KR102488854B1 - Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof - Google Patents

Abstract

Disclosed are an organic electric device including a compound represented by Chemical Formula 1, a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode, and an electronic device including the organic electric device. By including the compound represented by Chemical Formula 1 in the organic material layer, the driving voltage of the organic electric element can be lowered and the luminous efficiency and lifetime can be improved.

Description

Compound for organic electric element, organic electric element using the same, and electronic device thereof

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as organic layers in organic electric devices may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions. In addition, the light emitting material can be classified into a high molecular weight type and a low molecular weight type according to molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. can In addition, light emitting materials may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural colors according to the light emitting color.

On the other hand, when only one material is used as a light emitting material, the maximum emission wavelength moves to a longer wavelength due to intermolecular interactions, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. Therefore, color purity increases and energy transfer A host/dopant system may be used as a light emitting material in order to increase luminous efficiency. The principle is that when a small amount of a dopant having a smaller energy band gap than the host forming the light emitting layer is mixed into the light emitting layer, excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength range of the dopant, light of a desired wavelength can be obtained according to the type of dopant used.

Currently, the size of the portable display market tends to increase with large-area displays, and as a result, power consumption greater than that required for existing portable displays is required. Therefore, power consumption has become a very important factor for portable displays that have a limited power supply source such as a battery, and efficiency and lifespan problems must also be solved.

Efficiency, lifespan, driving voltage, etc. are related to each other, and as efficiency increases, driving voltage relatively decreases. indicates a tendency to increase life expectancy. However, efficiency cannot be maximized by simply improving the organic layer. This is because long life and high efficiency can be achieved at the same time when the optimal combination of the energy level and T ₁ value between each organic material layer and the intrinsic properties of the material (mobility, interfacial property, etc.) is achieved. .

Therefore, it is necessary to develop a light emitting material that has high thermal stability and can efficiently balance charge in the light emitting layer. That is, in order to fully exhibit the excellent characteristics of organic electric devices, materials constituting the organic layer in the device, such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. are supported by stable and efficient materials. Although this should be preceded, development of stable and efficient organic material layer materials for organic electric devices has not yet been sufficiently achieved, and in particular, development of a host material for a light emitting layer is urgently required.

An object of the present invention is to provide a compound capable of lowering the driving voltage of the device and improving the luminous efficiency and lifetime of the device, an organic electric device using the same, and an electronic device thereof.

In one aspect, the present invention provides a compound represented by the formula below.

In another aspect, the present invention provides an organic electric device and an electronic device using the compound represented by the above formula.

By using the compound according to the embodiment of the present invention, the driving voltage of the device can be lowered, and the luminous efficiency and lifespan of the device can be remarkably improved.

1 is an exemplary view of an organic electroluminescent device according to an embodiment of the present invention.

In the present specification, the 'group name' corresponding to an aryl group, an arylene group, a heterocyclic group, etc. exemplified as examples of each symbol and its substituent may be described as a 'name of a group reflecting a valence', but described as a 'parent compound name' You may. For example, in the case of 'phenanthrene', which is a kind of aryl group, the name of the group may be described by dividing the valence, such as 'phenanthryl' for a monovalent group and 'phenanthrylene' for a divalent group, but the valence and Regardless, it can also be described as 'phenanthrene', which is the name of the parent compound. Similarly, in the case of pyrimidine, it can also be described as 'pyrimidine' regardless of the valence, or as the 'name of the group' of the corresponding valence, such as a pyrimidinyl group in the case of monovalent, or pyrimidinylene in the case of divalent. there is.

As used herein, the term "fluorenyl group" or "fluorenylene group" means a monovalent or divalent functional group in which R, R' and R" are all hydrogen in the following structure, respectively, unless otherwise specified, " Substituted fluorenyl group" or "substituted fluorenyl group" means that at least one of the substituents R, R', R" is a substituent other than hydrogen, and R and R' are bonded to each other to form a This includes cases where they form a spy compound together.

As used herein, the term "spiro compound" has a 'spiro union', which means a connection formed by two rings sharing only one atom. At this time, the atoms shared by the two rings are called 'spiro atoms', and according to the number of spiro atoms in a compound, they are called 'monospiro-', 'dispiro-', and 'trispiro-', respectively. ' It's called a compound.

As used herein, the term "heterocyclic group" refers to a ring containing heteroatoms such as N, O, S, P or Si instead of carbon forming a ring, and is referred to as a "heteroaryl group" or "heteroarylene group". It includes not only an aromatic ring but also a non-aromatic ring, such as the following compound instead of carbon forming a ring, SO ₂ , and a compound containing a heteroatom group such as P=O may also be included.

