WO2020130394A1 - Organic electric element comprising compound for organic electric element, and electronic device therefor - Google Patents
Organic electric element comprising compound for organic electric element, and electronic device therefor Download PDFInfo
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- WO2020130394A1 WO2020130394A1 PCT/KR2019/016423 KR2019016423W WO2020130394A1 WO 2020130394 A1 WO2020130394 A1 WO 2020130394A1 KR 2019016423 W KR2019016423 W KR 2019016423W WO 2020130394 A1 WO2020130394 A1 WO 2020130394A1
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- ZXVFTTRBWPOSLL-UHFFFAOYSA-N thieno[3,2-b][1]benzofuran Chemical compound O1C2=CC=CC=C2C2=C1C=CS2 ZXVFTTRBWPOSLL-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
Definitions
- the present invention relates to an organic electric element comprising a compound for an organic electric element and its electronic device.
- the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material.
- An organic electric device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween.
- the organic material layer is often composed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, 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 the organic material layer in the organic electric device 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, depending on the function.
- the luminescent material may be classified into a high molecular weight type and a low molecular weight type according to the molecular weight, and may be classified into a fluorescent material derived from the singlet excited state of the electron and a phosphorescent material derived from the triplet excited state of the electron according to the light emission mechanism. have.
- the luminescent material may be divided into blue, green, and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color according to the luminous color.
- a host/dopant system may be used as a luminescent material.
- the principle is that when a small amount of the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with the light emitting layer, excitons generated in the light emitting layer are transported to the dopant to produce light with high efficiency.
- the wavelength of the host moves to the wavelength of the dopant, light of a desired wavelength can be obtained according to the type of dopant used.
- Efficiency, life, and driving voltage are related to each other.
- the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic substances due to Joule heating generated during driving decreases, and as a result, It shows a tendency to increase life.
- simply improving the organic layer does not maximize efficiency. This is because long life and high efficiency can be achieved at the same time when the energy level and T 1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined. .
- An object of the present invention is to provide an organic electric device and an electronic device capable of lowering the driving voltage of the device and improving the luminous efficiency and lifetime of the device.
- the present invention provides an organic electric device comprising a first compound represented by the following formula (1) and a second compound represented by the following formula (2) in the light emitting layer.
- the present invention provides an electronic device including the organic electric element.
- the driving voltage of the device can be lowered, and the luminous efficiency and lifetime of the device can be improved.
- FIG. 1 is an exemplary view of an organic electroluminescent device according to the present invention.
- organic electrical element 110 substrate
- aryl group and arylene group used in the present invention have 6 to 60 carbon atoms, respectively, and are not limited thereto unless otherwise specified.
- an aryl group or an arylene group may include a monocyclic, ring aggregate, several conjugated ring systems, spiro compounds, and the like.
- the aryl group may include a fluorenyl group and the arylene group may include a fluorenylene group.
- fluorenyl group or "fluorenylene group” used in the present invention means a monovalent or divalent functional group in which R, R'and R" are both hydrogen in the following structures, unless otherwise specified.
- Substituted fluorenyl group” or “substituted fluorenylene 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 bonded carbon. It includes the case where a compound was formed as a spy together.
- spyro compound as used in the present invention has a'spyro linkage', and a spiro linkage refers to a linkage formed by two rings sharing only one atom. At this time, the atoms shared in the two rings are called'spyro atoms', and these are'monospyro-','dispiro-','trispyro' depending on the number of spy atoms in a compound, respectively. It is called a compound.
- heterocyclic group used in the present invention includes aromatic rings such as “heteroaryl group” or “heteroarylene group”, as well as non-aromatic rings, and each carbon number containing one or more heteroatoms unless otherwise specified. It means a ring of 2 to 60, but is not limited thereto.
- heteroatom refers to N, O, S, P or Si, unless otherwise specified, and the heterocyclic group is a monocyclic, ring aggregate, heterozygous multiple ring system, spy containing heteroatoms. Means a compound and the like.
- aliphatic ring group used in the present invention means a cyclic hydrocarbon excluding aromatic hydrocarbons, and includes monocyclic, ring aggregates, conjugated multiple ring systems, spiro compounds, and the like, unless otherwise indicated. It means a 3 to 60 ring, but is not limited thereto. For example, even when the aromatic ring benzene and the non-aromatic ring cyclohexane are fused, it corresponds to the aliphatic ring.
- the'group name' corresponding to an aryl group, an arylene group, a heterocyclic group, etc. exemplified as an example of each symbol and its substituent may describe'the name of a group reflecting a singer', but is described as a'parent compound name' You may.
- the monovalent'group' is'phenanthryl', and the divalent group can be classified as a singer such as'phenanthrylene', etc.
- the parent compound name may be described as'phenanthrene'.
- pyrimidine it can be described as'pyrimidine' regardless of the singer, or in the case of monovalent pyrimidinyl group, in the case of divalent pyrimidineylene, etc., as the'group name' of the corresponding singer. have.
- a number, an alphabet, etc. indicating a position may be omitted.
- pyrido[4,3-d]pyrimidine as pyridopyrimidine
- benzofuro[2,3-d]pyrimidine as benzofuropyrimidine
- 9,9-dimethyl-9H-flu Oren can be described as dimethylfluorene or the like. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be described as benzoquinoxaline.
- the substituent R 1 means non-existent, that is, when a is 0, it means that hydrogen is bonded to all the carbons forming the benzene ring.
- the formula or compound may be omitted.
- a is an integer of 1
- one substituent R 1 is bound to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3, for example, it can be bonded as follows, and a is 4 to 6 Even in the case of an integer, it is bonded to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R 1 may be the same or different.
- the rings formed by bonding with adjacent groups are C 6 ⁇ C 60 aromatic ring groups; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of 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; And combinations thereof.
- a component such as a layer, film, region, plate, etc. is said to be “above” or “on” another component, it is not only when the other component is “directly above”, but also with another component in the middle. It should be understood that the case may be included. Conversely, it should be understood that when a component is said to be “just above” another part, it means that there is no other part in between.
- FIG. 1 is an exemplary view of an organic electric device according to an embodiment of the present invention.
- an organic electric device 100 includes a first electrode 120, a second electrode 180, and a first electrode 120 formed on a substrate 110. Between the second electrode 180 includes an organic material layer containing the compound according to the present invention.
