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

Abstract

The present invention provides: a novel mixture capable of improving the luminous efficiency, stability and life of an element; an organic electric element using the mixture; and an electronic device thereof.

Description

Technical Field

[0001] The present invention relates to a compound for an organic electric element, an organic electric element using the compound, and an electronic device thereof. Background Art

[0002] Generally, organic light emitting diodes (OLEDs) are materials that convert electrical energy into light energy. Organic electrical components utilizing organic light emitting diodes typically have a structure comprising an anode, a cathode, and an organic material layer interposed therebetween. To improve the efficiency and stability of these components, the organic material layer typically comprises a multilayer structure composed of various materials, including, for example, a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, and an electron injection layer.

[0003] Materials used as the organic material layer in an organic electrical element can be divided into light-emitting materials and charge transport materials according to their functions, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like.

[0004] Bicyclic compounds containing heteroatoms have properties that vary greatly depending on the material structure and are therefore used in various layers as materials for organic electrical devices. Specifically, the number and fusion positions of the rings, as well as the type and arrangement of heteroatoms, lead to different band gaps (HOMO, LUMO), electrical properties, chemical properties, and physical properties. Consequently, these compounds have been developed for use in various layers of organic electrical devices.

[0005] In phosphorescent organic electrical elements using phosphorescent dopant materials, the LUMO and HOMO energy levels of the main material have a great influence on the efficiency and life of the organic electrical elements, and depending on whether the electron and hole injection in the emission layer, the charge balance in the emission layer, and the dopant quenching can be effectively controlled, the reduction in efficiency and life due to light emission at the interface of the hole transport layer can be prevented.

[0006] For fluorescent and phosphorescent host materials, we have recently studied the use of TADF (thermally activated delayed fluorescence), excimer complexes, etc. to improve the efficiency and life of organic electrical devices. Specifically, many studies have been conducted to determine the energy transfer method from the host material to the dopant material.

[0007] Although there are various methods for determining energy transfer in the emission layer of TADF (thermally activated delayed fluorescence) and excimer complexes, it can be easily confirmed by the PL lifetime (TRTP) measurement method.

[0008] The TRTP (time-resolved transient PL) measurement method involves observing the decay time after irradiating a host film with a pulsed light source. It allows the determination of energy transfer methods by observing the energy transfer and emission delay times. TRTP measurement is capable of distinguishing between fluorescence and phosphorescence, as well as energy transfer methods involving mixed host materials, excimer complex energy transfer, and TADF energy transfer methods.

[0009] As such, there are various factors that affect efficiency and lifetime depending on how energy is transferred from the host material to the dopant material.

[0010] Since energy transfer methods vary depending on the material, the development of stable and efficient host materials for organic electrical devices has not been sufficiently advanced. Therefore, there is a continuous demand for the development of new materials, and in particular, there is an urgent need to develop host materials for emission layers.

[0011] Reference KR101170666 B1 was used as prior art document.

[0012] Detailed description of the invention Summary of the Invention

[0013] The present invention is proposed to solve the problem of phosphorescent host materials, and the purpose of the present invention is to provide a compound that can control the charge balance and improve the efficiency and life in the emission layer by controlling the HOMO energy level of the host material of a phosphorescent emitting organic electrical element including a phosphorescent dopant, as well as an organic electrical element and an electronic device using the compound.

[0014] Technical Solution

[0015] In order to control the effective hole injection in the emission layer of the phosphorescent emitting organic electrical element, by including a second host material in combination with the first host material as the main component, the energy barrier between the emission layer and the adjacent layer can be reduced, and the charge balance in the emission layer can be maximized to provide high efficiency and long life of the organic electrical element.

[0016] The present invention provides an organic electrical element, which includes 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 includes an emission layer, wherein the emission layer is a phosphorescent emission layer and contains a first host compound represented by Formula 1 and a second host compound represented by Formula 2.

[0017]

[0018] The present invention also provides an organic electric element and an electronic device using the compound represented by the formula.

[0019] Effects of the Invention

[0020] By using the mixture according to the present invention as a phosphorescent host material, high luminous efficiency and low driving voltage of an organic electrical element can be achieved, and the lifetime of the device can be greatly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 is an example of an organic electroluminescent device according to the present invention.

[0022] 100: Organic electrical components, 110: Substrate

[0023] 120: first electrode (anode), 130: hole injection layer

[0024] 140: hole transport layer, 141: buffer layer

[0025] 150: Emission layer, 151: Emission auxiliary layer

[0026] 160: electron transport layer, 170: electron injection layer

[0027] 180: Second electrode (cathode) DETAILED DESCRIPTION

[0028] Hereinafter, some embodiments of the present invention will be described in detail.In addition, in the following description of the present invention, when incorporating known functions and configurations herein may make the subject matter of the present invention rather unclear, their detailed description will be omitted.

[0029] In addition, when describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used herein. Each of these terms is not used to limit the nature, order, or sequence of the corresponding component, but is only used to distinguish the corresponding component from other components. It should be noted that if a component is described as being "connected," "coupled," or "connected" to another component, the component may be directly connected or coupled to the other component, but other components may be "connected," "coupled," or "connected" between the components.

[0030] As used in the specification and appended claims, unless otherwise stated, the following terms have the following meanings.

[0031] Unless otherwise stated, the term "halo" or "halogen" as used herein includes fluorine, bromine, chlorine, or iodine.

[0032] Unless otherwise indicated, the term "alkyl" or "alkyl group" as used herein has single bonds of 1 to 60 carbon atoms and means a saturated aliphatic functional group, including a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl group (alicyclic), a cycloalkyl group substituted by an alkyl group, or an alkyl group substituted by a cycloalkyl group.

[0033] Unless otherwise stated, the term "haloalkyl" or "haloalkyl" as used herein includes alkyl groups substituted with a halogen.

[0034] Unless otherwise specified, the term "heteroalkyl" as used herein means an alkyl group in which one or more carbon atoms constituting the alkyl group are substituted with a heteroatom.

[0035] Unless otherwise specified, the term "alkenyl" or "alkynyl" as used herein has a double bond or triple bond of 2 to 60 carbon atoms, but is not limited thereto, and includes straight chain or branched chain groups.

[0036] Unless otherwise specified, the term "cycloalkyl group" as used herein means an alkyl group forming a ring having 3 to 60 carbon atoms, but is not limited thereto.

[0037] Unless otherwise specified, the term "alkoxy," "alkoxy group," or "alkyloxy group" as used herein means an oxy group attached to an alkyl group, and has 1 to 60 carbon atoms, but is not limited thereto.

[0038] Unless otherwise specified, the term "alkenoxy," "alkenyloxy group," or "alkenyloxy group" as used herein means an oxy group attached to an alkenyl group and has 2 to 60 carbon atoms, but is not limited thereto.

[0039] Unless otherwise specified, the term "aryloxy group" or "aryloxy group" as used herein means an oxy group is attached to an aryl group, and has 6 to 60 carbon atoms, but is not limited thereto.

[0040] Unless otherwise specified, the term "aryl group" or "arylene group" as used herein has 6 to 60 carbon atoms, but is not limited thereto. As used herein, aryl groups or arylene groups refer to monocyclic and polycyclic aromatic groups, and may also be formed by combining with adjacent groups. Examples of "aryl groups" may include phenyl groups, biphenyl groups, fluorene groups, or spirofluorene groups.

[0041] The prefix "aryl" or "ar" means a group substituted with an aryl group. For example, arylalkyl can be an alkyl substituted with an aryl group, and arylalkenyl can be an alkenyl substituted with an aryl group, and the group substituted with an aryl group has the number of carbon atoms as defined herein.

[0042] In addition, when the prefix is ​​named sequentially, it means that the substituents are listed in the order in which they are first described. For example, arylalkoxy means an alkoxy group substituted by an aryl group, alkoxycarbonyl means a carbonyl group substituted by an alkoxy group, and arylcarbonylalkenyl also means an alkenyl group substituted by an arylcarbonyl group, wherein the arylcarbonyl group can be a carbonyl group substituted by an aryl group.