In addition, unless explicitly stated otherwise, the chemical formula used in the present invention applies the same as the substituent definition by the exponent definition of the following formula.

Here, when a is an integer of 0, substituent R ¹ does not exist, and when a is an integer of 1, one substituent R ¹ is bonded to any one of the carbon atoms forming the benzene ring, and when a is an integer of 2 or 3 Each is combined as follows, wherein R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the hydrogen bonded to the carbon forming the benzene ring is omit

Hereinafter, a layered structure of an organic electric element including the compound of the present invention will be described with reference to FIG. 1 .

1 is a diagram illustrating a stacked structure of an organic electric element according to an embodiment of the present invention.

Referring to FIG. 1, an organic electric element 100 according to the present invention includes a first electrode 120, a second electrode 180, and a first electrode 110 and a second electrode 180 formed on a substrate 110. ) is provided with an organic material layer containing the compound according to the present invention. In this case, the first electrode 120 may be an anode (anode), and the second electrode 180 may be a cathode (negative electrode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may sequentially include a hole injection layer 130 , a hole transport layer 140 , a light emitting layer 150 , an electron transport layer 160 , and an electron injection layer 170 on the first electrode 120 . At this time, at least one of these layers may be omitted, or a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and the electron transport layer 160 and the like may serve as the hole blocking layer. Maybe.

In addition, although not shown, the organic electric element according to the present invention may further include a protective layer or a capping layer formed on a surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode.

The compound according to the present invention applied to the organic layer is a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, an electron injection layer 170, a light emitting layer 150, a light efficiency improving layer, a light emitting auxiliary layer, etc. can be used as a material for For example, the compound of the present invention may be used as a material of the light emitting layer 150, preferably a host material of the light emitting layer.

An organic light emitting device according to an embodiment of the present invention may be manufactured using various deposition methods. It can be manufactured using a deposition method such as PVD or CVD, for example, depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form an anode 120, and a hole injection layer 130 thereon , After forming an organic material layer including a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170, it can be manufactured by depositing a material that can be used as the cathode 180 thereon. there is. In addition, an auxiliary light emitting layer 151 may be additionally formed between the hole transport layer 140 and the light emitting layer 150 .

In addition, the organic layer may be formed by a solution process or a solvent process using various polymer materials, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, a roll-to-roll process, a doctor blading process, It can be manufactured with fewer layers by a method such as a screen printing process or a thermal transfer method. Since the organic layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric device according to the present invention may be one of an organic light emitting device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a device for monochromatic or white lighting, and a device for quantum dot display.

Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electric element of the present invention and a control unit controlling the display device. At this time, the electronic device may be a current or future wired/wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, and various computers. The display device may include an organic light emitting display, a quantum dot display, and the like.

Hereinafter, a compound according to an aspect of the present invention will be described.

A compound according to one aspect of the present invention is represented by Formula 1 below.

<Formula 1>

In Formula 1, the following Formula 1-1 is bonded to at least one of Ring A, Ring B, Ring C, and X.

<Formula 1-1>

In Formula 1 and Formula 1-1, each symbol may be defined as follows.

A ring, B ring and C ring are each independently a C ₆ ~ C ₂₄ aromatic ring; Or a C ₂ ~C ₂₀ heterocycle containing at least one heteroatom selected from O, N, S, Si, and P. However, at least one of the A ring, the B ring, and the C ring is a C ₁₀ ~ C ₂₄ aromatic ring, or a C ₈ ~ C ₂₀ hetero ring containing at least one heteroatom selected from O, N, S, Si, and P. It is preferable that it is a ring.

When ring A, ring B, and ring C are aromatic rings, they are preferably C ₆ -C ₂₀ aromatic rings, more preferably C ₆ -C ₁₀ aromatic rings, such as benzene and naphthalene.

R ¹ to R ⁵ are each independently hydrogen; heavy hydrogen; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ) It is selected from the group consisting of, and adjacent R ⁴ or adjacent R ⁵ may bond to each other to form a ring, wherein the ring is C ₆ ~ C ₆₀ Aromatic ring of; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; and combinations thereof.

l, m, and n are independently integers of 0 to 6, and when each of them is an integer of 2 or more, each of R ¹ , each of R ² , and each of R ³ are the same as or different from each other, and o is 0 to 4 When o is an integer of 2 or more, each R ⁴ is the same as or different from each other, p is an integer of 0 to 3, and when p is an integer of 2 or more, each R ⁵ is the same as or different from each other.