- the first electrode 120 may be an anode (anode)
- the second electrode 180 may be a cathode (cathode)
- the first electrode may be a cathode and the second electrode may be an anode.
- the organic material layer may 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 sequentially stacked on the first electrode 120. . At this time, at least one of these layers may be omitted, or may further include a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, etc., and the electron transport layer 160, etc. It can also serve as a hole blocking layer.
- the organic electric device may further include a protective layer or a light efficiency improving layer.
- the light efficiency improving layer may be formed on a surface of both surfaces of the first electrode that does not contact the organic material layer or a surface of both surfaces of the second electrode that does not contact the organic material layer.
- the compound according to an embodiment of the present invention applied to the organic layer is a hole injection layer 130, a hole transport layer 140, a light emitting auxiliary layer 151, an electron transport auxiliary layer, an electron transport layer 160, an electron injection layer ( 170), a host or a dopant of the light emitting layer 150, or may be used as a material for a light efficiency improving layer, but preferably a mixture of a compound represented by Formula 1 and a compound represented by Formula 2 of the present invention of the light emitting layer Used as a host.
- the band gap, electrical characteristics, and interfacial characteristics may vary depending on which substituent is attached to which position, and thus, the selection of the core and the combination of sub-substituents coupled thereto. It is necessary to study, especially when the energy level and T 1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined, long life and high efficiency can be achieved simultaneously.
- the organic electroluminescent device may be manufactured using various deposition methods. It may be manufactured using a deposition method such as PVD or CVD, for example, by depositing a metal or conductive metal oxide or an alloy thereof on a substrate to form the anode 120, and a hole injection layer 130 thereon , After forming an organic material layer including the hole transport layer 140, the light emitting layer 150, the electron transport layer 160 and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon. have.
- the light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150
- the electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160.
- the organic material layer is a solution process or a solvent process that is not a deposition method 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, a screen It can be produced with fewer layers by a printing process or a method such as thermal transfer. Since the organic material layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the formation method.
- the organic electric device may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.
- the organic electroluminescent device may be selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a monochromatic lighting device, and a quantum dot display device.
- 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 for controlling the display device.
- the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game machines, various TVs, and various computers.
- the organic electric device 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 a phosphorescent emission layer, and the phosphorescent emission layer
- X 1 is O or S.
- Ar 1 and Ar 2 are independently of each other C 6 ⁇ C 60 aryl group; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 60 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; C 2 ⁇ C 20 alkenyl group; C 2 ⁇ C 20 alkynyl group; C 1 ⁇ C 30 Alkoxy group; And C 6 ⁇ C 30 It may be selected from the group consisting of an aryloxy group.
- Ar 1 and Ar 2 are aryl groups, preferably C 6 to C 30 aryl groups, more preferably C 6 to C 18 aryl groups, such as phenyl, biphenyl, naphthyl, terphenyl, phenanthrene, Pyrene, triphenylene, and the like.
- Ar 1 and Ar 2 are heterocyclic groups, preferably C 2 to C 30 heterocyclic groups, more preferably C 2 to C 18 heterocyclic groups, such as pyridine, quinoline, isoquinoline, carbazole, phenyl Carbazole, dibenzothiophene, dibenzofuran, dibenzodioxin, and the like.
- Ar 1 and Ar 2 are fluorenyl groups, it may be 9,9-diphenylfluorene, 9,9-dimethylfluorene, and the like.
- Ar 1 and Ar 2 are an aliphatic ring group, preferably an aliphatic ring of C 3 to C 30 , more preferably an aliphatic ring of C 3 to C 12 , such as cyclohexane, cyclohexylcyclohexane, and the like.
- Ar 1 and Ar 2 are alkyl groups, preferably C 2 to C 10 alkyl groups, such as methyl, t-butyl, and the like.
- Ar 1 and Ar 2 are alkenyl groups, preferably a C 2 to C 10 alkenyl group, for example, ethene, propene, or the like.
- L 1 to L 3 are each independently a single bond; C 6 ⁇ C 60 Arylene group; Fluorylene group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 60 aliphatic ring group; And it may be selected from the group consisting of a fused ring of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60.
- L 1 to L 3 are arylene groups, preferably an arylene group of C 6 to C 30 , more preferably an arylene group of C 6 to C 18 , such as phenyl, biphenyl, naphthyl, terphenyl, etc. .
- L 1 to L 3 are heterocyclic groups, preferably C 2 to C 30 heterocyclic groups, more preferably C 2 to C 18 heterocyclic groups, such as carbazole, phenylcarbazole, dibenzofuran, Dibenzothiophene, and the like.
- R 1 is hydrogen; heavy hydrogen; halogen; Cyano group; C 6 ⁇ C 60 Aryl group; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 60 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; C 2 ⁇ C 20 alkenyl group; C 2 ⁇ C 20 alkynyl group; C 1 ⁇ C 30 Alkoxy group; C 6 ⁇ C 30 Aryloxy group; And -L'-N (R a ) (R b ); is selected from the group consisting of, adjacent groups may be bonded to each other to form a ring.
- a is an integer of 0-9, and when a is an integer of 2 or more, a plurality of R 1 s are the same as or different from each other.
- Rings formed by bonding adjacent R 1 to each other include an aromatic ring group of C 6 to C 60 ; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 60 aliphatic ring group; Or it may be a fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60.
- adjacent R 1 is bonded to each other to form an aromatic ring, preferably an aromatic ring of C 6 ⁇ C 30 , more preferably an aromatic ring of C 6 ⁇ C 14 , such as benzene, naphthalene, phenanthrene, etc.
- the same aromatic ring can be formed.
- R 1 is an aryl group, preferably an aryl group of C 6 to C 30 , more preferably an aryl group of C 6 to C 18 , such as phenyl, naphthyl, biphenyl, terphenyl, phenanthrene, etc. .
- L' is independently of each other a single bond; C 6 ⁇ C 60 Arylene group; Fluorylene group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 60 aliphatic ring group; And fused ring groups of the aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; may be selected from the group consisting of.
- R a and R b are independently of each other C 6 ⁇ C 60 aryl group; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 60 aliphatic ring group; And fused ring groups of the aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; may be selected from the group consisting of.
- the compound derived from Formula 1-1 below in Formula 1 may be excluded.