[0043] Unless otherwise specified, the term "heteroalkyl" as used herein means an alkyl group containing one or more heteroatoms. Unless otherwise specified, the term "heteroaryl group" or "heteroarylene group" as used herein means a C2 to C60 aryl or arylene group containing one or more heteroatoms, but is not limited thereto, and includes at least one of a monocyclic ring and a polycyclic ring, and may also be formed by combining with adjacent groups.

[0044] Unless otherwise specified, the term "heterocyclic group" as used herein contains one or more heteroatoms, has 2 to 60 carbon atoms, but is not limited thereto, includes any one of a monocyclic ring and a polycyclic ring, and may include a heteroaliphatic ring and / or a heteroaromatic ring. In addition, it may also combine with adjacent groups to form a heterocyclic group.

[0045] Unless otherwise specified, the term "heteroatom" as used herein means at least one of N, O, S, P or Si.

[0046] In addition, the term "heterocyclic group" may include a ring containing SO2 instead of carbon constituting the ring. For example, the "heterocyclic group" includes the following compounds.

[0047]

[0048] Unless otherwise specified, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the term "aliphatic cyclo" as used herein means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

[0049] Unless otherwise specified, the term "ring" as used herein means an aliphatic ring having 3 to 60 carbon atoms, or an aromatic ring having 6 to 60 carbon atoms, or a heterocyclic ring having 2 to 60 carbon atoms, or a condensed ring formed by a combination thereof, and includes a saturated ring or an unsaturated ring.

[0050] In addition to the above-mentioned heterocompounds, other heterocompounds or heterogroups contain, but are not limited to, one or more heteroatoms.

[0051] Unless otherwise indicated, the term "carbonyl" as used herein is represented by -COR', where R' can be hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination of these.

[0052] Unless otherwise indicated, the term "ether" as used herein is represented by -RO-R', wherein R or R' can independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination of these.

[0053] Unless otherwise indicated, the term "substituted or unsubstituted" as used herein means that the substituent is substituted with at least one substituent including, but not limited to, deuterium, hydrogen, halogen, amino group, nitrile group, nitro group, C1-C 20 Alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylamine group, C1-C 20 Alkylthiophene group, C6-C 20 Arylthiophene group, C2-C 20 Alkenyl groups, C2-C 20 Alkynyl group, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, deuterium-substituted C6-C 20 Aryl group, C8-C 20 Arylene groups, silane groups, boron groups, germanium groups and C2-C 20 Heterocyclic group.

[0054] Unless otherwise specifically stated, the formulae used in the present invention as used herein apply in the same manner as the definitions of substituents according to the definitions of the indices of the following formulae.

[0055]

[0056] Here, when a is an integer of 0, this means that the substituent R 1 Absent, that is, when a is 0, this means that all hydrogens are bonded to carbons forming the benzene ring, and in this case, the display of hydrogen bonded to carbon may be omitted, and the chemical formula or compound may be described.

[0057] When a is an integer of 1, a substituent R 1 are bonded to any one of the carbon atoms forming the benzene ring, and when a is an integer of 2 or 3, they are bonded as follows, respectively, wherein R 1 They may be the same as 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 but omitting the symbol of hydrogen bonded to the carbon forming the benzene ring.

[0058]

[0059] Hereinafter, a compound according to aspects of the present invention and an organic electric element including the compound will be described.

[0060] The present invention provides an organic electrical element, which includes 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 includes an emission layer, wherein the emission layer contains a first host compound represented by Formula 1 and a second host compound represented by Formula 2 as the phosphorescent emission layer.

[0061]

[0062] {In Equation 1 and Equation 2,

[0063] 1)Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 and Ar 7 Each independently selected from hydrogen; deuterium; halogen; C6-C 60 Aryl group; Fluorenyl group; C2-C containing at least one heteroatom of O, N, S, Si, P 60 Heterocyclic group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; C1-C 50 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 Aryloxy group; and -L'-N(R a )(R b ); and Ar 1 and Ar 2 or Ar 3 and Ar 4 can combine with each other to form a ring,

[0064] 2) wherein L' is selected from a single bond; C6-C 60 Arylene group; Fluorenylene group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; and C2-C 60 heterocyclic ring, and R a and R b Each independently selected from C6-C 60 Aryl group; Fluorenyl group; C3-C 60 Aliphatic ring and C6-C 60A fused ring group of an aromatic ring; and a C2-C 60 Heterocyclic groups,

[0065] 3)L 1 , L 2 , L 3 , L 4 and L 5 independently selected from single bonds; C6-C 60 Arylene group; Fluorenylene group; or C2-C containing at least one heteroatom of O, N, S, Si and P 60 heteroarylene groups;

[0066] 4)X 1 It is O or S,

[0067] 5) Ring A and Ring B are independently C6-C 60 Aryl group; or C2-C 20 Heterocyclic groups,

[0068] 6)X 2 Is a single key, NL 6 -Ar 7 , O, S or CR'R",

[0069] wherein R' and R" are independently hydrogen; C6-C 60 Aryl group; Fluorenyl group; C3-C 60 Heterocyclic group; or C1-C 50 an alkyl group; R' and R" may be combined with each other to form a spiro ring,

[0070] 7) x is an integer from 0 to 4, y is an integer from 0 to 3, R c and R d Each independently selected from hydrogen; C6-C 60 Aryl group; Fluorenyl group; C2-C containing at least one heteroatom of O, N, S, Si and P 60 Heterocyclic group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; C1-C 50 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 Aryloxy group; and -L'-N(R a )(R b ),

[0071] 8) wherein the aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, condensed ring group, alkyl group, alkenyl group, alkoxy group and aryloxy group may be substituted by one or more substituents selected from deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C1-C 20 Alkylthio group; C1-C 20 Alkoxy group; C1-C 20 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C6-C 20 Aryl group; C6-C substituted by deuterium 20 Aryl group; Fluorenyl group; C2-C 20 Heterocyclic group; C3-C 20 Cycloalkyl group; C7-C 20 Arylalkyl groups and C8-C 20 Arylalkenyl groups, wherein the substituents may be combined with each other to form a saturated or unsaturated ring, wherein the term "ring" means a C3-C 60 Aliphatic ring or C6-C 60 Aromatic ring or C2-C 60 a heterocyclic group or a condensed ring formed by combining them.

[0072] Furthermore, the present invention provides an organic electric element, wherein A and B in Formula 1 each independently include a compound represented by any one of the following Formulas a-1 to a-7:

[0073]

[0074]

[0075] In formula a-1 to formula a-7,

[0076] Z 1 to Z 48 Each is independently CR c or N,

[0077] Bind to L 1 To L 3 Z 1 to Z 48 is carbon (C),

[0078] R c With R a The same definition as

[0079] *Indicates the position to be condensed.

[0080] The present invention provides an organic electrical device comprising the following compound, wherein L in Formula 1 or Formula 2 1 To L 5 It is represented by any one of the following formulas b-1 to b-13.

[0081]

[0082] In formula b-1 to formula b-13,

[0083] Y is NL 5 -Ar 7 , O, S or CR d R e ,

[0084] L 5 With L 3 The same definition as

[0085] Ar 7 with Ar 5 The same definition as

[0086] R d and R e With R a The same definition as

[0087] a, c, d and e are each independently an integer from 0 to 4, b is an integer from 0 to 6,

[0088] f and g are each independently an integer from 0 to 3, h is an integer from 0 to 2, i is an integer from 0 or 1,

[0089] R 1 、R 2 and R 3 are each independently hydrogen; deuterium; tritium; halogen; cyano group; nitro group; C6-C 60 Aryl group; Fluorenyl group; C2-C2 containing at least one heteroatom of O, N, S, Si or P 60 Heterocyclic group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; C1-C 50 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 an aryloxy group; and -L a -N(R f )(R g ); or when a, b, c, d, e, f and g are 2 or greater, and h is 2 or greater, each of the plurality is the same as or different from each other, and the plurality of R1 or multiple R 2 or multiple R 3 , or adjacent R 1 and R 2 , or adjacent R 2 and R 3 may combine with each other to form an aromatic ring or a heteroaromatic ring,

[0090] Among them, L a Selected from single bond; C6-C 60 Arylene group; Fluorenylene group; C2-C containing at least one heteroatom of O, N, S, Si and P 60 Heterocyclic group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; and C3-C 60 aliphatic hydrocarbon groups;

[0091] R f and R g Each independently selected from C6-C 60 Aryl group; Fluorenyl group; C2-C containing at least one heteroatom of O, N, S, Si and P 60 Heterocyclic group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group,

[0092] Z 49 、Z 50 and Z 51 Each is independently CR h or N,

[0093] Z 4 、Z 50 and Z 51 At least one of them is N,

[0094] R h Selected from hydrogen; deuterium; tritium; halogen; cyano group; nitro group; C6-C 60 Aryl group; Fluorenyl group; C2-C2 containing at least one heteroatom of O, N, S, Si or P 60 Heterocyclic group; C3-C 60 Aliphatic ring and C6-C 60 Aromatic ring fused ring group; C1-C 50 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 aryloxy group; and the adjacent R 1 and Rh They may be combined with each other to form an aromatic ring or a heteroaromatic ring.