When R ¹ to R ⁵ are heterocyclic groups, preferably C ₂ ~ C ₃₀ heterocyclic groups, more preferably C ₂ ~ C ₁₀ heterocyclic groups, such as triazine, quinazoline, benzothieno pyrimidine, benzofuropyrimidine, and the like.

L ₁ is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; And it may be selected from the group consisting of combinations thereof.

X and Y are independently of each other O, S, N(-L ¹ -Ar ¹ ) or C(R′)(R″). Preferably, when X is N(-L ¹ -Ar ¹ ), adjacent R ⁴ or adjacent R ⁵ bonds to each other to form a ring. At this time, the ring is a C ₆ ~ C ₆₀ aromatic ring; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; And it may be selected from combinations thereof, preferably a C ₆ ~ C ₂₀ aromatic ring, more preferably a C ₆ ~ C ₁₀ aromatic ring, such as benzene and naphthalene.

L ¹ is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; And it may be selected from the group consisting of combinations thereof.

When L ¹ is an arylene group, it may be preferably a C ₆ ~ C ₃₀ arylene group, more preferably a C ₆ ~ C ₁₂ aryl group, such as phenyl, naphthalene, or biphenyl. When L ¹ is a heterocyclic group, it is preferably a C ₂ -C ₃₀ heterocycle, more preferably a C ₂ -C ₁₂ heterocycle, such as triazine, pyrimidine, pyridine, quinazoline, quinoxaline, and benzoquina. It can be zoline, benzoquinoxaline, benzocyenoquinoxaline, benzothienopyrimidine, benzofuropyrimidine, benzothienopyrazine, benzofuropyrazine, carbazole, dibenzofuran, dibenzothiophene, etc. there is. When L ¹ is a fluorenyl group, it may be dimethylfluorene, diphenylfluorene or the like.

Ar ¹ is a C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); may be selected from the group consisting of.

When Ar ¹ is an aryl group, it is preferably a C ₆ -C ₃₀ aryl group, more preferably a C ₆ -C ₁₂ aryl group, such as phenyl, biphenyl, naphthyl, and the like. When Ar ¹ is a heterocyclic group, it is preferably a C ₂ ~ C ₃₀ heterocyclic group, more preferably a C ₂ ~ C ₁₂ heterocyclic group, such as triazine, pyrimidine, pyridine, quinazoline, and benzoquinazoline. , quinoxaline, benzoquinoxaline, benzocyenoquinoxaline, carbazole, benzothienopyrimidine, benzofuropyrimidine, benzothienopyrazine, benzofuropyrazine, dibenzofuran, dibenzothiophene etc.

Wherein R' and R" are hydrogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group including at least one heteroatom selected from O, N, S, Si and P; It is selected from the group consisting of C ₁ ~ C ₅₀ alkyl group; and -L'-N(R _a )(R _b ), and R' and R" may combine with each other to form a ring. At this time, the ring is a C ₆ ~ C ₆₀ aromatic ring; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; And it may be selected from combinations thereof, preferably may be an aromatic ring or a fused ring of an aromatic ring and an aliphatic ring, for example, may form a ring such as fluorene. Therefore, when R' and R" are bonded to each other to form a fluorene derivative, as a result, spirobifluorene can be formed together with the fluorene ring to which C(R')(R") is bonded.

When R' and R" are aryl groups, they are preferably C ₆ -C ₃₀ aryl groups, more preferably C ₆ -C ₁₂ aryl groups, such as phenyl, biphenyl, naphthyl, etc. R' And when R" is an alkyl group, it may be preferably a C ₁ -C ₂₀ aryl group, more preferably a C ₆ -C ₁₀ aryl group, such as methyl and propyl.

L' is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; And it may be selected from the group consisting of combinations thereof.

Wherein R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; And it may be selected from the group consisting of combinations thereof.

R ¹ to R ⁵ , Ar ¹ , L ₁ , L ¹ , R', R", L', R _a , R _b , a ring formed by bonding adjacent R ⁴ groups, and adjacent R ⁵ groups to each other Rings formed by bonding are each selected from heavy hydrogen; halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; a siloxane group; a boron group; a germanium group; a cyano group; a nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxyl group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ Aryl group; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heteroatom containing at least one heteroatom selected from the group consisting of O, N, S, Si and P It may be further substituted with one or more substituents selected from the group consisting of a ring group; a C ₃ -C ₂₀ cycloalkyl group; a C ₇ -C ₂₀ arylalkyl group; a C ₈ -C ₂₀ arylalkenyl group; and combinations thereof.