- Ar 1 and Ar 2 are independently of each other C 6 ⁇ C 18 aryl group; Fluorenyl group; C 2 ⁇ C 16 heterocyclic group containing at least one heteroatom of 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; C 2 ⁇ C 20 alkenyl group; C 2 ⁇ C 20 alkynyl group; C 1 ⁇ C 30 Alkoxy group; And C 6 ⁇ C 30 It is selected from the group consisting of an aryloxy group.
- Chemical Formula 1 may be represented by one of the following Chemical Formulas 1-A to 1-E.
- Ar 1 , Ar 2 , L 1 to L 3 , X 1 , R 1 , a are as defined in Formula 1.
- X 2 and X 3 are each independently O or S.
- R 4 , R 8 and R 9 are independently of each other hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; C 6 ⁇ C 20 aryl group; Fluorenyl group; C 2 ⁇ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 20 aliphatic ring group; C 3 ⁇ C 20 aliphatic ring and C 6 ⁇ C 20 aromatic ring fused ring group; C 1 ⁇ C 20 alkyl group; C 2 ⁇ C 20 alkenyl group; C 2 ⁇ C 20 alkynyl group; C 1 ⁇ C 20 Alkoxy group; C 6 ⁇ C 30 Aryloxy group; And -L a -N(R a )(R b ); and adjacent groups may combine with each other to form a ring.
- d1 is an integer from 0 to 7
- i and j are integers from 0 to 6, and when each of them is an integer of 2 or more, each of a plurality of R 4, each of a plurality of R 8, and each of a plurality of R 9 are the same or different from each other Do.
- L a is a single bond independently of each other; C 6 ⁇ C 20 Arylene group; Fluorylene group; C 2 ⁇ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 20 aliphatic ring group; And combinations thereof.
- R a and R b are independently of each other C 6 ⁇ C 20 aryl group; Fluorenyl group; C 2 ⁇ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 20 aliphatic ring group; And combinations thereof.
- the formula 1-A may be represented by one of the following formulas 1-A-1 to 1-A-6.
- Each symbol in Formula 1, Formula 1-A to 1-E, and Formula 1-A-1 to 1-A-6 may be further substituted.
- Ar 1 , Ar 2 , L 1 ⁇ L 3 , L', L a , R 1 , R 4 , R 8 , R 9 , R a , R b , R a , R b , and adjacent groups are bonded to each other Rings formed by deuterium, respectively; halogen; A silane group unsubstituted or substituted with an alkyl group of C 1 -C 20 or an aryl group of C 6 -C 20 ; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C 1 -C 20 alkylthio; C 1 -C 20 Alkoxy group; C 6 -C 20 Aryloxy group; C 1 -C 20 alkyl group; Alkenyl group of C 2 -C 20 ; Alkynyl group of C 2 -C 20 ; C 6 -C
- the compound represented by Formula 1 may be one of the following compounds, but is not limited thereto.
- Ar 4 to Ar 6 are independently of each other C 6 ⁇ C 60 aryl group; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 60 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; C 2 ⁇ C 20 alkenyl group; C 2 ⁇ C 20 alkynyl group; C 1 ⁇ C 30 Alkoxy group; And C 6 ⁇ C 30 It may be selected from the group consisting of an aryloxy group.
- Ar 4 to Ar 6 are aryl groups, preferably, C 6 to C 30 aryl groups, more preferably C 6 to C 18 aryl groups, such as phenyl, biphenyl, naphthyl, terphenyl, phenanthrene Etc.
- Ar 4 to Ar 6 are heterocyclic groups, preferably C 2 to C 30 heterocyclic groups, more preferably C 2 to C 20 heterocyclic groups, such as dibenzothiophene, dibenzofuran, benzo Thienopyrimidine, carbazole, phenylcarbazole, benzonaphthothiophene, benzofurothiophene, dynaphthothiophene, dynaphthofuran, and the like.
- heterocyclic groups preferably C 2 to C 30 heterocyclic groups, more preferably C 2 to C 20 heterocyclic groups, such as dibenzothiophene, dibenzofuran, benzo Thienopyrimidine, carbazole, phenylcarbazole, benzonaphthothiophene, benzofurothiophene, dynaphthothiophene, dynaphthofuran, and the like.
- Ar 4 to Ar 6 are fluorenyl groups, it may be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spirobifluorene, or the like.
- L 4 to L 6 are each independently a single bond; C 6 ⁇ C 60 Arylene group; Fluorylene group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 60 aliphatic ring group; And combinations thereof.
- L 4 to L 6 are arylene groups, preferably C 6 to C 30 arylene groups, more preferably C 6 to C 18 arylene groups, such as phenylene, biphenyl, naphthyl, terphenyl, etc. Can.
- L 4 to L 6 are fluorenyl groups, 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spyrobifluorene, and the like may be used.
- the Chemical Formula 2 may be represented by one of the following Chemical Formulas 2-A to 2-I.
- Ar 5 , Ar 6 , L 4 to L 6 are the same as defined in Formula 2, and Y 1 to Y 3 are each independently O, S, C(R') (R").
- R 11 to R 16 , R'and R" are independently of each other hydrogen; deuterium; halogen; C 1 -C 20 alkyl group or C 6 -C 20 aryl group unsubstituted or substituted silane group; cyano group; nitro group ; C 1 -C 20 alkoxy group; C 6 -C 20 aryloxy group; C 1 -C 20 alkyl group; C 2 -C 20 alkenyl group; C 2 -C 20 alkynyl group; C 6 -C Aryl group of 20 ; fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; and aliphatic ring of C 3 -C 20 Group; selected from the group consisting of, adjacent groups can be bonded to each other to form a ring, R'and R" can be bonded to each other to form a ring.
- R'and R" combine with each other to form
- Rings formed by bonding adjacent groups to each other include an aromatic ring group of C 6 ⁇ C 60 ; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 60 aliphatic ring group; Or it may be a fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60.
- neighboring R 1 , neighboring R 12 , neighboring R 13 , neighboring R 14 , neighboring R 15 , neighboring R 16, or R'and R" are bonded to each other to form an aromatic ring.
- an aromatic ring of C 6 to C 30 preferably an aromatic ring of C 6 to C 14 , for example, an aromatic ring such as benzene, naphthalene, and phenanthrene can be formed.