[0095] The present invention provides a compound, wherein the first host compound represented by Formula 1 includes a compound represented by any one of Formulas 3 to 5 below.

[0096] Formula 3

[0097]

[0098] Formula 4

[0099]

[0100] Formula 5

[0101]

[0102] In Equations 3 to 5,

[0103] X 1 , A, B, L 1 , L 2 、Ar 2 、Ar 3 and Ar 4 Same as defined above,

[0104] C and D have the same definition as A,

[0105] W is NL 7 -Ar 8 , O, S or CR i R j ,

[0106] L 6 and L 7 With L 4 The same definition as

[0107] Ar 8 with Ar 5 The same definition as

[0108] R i and R j With R a The same definition as

[0109] Two Ar 8 The two Ws are the same or different, the two Cs are the same or different, and the two Ds are the same or different.

[0110] The present invention provides a compound, wherein the first host compound represented by Formula 1 includes a compound represented by Formula 6.

[0111] Formula 6

[0112]

[0113] In Equation 6,

[0114] X 1 、Ar 2 、Ar 3 and Ar 4 Same as defined above,

[0115] Z 1 、Z 2 、Z 3 and Z 4 Each is independently CR c or N,

[0116] Z bound to N 1 to Z 4 is carbon (C),

[0117] R c With R a The same definition as

[0118] W is NL 7 -Ar 8 , O, S or CR i R j ,

[0119] L 7 With L 4 The same definition as

[0120] Ar 8 with Ar 5 The same definition as

[0121] R i and R j With R a The definition is the same.

[0122] In the present invention, as another example, the first host compound represented by Formula 1 includes a compound represented by Formula 7, Formula 8, or Formula 9.

[0123] Formula 7

[0124]

[0125] Formula 8

[0126]

[0127] Formula 9

[0128]

[0129] In equations 7 to 9,

[0130] X 1 、Ar 2 、Ar 3 and Ar 4 , Z 1 、Z 2 、Z 3 、Z 4 and W are the same as defined above.

[0131] In another aspect, the second host compound represented by Formula 2 includes a compound represented by any one of Formulas 10 to 13.

[0132]

[0133] In Equations 10 to 13,

[0134] X 2 , L 3 , L 4 , L 5 、Ar 5 、Ar 6 、R c 、R d , x, y are the same as defined above.

[0135] In addition, the second host compound represented by Formula 2 includes a compound represented by Formula 14.

[0136]

[0137] In formula 14,

[0138] 1)X 2 , L 3 , L 4 , L 5 、Ar 5 、R c 、R d , x, y are the same as defined above,

[0139] 2)X 3 With X 2 The same definition as

[0140] 3) R e and R f With R d and R c The same definition as

[0141] 4) n and y have the same definition, and m and x have the same definition.

[0142] The second host compound represented by Formula 2 includes compounds represented by Formulas 15 to 18.

[0143]

[0144] X 2 , L 3 , L 4 , L 5 、Ar 5 、R c 、R d , x, y, X 3 、R e 、R f , m, and n are the same as defined above.

[0145] In addition, the compound represented by Formula 2 includes a compound represented by Formula 19.

[0146]

[0147] In formula 19,

[0148] A is the following formula A-1 or formula A-2,

[0149]

[0150] X 11 and X 12 are each independently O or S,

[0151] a', b', c' and d' are each independently 0 or 1,

[0152] Ar 11 、Ar 12 、Ar 13 and Ar 14 Each independently is C6-C 18 Aryl group.

[0153] The compound represented by Formula 19 includes a compound represented by Formula 20 or Formula 21 below.

[0154]

[0155] In Equations 20 and 21,

[0156] X 11 、X 12 , a', b', c' and d' are the same as defined above.

[0157] As another example, the compound represented by Formula 2 includes a compound represented by Formula 22.

[0158] These compounds can be mixed with secondary hosts such as biscarbazoles, tertiary amines, and polycyclic heterocyclic compounds for use in the emissive layer.

[0159] <Formula 22>

[0160]

[0161] In formula 22,

[0162] A is the following formula A-1 or formula A-2,

[0163]

[0164]

[0165] Ar 11 It is C6-C 18 aryl groups,

[0166] X 11 、X 12 and X 13 are each independently O or S,

[0167] m' and n' are each independently 0 or 1,

[0168] a' and c' are each independently an integer of any one of 0 to 5,

[0169] d' is an integer of any one of 0 to 4,

[0170] R 21 It is C6-C 18 aryl groups,

[0171] Ar 13 and Ar 14 Each independently is C6-C 18 Aryl group.

[0172] In addition, the compound represented by Formula 22 may be represented by the following Formula 23 or Formula 24.

[0173]

[0174] In Equations 23 and 24,

[0175] X 11 、X 12 、X 13 ,a',c',d',m',n',Ar 13 、Ar 14 、R 21 Same as defined above.

[0176] The compound included in Formula 2 may be mixed with a second host such as biscarbazole, tertiary amine, and polycyclic heterocyclic compound for use in an emission layer, and more specifically, the compound included in Formula 19 or Formula 22 may be used.

[0177] As another example, the first host compound represented by Formula 1 includes Compound 1-1 to Compound 1-175.

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186] As another example, the second host compound represented by Formula 2 includes the following compounds: Compounds 1′-1 to 1′-84, Compounds 2-1 to 2-60, Compounds 3-1 to 3-36, Compounds P-1 to P-120, Compounds 4-1 to 4-12, Compounds 5-1 to 5-20, Compounds 6-1 to 6-16, and Compounds 7-1 to 7-24.

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203] refer to Figure 1 The organic electrical element (100) according to the present invention includes a first electrode (120) and a second electrode (180) formed on a substrate (110), and an organic material layer containing a compound represented by Formula 1 between the first electrode (120) and the second electrode (180). Here, the first electrode (120) may be an anode (positive electrode), and the second electrode (180) may be a cathode (negative electrode). In the case of an inverted organic electrical element, the first electrode may be a cathode, and the second electrode may be an anode.

[0204] The organic material layer may include a hole injection layer (130), a hole transport layer (140), an emission layer (150), an emission auxiliary layer (151), an electron transport layer (160), and an electron injection layer (170) sequentially formed on the first electrode (120). Here, the remaining layers except the emission layer (150) may not be formed. The organic material layer may also include a hole blocking layer, an electron blocking layer, an emission auxiliary layer (151), an electron transport auxiliary layer, a buffer layer (141), etc., and the electron transport layer (160), etc. may function as a hole blocking layer.

[0205] Although not shown, the organic electric element according to the present invention may further include a protective layer formed on at least one side of the first electrode and the second electrode, the side being a side opposite to the organic material layer.

[0206] Otherwise, even if the same core is used, the band gap, electrical properties, interface properties, etc. may vary depending on which substituent is bound to which position. Therefore, the selection of the combination of the core and its associated sub-substituents is also very important. In particular, when the optimal combination of the energy levels and T1 values ​​of each organic material layer and the unique properties of the material (mobility, interface properties, etc.) is achieved, long life and high efficiency can be achieved at the same time.

[0207] The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a PVD (physical vapor deposition) method. For example, an anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and an organic material layer including a hole injection layer (130), a hole transport layer (140), an emission layer (150), an electron transport layer (160), and an electron injection layer (170) is formed thereon. After that, the organic electroluminescent device according to an embodiment of the present invention can be manufactured by depositing a material that can be used as a cathode thereon.