Preferably, Formula 1 may be represented by one of Formulas 2 to 7 below.

<Formula 2> <Formula 3> <Formula 4>

<Formula 5> <Formula 6> <Formula 7>

In Chemical Formulas 2 to 7, each symbol may be defined as follows.

X ¹ , R ¹ to R ³ , l, m and n are as defined in Formula 1, and ring A, ring B and ring C are C ₁₀ to C ₂₄ aromatic rings, or O, N, S, Si and It is a C ₈ ~ C ₂₀ heterocyclic group containing at least one heteroatom of P.

V ¹ to V ¹¹ are CH, CR or N, where R are independently hydrogen; heavy hydrogen; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ) It is selected from the group consisting of, L', R _a and R _b are as defined above.

Preferably, Ring A, Ring B and Ring C may be selected from the group consisting of the following Formulas B-1 to Formulas B-7.

In the formulas B-1 to B-7, "*" indicates condensed positions, Z ⁴ to Z ⁵⁰ are CR ⁰ or N, where R ⁰ is hydrogen; heavy hydrogen; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And it is selected from the group consisting of -L'-N(R _a )(R _b ), and L', R _a and R _b are as defined above.

Also, preferably, Formula 1 may be represented by one of Formulas 8 to 16 below.

<Formula 8> <Formula 9> <Formula 10>

<Formula 11> <Formula 12> <Formula 13>

<Formula 14> <Formula 15> <Formula 16>

In Formulas 8 to 16, ring A, ring B, ring C, R ¹ to R ⁵ , L ₁ , X, and Y are as defined in claim 1, and l, m, n, o, and p are each As defined above independently of each other, l' is an integer of 0 to 2, n' is an integer of 0 to 5.

Specifically, the compound represented by Formula 1 may be one of the following compounds.

.

.

Another embodiment of the present invention provides an organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer is a single compound represented by Formula 1 or two or more compounds, and the organic material layer includes at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport supplement, an electron transport layer, and an electron injection layer. Preferably, the compound represented by Formula 1 may be included in the light emitting layer.

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

synthesis example

The compound represented by Chemical Formula 1 according to the present invention (Final Products) may be synthesized using Sub 1 to Sub 3 as shown in Scheme 1 below.

<Scheme 1> (where R ⁵ is H or Br)

Synthesis example of Sub-1(17)

Synthesis of Sub 1-17A

After dissolving 3-bromo-9,9-diphenyl-9,10-dihydroacridine (20g, 48.5 mmol) in toluene, 2-bromo-1-chloronaphthalene (17.57g, 72.76 mmol) was added and NaO t -Bu (16.33 g , 145.51 mmol), Pd ₂ (dba) ₃ (0.44 g, 0.49 mmol), P(t-Bu) ₃ (0.49 g, 2.43 mmol), and toluene (200 mL) were added, respectively, Stir and reflux at 100 ° C for 20 hours. After the reaction was completed, after extraction with dichloromethane and water, the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was passed through a silica gel column and recrystallized to obtain 20 g of Sub 1-17A (yield: 71.97%).

Synthesis of Sub 1-17

After dissolving Sub 1-17A (5 g, 8.73 mmol) in DMA, fluoroboric acid (1.7 g, 10.47 mmol), palladium acteate (0.06 g, 0.26 mmol), Potassum carbonate (3.62 g, 26.18 mmol), P( After adding t-Bu) ₃ (0.18g, 0.87 mmol), the reaction proceeds at 180°C. After the reaction was completed, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was passed through a silica gel column and recrystallized to obtain 4 g of Sub-1-17 (yield: 85%).

Synthesis example of Sub-2(3)

Synthesis of Sub 2-3A

After dissolving 5,10-dihydrophenazine (20g, 109.75 mmol) in toluene, 1-bromo-2-chloronaphthalene (31.81g, 131.70 mmol) was added and NaO t -Bu (31.64 g, 329.25 mmol), Pd(OAc) ₂ (0.25 g, 1.10 mmol), P(t-Bu) ₃ (1.11 g, 5.49 mmol), and toluene (200 mL) were added, respectively, The mixture was stirred and refluxed at 100°C for 20 hours. After the reaction was completed, the mixture was extracted with dichloromethane and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was passed through a silica gel column and recrystallized to obtain 18 g of Sub 2-3A (yield: 47.84%).

Synthesis of Sub 2-3

After dissolving Sub 2-3A (5 g, 8.73 mmol) in DMA, fluoroboric acid (2.83 g, 17.50 mmol), palladium acteate (0.03 g, 0.15 mmol), Potassum carbonate (6.05 g, 43.75 mmol), P( After adding t-Bu) ₃ (0.15g, 0.73 mmol), the reaction proceeds at 180°C. After the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was passed through a silica gel column and recrystallized to obtain 3.8 g of Sub 2-3 (yield: 85%).