- b is an integer from 0 to 4, and when b is an integer of 2 or more, each of a plurality of R 11, each of a plurality of R 13, and each of a plurality of R 15 are the same or different from each other, c is an integer from 0 to 3, c is In the case of an integer of 2 or more, each of the plurality of R 12, each of the plurality of R 14, and each of the plurality of R 16 are the same or different from each other.
- the Ar 4 ⁇ Ar 6 , L 4 ⁇ L 6 , R 11 ⁇ R 16 , R', R" and the ring formed by bonding adjacent groups are each deuterium; halogen; C 1 -C 20 alkyl group or C 6- Silane group unsubstituted or substituted with C 20 aryl group; siloxane group; boron group; germanium group; cyano group; nitro group; C 1 -C 20 alkylthio group; C 1 -C 20 alkoxy group; C 6- C 20 -C20 aryloxy 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 substituted with deuterium
- Aryl group of 20 fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; aliphatic
- the compound represented by Formula 2 may be one of the following compounds, but is not limited thereto.
- L 1 to L 6 may be each independently one of the following Formulas b-1 to b-13.
- each symbol may be defined as follows.
- R 5 to R 7 are independently of each other hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; C 6 ⁇ C 20 aryl group; Fluorenyl group; C 2 ⁇ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 20 aliphatic ring group; C 3 ⁇ C 20 aliphatic ring and C 6 ⁇ C 20 aromatic ring fused ring group; C 1 ⁇ C 20 alkyl group; C 2 ⁇ C 20 alkenyl group; C 2 ⁇ C 20 alkynyl group; C 1 ⁇ C 20 Alkoxy group; C 6 ⁇ C 30 Aryloxy group; And -L a -N(R a )(R b ); and adjacent groups may combine with each other to form a ring.
- Y is N-(L a -Ar a ), O, S or C(R')(R").
- Z 1 to Z 3 are each independently C, C(R') or N, and at least one of Z 1 to Z 3 is N.
- each of the plurality of R 5, each of the plurality of R 6, and each of the plurality of R 7 may be the same or different from each other.
- R'and R" are independently of each other hydrogen; deuterium; halogen; cyano group; nitro group; C 6 ⁇ C 20 aryl group; fluorenyl group; O, N, S, Si and P at least one heteroatom C 2 ⁇ C 20 heterocyclic group containing; C 3 ⁇ C 20 aliphatic ring group; C 3 ⁇ C 20 aliphatic ring and C 6 ⁇ C 20 aromatic ring fused ring group; C 1 ⁇ C 20 Alkyl group of; C 2 ⁇ C 20 alkenyl group; C 2 ⁇ C 20 alkynyl group; C 1 ⁇ C 20 alkoxy group; C 6 ⁇ C 30 aryloxy group; and -L a -N (R a ) (R b ); may be selected from the group consisting of.
- R'and R" may combine with each other to form a ring, and in C(R'), adjacent R's may combine with each other to form a ring.
- the Ar a is C 6 ⁇ C 20 aryl group; Fluorenyl group; C 2 ⁇ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 20 aliphatic ring group; And combinations thereof.
- L a is a single bond independently of each other; C 6 ⁇ C 20 Arylene group; Fluorylene group; C 2 ⁇ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 20 aliphatic ring group; And combinations thereof.
- R a and R b are independently of each other C 6 ⁇ C 20 aryl group; Fluorenyl group; C 2 ⁇ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ⁇ C 20 aliphatic ring group; And combinations thereof.
- the R 5 to R 7 , L a , Ar a , R', R", R a , R b , rings formed by bonding adjacent groups, rings formed by bonding R'and R" to each other, are deuterium; halogen; A silane group unsubstituted or substituted with an alkyl group of C 1 -C 20 or an aryl group of C 6 -C 20 ; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C 1 -C 20 alkylthio; C 1 -C 20 Alkoxy group; C 6 -C 20 Aryloxy group; C 1 -C 20 alkyl group; Alkenyl group of C 2 -C 20 ; Alkynyl group of C 2 -C 20 ; C 6 -C 20 Aryl group; A C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; A C 2 -C 20 heterocyclic group including at least one heteroatom selected
- the weight ratio of the first compound and the second compound is 1:9 to 9:1, preferably 3:7 to 7:3, and more preferably 3:7 to 5:5.
- the compound represented by Chemical Formula 1 according to the present invention may be prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below, but is not limited thereto.
- the compound belonging to Sub 1 of Reaction Scheme 1 may be the following compound, but is not limited thereto.
- Sub 1 of Reaction Scheme 1 may be synthesized by the reaction route of Reaction Scheme 2 below, but is not limited thereto.
- the compound belonging to Sub 2 of Reaction Scheme 1 may be the following compound, but is not limited thereto.
- Sub 2 of Reaction Scheme 1 may be synthesized by the reaction route of Reaction Scheme 3 below, but is not limited thereto.
- Sub 1-1 (40.8 g, 80 mmol) was used instead of Sub 1-11, and Sub 2-51 (37.0 g, 80 mmol) was used instead of Sub 2-25 to proceed in the same manner as the synthesis method of 1-13 above.
- Product (45.4 g, 70%) was obtained.
- Sub 1-4 (44.0 g, 80 mmol) was used instead of Sub 1-11, and Sub 2-16 (29.6 g, 80 mmol) was used instead of Sub 2-25. Product (41.2 g, 68%) was obtained.
- the compound represented by Formula 2 of the present invention (Final product 2) may be prepared by reacting Sub 3 and Sub 4 as shown in Reaction Scheme 4 below, but is not limited thereto.
- Sub 3 of Reaction Scheme 4 may be synthesized as in Reaction Scheme 5 below, but is not limited thereto.
- a 60 nm thick hole is deposited by vacuum depositing a 4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as "2-TNATA”) film on an ITO layer (anode) formed on a glass substrate.
- 2-TNATA 4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine
- ITO anode
- NPD 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl
- a light emitting layer having a thickness of 30 nm was formed on the hole transport layer.
- the compound represented by Chemical Formula 1 (first host) and the compound represented by Chemical Formula 2 of the present invention (second) The mixture of the host) in a weight ratio of 3:7 is used as a host, and bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter abbreviated as "(piq) 2 Ir(acac)”) is used as a dopant.
- the host and dopant were used in a 95:5 weight ratio.
- a hole blocking layer by vacuum-depositing (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as "BAlq") on the light emitting layer to a thickness of 10 nm Formed.
