickness ratio of 15% based on 50 nm. Except for that, a tandem organic light emitting device was manufactured in the same manner as in Example 136.

[Example 172] and [Example 175]

As shown in Table 13 below, compounds P1-17 and P3-8 were used as hole transport layer materials of each of the first to third stacks, and the thickness of each hole transport layer was doped with HATCN at a thickness ratio of 20% based on 50 nm. Except for that, a tandem organic light emitting device was manufactured in the same manner as in Example 136.

[Example 173] and [Example 176]

As shown in Table 13 below, compounds P1-17 and P3-8 were used as hole transport layer materials of each of the first to third stacks, and the thickness of each hole transport layer was doped with HATCN at a thickness ratio of 25% based on 50 nm. Except for that, a tandem organic light emitting device was manufactured in the same manner as in Example 136.

[Comparative Example 12] and [Comparative Example 14]

Compounds 1-17 and 3-8 were used as hole transport layer materials of each of the first to third stacks as described in Table 13 below, and HATCN was doped with a thickness ratio of 10% based on 50 nm of each of the hole transport layers. Except for that, a tandem organic light emitting device was manufactured in the same manner as in Example 136.

[Comparative Example 13] and [Comparative Example 15]

As shown in Table 13 below, compounds P1-17 and P3-8 were used as hole transport layer materials of each of the first to third stacks, and the thickness of each hole transport layer was doped with HATCN at a thickness ratio of 55% based on 50 nm. Except for that, a tandem organic light emitting device was manufactured in the same manner as in Example 1.

As shown in Table 13, a tandem device was fabricated and measured for each thickness ratio to which a doping material is doped based on the thickness of each hole transport layer constituting the first stack to the third stack of the present invention. P1-17 and P3-8 were described as examples of the compounds of this Example, and as can be seen from the results of Table 13, the thickness ratio to which the doping material is doped based on the total thickness of the hole transport layer is less than 15% or 50 In the case of doping in excess of %, it can be seen that the results of driving voltage efficiency and lifetime are gradually lower than the device results of Examples 171 to 176 in which the doping material is doped at a ratio of 15%, 20%, and 25%, respectively. .

This depends on the thickness of the doping material doped in the hole transport layer, that is, it is proportional to the weight ratio of the doping material doped in the hole transport layer.If the thickness of the doping material doped in the hole transport layer is too thin, holes and charges are insufficient Hole injection into the light emitting layer is not smooth, resulting in a problem of deteriorating device characteristics. On the other hand, when the thickness of the doping material doped in the hole transport layer is too thick, a device short-circuit problem occurs or a problem of an increase in the total cost required for device fabrication itself occurs.

In the above, the present invention has been exemplarily described, and various modifications may be made without departing from the essential characteristics of the present invention to those of ordinary skill in the art. Accordingly, the embodiments disclosed in the present specification are not intended to limit the present invention, but to explain the present invention, 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 the scope equivalent thereto should be construed as being included in the scope of the present invention.

110: first electrode
120: organic material layer
130: second electrode
141: first stack
142: second stack
143: third stack
144: fourth stack
150: charge generation layer
160: capping layer

Claims (22)

A first electrode;
A second electrode; And
An organic material layer disposed between the first electrode and the second electrode and including a first stack, a second stack, and a third stack,
The first stack,
And a first hole transport region, a first emission layer, and a first electron transport region,
The first hole transport region includes a first hole transport layer and a first light emission auxiliary layer,
The first hole transport layer or the first light emission auxiliary layer comprises a first compound represented by the following formula (1),
The thickness of the first hole transport layer is 250Å to 700Å,
The first hole transport layer is an organic electric device in which 10% to 50% of the thickness of the first hole transport layer is doped with a first doping material:
<Formula 1>