Synthesis example of Sub-3(31)

Synthesis of Sub 3-31A

After dissolving 3-bromo-10H-phenoxazine (20g, 76.30 mmol) in toluene, 2-bromo-1-chloronaphthalene (22.11g, 91.56 mmol) was added and NaO t -Bu (22 g, 228.91 mmol) and Pd ₂ ( After adding dba) ₃ (0.70 g, 0.76 mmol), P(t-Bu) ₃ (0.77 g, 3.82 mmol), and toluene (200 mL), The mixture was stirred and refluxed at 100°C for 20 hours. After the reaction was completed, extraction was performed with dichloromethane and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was passed through a silica gel column and recrystallized to obtain 24 g of desired Sub 3-31A (yield: 74.41%).

Synthesis of Sub 3-31

After dissolving Sub 3-31A (5 g, 11.83 mmol) in DMA, adding fluoroboric acid (2.30 g, 14.19 mmol), palladium acteate (0.03g, 0.12 mmol), Potassum carbonate (4.90g, 35.49 mmol), P(t-Bu) ₃ (0.12g, 0.59 mmol) was reacted at 180°C. After the reaction was completed, extraction was performed with CH2Cl2 and water, and the organic layer was dried with MgSO4, concentrated, and the resulting organic material was passed through a silica gel column and recrystallized to obtain 3.8 g of Sub 3-31 (yield: 83.17%).

Synthesis example of Sub-4(25)

Synthesis of Sub 4-25A

After dissolving 2-bromo-10H-phenothiazine (20g, 71.90mm) in toluene, 2-bromo-1-chloronaphthalene (20.84g, 86.28 mmol) was added and NaO t -Bu (20.73 g, 215.70 mmol), Pd ₂ ( After adding dba) ₃ (0.66 g, 0.72 mmol), P(t-Bu) ₃ (0.73 g, 3.59 mmol), and toluene (200 mL), The mixture was stirred and refluxed at 100°C for 20 hours. After the reaction was completed, extraction was performed with dichloromethane and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was passed through a silica gel column and recrystallized to obtain 24 g of desired Sub 3-31A (yield: 76.08%).

Synthesis of Sub 4-25

After dissolving Sub 4-25A (5 g, 11.40 mmol) in DMA, fluoroboric acid (2.21 g, 13.67 mmol), palladium acteate (0.03 g, 0.11 mmol), Potassum carbonate (4.72 g, 34.19 mmol), P( After adding t-Bu) ₃ (0.12g, 0.57 mmol), the reaction proceeds at 180°C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried with MgSO ₄ , concentrated, and then the resulting organic material was passed through a silica gel column and recrystallized to obtain 3.5 g of Sub 4-25. (Yield: 79.52%)

Compounds belonging to Sub 1 to Sub 4 may be as follows, but are not limited thereto, and FD-MS values for the following compounds are shown in Table 1.

[Table 1]

II. Example of Sub 5

Meanwhile, the compound belonging to Sub 5 may be the following compounds, but is not limited thereto, and Table 2 shows the FD-MS values of the compounds belonging to Sub 5.

[Table 2]

III. of the final compound synthesis example

Synthesis example of 1-19

Synthesis of Sub 1-19-A

After dissolving Sub 1-17 (10 g, 18.64 mmol) in toluene, (9H-carbazol-2-yl)boronic acid (5.90 g, 27.96 mmol), K ₂ CO ₃ (7.73 g, 55.92 mmol), Pd ( After adding PPh ₃ ) ₄ (0.65 g, 0.56 mmol), toluene (100 mL) and water (50ml), Stir and reflux for 24 hours at 90 ° C. After the reaction was completed, extraction was performed with dichloromethane and water, and the organic layer was dried with MgSO ₄ , concentrated, and then the organic material produced was passed through a silica gel column and recrystallized to obtain 9.8 g of Sub 1-19-A (yield: 84.42%).

Synthesis of 1-19

After dissolving Sub 1-19-A (5g, 8.03 mmol) in toluene, sub 5-28 (3.3g, 9.63 mmol), NaO t -Bu (2.31 g, 24.09 mmol), Pd ₂ (dba) ₃ (0.07 g, 0.08 mmol), P(t-Bu) ₃ (0.08 g, 0.4 mmol), and toluene (50 mL) were added, Stir and reflux at 100°C for 20 hours. After the reaction was completed, extraction was performed with dichloromethane and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting organic material was passed through a silica gel column and recrystallized to obtain 5.8 g of 1-19 (yield: 77.75%).