- Alq 3 tris-(8-hydroxyquinoline)aluminum
- BeBq 2 bis (10-hydroxybenzo[h]quinolinato)beryllium
- An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound represented by Formula 1 of the present invention was used alone as the host material of the light emitting layer.
- Electro-luminescence (EL) characteristics of the organic electroluminescent device manufactured by Examples 1 to 90 and Comparative Examples 1 to 6 of the present invention were applied to a PR-650 manufactured by Photoresearch by applying a direct bias DC voltage.
- the T95 lifespan was measured through the life measurement equipment of Mac Science at a reference luminance of 2500 cd/m 2 , and the measurement results are shown in Table 7 below.
- Comparing Comparative Examples 1 to 6 the properties of the device were further improved when the compounds of the present invention were used by mixing two types of comparative compounds (Comparative Examples 5 to 6) than when the compounds of the present invention were used alone (Comparative Examples 1 to 4). .
- the inventors of the present invention determined that, in the case of a mixture of the substance of Formula 1 and the substance of Formula 2, it has novel characteristics other than those of each substance, and uses each of these substances and mixtures to PL The lifetime was measured. As a result, in the case of the mixture of the present invention formula 1 and formula 2, it was confirmed that a new PL wavelength was formed unlike the single compound.
- the compound of the present invention When the compound of the present invention is used in combination, not only electrons and holes are moved through the energy level of each material, but also electrons and holes are moved by a new exciplex having a new energy level formed due to mixing. Or, it is judged that the efficiency and lifetime have increased due to energy transfer. This can be said to be an important example in which the mixed thin film shows an exciplex energy transfer and luminescence process when using the mixture of the present invention.
- An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the first host and the second host were mixed by a certain ratio as described in Table 7 below.
- Electroluminescence (EL) characteristics were measured by PR-650 of photoresearch by applying a net bias DC voltage to the organic electroluminescent devices manufactured in Examples 91 to 94 of the present invention, and based on 2500 cd/m 2
- the T95 life was measured at a luminance through a life measurement equipment of Max Science.
- the results are shown in Table 8 below.
- Example 3 and Example 80 is the result of measuring the device characteristics when the first host and the second host are mixed in a ratio of 3:7 as in Table 6.
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Abstract
The present invention provides: an organic electric element comprising a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode; and an electronic device comprising the organic electric element, wherein compounds represented by chemical formulas 1 and 2 are included in the organic material layer such that a driving voltage of the organic electric element can be lowered, and luminous efficiency and lifespan of the organic electric element can be improved.
Description
본 발명은 유기전기소자용 화합물을 포함하는 유기전기소자 및 그 전자 장치에 관한 것이다.The present invention relates to an organic electric element comprising a compound for an organic electric element and its electronic device.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛 에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물 층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다.In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다. 그리고 상기 발광 재료는 분자량에 따라 고분자형과 저분자형으로 분류될 수 있고, 발광 메커니즘에 따라 전자의 일중항 여기상태로부터 유래되는 형광 재료와 전자의 삼중항 여기상태로부터 유래되는 인광 재료로 분류될 수 있다. 또한, 발광 재료는 발광색에 따라 청색, 녹색, 적색 발광 재료와 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광 재료로 구분될 수 있다.Materials used as the organic material layer in the organic electric device 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, depending on the function. In addition, the luminescent material may be classified into a high molecular weight type and a low molecular weight type according to the molecular weight, and may be classified into a fluorescent material derived from the singlet excited state of the electron and a phosphorescent material derived from the triplet excited state of the electron according to the light emission mechanism. have. In addition, the luminescent material may be divided into blue, green, and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color according to the luminous color.
한편, 발광 재료로서 하나의 물질만 사용하는 경우 분자간 상호 작용에 의하여 최대 발광 파장이 장파장으로 이동하고 색순도가 떨어지거나 발광 감쇄 효과로 소자의 효율이 감소되는 문제가 발생하므로, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여 발광 재료로서 호스트/도판트계를 사용할 수 있다. 그 원리는 발광층을 형성하는 호스트보다 에너지 대역 간극이 작은 도판트를 발광층에 소량 혼합하면, 발광층에서 발생한 엑시톤이 도판트로 수송되어 효율이 높은 빛을 내는 것이다. 이때 호스트의 파장이 도판트의 파장대로 이동하므로, 이용하는 도판트의 종류에 따라 원하는 파장의 빛을 얻을 수 있다.On the other hand, when only one material is used as the light emitting material, the problem of the maximum light emission wavelength shifting to a long wavelength due to intermolecular interaction and a decrease in color purity or a decrease in the efficiency of the device due to the light emission attenuation effect, increases color purity and energy transfer. To increase the luminous efficiency through, a host/dopant system may be used as a luminescent material. The principle is that when a small amount of the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with the light emitting layer, excitons generated in the light emitting layer are transported to the dopant to produce light with high efficiency. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of a desired wavelength can be obtained according to the type of dopant used.
현재 휴대용 디스플레이 시장은 대면적 디스플레이로 그 크기가 증가하고 있는 추세이며, 이로 인해 기존 휴대용 디스플레이에서 요구되던 소비적력보다 더 큰 소비전력이 요구되고 있다. 따라서, 배터리라는 제한적인 전력 공급원을 가지고 있는 휴대용 디스플레이 입장에서는 소비전력이 매우 중요한 요소가 되었고, 효율과 수명 문제 또한 반드시 해결해야 하는 상황이다.Currently, the size of the portable display market is increasing as a large-area display, and accordingly, power consumption greater than that required in the existing portable display is required. Therefore, power consumption has become a very important factor for portable displays that have a limited power supply, such as batteries, and the efficiency and lifespan problems must also be solved.
효율과 수명, 구동전압 등은 서로 연관이 있으며, 효율이 증가되면 상대적으로 구동전압이 떨어지고, 구동전압이 떨어지면서 구동 시 발생하는 주울열(Joule heating)에 의한 유기물질의 결정화가 적어져 결과적으로 수명이 높아지는 경향을 나타낸다. 하지만, 유기물층을 단순히 개선한다고 하여 효율을 극대화시킬 수는 없다. 왜냐하면, 각 유기물층 간의 에너지 준위(energy level) 및 T1 값, 물질의 고유특성(이동도, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있기 때문이다.Efficiency, life, and driving voltage are related to each other. When the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic substances due to Joule heating generated during driving decreases, and as a result, It shows a tendency to increase life. However, simply improving the organic layer does not maximize efficiency. This is because long life and high efficiency can be achieved at the same time when the energy level and T 1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined. .