[0208] In addition, an emission auxiliary layer (151) may be formed between the hole transport layer (140) and the emission layer (150), and an electron transport auxiliary layer may be formed between the emission layer (150) and the electron transport layer (160).

[0209] Therefore, the present invention includes at least one hole transport layer between the first electrode and the emission layer, wherein the hole transport layer includes a hole transport layer, an emission assist layer, or both, and wherein the hole transport layer contains the compound represented by Formula 1.

[0210] In addition, the compounds represented by Formula 1 and Formula 2 are mixed in a ratio of any one of 1:9 to 9:1, preferably 1:9 to 5:5, and more preferably 2:8 or 3:7 to be included in the emission layer.

[0211] The present invention may further include a light efficiency enhancement layer formed on at least one of a side of the first electrode opposite to the organic material layer or a side of the second electrode opposite to the organic material layer.

[0212] In addition, the organic material layer is formed by one of a spin coating process, a nozzle printing process, an inkjet printing process, a narrow coating process, a dip coating process or a roll-to-roll process, and since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the method of forming the organic material layer.

[0213] The organic electric element according to an embodiment of the present invention may be a front emission type, a rear emission type, or a double-side emission type according to the material used.

[0214] WOLEDs (white organic light-emitting devices) easily achieve high resolution and excellent processability, while having the advantage of being manufactured using existing LCD color filter technology. Various structures of white organic light-emitting devices, mainly used as backlight devices, have been proposed and patented. Generally, R (red), G (green), and B (blue) light-emitting components are arranged in a side-by-side manner, and the R light-emitting layer, G light-emitting layer, and B light-emitting layer are stacked one above the other. The blue (B) electroluminescence is generated by the organic emission layer, and the color conversion material (CCM) method using the photoluminescence of inorganic phosphors using light from this light and the present invention can be applied to such WOLEDs.

[0215] The present invention also provides an electronic device including a display device having an organic electric element; and a control unit for driving the display device.

[0216] According to another aspect, the present invention provides an electronic device, wherein the organic electrical element is at least one of an OLED, an organic solar cell, an organic photoconductor, an organic transistor, and an element for monochrome or white lighting. In this case, the electronic device may be a wired or wireless communication terminal currently in use or to be used in the future, and encompasses all types of electronic devices, including mobile communication terminals, such as portable phones, personal digital assistants (PDAs), electronic dictionaries, point-to-multipoint devices (PMPs), remote controllers, navigation units, game consoles, various types of televisions, and various types of computers.

[0217] Hereinafter, synthesis examples of the compounds represented by Formula 1 and Formula 2 according to the present invention and preparation examples of the organic electric element according to the present invention will be described in detail by way of examples, but the present invention is not limited to the following examples.

[0218] [Synthesis example 1]

[0219] The final product 1 represented by Formula 1 according to the present invention can be synthesized by the reaction between Sub 1 and Sub 2 as shown in the following Reaction Scheme 1, but is not limited thereto. 1 , A, B, L 1 , L 2 、Ar 1 or Ar 4 can be the same as defined in Equation 1, and Hal 1 It is Br or Cl.

[0220] <Reaction Scheme 1>

[0221]

[0222] I. Synthesis example of Sub 1

[0223] Sub 1 of Reaction Scheme 1 is synthesized through the reaction path of the following Reaction Scheme 2, but is not limited thereto.

[0224] <Reaction Scheme 2>

[0225]

[0226] 1. Synthesis example of Sub 1-1

[0227]

[0228] The starting material Sub 2-1 (15.22 g, 89.94 mmol) was added to a round-bottom flask and dissolved in toluene (750 mL). Sub 1-1-c (CAS Reg. No.: 669773-34-6) (46.14 g, 134.91 mmol), Pd2(dba)3 (2.47 g, 2.70 mmol), P(t-Bu)3 (1.46 g, 7.19 mmol), NaOt-Bu (25.93 g, 269.81 mmol) were added and stirred at 80°C. After the reaction was completed, the reaction mixture was extracted with CH2Cl2 and water. The organic layer was dried over MgSO4 and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 23.61 g of the product. (Yield: 61%)

[0229] 2. Synthesis example of Sub 1-3

[0230]

[0231] To the starting material Sub 2-12 (13.94 g, 63.57 mmol) were added Sub 1-3-e (CAS Reg. No.: 201138-91-2) (31.08 g, 95.35 mmol), Pd2(dba)3 (1.75 g, 1.91 mmol), P(t-Bu)3 (1.03 g, 5.09 mmol), NaOt-Bu (18.33 g, 190.71 mmol), and toluene (530 ml), and the same steps as described in the synthesis method of Sub 1-1 were followed to obtain 19.78 g of the product (yield: 67%).

[0232] 3. Synthesis examples of Sub 1-5

[0233]

[0234] (1) Synthesis of Sub 1-5-a

[0235] The starting material (2-bromo-6-iodophenyl)(ethyl)sulfane (9.94 g, 28.98 mmol) was added to a round-bottom flask and dissolved in THF (100 mL). (4-chlorophenyl)boronic acid (4.53 g, 28.98 mmol), Pd(PPh3)4 (1.00 g, 0.87 mmol), NaOH (2.32 g, 57.96 mmol), and water (50 ml) were added and stirred at 80°C. After the reaction was completed, the reaction mixture was extracted with CH2Cl2 and water. The organic layer was dried over MgSO4 and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 8.55 g of the product. (Yield: 90%)

[0236] (2) Synthesis of Sub 1-5-b

[0237] Acetic acid (90 ml) was added to Sub 1-5-a (8.55 g, 26.09 mmol) obtained in the above synthesis, and 35% hydrogen peroxide (H2O2) (2.66 g, 78.28 mmol) was added and stirred at room temperature. When the reaction was complete, after neutralization with an aqueous NaOH solution, extraction was performed with EA and washed with water. The organic layer was dried over MgSO4 and concentrated. The resulting compound was separated by silica gel column chromatography to obtain 8.70 g of the product. (Yield: 97%)

[0238] (3) Synthesis of Sub 1-5-c

[0239] To Sub 1-5-b (8.70 g, 25.32 mmol) obtained in the above synthesis was added sulfuric acid (H2SO4) (50 ml) and stirred at room temperature. When the reaction was complete, after neutralization with an aqueous NaOH solution, extraction was performed with MC and washed with water. The organic layer was dried over MgSO4 and concentrated. The resulting compound was separated by silica gel column chromatography to obtain 7.16 g of the product. (Yield: 95%)

[0240] (4) Synthesis of Sub 1-5

[0241] The obtained Sub 1-5-c (7.16 g, 24.06 mmol) was added to a round-bottom flask and dissolved in toluene (240 mL). Sub 2-11 (5.28 g, 24.06 mmol), Pd2(dba)3 (0.66 g, 0.72 mmol), P(t-Bu)3 (0.49 g, 2.41 mmol), and NaOt-Bu (4.62 g, 48.12 mmol) were added and stirred at 80°C. After the reaction was complete, the reaction mixture was extracted with CH2Cl2 and water. The organic layer was dried over MgSO4 and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 8.08 g of the product. (Yield: 77%)

[0242] 4. Synthesis Example of Sub 1-17

[0243]

[0244]

[0245] (1) Synthesis of Sub 1-17-a

[0246] To the starting material (4-bromo-2-iodophenyl)(ethyl)sulfane (10.65 g, 31.05 mmol) were added (4-chloro-[1,1'-biphenyl]-2-yl)boronic acid (7.22 g, 31.05 mmol), Pd(PPh3)4 (1.08 g, 0.93 mmol), NaOH (2.48 g, 62.10 mmol), THF (100 ml), and water (50 ml), and the same steps as described in the synthesis method of Sub 1-5-a were followed to obtain 9.90 g of the product (yield: 79%).

[0247] (2) Synthesis of Sub 1-17-b

[0248] Sub 1-17-a (9.90 g, 24.52 mmol) obtained in the above synthesis, acetic acid (80 ml), and 35% hydrogen peroxide (H2O2) (2.50 g, 73.56 mmol) were used in the synthesis of Sub 1-5-b. Thus, 9.78 g of product was obtained (yield: 95%).