Synthesis example of 2-26

Synthesis of Sub 2-12-A

Sub 2-12 (10 g, 21.68 mmol), toluene, (7H-benzo[c]carbazol-9-yl)boronic acid (8.49 g, 32.51 mmol), K ₂ CO ₃ (8.99 g, 65.03 mmol), Pd (PPh ₃ ) ₁₀ g of Sub 2-12-A (yield: 77.19%) was obtained.

Synthesis of Sub 2-26

Sub 2-12-A (5 g, 8.37 mmol), toluene, chlorobenzene (1.13 g, 10.04 mmol), NaO t -Bu (2.41 g, 25.10 mmol), Pd ₂ (dba) ₃ (0.08 g, 0.08 mmol), Using P(t-Bu) ₃ (0.08 g, 0.42 mmol) and toluene (50 mL), 5.5 g (yield: 70.76%) of final compound 2-26 was prepared in the same manner as in the synthesis of final compound 1-19. got it

Synthesis example of 2-40

Synthesis of Sub 2-7-A

Sub 2-7 (15 g, 48.96 mmol), toluene, 4-bromo-9H-carbazole (13.86 g, 56.30 mmol), NaO t -Bu (14.12 g, 146.88 mmol), Pd ₂ (dba) ₃ (2.24 g, 2.45 mmol), P(t-Bu) ₃ (0.99 g, 4.90 mmol), and toluene (200 mL) were used to obtain 6.26 g of Sub 2-7-A (yield) in the same manner as for the synthesis of Sub 1-19-A. : 27.1%) was obtained.

Synthesis of 2-40

Sub 2-7-A (5 g, 10.6 mmol), toluene, Sub 5-46 (3.62 g, 12.19 mmol), NaO t -Bu (3.06 g, 31.81 mmol), Pd ₂ (dba) ₃ (0.49 g, 4.76 g of final compound _2-40 (yield: 61.3%) was obtained.

Synthesis example of 3-36

Sub 3-31 (10 g, 25.89 mmol), toluene, dibenzo[b,d]thiophen-3-ylboronic acid (8.86 g, 38.83 mmol), K ₂ CO ₃ (10.73 g, 77.67 mmol), Pd (PPh ₃ ) ₄ (0.90 g, 0.78 mmol), toluene (100 mL), water (50ml) was used to prepare 10 g (yield: 78.89%) of final compound 3-36 in the same manner as in the synthesis of final compound 1-19. got it

Synthesis example of 3-25

Synthesis of Sub 3-21-A

Sub 3-21 (10 g, 25.89 mmol), toluene, (9H-carbazol-3-yl)boronic acid (8.20 g, 38.83 mmol), K ₂ CO ₃ (10.73 g, 77.67 mmol), Pd (PPh ₃ ) 9.5 g (yield: 77.65%) of Sub 3-21-A was prepared in the same manner as in the synthesis method of Sub 1-19-A using ₄ (0.90 g, 0.78 mmol), toluene (100 mL), and water (50 ml). got it

Synthesis of 3-25

Sub 3-21-A (5 g, 10.58 mmol), toluene, Sub 5-75 (4.02 g, 12.70 mmol), NaO t -Bu (3.05 g, 31.74 mmol), Pd ₂ (dba) ₃ (0.10 g, 0.11 mmol), P(t-Bu) ₃ (0.11 g, 0.53 mmol), and toluene (50 mL) to obtain 6.8 g of final compound 3-25 (yield: 69.17 %) was obtained.

Synthesis example of 4-22

Synthesis of Sub 4-26-A

Sub 4-26 (10 g, 24.86 mmol), toluene, (9H-carbazol-3-yl)boronic acid (7.87 g, 37.28 mmol), K ₂ CO ₃ (10.31 g, 74.57 mmol), Pd (PPh ₃ ) 9.7 g (yield: 79.87%) of Sub 4-26-A was prepared in the same manner as in the synthesis method of Sub 1-19-A using ₄ (0.86 g, 0.75 mmol), toluene (100 mL), and water (50 ml). got it

Synthesis of 4-22

Sub 4-26-A (5 g, 10.23 mmol), toluene, sub 5-76 (4.75 g, 12.28 mmol), NaO t -Bu (2.95 g, 30.70 mmol), Pd ₂ (dba) ₃ (0.09 g, 0.10 mmol), P(t-Bu) ₃ (0.10 g, 0.51 mmol), and toluene (50 mL) to obtain 6.5 g of final compound 4-22 (yield: 75.71 %) was obtained.