따라서 높은 열적 안정성을 가지며 발광층 내에서 효율적으로 전하 균형(charge balance)을 이룰 수 있는 발광 재료의 개발이 필요한 실정이다. 즉, 유기전기소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 하나, 아직까지 안정하고 효율적인 유기전기소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이며, 그 중에서도 특히 발광층의 호스트 물질에 대한 개발이 절실히 요구되고 있다.Therefore, there is a need to develop a light emitting material having high thermal stability and efficiently achieving charge balance in the light emitting layer. That is, in order to sufficiently exhibit the excellent characteristics of the organic electric device, materials constituting an organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, are supported by stable and efficient materials It should be preceded, but the development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently performed, and among them, development of a host material of a light emitting layer is urgently required.
본 발명은 소자의 구동전압을 낮추고, 소자의 발광효율 및 수명을 향상시킬 수 있는 유기전기소자 및 그 전자장치를 제공하는 것을 목적으로 한다.An object of the present invention is to provide an organic electric device and an electronic device capable of lowering the driving voltage of the device and improving the luminous efficiency and lifetime of the device.
일 측면에서, 본 발명은 하기 화학식 1로 표시되는 제 1화합물과 하기 화학식 2로 표시되는 제 2화합물을 발광층에 포함하는 유기전기소자를 제공한다.In one aspect, the present invention provides an organic electric device comprising a first compound represented by the following formula (1) and a second compound represented by the following formula (2) in the light emitting layer.
<화학식 1> <화학식 2> <Formula 1> <Formula 2>
다른 측면에서, 본 발명은 상기 유기전기소자를 포함하는 전자장치를 제공한다.In another aspect, the present invention provides an electronic device including the organic electric element.
본 발명의 화학식 1로 표시되는 화합물과 화학식 2로 표시되는 화합물을 혼합한 혼합물을 발광층의 재료로 사용함으로써 소자의 구동전압을 낮출 수 있고, 소자의 발광효율 및 수명을 향상시킬 수 있다.By using the mixture of the compound represented by Formula 1 and the compound represented by Formula 2 as the material of the light emitting layer of the present invention, the driving voltage of the device can be lowered, and the luminous efficiency and lifetime of the device can be improved.
도 1은 본 발명에 따른 유기전기발광소자의 예시도이다.1 is an exemplary view of an organic electroluminescent device according to the present invention.
[부호의 설명][Description of codes]
100: 유기전기소자 110: 기판100: organic electrical element 110: substrate
120: 제 1전극 130: 정공주입층120: first electrode 130: hole injection layer
140: 정공수송층 141: 버퍼층140: hole transport layer 141: buffer layer
150: 발광층 151: 발광보조층150: light-emitting layer 151: light-emitting auxiliary layer
160: 전자수송층 170: 전자주입층160: electron transport layer 170: electron injection layer
180: 제 2전극180: second electrode
본 발명에서 사용된 용어 "아릴기" 및 "아릴렌기"는 다른 설명이 없는 한 각각 6 내지 60의 탄소수를 가지며, 이에 제한되는 것은 아니다. 본 발명에서 아릴기 또는 아릴렌기는 단일고리형, 고리집합체, 접합된 여러 고리계, 스파이로 화합물 등을 포함할 수 있다. 또한, 본 명세서에서 다른 설명이 없는 한 아릴기에는 플루오렌일기가 포함될 수 있고 아릴렌기에는 플루오렌일렌기가 포함될 수 있다.The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, and are not limited thereto unless otherwise specified. In the present invention, an aryl group or an arylene group may include a monocyclic, ring aggregate, several conjugated ring systems, spiro compounds, and the like. In addition, unless otherwise specified herein, the aryl group may include a fluorenyl group and the arylene group may include a fluorenylene group.
본 발명에서 사용된 용어 "플루오렌일기" 또는 "플루오렌일렌기"는 다른 설명이 없는 한 각각 하기 구조에서 R, R' 및 R"이 모두 수소인 1가 또는 2가 작용기를 의미하며, "치환된 플루오렌일기" 또는 "치환된 플루오렌일렌기"는 치환기 R, R', R" 중 적어도 하나가 수소 이외의 치환기인 것을 의미하며, R과 R'이 서로 결합되어 이들이 결합된 탄소와 함께 스파이로 화합물을 형성한 경우를 포함한다.The term "fluorenyl group" or "fluorenylene group" used in the present invention means a monovalent or divalent functional group in which R, R'and R" are both hydrogen in the following structures, unless otherwise specified. Substituted fluorenyl group" or "substituted fluorenylene 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 bonded carbon. It includes the case where a compound was formed as a spy together.
본 발명에서 사용된 용어 "스파이로 화합물"은 '스파이로 연결'을 가지며, 스파이로 연결은 2개의 고리가 오로지 1개의 원자를 공유함으로써 이루어지는 연결을 의미한다. 이때, 두 고리에 공유된 원자를 '스파이로 원자'라 하며, 한 화합물에 들어 있는 스파이로 원자의 수에 따라 이들을 각각 '모노스파이로-', '다이스파이로-', '트라이스파이로-' 화합물이라 한다.The term "spyro compound" as used in the present invention has a'spyro linkage', and a spiro linkage refers to a linkage formed by two rings sharing only one atom. At this time, the atoms shared in the two rings are called'spyro atoms', and these are'monospyro-','dispiro-','trispyro' depending on the number of spy atoms in a compound, respectively. It is called a compound.
본 발명에 사용된 용어 "헤테로고리기"는 "헤테로아릴기" 또는 "헤테로아릴렌기"와 같은 방향족 고리뿐만 아니라 비방향족 고리도 포함하며, 다른 설명이 없는 한 각각 하나 이상의 헤테로원자를 포함하는 탄소수 2 내지 60의 고리를 의미하나 여기에 제한되는 것은 아니다. 본 명세서에서 사용된 용어 "헤테로원자"는 다른 설명이 없는 한 N, O, S, P 또는 Si를 나타내며, 헤테로고리기는 헤테로원자를 포함하는 단일고리형, 고리집합체, 접합된 여러 고리계, 스파이로 화합물 등을 의미한다.The term "heterocyclic group" used in the present invention includes aromatic rings such as "heteroaryl group" or "heteroarylene group", as well as non-aromatic rings, and each carbon number containing one or more heteroatoms unless otherwise specified. It means a ring of 2 to 60, but is not limited thereto. The term "heteroatom" as used herein refers to N, O, S, P or Si, unless otherwise specified, and the heterocyclic group is a monocyclic, ring aggregate, heterozygous multiple ring system, spy containing heteroatoms. Means a compound and the like.