[0249] (3) Synthesis of Sub 1-17-c

[0250] Sub 1-17-b (9.78 g, 23.30 mmol) obtained in the above synthesis was used in the synthesis method of Sub 1-5-c. Thus, 7.84 g of the product was obtained (yield: 90%).

[0251] (4) Synthesis of Sub 1-17

[0252] To Sub 1-17-c (7.84 g, 20.98 mmol) obtained in the above synthesis were added Sub 2-78 (7.02 g, 20.98 mmol), Pd2(dba)3 (0.58 g, 0.63 mmol), P(t-Bu)3 (0.42 g, 2.10 mmol), NaOt-Bu (4.03 g, 41.96 mmol) and toluene (210 ml), and the same steps as described in the synthesis method of Sub 1-5 were carried out to obtain 10.79 g of the product. (Yield: 82%).

[0253] 5. Synthesis Example of Sub 1-82

[0254]

[0255] To the starting material Sub 2-1 (16.48 g, 97.38 mmol), Sub 1-82-c (CAS Reg. No.: 83834-10-0) (49.96 g, 146.07 mmol), Pd2(dba)3 (2.68 g, 2.92 mmol), P(t-Bu)3 (1.58 g, 7.79 mmol), NaOt-Bu (28.08 g, 292.15 mmol), and toluene (810 ml) were added, and the same steps as described in the synthesis method of Sub 1-1 were performed to obtain 26.40 g of the product (yield: 63%).

[0256] 6. Synthesis Example of Sub 1-102

[0257]

[0258] (1) Synthesis of Sub 1-102-d

[0259] To the starting material 4-bromo-2-iodophenol (39.85 g, 133.32 mmol) were added (2-chlorophenyl)boronic acid (20.85 g, 133.32 mmol), Pd(PPh3)4 (4.62 g, 4.00 mmol), NaOH (10.67 g, 266.64 mmol), THF (440 ml), and water (220 ml), and the same steps as described in the synthesis method of Sub1-5-a were carried out to obtain 28.73 g of the product (yield: 76%).

[0260] (2) Synthesis of Sub 1-102-e

[0261] To Sub 1-102-d (28.73 g, 101.32 mmol) obtained in the above synthesis was added Pd (OAc) 2 (2.27 g, 10.13 mmol), 3-nitropyridine (1.26 g, 10.13 mmol), BzOOtBu (tert-butyl peroxybenzoate) (39.36 g, 202.65 mmol), C 6 F 6 (hexafluorobenzene) (150 ml), DMI (N, N'-dimethylimidazolidinone) (100 ml) and refluxed at 90 ° C for 3 hours. When the reaction was complete, the temperature of the reaction product was cooled to room temperature, extracted with EA, and washed with water. The organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was separated using a silica gel column to obtain 13.69 g (48%) of the product.

[0262] (3) Synthesis of Sub 1-102

[0263] To Sub 1-102-e (13.69 g, 48.63 mmol) obtained in the above synthesis were added Sub 2-29 (13.39 g, 48.63 mmol), Pd2(dba)3 (1.34 g, 1.46 mmol), P(t-Bu)3 (0.98 g, 4.86 mmol), NaOt-Bu (9.35 g, 97.25 mmol), and toluene (490 ml), and the same steps as described in the synthesis method of Sub 1-5 were performed to obtain 19.67 g of the product. (Yield: 85%).

[0264] 7. Synthesis Example of Sub 1-104

[0265]

[0266] To the starting material Sub 2-1 (9.15 g, 54.04 mmol) were added Sub 1-104-c (CAS Reg. No.: 31574-87-5) (27.73 g, 81.07 mmol), Pd2(dba)3 (1.48 g, 1.62 mmol), P(t-Bu)3 (0.87 g, 4.32 mmol), NaOt-Bu (15.58 g, 162.13 mmol), and toluene (450 ml), and the same steps as described in the synthesis method of Sub 1-1 were performed to obtain 15.12 g of the product. (Yield: 65%).

[0267] 8. Synthesis Example of Sub 1-112

[0268]

[0269]

[0270] (1) Synthesis of Sub 1-112-a

[0271] To the starting material (3-bromo-2-iodophenyl) (and) sulfane (12.73 g, 37.11 mmol) were added (2-chlorophenyl)boronic acid (5.80 g, 37.11 mmol), Pd(PPh3)4 (1.29 g, 1.11 mmol), NaOH (2.97 g, 74.22 mmol), THF (120 ml), and water (60 ml), and the same steps as described in the synthesis method of Sub 1-5-a were followed to obtain 9.48 g of the product (yield: 78%).

[0272] (2) Synthesis of Sub 1-112-b

[0273] Sub 1-112-a (9.48 g, 28.93 mmol) obtained in the above synthesis, acetic acid (95 ml), 35% hydrogen peroxide (H2O2) (2.95 g, 86.80 mmol) were added, and the same steps as described in the synthesis method of Sub 1-5-b were carried out to obtain 9.74 g of the product. (Yield: 98%).

[0274] (3) Synthesis of Sub 1-112-c

[0275] Sub 1-112-b (9.74 g, 28.34 mmol) obtained in the above synthesis and sulfuric acid (H2SO4) (60 ml) were added, and the same steps as described in the synthesis method of Sub 1-5-c were performed to obtain 7.76 g of the product. (Yield: 92%).

[0276] (4) Synthesis of Sub 1-112

[0277] To Sub 1-112-c (7.76 g, 26.08 mmol) obtained in the above synthesis were added Sub 2-1 (4.41 g, 26.08 mmol), Pd2(dba)3 (0.72 g, 0.78 mmol), P(t-Bu)3 (0.53 g, 2.61 mmol), NaOt-Bu (5.01 g, 52.15 mmol), and toluene (260 ml), and the same steps as described in the synthesis method of Sub 1-5 were performed to obtain 5.84 g of the product. (Yield: 58%).

[0278] The compounds belonging to Sub 1 may be the following compounds, but are not limited thereto, and Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values ​​of some compounds belonging to Sub 1.

[0279]

[0280]

[0281]

[0282] [Table 1]

[0283]

[0284]

[0285]

[0286] II. Synthesis of Sub 2

[0287] Sub 2 of Reaction Scheme 3 can be synthesized by the reaction path of the following Reaction Scheme 3 (starting from Korean Patent Registration No. 10-1251451 (registered on April 5, 2013) of the present applicant), but is not limited thereto.

[0288] Z 1 It is Ar 1 or Ar 3 , Z 2 It is Ar 2 or Ar 4 .

[0289] <Reaction Scheme 3>

[0290]

[0291] The compounds belonging to Sub 2 may be the following compounds, but are not limited thereto, and Table 2 shows FD-MS (Field Desorption-Mass Spectrometry) values ​​of some compounds belonging to Sub 2.

[0292]

[0293]

[0294]

[0295] [Table 2]

[0296]

[0297]

[0298] III. Synthesis of the final product

[0299] After dissolving Sub 1 (1 equivalent) with toluene in a round-bottom flask, Sub 2 (1 equivalent), Pd (dba) (0.03 equivalent), (t-Bu) P (1.00 equivalent) and NaOt-Bu (2 equivalents) were stirred at 100° C. When the reaction was completed, the resulting compound was extracted with CH Cl and water, the organic layer was dried over MgSO and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain the final product 1.

[0300] Compound 1-30, Compound 1-32, Compound 1-35, Compound 1-37, Compound 1-67, Compound 1-80, Compound 1-86, Compound 1-94, Compound 1-111, Compound 1-119, and Compound 1-133 of the present invention were manufactured by the synthesis method disclosed in Korean Patent Registration No. 10-1668448 (registered on October 17, 2016) and Korean Patent Registration No. 10-1789998 (registered on October 19, 2017) of the present applicant.