On the other hand, the FD-MS values of the compounds 1-1 to 4-38 of the present invention prepared according to the Synthesis Example as described above are shown in Table 3 below.

[Table 3]

Manufacturing evaluation of organic electric devices

[Example 1] Red organic light emitting device

N ¹ -(naphthalen-2-yl)-N ⁴ ,N ⁴ -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N ¹ -phenylbenzene on the ITO layer (anode) formed on the glass substrate A -1,4-diamine (hereinafter abbreviated as "2-TNATA") film was vacuum deposited to form a 60 nm thick hole injection layer. On the hole injection layer, Bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (hereinafter abbreviated as "NPB") was applied to a thickness of 60 nm. After vacuum deposition to form a hole transport layer, compounds 1-3 of the present invention as a host and bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter referred to as "(piq) ₂ Ir(acac)" as a dopant) Abbreviated) was used, but a dopant was doped so that the weight ratio was 95:5, and a light emitting layer having a thickness of 30 nm was deposited on the hole transport layer. Next, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as "BAlq") was vacuum coated to a thickness of 10 nm on the light emitting layer. A hole blocking layer was formed by vapor deposition, and tris(8-quinolinol) aluminum (hereinafter abbreviated as “Alq ₃ ”) was deposited to a thickness of 40 nm on the hole transport layer to form an electron transport layer. Thereafter, LiF was deposited on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited on the electron injection layer to a thickness of 150 nm to form a cathode.

[ Example 2] to [ Example 31]

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the compound of the present invention shown in Table 4 was used instead of Compound 1-2 of the present invention as a host material of the light emitting layer.

[ comparative example 1] to [ comparative example 4]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound A to Comparative Compound D were used instead of Compound 1-2 of the present invention as a host material for the light emitting layer.

<Comparative Compound A> <Comparative Compound B> <Comparative Compound C> <Comparative Compound D>

A forward bias DC voltage was applied to the organic light emitting devices of Examples 1 to 31 and Comparative Examples 1 to 4 prepared as described above, and electroluminescence (EL) characteristics were measured with PR-650 of Photoresearch Co., Ltd. , As a result of the measurement, T95 life was measured at a standard luminance of 2500 cd/m ² through life measurement equipment manufactured by McScience. Table 4 below shows the measurement results.

[Table 4]

As can be seen from the results of Table 4, when the compound of the present invention is used as a phosphorescent host, the driving voltage of the organic light emitting device can be lowered, and the efficiency and lifetime can be significantly improved.

More specifically, comparative compound B containing phenothiazine condensed with indole rather than comparative compound A, which is CBP generally used as a host material, and indoloacridine having a spiral structure (fluorene) formed When Comparative Compound C and Comparative Compound D including dihydrophenazine were used as host materials, the results of the device were remarkably excellent. When the compound of the present invention to which a benzothiophene, carbazole derivative or fluorene derivative is bound was used as a host material, the results of the device were the best. This lowers the HOMO level by binding a specific substituent to the outer benzene ring of the main skeleton, which is advantageous in terms of physical properties such as hole transport and thermal stability. It seems that the characteristics of the device are improved because the change in physical properties and the like acted as a major factor in improving the device performance.

The above description is merely illustrative of the present invention, and those skilled in the art will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in this specification are intended to explain, not limit, the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed according to the following claims, and all techniques within the scope equivalent thereto should be construed as being included in the scope of the present invention.

100: organic electric element 110: substrate
120: first electrode 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (12)

A compound represented by Formula 1 below:
<Formula 1>

In Formula 1,
A ring, B ring and C ring are each independently a C ₆ ~ C ₂₄ aromatic ring; Or a C ₂ ~ C ₂₀ heterocyclic ring containing at least one heteroatom selected from O, N, S, Si, and P, provided that at least one of the A ring, the B ring, and the C ring is a C ₁₀ ~C ₂₄ aromatic ring. A ring or a C ₈ ~ C ₂₀ heterocyclic ring containing at least one heteroatom selected from O, N, S, Si, and P;
X is O, S, N(-L ¹ -Ar ¹ ) or C(R′)(R″);
Formula 1-1 is bonded to at least one of ring A, ring B, ring C and X,
<Formula 1-1>