본 발명에 사용된 용어 "헤테로고리기"는 고리를 형성하는 탄소 대신 하기 화합물과 같이 SO2, P=O 등과 같은 헤테로원자단을 포함하는 화합물도 포함될 수 있다.The term "heterocyclic group" used in the present invention may also include a compound containing a heteroatom group such as SO 2 , P=O, and the like, instead of carbon forming a ring.
본 발명에 사용된 용어 "지방족고리기"는 방향족탄화수소를 제외한 고리형 탄화수소를 의미하며, 단일고리형, 고리집합체, 접합된 여러 고리계, 스파이로 화합물 등을 포함하며, 다른 설명이 없는 한 탄소수 3 내지 60의 고리를 의미하나 여기에 제한되는 것은 아니다. 예컨대, 방향족고리인 벤젠과 비방향족고리인 사이클로헥산이 융합된 경우에도 지방족고리에 해당한다.The term "aliphatic ring group" used in the present invention means a cyclic hydrocarbon excluding aromatic hydrocarbons, and includes monocyclic, ring aggregates, conjugated multiple ring systems, spiro compounds, and the like, unless otherwise indicated. It means a 3 to 60 ring, but is not limited thereto. For example, even when the aromatic ring benzene and the non-aromatic ring cyclohexane are fused, it corresponds to the aliphatic ring.
본 명세서에서 각 기호 및 그 치환기의 예로 예시되는 아릴기, 아릴렌기, 헤테로고리기 등에 해당하는 '기 이름'은 '가수를 반영한 기의 이름'을 기재할 수도 있지만, '모체화합물 명칭'으로 기재할 수도 있다. 예컨대, 아릴기의 일종인 '페난트렌'의 경우, 1가의 '기'는 '페난트릴'로 2가의 기는 '페난트릴렌' 등과 같이 가수를 구분하여 기의 이름을 기재할 수도 있지만, 가수와 상관없이 모체 화합물 명칭인 '페난트렌'으로 기재할 수도 있다. 유사하게, 피리미딘의 경우에도, 가수와 상관없이 '피리미딘'으로 기재하거나, 1가인 경우에는 피리미딘일기, 2가의 경우에는 피리미딘일렌 등과 같이 해당 가수의 '기의 이름'으로 기재할 수도 있다. In the present specification, the'group name' corresponding to an aryl group, an arylene group, a heterocyclic group, etc. exemplified as an example of each symbol and its substituent may describe'the name of a group reflecting a singer', but is described as a'parent compound name' You may. For example, in the case of'phenanthrene', which is a type of aryl group, the monovalent'group' is'phenanthryl', and the divalent group can be classified as a singer such as'phenanthrylene', etc. Regardless, the parent compound name may be described as'phenanthrene'. Similarly, in the case of pyrimidine, it can be described as'pyrimidine' regardless of the singer, or in the case of monovalent pyrimidinyl group, in the case of divalent pyrimidineylene, etc., as the'group name' of the corresponding singer. have.
또한, 본 명세서에서는 화합물 명칭이나 치환기 명칭을 기재함에 있어 위치를 표시하는 숫자나 알파벳 등은 생략할 수도 있다. 예컨대, 피리도[4,3-d]피리미딘을 피리도피리미딘으로, 벤조퓨로[2,3-d]피리미딘을 벤조퓨로피리미딘으로, 9,9-다이메틸-9H-플루오렌을 다이메틸플루오렌 등과 같이 기재할 수 있다. 따라서, 벤조[g]퀴녹살린이나 벤조[f]퀴녹살린을 모두 벤조퀴녹살린이라고 기재할 수 있다.In addition, in this specification, in describing a compound name or a substituent name, a number, an alphabet, etc. indicating a position may be omitted. For example, pyrido[4,3-d]pyrimidine as pyridopyrimidine, benzofuro[2,3-d]pyrimidine as benzofuropyrimidine, 9,9-dimethyl-9H-flu Oren can be described as dimethylfluorene or the like. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be described as benzoquinoxaline.
또한, 명시적인 설명이 없는 한, 본 발명에서 사용되는 화학식은 하기 화학식의 지수 정의에 의한 치환기 정의와 동일하게 적용된다.In addition, unless explicitly stated, the formula used in the present invention is applied in the same manner as the definition of a substituent based on the index definition of the following formula.
여기서, a가 0의 정수인 경우 치환기 R1은 부존재하는 것을 의미하는데, 즉 a가 0인 경우는 벤젠고리를 형성하는 탄소에 모두 수소가 결합된 것을 의미하며, 이때 탄소에 결합된 수소의 표시를 생략하고 화학식이나 화합물을 기재할 수 있다. 또한, a가 1의 정수인 경우 하나의 치환기 R1은 벤젠 고리를 형성하는 탄소 중 어느 하나의 탄소에 결합하며, a가 2 또는 3의 정수인 경우 예컨대 아래와 같이 결합할 수 있고, a가 4 내지 6의 정수인 경우에도 이와 유사한 방식으로 벤젠 고리의 탄소에 결합하며, a가 2 이상의 정수인 경우 R1은 서로 같거나 상이할 수 있다.Here, when a is an integer of 0, the substituent R 1 means non-existent, that is, when a is 0, it means that hydrogen is bonded to all the carbons forming the benzene ring. The formula or compound may be omitted. In addition, when a is an integer of 1, one substituent R 1 is bound to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3, for example, it can be bonded as follows, and a is 4 to 6 Even in the case of an integer, it is bonded to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R 1 may be the same or different.
또한, 본 명세서에서 다른 설명이 없는 한, 이웃한 기끼리 서로 결합하여 형성한 고리는 C6~C60의 방향족고리기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 이들의 조합으로 이루어진 군에서 선택될 수 있다. In addition, unless otherwise specified in the present specification, the rings formed by bonding with adjacent groups are C 6 ~ C 60 aromatic ring groups; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of 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; And combinations thereof.