[0301] Synthesis Example of 1.1-1

[0302]

[0303] The obtained Sub 1-1 (5.97 g, 13.87 mmol) was added to a round-bottom flask and dissolved in toluene (140 mL). Sub 2-17 (3.74 g, 13.87 mmol), Pd2(dba)3 (0.38 g, 0.42 mmol), P(t-Bu)3 (0.28 g, 1.39 mmol), and NaOt-Bu (2.67 g, 27.74 mmol) were added and stirred at 100°C. After the reaction was completed, the reaction mixture was extracted with CH2Cl2 and water. The organic layer was dried over MgSO4 and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 6.09 g of the product. (Yield: 71%)

[0304] Synthesis Example 2.1-2

[0305]

[0306] To Sub 1-1 (5.29 g, 12.29 mmol) obtained in the above synthesis, Sub 2-37 (4.32 g, 12.29 mmol), Pd2(dba)3 (0.34 g, 0.37 mmol), P(t-Bu)3 (0.25 g, 1.23 mmol), NaOt-Bu (2.36 g, 24.58 mmol), and toluene (125 ml) were added, and the same steps as described in the synthesis method of 1-1 were performed to obtain 6.81 g of the product. (Yield: 79%).

[0307] Synthesis Example 3.1-4

[0308]

[0309] To Sub 1-3 (6.13 g, 13.20 mmol) obtained in the above synthesis were added Sub 2-41 (4.08 g, 13.20 mmol), Pd2(dba)3 (0.36 g, 0.40 mmol), P(t-Bu)3 (0.27 g, 1.32 mmol), NaOt-Bu (2.54 g, 26.40 mmol), and toluene (130 ml), and the same steps as described in the synthesis method of 1-1 were performed to obtain 7.32 g of the product. (Yield: 80%).

[0310] Synthesis Example of 4.1-10

[0311]

[0312] To Sub 1-5 (5.56 g, 12.75 mmol) obtained in the above synthesis were added Sub 2-43 (4.28 g, 12.75 mmol), Pd2(dba)3 (0.35 g, 0.38 mmol), P(t-Bu)3 (0.26 g, 1.28 mmol), NaOt-Bu (2.45 g, 25.51 mmol), and toluene (130 ml), and the same steps as described in the synthesis method of 1-1 were performed to obtain 8.06 g of the product. (Yield: 86%).

[0313] Synthesis Example of 5.1-24

[0314]

[0315] To Sub 1-17 (6.18 g, 9.85 mmol) obtained in the above synthesis, Sub 2-1 (1.67 g, 9.85 mmol), Pd2(dba)3 (0.27 g, 0.30 mmol), P(t-Bu)3 (0.20 g, 0.99 mmol), NaOt-Bu (1.89 g, 19.71 mmol), and toluene (100 ml) were added, and the same steps as described in the synthesis method of 1-1 were carried out to obtain 5.62 g of the product. (Yield: 75%).

[0316] Synthesis Example of 6.1-122

[0317]

[0318] To Sub 1-82 (5.05 g, 11.73 mmol) obtained in the above synthesis were added Sub 2-49 (4.12 g, 11.73 mmol), Pd2(dba)3 (0.32 g, 0.35 mmol), P(t-Bu)3 (0.24 g, 1.17 mmol), NaOt-Bu (2.26 g, 23.47 mmol), and toluene (120 ml), and the same steps as described in the synthesis method of 1-1 were performed to obtain 7.65 g of the product. (Yield: 93%).

[0319] Synthesis Example of 7.1-125

[0320]

[0321] To Sub 1-82 (5.20 g, 12.08 mmol) obtained in the above synthesis were added Sub 2-40 (3.13 g, 12.08 mmol), Pd2(dba)3 (0.33 g, 0.36 mmol), P(t-Bu)3 (0.24 g, 1.21 mmol), NaOt-Bu (2.32 g, 24.17 mmol), and toluene (120 ml), and the same steps as described in the synthesis method of 1-1 were performed to obtain 6.69 g of the product. (Yield: 91%).

[0322] Synthesis Example of 8.1-141

[0323]

[0324] To Sub 1-102 (6.26 g, 13.15 mmol) obtained in the above synthesis, Sub 2-1 (2.23 g, 13.15 mmol), Pd2(dba)3 (0.36 g, 0.39 mmol), P(t-Bu)3 (0.27 g, 1.32 mmol), NaOt-Bu (2.53 g, 26.30 mmol), and toluene (130 ml) were added, and the same steps as described in the synthesis method of 1-1 were carried out to obtain 6.57 g of the product. (Yield: 82%).

[0325] Synthesis Example of 9.1-146

[0326]

[0327] To Sub 1-104 (6.12 g, 14.22 mmol) obtained in the above synthesis were added Sub 2-83 (5.84 g, 14.22 mmol), Pd2(dba)3 (0.39 g, 0.43 mmol), P(t-Bu)3 (0.29 g, 1.42 mmol), NaOt-Bu (2.73 g, 28.43 mmol), and toluene (140 ml), and the same steps as described in the synthesis method of 1-1 were performed to obtain 8.00 g of the product. (Yield: 74%).

[0328] Synthesis Example of 10.1-158

[0329]

[0330] To Sub 1-112 (5.75 g, 14.90 mmol) obtained in the above synthesis were added Sub 2-29 (4.10 g, 14.90 mmol), Pd2(dba)3 (0.41 g, 0.45 mmol), P(t-Bu)3 (0.30 g, 1.49 mmol), NaOt-Bu (2.86 g, 29.80 mmol), and toluene (150 ml), and the same steps as described in the synthesis method of 1-1 were performed to obtain 6.24 g of the product. (Yield: 67%).

[0331] Meanwhile, the FD-MS values ​​of Compound 1-1 to Compound 1-175 of the present invention prepared according to the above-described Synthesis Examples are shown in Table 3 below.

[0332] [Table 3]

[0333]

[0334]

[0335]

[0336] [Synthesis example 2]

[0337] The compound represented by Formula 2 according to the present invention (final product) may be prepared by reacting Sub 3 and Sub 4 as shown in the following Reaction Scheme 4, but is not limited thereto.

[0338] <Reaction Scheme 4>

[0339]

[0340] Synthesis Example of 1'-1

[0341]

[0342] Sub 1 (1) (34.7 g, 80 mmol) and Sub 2 (1) (30.9 g, 80 mmol), K CO (19.3 g, 140 mmol), Pd (PPh) (2.8 g, 2.4 mmol) were placed in a round-bottom flask, and THF and water were added to dissolve them, followed by reflux at 80° C. for 12 hours. When the reaction was completed, the reaction product was cooled to room temperature, extracted with CH Cl, and washed with water. The organic layer was dried over MgSO and concentrated, and the resulting organic material was separated using a silica gel column to obtain the desired product (37.4 g, 71%).

[0343] Synthesis Example of 1'-6

[0344]

[0345] The synthetic method of 1'-1 was used with Sub 1(6) (44.6 g, 80 mmol) and Sub 2(2) (30.9 g, 80 mmol) to obtain the product (43.2 g, 69%).

[0346] Synthesis Example of 1'-12

[0347]

[0348] The synthetic method of 1'-1 was used with Sub 1 (12) (42.7 g, 80 mmol) and Sub 2 (33) (34.9 g, 80 mmol) to obtain the product (42.7 g, 66%).

[0349] Synthesis Example of 1'-33

[0350]

[0351] The synthetic method of 1′-1 was used with Sub 1 (27) (40.8 g, 80 mmol) and Sub 2 (9) (43.1 g, 80 mmol) to obtain the product (51.0 g, 72%).

[0352] Synthesis Example of 1'-44

[0353]

[0354] The synthetic method of 1′-1 was used with Sub 1 (27) (40.8 g, 80 mmol) and Sub 2 (10) (37.0 g, 80 mmol) to obtain the product (45.4 g, 70%).

[0355] Synthesis Example of 1'-53

[0356]

[0357] The synthetic method of 1'-1 was used with Sub 1 (34) (44.0 g, 80 mmol) and Sub 2 (29) (29.6 g, 80 mmol) to obtain the product (41.2 g, 68%).

[0358] Synthesis Example of 1'-64

[0359]

[0360] The synthetic method of 1'-1 was used with Sub 1 (37) (48.2 g, 80 mmol) and Sub 2 (34) (34.9 g, 80 mmol) to obtain the product (45.6 g, 71%).

[0361] Synthesis Example of 1'-75

[0362]

[0363] The synthetic method of 1'-1 was used with Sub 1 (25) (34.7 g, 80 mmol) and Sub 2 (35) (41.8 g, 80 mmol) to obtain the product (46.4 g, 73%).