R ¹ to R ⁵ are each independently hydrogen; heavy hydrogen; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ) It is selected from the group consisting of, and adjacent R ⁴ or adjacent R ⁵ may bond to each other to form a ring, wherein the ring is C ₆ ~ C ₆₀ Aromatic ring of; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; And selected from combinations thereof,
l, m, and n are independently integers of 0 to 6, and when each of them is an integer of 2 or more, each of R ¹ , each of R ² , and each of R ³ are the same as or different from each other, and o is 0 to 4 is an integer of, and when o is an integer of 2 or more, each R ⁴ is the same as or different from each other, p is an integer of 0 to 3, and when p is an integer of 2 or more, each R ⁵ is the same as or different from each other,
L ₁ is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; And it is selected from the group consisting of combinations thereof,
Y is O, S, N(-L ¹ -Ar ¹ ) or C(R′)(R″);
L ¹ is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; And it is selected from the group consisting of combinations thereof,
Ar ¹ is a C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); is selected from the group consisting of,
Wherein R' and R" are hydrogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group including at least one heteroatom selected from O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; and -L'-N (R _a ) (R _b ) It is selected from the group consisting of, R', R" may be bonded to each other to form a ring,
L' is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; And it is selected from the group consisting of combinations thereof,
Wherein R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; And it is selected from the group consisting of combinations thereof,
R ¹ to R ⁵ , Ar ¹ , L ₁ , L ¹ , R', R", L', R _a , R _b , a ring formed by bonding adjacent R ⁴ groups, and adjacent R ⁵ groups to each other Rings formed by bonding are each selected from heavy hydrogen; halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; a siloxane group; a boron group; a germanium group; a cyano group; a nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxyl group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ Aryl group; Deuterium-substituted C ₆ -C ₂₀ Aryl group; Fluorenyl group; C ₂ -C ₂₀ heteroatom containing at least one heteroatom selected from the group consisting of O, N, S, Si and P It may be further substituted with one or more substituents selected from the group consisting of a ring group; a C ₃ -C ₂₀ cycloalkyl group; a C ₇ -C ₂₀ arylalkyl group; a C ₈ -C ₂₀ arylalkenyl group; and combinations thereof. According to claim 1,
A compound characterized in that Formula 1 is represented by one of the following Formulas 2 to 7:
<Formula 2><Formula3><Formula4>

<Formula 5><Formula6><Formula7>

In Formulas 2 to 7,
X ¹ , R ¹ to R ³ , l, m, n are as defined in claim 1,
A ring, B ring and C ring are C ₁₀ ~ C ₂₄ aromatic rings or C ₈ ~ C ₂₀ heterocyclic groups containing at least one heteroatom selected from O, N, S, Si and P;
V ¹ to V ¹¹ are CH, CR or N, where R are independently hydrogen; heavy hydrogen; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ) It is selected from the group consisting of, L', R _a and R _b are as defined in claim 1. According to claim 1,
A compound characterized in that ring A, ring B and ring C are selected from the group consisting of the following formulas B-1 to formulas B-7:

In the above formulas B-1 to formula B-7,
The "*" mark indicates the location of condensation,
Z ⁴ to Z ⁵⁰ are CR ⁰ or N, where R ⁰ is hydrogen; heavy hydrogen; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ) It is selected from the group consisting of, L', R _a and R _b are as defined in claim 1. According to claim 1,
A compound characterized in that when X is N(-L ¹ -Ar ¹ ), adjacent R ⁴ or adjacent R ⁵ bond to each other to form a ring. According to claim 1,
Formula 1 is a compound characterized in that represented by one of the following formulas 8 to 16:
<Formula 8><Formula9><Formula10>

<Formula 11><Formula12><Formula13>

<Formula 14><Formula15><Formula16>

In Formulas 8 to 16,
A ring, B ring, C ring, R ¹ to R ⁵ , L ₁ , X, Y are as defined in claim 1, and l, m, n, o, p are each independently defined in claim 1 , l' is an integer from 0 to 2, and n' is an integer from 0 to 5. According to claim 1,
A compound, characterized in that the compound represented by Formula 1 is one of the following compounds:

. In the organic electric element including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode,
The organic material layer is an organic electric device characterized in that it comprises a single compound or two or more compounds represented by the formula (1) of claim 1. According to claim 7,
The organic material layer comprises at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer. According to claim 8,
The organic electric device, characterized in that the compound is included in the light emitting layer. According to claim 7,
The organic layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, or a roll-to-roll process. A display device comprising the organic electric element of claim 7; and
An electronic device comprising a controller for driving the display device. According to claim 11,
The electronic device, characterized in that the organic electric device is selected from the group consisting of organic light emitting devices, organic solar cells, organic photoreceptors, organic transistors, devices for monochromatic lighting and devices for quantum dot displays.

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