In Formula 1,
m and n are each independently 0 or 1, m+n is 1,
Ar ¹ and Ar ² are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60,
Ar ³ and Ar ⁴ are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60,
L ¹ to L ⁶ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60,
X is hydrogen; heavy hydrogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; And C ₂ -C ₂₀ alkynyl group; is selected from the group consisting of,
Y is i) hydrogen when n is 0; heavy hydrogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; And C ₂ -C ₂₀ alkynyl group; is selected from the group consisting of, ii) when n is 1, C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ fused ring group of an aromatic ring of C ₆₀ of aliphatic rings and C ₆ ~ C _60; is selected from the group consisting of,
X and Y can combine with each other to form a compound as a spy,
Ring A and Ring B are each independently a C ₆ -C ₁₀ aryl group,
R ¹ and R ² are each independently deuterium; halogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ ~ C ₃₀ aryloxy group; is selected from the group consisting of,
a is an integer from 0 to 7, b is an integer from 0 to 8,
The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group and fluorenylene group, respectively, deuterium; Halogen group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₆ ~ C ₂₅ aryl group; C ₆ ~ C ₂₅ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; And C ₃ ~ C ₂₀ cycloalkyl group; one or more substituents selected from the group consisting of may be further substituted,
Each of the additionally substituted substituents is deuterium; Halogen group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₆ ~ C ₂₅ aryl group; C ₆ ~ C ₂₅ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; And C ₃ ~ C ₂₀ cycloalkyl group; one or more substituents selected from the group consisting of may be further substituted, and these substituents may be bonded to each other to form a ring. The method of claim 1,
The first stack,
An organic electric device in which the first hole transport layer and the first light-emitting auxiliary layer include a first compound represented by Chemical Formula 1. The method of claim 1,
The first compound is an organic electric device represented by any one of the following Formulas 2 to 5:
<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

In Formulas 2 to 5,
c and d are each independently an integer of 0 to 4, e is an integer of 0 to 5,
R ³ , R ⁴ and R ⁶ are, i) each independently, deuterium; halogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ ~ C ₃₀ aryloxy group; is selected from the group consisting of, ii) a plurality of R ⁴ and a plurality of R ⁶ may be bonded to each other to form a ring,
R ⁵ is hydrogen; heavy hydrogen; halogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ ~ C ₃₀ aryloxy group; may be selected from the group consisting of,
Ar ¹ to Ar ⁴ , L ¹ to L ⁶ , R ¹ , R ² , a and b are the same as defined in claim 1. The method of claim 1,
The first compound is an organic electric device represented by any one of the following Formulas 6 to 9:
<Formula 6>

<Formula 7>

<Formula 8>

<Formula 9>

In Formula 6 to Formula 9,
Z is O, S, NR' or CR'R",
R'and R" are each independently a C ₁ -C ₃₀ alkyl group; C ₆ -C ₃₀ aryl group; And O, N, S, Si, and C ₃ -including at least one heteroatom of P C ₃₀ heterocyclic group; or selected from the group consisting of, these may be bonded to each other to form a spy compound,
R ⁷ and R ⁸ are, i) each independently, deuterium; halogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ ~ C ₃₀ aryloxy group; is selected from the group consisting of, ii) a plurality of R ⁷ and a plurality of R ⁸ may be bonded to each other to form a ring,
f is an integer from 0 to 4, g is an integer from 0 to 3,
Ar ² , L ¹ to L ³ , A ring, B ring, X, Y, R ¹ , R ² , a and b are the same as defined in claim 1. The method of claim 1,
The first compound is an organic electric device represented by any one of the following Formulas 10 to 12:
<Formula 10>

<Formula 11>

<Formula 12>

In Formulas 10 to 12,
R ⁹ is, i) each independently, deuterium; halogen; C ₆ -C ₃₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ ~ C ₃₀ aryloxy group; is selected from the group consisting of, ii) a plurality of R ⁹ may be bonded to each other to form a ring,
Ar ¹ , Ar ³ , L ¹ , L ⁴ , A ring, B ring, X, Y, R ¹ , R ² , a and b are the same as defined in claim 1. The method of claim 1,
The first compound is an organic electric device comprising at least one of the following compounds:

. The method of claim 1,
The first doping material is an organic electric device represented by the following formula E:
<Formula E>

In Formula E,
R _p1 to R _p6 are each independently hydrogen; Halogen group; Nitrile group; Nitro group; -SO ₂ R; -SOR; -SO ₂ NR ₂ ; -SO ₃ R; Trifluoromethyl group; -COOR; -CONHR; -CONRR'; An alkoxyl group of C ₁ -C ₃₀ ; A C ₁ -C ₃₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; O, N, S, Si, and C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom of P; Fluorenyl group; C ₆ -C ₃₀ aryl group; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; And -NRR'; is selected from the group consisting of,
Each of R and R'is a C ₁ -C ₃₀ alkyl group; Fluorenyl group; C ₆ -C ₃₀ aryl group; A fused ring group of a C ₃ -C ₃₀ aliphatic ring and a C ₆ -C ₃₀ aromatic ring; And a C ₂ -C ₃₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P; is selected from the group consisting of,
In Formula E, an aryl group, a fluorenyl group, a heterocyclic group, a fused ring group, an alkyl group, an alkenyl group, an alkynyl group and an alkoxyl group, respectively, are deuterium; Halogen group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₆ ~ C ₂₅ aryl group; C ₆ ~ C ₂₅ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; And C ₃ ~ C ₂₀ cycloalkyl group; one or more substituents selected from the group consisting of may be substituted. The method of claim 1,
The first hole transport layer includes a first doped material doped layer doped with the first doping material and a first doped material undoped layer doped with the first doping material,
The first doping material doping layer includes the first compound, and an organic electric device comprising 5 parts by weight to 15 parts by weight of the first doping material relative to 100 parts by weight of the first compound. The method of claim 1,
The second stack,
It includes a second hole transport region, a second emission layer and a second electron transport region,
The second hole transport region includes a second hole transport layer and a second light emission auxiliary layer,
The second hole transport layer or the second light emission auxiliary layer comprises a second compound represented by Formula 1,
The thickness of the second hole transport layer is 250Å to 700Å,
In the second hole transport layer, 10% to 50% of the thickness of the second hole transport layer is doped with a second doping material,
The third stack,
A third hole transport region, a third emission layer, and a third electron transport region,
The third hole transport region includes a third hole transport layer and a third light emission auxiliary layer,
The third hole transport layer or the third light emission auxiliary layer contains a third compound represented by Formula 1,
The thickness of the third hole transport layer is 250Å to 700Å,
The third hole transport layer is an organic electric device in which 10% to 50% of the thickness of the third hole transport layer is doped with a third doping material. The method of claim 9,
The first compound, the second compound, and the third compound are the same compound as each other. The method of claim 1,
The first hole transport layer or the first light emission auxiliary layer comprises at least one of the first compound and the fourth compound,
The fourth compound includes a radical of a compound represented by the following formula A or the following formula B, and is represented by at least one of the compounds represented by the following formula C or the following formula D,
The thickness of the second hole transport layer is 250Å to 700Å,
The second hole transport layer is an organic electric device in which 10% to 50% of the thickness of the first hole transport layer is doped with a second doping material:

In the formula A,
1) a and b are each independently an integer of 0 to 4,
2) X is O, S, CR'R'' or NL ₁ -Ar ₁ ,
3) R ₁ and R ₂ are each independently deuterium; Tritium; halogen; Cyano group; Nitro group; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ -C ₃₀ is selected from the group consisting of aryloxy group, R ¹ and R ² may each be bonded to each other to form a ring,
4) R'and R'' are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60, R 'and R''may bond to one another to form a ring,
5) L ₁ is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60,
6) Ar ₁ is a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60,
In Formula B,
1) l is an integer from 0 to 5; m is an integer from 0 to 4; y and z are integers from 0 to 4, y+z is not 0,
2) R _a and R _b are each independently deuterium; Tritium; halogen; Cyano group; Nitro group; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ -C ₃₀ is selected from the group consisting of an aryloxy group, R _a and R _b may each be bonded to each other to form a ring,
In Formula C,
1) n is 1 or 2,
2) Ar ₂ is a radical of a compound represented by Formula A or a radical of a compound represented by Formula B,
3) Ar ₃ and Ar ₄ are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60,
4) L ₂ to L ₄ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; And O, N, S, Si and P is selected from the group consisting of a heterocyclic group of C ₂ ~ C ₆₀ containing at least one heteroatom,
In Formula D,
1) o is an integer from 1 to 4,
2) Ar ₅ to Ar ₈ are each independently a C ₆ to C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60,
3) L ₅ to L ₉ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C doedoe of ₆₀ alicyclic and C ₆ ~ C ₆₀ selected from the group consisting of a fused ring of an aromatic ring, L ₉ is a radical of a compound represented by the radical or the formula (B) of the compound of the formula A Can be
In Formulas A to D, the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group and fluorenylene group are each deuterium; Nitro group; Nitrile group; Halogen group; Amino group; C ₁ ~ C ₂₀ alkylthio group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₆ ~ C ₂₅ aryl group; C ₆ ~ C ₂₅ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; A C ₃ ~C ₂₀ cycloalkyl group; One or more substituents selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group and C ₈ ~ C ₂₀ arylalkenyl group may be further substituted, and the additionally substituted substituents may be bonded to each other to form a ring. And
Each of the additionally substituted substituents is deuterium; Nitro group; Nitrile group; Halogen group; Amino group; C ₁ ~ C ₂₀ alkylthio group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₆ ~ C ₂₅ aryl group; C ₆ ~ C ₂₅ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; A C ₃ ~C ₂₀ cycloalkyl group; C ₇ ~ C ₂₀ arylalkyl group; And one or more substituents selected from the group consisting of C ₈ ~ C ₂₀ arylalkenyl group may be further substituted, and these substituents may be bonded to each other to form a ring. The method of claim 9,
The first hole transport layer includes a first doped material doped layer doped with the first doping material and a first doped material undoped layer doped with the first doping material,
The first doping material doping layer includes the first compound, and includes 5 parts by weight to 15 parts by weight of the first doping material relative to 100 parts by weight of the first compound,
The second hole transport layer includes a second doped material doped layer doped with the second doping material and a second doped material undoped layer not doped with the second doping material,
The second doping material doping layer includes the second compound, and includes 5 parts by weight to 15 parts by weight of a second doping material based on 100 parts by weight of the second compound,
The third hole transport layer includes a third doped material-doped layer doped with the third doping material and a third doped material undoped layer not doped with the third doping material,
The third doping material doping layer includes the third compound, and an organic electric device comprising 5 parts by weight to 15 parts by weight of a third doping material based on 100 parts by weight of the third compound. The method of claim 10,
The first hole transport layer includes a first doped material doped layer doped with the first doping material and a first doped material undoped layer doped with the first doping material,
The first doping material doping layer includes at least one of the first compound and the fourth compound, and includes 5 parts by weight to 15 parts by weight of the first doping material based on 100 parts by weight of the total of the first compound and the fourth compound. Organic electric devices. The method of claim 1,
The organic material layer further includes a fourth stack,
The fourth stack,
A fourth hole transport region, a fourth emission layer, and a fourth electron transport region,
The fourth hole transport region includes a fourth hole transport layer and a fourth light emission auxiliary layer,
The fourth hole transport layer or the fourth light emission auxiliary layer comprises at least one of a fifth compound and a sixth compound,
The fifth compound is represented by Formula 1,
The sixth compound includes a radical of a compound represented by the following formula A or the following formula B, and is represented by the following formula C or the following formula D,
The thickness of the fourth hole transport layer is 250Å to 700Å,
The fourth hole transport layer is an organic electric device in which 10% to 50% of the thickness of the fourth hole transport layer is doped with a fourth doping material:

In the formula A,
1) a and b are each independently an integer of 0 to 4,
2) X is O, S, CR'R'' or NL ₁ -Ar ₁ ,
3) R ₁ and R ₂ are each independently deuterium; Tritium; halogen; Cyano group; Nitro group; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ -C ₃₀ is selected from the group consisting of aryloxy group, R ¹ and R ² may each be bonded to each other to form a ring,
4) R'and R'' are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60, R 'and R''may bond to one another to form a ring,
5) L ₁ is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60,
6) Ar ₁ is a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60,
In Formula B,
1) l is an integer from 0 to 5; m is an integer from 0 to 4; y and z are integers from 0 to 4, y+z is not 0,
2) R _a and R _b are each independently deuterium; Tritium; halogen; Cyano group; Nitro group; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; Alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ -C ₃₀ is selected from the group consisting of an aryloxy group, R _a and R _b may each be bonded to each other to form a ring,
In Formula C,
1) n is 1 or 2,
2) Ar ₂ is a radical of a compound represented by Formula A or a radical of a compound represented by Formula B,
3) Ar ₃ and Ar ₄ are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60,
4) L ₂ to L ₄ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; And O, N, S, Si and P is selected from the group consisting of a heterocyclic group of C ₂ ~ C ₆₀ containing at least one heteroatom,
In Formula D,
1) o is an integer from 1 to 4,
2) Ar ₅ to Ar ₈ are each independently a C ₆ to C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And it is selected from the group consisting of a fused ring of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60,
3) L ₅ to L ₉ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And C ₃ ~ C doedoe of ₆₀ alicyclic and C ₆ ~ C ₆₀ selected from the group consisting of a fused ring of an aromatic ring, L ₉ is a radical of a compound represented by the radical or the formula (B) of the compound of the formula A Can be
In Formulas A to D, the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group and fluorenylene group are each deuterium; Nitro group; Nitrile group; Halogen group; Amino group; C ₁ ~ C ₂₀ alkylthio group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₆ ~ C ₂₅ aryl group; C ₆ ~ C ₂₅ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; A C ₃ ~C ₂₀ cycloalkyl group; One or more substituents selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group and C ₈ ~ C ₂₀ arylalkenyl group may be further substituted, and the additionally substituted substituents may be bonded to each other to form a ring. And
Each of the additionally substituted substituents is deuterium; Nitro group; Nitrile group; Halogen group; Amino group; C ₁ ~ C ₂₀ alkylthio group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; C ₆ ~ C ₂₅ aryl group; C ₆ ~ C ₂₅ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; A C ₃ ~C ₂₀ cycloalkyl group; C ₇ ~ C ₂₀ arylalkyl group; And one or more substituents selected from the group consisting of C ₈ ~ C ₂₀ arylalkenyl group may be further substituted, and these substituents may be bonded to each other to form a ring. The method of claim 1,
At least one of the first emission layer, the second emission layer, and the third emission layer is an emission layer that emits blue light. The method of claim 1,
The first, second, and third emission layers are light-emitting layers that emit blue light. The method of claim 1,
One to two of the first, second, and third light emitting layers are light-emitting layers that emit blue light, and one to two are light-emitting layers that emit green light. The method of claim 1,
Two of the first emission layer, the second emission layer, and the third emission layer are emission layers emitting blue light, and the other emission layer is an emission layer emitting green light. The method of claim 18,
An organic electronic device in which the emission layer emitting green light is positioned between two emission layers emitting blue light. The method of claim 1,
At least one of the first emission layer, the second emission layer, and the third emission layer is a multi-emission layer emitting green light and blue light. The method of claim 14,
Among the first to fourth emission layers, three emission layers are emission layers emitting blue light, and the other emission layer is an emission layer emitting green light. The method of claim 14,
The organic electric device in which the fourth hole transport layer includes the fifth compound.

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