[0364] Synthesis Example 2-1

[0365]

[0366] The synthetic method of 1'-1 was used with Sub 1(1) (34.7 g, 80 mmol) and Sub 2(27) (37.0 g, 80 mmol) to obtain the product (42.3 g, 72%).

[0367] Synthesis Example of 2-22

[0368]

[0369] The synthetic method of 1'-1 was used with Sub 1 (38) (50.7 g, 80 mmol) and Sub 2 (24) (37.0 g, 80 mmol) to obtain the product (51.6 g, 69%).

[0370] Synthesis Example of 2-33

[0371]

[0372] The synthetic method of 1′-1 was used with Sub 1 (27) (40.8 g, 80 mmol) and Sub 2 (36) (49.2 g, 80 mmol) to obtain the product (53.9 g, 70%).

[0373] Synthesis Example of 2-40

[0374]

[0375] The synthetic method of 1′-1 was used with Sub 1 (25) (34.7 g, 80 mmol) and Sub 2 (37) (43.1 g, 80 mmol) to obtain the product (44.7 g, 69%).

[0376] Synthesis Example of 2-51

[0377]

[0378] The synthetic method of 1'-1 was used with Sub 1 (33) (36.0 g, 80 mmol) and Sub 2 (38) (35.7 g, 80 mmol) to obtain the product (41.1 g, 70%).

[0379] Synthesis Example of 2-55

[0380]

[0381] The synthetic method of 1'-1 was used with Sub 1 (39) (42.1 g, 80 mmol) and Sub 2 (23) (37.0 g, 80 mmol) to obtain the product (44.9 g, 68%).

[0382] Synthesis Example of 2-58

[0383]

[0384] The synthetic method of 1'-1 was used with Sub 1 (25) (34.7 g, 80 mmol) and Sub 2 (39) (47.9 g, 80 mmol) to obtain the product (45.9 g, 66%).

[0385] Synthesis Example 3-10

[0386]

[0387] The synthetic method of 1'-1 was used with Sub 1(37) (28.6 g, 80 mmol) and Sub 2(10) (37.0 g, 80 mmol) to obtain the product (38.9 g, 74%).

[0388] Synthesis Example of P-41

[0389]

[0390] Core 2 (5 g, 14 mmol), Sub 1 (4.6 g, 15.2 mmol), Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (5.7 g, 41.3 mmol), THF, and water were added to a round-bottom flask and stirred at 90° C. After the reaction was complete, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 4.6 g of P-41. (Yield: 57%)

[0391] Synthesis Example of P-91

[0392]

[0393] Core 1 (5 g, 14 mmol), Sub 9 (5.8 g, 15.4 mmol), Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (5.8 g, 41.9 mmol), THF, and water were added to a round-bottom flask and stirred at 90° C. After the reaction was complete, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 4.7 g of P-91. (Yield: 51%)

[0394] Synthesis Example of P-106

[0395]

[0396] Core 1 (5 g, 14 mmol), Sub 16 (5.8 g, 15.4 mmol), Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (5.8 g, 41.9 mmol), THF, and water were added to a round-bottom flask and stirred at 90° C. After the reaction was complete, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 5.8 g of P-106. (Yield: 63%)

[0397] Synthesis Example of P-146

[0398]

[0399] Core 1 (5 g, 14 mmol), Sub 2 (5.8 g, 15.4 mmol), Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (5.8 g, 41.9 mmol), THF, and water were added to a round-bottom flask and stirred at 90° C. After the reaction was complete, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 4.7 g of P-146. (Yield: 51%)

[0400] Synthesis Example of P-4

[0401]

[0402] Core 1 (5 g, 14 mmol), Sub 6 (5.9 g, 15.4 mmol), Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (5.8 g, 41.9 mmol), THF, and water were added to a round-bottom flask and stirred at 90° C. After the reaction was complete, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 6.1 g of P-4. (Yield: 66%)

[0403] Synthesis Example 4-1

[0404]

[0405] The obtained Sub 1-1' (50 g, 98.04 mmol) was added to a round-bottom flask and dissolved in toluene (359 mL). Sub 2-1' (52.51 g, 117.65 mmol), Pd(PPh3)4 (4.53 g, 3.92 mmol), K2CO3 (40.65 g, 294.12 mmol), and water (180 mL) were added and stirred at reflux. After the reaction was complete, the reaction mixture was extracted with CH2Cl2 and water. The organic layer was dried over MgSO4 and concentrated. Thereafter, the concentrate was passed through a silica gel column and recrystallized to obtain 64.61 g of the product. (Yield: 83%)

[0406] Synthesis Example 5-3

[0407]

[0408] The obtained Sub 1-1 (60 g, 133.35 mmol) was added to a round-bottom flask and dissolved with toluene (489 mL), and Sub 2-3 (58.28 g, 160.01 mmol), Pd(PPh 3 ) 4 (6.16 g, 5.33 mmol), K 2 CO 3 (55.29 g, 400.04 mmol) and water (244 mL) were added and stirred under reflux. After the reaction was completed, the resulting mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 73.40 g of the product. (Yield: 75%)

[0409] Synthesis Example 7-8

[0410]

[0411] 2-Chloro-4-phenyl-6-(7-phenyldibenzo[b,d]furan-2-yl)-1,3,5-triazine (58 g, 133.35 mmol) was added to a round-bottom flask and dissolved with THF (489 mL), and [1,1':3',1":3",1"'-tetraphenyl]-3-ylboronic acid (56 g, 160.01 mmol), Pd(PPh3)4 (6.16 g, 5.33 mmol), K2CO3 (55.29 g, 400.04 mmol) and water (244 mL) were added and stirred under reflux. After the reaction was completed, the resulting mixture was extracted with ether and water. The organic layer was dried over MgSO4 and concentrated. The resulting compound was separated by silica gel column chromatography and recrystallized to obtain 71.33 g of the product. (Yield: 76%)

[0412] [Table 4]

[0413]

[0414]

[0415]

[0416]

[0417]

[0418]

[0419] Manufacturing and evaluation of organic electrical components

[0420] Example 1) Fabrication and evaluation of green organic light-emitting diodes

[0421] First, N 1 -(naphthalen-2-yl)-N 4 ,N 4 -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N 1 -phenylbenzene-1,4-diamine (hereinafter abbreviated as 2-TNATA) is vacuum deposited to form a hole injection layer with a thickness of 60nm. 4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter abbreviated as -NPD) is vacuum deposited to form a hole transport layer with a thickness of 60nm. Subsequently, a 6:4 mixture of the compound of the present invention represented by Formula 1 and Formula 2 is used as the main body, and by doping Ir(ppy)3[tris(2-phenylpyridine)-iridium] with 95:5 weight as a dopant, an emission layer with a thickness of 30nm is deposited on the hole transport layer. (1,1'-biphenyl)-4-root)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as BAlq) is vacuum deposited to a thickness of 10nm as a hole blocking layer, and tris(8-hydroxyquinoline)aluminum (hereinafter abbreviated as Alq3) is deposited to a thickness of 40nm as an electron transport layer. Thereafter, alkali metal halide (LiF) was vacuum-deposited to a thickness of 0.2 nm as an electron injection layer, and Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an OLED.

[0422] A forward bias DC voltage was applied to the OLEDs manufactured in Examples and Comparative Examples, and electroluminescence (EL) properties were measured using PR-650 manufactured by Photoresearch Co., and a lifetime measurement device manufactured by McScience Inc. was used at 5000 cd / m 2 The T95 lifetime was measured at a reference brightness of . The following table shows the results of device fabrication and evaluation.

[0423] [Comparative Example 1]

[0424] An organic electroluminescent device was manufactured in the same manner as in Example 1, except that only Comparative Compound 1 was used as a host.

[0425] [Comparative Example 2]

[0426] An organic electroluminescent device was manufactured in the same manner as in Example 1, except that only Comparative Compound 2 was used as a host.

[0427] [Comparative Example 3]

[0428] An organic electroluminescent device was manufactured in the same manner as in Example 1, except that only Comparative Compound 3 was used as a host.

[0429] [Comparative Example 4, Comparative Example 5]

[0430] An organic electroluminescent device was manufactured in the same manner as in Example 1, except that only the compound represented by Formula 2 was used as a host.

[0431] [Comparative Example 6]

[0432] An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 and the compound represented by Formula 2 were mixed and used as a host.

[0433] [Comparative Example 7]

[0434] An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 2 and the compound represented by Formula 2 were mixed and used as a host.

[0435] [Comparative Example 8]

[0436] An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 3 and the compound represented by Formula 2 were mixed and used as a host.

[0437]

[0438] [Table 5]

[0439]

[0440]

[0441] As can be seen from the results of Table 5, compared with the device using a single compound (Comparative Example 1 to Comparative Example 5) or the device mixed with the comparative compound (Comparative Example 6 to Comparative Example 8), when the material of the organic electroluminescent device of the present invention represented by Formula 1 and Formula 2 is mixed and used as a phosphorescent host (Example 1 to Example 56), significantly improved driving voltage, efficiency and lifespan. When tertiary amine compound, comparative compound 2 and comparative compound 3 are used as the phosphorescent host of a single material, driving, efficiency and lifespan all show poor results, and comparative compound 1 is the best in terms of lifespan. When the compound represented by Formula 2 is used alone, compared with the comparative compound, there is a slight increase in driving voltage and efficiency, but when comparative compound 1 to comparative compound 3 are mixed with the compound represented by Formula 2 and used as a phosphorescent host, all effects are improved compared with being used as a single compound. When the comparative compound 1 with strong hole transport ability is mixed with the compound represented by Formula 2, it shows a significant effect in terms of lifespan, and when the tertiary amine compound, comparative compound 2 and comparative compound 3 are mixed, it shows a significant effect in terms of driving. From this result alone it can be seen that even compounds with poor performance as a single host can have improved effects when mixed with compounds with good charge balance.

[0442] Furthermore, it was confirmed that Examples 1 to 56 in which the compounds of Formula 1 and Formula 2 of the present invention were mixed and used as a host were significantly improved compared to the cases of Comparative Examples 1 to 8.

[0443] Based on the above experimental results, the inventors determined that in the case of a mixture of the compound of Formula 1 and the compound of Formula 2, each compound has a new property in addition to the property of the compound, and measured the PL lifespan of the compound of Formula 1, the compound of Formula 2 and the mixture of the present invention, respectively. As a result, it was confirmed that when the compounds of the present invention (Formula 1 and Formula 2) were mixed, unlike the single compound, a new PL wavelength was formed, and the reduction and disappearance time of the newly formed PL wavelength was less than about 60 times to about 360 times the reduction and disappearance time of each of the compounds of Formula 1 and Formula 2. It is believed that when mixed with the compound of the present invention, not only electrons and holes move through the energy levels of each compound, but also electrons, holes, or energy transfer in a new region (exciplex) with a new energy level formed due to mixing also increase efficiency and lifespan. As a result, when using the mixture of the present invention, the mixed film is an important example of showing exciplex energy transfer and luminescence processes.

[0444] Furthermore, the combination of the present invention is superior to Comparative Examples 6 to 8, in which comparative compounds are mixed and used as phosphorescent hosts, because the hole characteristics are improved by using the compound represented by Formula 1, in which one more amine group is added to Comparative Compounds 2 and 3, and has a good electrochemical synergistic effect with the compound represented by Formula 2, which has strong electronic properties. Therefore, the charge balance between holes and electrons in the emission layer is increased, allowing good light emission within the emission layer rather than at the hole transport layer interface, thereby reducing degradation at the HTL interface and maximizing the driving voltage, efficiency, and life of the entire device.

[0445] Example 2) Production and evaluation of green organic light-emitting diodes by mixing ratio

[0446] [Table 6]

[0447]

[0448] As shown in Table 6, by using a mixture of the compound of the present invention of different ratios (7: 3, 5: 5, 4: 6, 3: 7), the device was manufactured and measured in the same manner as in Example 1. As a result of measuring by ratio, in the case of 7: 3, it is similar to the result of Example 1 measured at 6: 4, but in the case of 5: 5, 4: 6 and 3: 7 where the ratio of the first host is reduced, the results of driving voltage, efficiency and lifespan gradually decrease. This can be explained as, because when an appropriate amount of a compound represented by Formula 1 with strong hole properties is mixed, such as with 7: 3 and 4: 6, the charge balance in the emission layer is maximized.

[0449] Example 3) Fabrication and Evaluation of Green Organic Light Emitting Diodes

[0450] First, N 1 -(naphthalen-2-yl)-N 4 ,N 4 -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N 1-phenylbenzene-1,4-diamine (hereinafter abbreviated as 2-TNATA) is vacuum deposited to form a hole injection layer with a thickness of 60nm. Subsequently, 4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter abbreviated as NPD) is vacuum deposited on the film to form a hole transport layer with a thickness of 60nm. Subsequently, the compound of the present invention represented by Formula 19 and Formula 21 is used as the main body, and by doping Ir(ppy)3[tris(2-phenylpyridine)-iridium] with 5:5 weight as a dopant, an emission layer with a thickness of 30nm is deposited on the hole transport layer. (1,1'-biphenyl)-4-root)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as BAlq) is vacuum deposited to a thickness of 10nm as a hole blocking layer, and tris(8-hydroxyquinoline)aluminum (hereinafter abbreviated as Alq3) is deposited to a thickness of 40nm as an electron transport layer. Thereafter, alkali metal halide (LiF) was vacuum-deposited to a thickness of 0.2 nm as an electron injection layer, and Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an OLED.

[0451] A forward bias DC voltage was applied to the OLEDs manufactured in the examples and comparative examples, and electroluminescence (EL) was measured using PR-650 manufactured by Photoresearch Co., and a lifetime measurement device manufactured by McScience Inc. was used at 5000 cd / m 2 The T95 lifetime was measured at a reference brightness of . The following table shows the results of device fabrication and evaluation.

[0452] [Comparative Example 9-Comparative Example 12]

[0453] Organic electroluminescent devices were manufactured in the same manner as in Example 3, except that Comparative Compounds 4 to 7 were respectively used as a single host.

[0454]

[0455] [Table 7]

[0456]

[0457]

[0458] As described above, it can be seen that compared with the organic electroluminescent device using comparative compound, the organic electroluminescent device using the compound of the present invention as phosphorescent host significantly improves all driving voltages, efficiency and lifespan.The difference between comparative compound 4 and the present invention is the presence or absence of the linking group of metaphenylene, and comparative compound 5 and comparative compound 6 difference is in the presence or absence of the secondary substituent such as phenyl or biphenyl in dibenzofuran, and comparative compound 7 difference is the substituent number of dibenzofuran.Comprehensive judgment device data, confirmed that the linking group of metaphenylene has the effect of improving efficiency, and the secondary substituent of particularly dibenzofuran has the effect of significantly improving lifespan.This means that, even with identical core, the energy level (HOMO level, LUMO level, T1 level) of compound is significantly different due to specific substituent being substituted, and this difference of the physical property of compound serves as the main factor (for example, energy balance) of improving device performance during device deposition, shows that these different device results can be obtained.

[0459] Although exemplary embodiments of the present invention have been described for illustrative purposes, it will be understood by those skilled in the art that various modifications, additions, and substitutions are possible without departing from the scope and spirit of the present invention as disclosed in the appended claims. Therefore, the embodiments disclosed in the present invention are intended to illustrate the scope of the technical concept of the present invention, and the scope of the present invention is not limited by the embodiments.

[0460] The scope of the present invention should be interpreted based on the appended claims, and should be interpreted as all technical concepts included in the scope equivalent to the claims belong to the present invention.

[0461] Industrial Applicability

[0462] According to the present invention, an organic device having excellent device characteristics of high brightness, high luminescence, and long life can be manufactured, and thus has industrial applicability.

Claims

1. Compound represented by Formula 19 In formula 19, A is the following formula A-1 or formula A-2, X 11 and X 12 are each independently O or S, a', b', c' and d' are each independently 0 or 1, Ar 11 、Ar 12 、Ar 13 and Ar 14 Each independently is C6-C 18 Aryl group.

2. The compound according to claim 1, wherein the compound represented by Formula 19 comprises a compound represented by the following Formula 20 or Formula 21, In Equations 20 and 21, X 11 、X 12 , a', b', c' and d' are the same as defined in claim 1.

3. The compound according to claim 1, wherein the compound represented by Formula 19 is any one of the following compounds:

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