이하, 본 발명의 화합물이 포함된 유기전기소자의 적층구조에 대하여 도 1을 참조하여 설명한다.Hereinafter, a stacked structure of an organic electric device including the compound of the present invention will be described with reference to FIG. 1.
본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.In describing the present invention, when it is determined that detailed descriptions of related known configurations or functions may obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.
또한, 층, 막, 영역, 판 등의 구성 요소가 다른 구성 요소 "위에" 또는 "상에" 있다고 하는 경우, 이는 다른 구성 요소 "바로 위에" 있는 경우뿐만 아니라 그 중간에 또 다른 구성 요소가 있는 경우도 포함할 수 있다고 이해되어야 할 것이다. 반대로, 어떤 구성 요소가 다른 부분 "바로 위에" 있다고 하는 경우에는 중간에 또 다른 부분이 없는 것을 뜻한다고 이해되어야 할 것이다.Also, if a component such as a layer, film, region, plate, etc. is said to be "above" or "on" another component, it is not only when the other component is "directly above", but also with another component in the middle. It should be understood that the case may be included. Conversely, it should be understood that when a component is said to be “just above” another part, it means that there is no other part in between.
도 1은 본 발명의 일 실시예에 따른 유기전기소자에 대한 예시도이다.1 is an exemplary view of an organic electric device according to an embodiment of the present invention.
도 1을 참조하면, 본 발명의 일 실시예에 따른 유기전기소자(100)는 기판(110) 상에 형성된 제 1전극(120), 제 2전극(180), 및 제 1전극(120)과 제 2전극(180) 사이에 본 발명에 따른 화합물을 포함하는 유기물층을 포함한다. 이때, 제 1전극(120)은 애노드(양극)이고, 제 2전극(180)은 캐소드(음극)일 수 있으며, 인버트형의 경우에는 제 1전극이 캐소드이고 제 2전극이 애노드일 수 있다.Referring to FIG. 1, an organic electric device 100 according to an embodiment of the present invention includes a first electrode 120, a second electrode 180, and a first electrode 120 formed on a substrate 110. Between the second electrode 180 includes an organic material layer containing the compound according to the present invention. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.
유기물층은 제 1전극(120) 상에 순차적으로 적층된 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160), 전자주입층(170) 등을 포함할 수 있다. 이때, 이들 층 중 적어도 하나가 생략되거나, 정공저지층, 전자저지층, 발광보조층(151), 전자수송보조층, 버퍼층(141) 등을 더 포함할 수도 있고, 전자수송층(160) 등이 정공저지층의 역할을 할 수도 있다.The organic material layer may 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 sequentially stacked on the first electrode 120. . At this time, at least one of these layers may be omitted, or may further include a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, etc., and the electron transport layer 160, etc. It can also serve as a hole blocking layer.
또한, 미도시하였지만, 본 발명의 일 실시예에 따른 유기전기소자는 보호층 또는 광효율 개선층을 더 포함할 수 있다. 이러한 광효율 개선층은 제 1전극의 양면 중 유기물층과 접하지 않는 면 또는 제 2전극의 양면 중 유기물층과 접하지 않는 면에 형성될 수 있다.In addition, although not shown, the organic electric device according to an embodiment of the present invention may further include a protective layer or a light efficiency improving layer. The light efficiency improving layer may be formed on a surface of both surfaces of the first electrode that does not contact the organic material layer or a surface of both surfaces of the second electrode that does not contact the organic material layer.
상기 유기물층에 적용되는 본 발명의 일 실시예에 따른 화합물은 정공주입층(130), 정공수송층(140), 발광보조층(151), 전자수송보조층, 전자수송층(160), 전자주입층(170), 발광층(150)의 호스트 또는 도펀트, 또는 광효율 개선층의 재료로 사용될 수 있을 것이나, 바람직하게는 본 발명의 화학식 1로 표시되는 화합물과 화학식 2로 표시되는 화합물을 혼합한 혼합물이 발광층의 호스트로 사용된다.The compound according to an embodiment of the present invention applied to the organic layer is a hole injection layer 130, a hole transport layer 140, a light emitting auxiliary layer 151, an electron transport auxiliary layer, an electron transport layer 160, an electron injection layer ( 170), a host or a dopant of the light emitting layer 150, or may be used as a material for a light efficiency improving layer, but preferably a mixture of a compound represented by Formula 1 and a compound represented by Formula 2 of the present invention of the light emitting layer Used as a host.
한편, 동일유사한 코어일지라도 어느 위치에 어느 치환기를 결합시키냐에 따라 밴드갭(band gap), 전기적 특성, 계면 특성 등이 달라질 수 있으므로, 코어의 선택 및 이에 결합된 서브(sub)-치환체의 조합에 대한 연구가 필요하며, 특히 각 유기물층 간의 에너지 준위 및 T1 값, 물질의 고유특성(이동도, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있다.On the other hand, even in the case of the same core, the band gap, electrical characteristics, and interfacial characteristics may vary depending on which substituent is attached to which position, and thus, the selection of the core and the combination of sub-substituents coupled thereto. It is necessary to study, especially when the energy level and T 1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined, long life and high efficiency can be achieved simultaneously.
따라서, 본 발명에서는 화학식 1로 표시되는 화합물과 화학식 2로 표시되는 화합물을 혼합한 혼합물을 발광층의 호스트로 사용함으로써, 각 유기물층 간의 에너지 레벨 및 T1 값, 물질의 고유특성(이동도, 계면특성 등) 등을 최적화하여 유기전기소자의 수명 및 효율을 동시에 향상시킬 수 있다.Therefore, in the present invention, by using a mixture of a compound represented by Formula 1 and a compound represented by Formula 2 as a host of a light emitting layer, the energy level and T 1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties) Etc.) to optimize the lifespan and efficiency of organic electric devices at the same time.
본 발명의 일 실시예에 따른 유기전기발광소자는 다양한 증착법(deposition)을 이용하여 제조될 수 있을 것이다. PVD나 CVD 등의 증착 방법을 사용하여 제조될 수 있는데, 예컨대, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극(120)을 형성하고, 그 위에 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함하는 유기물층을 형성한 후, 그 위에 음극(180)으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 또한, 정공수송층(140)과 발광층(150) 사이에 발광보조층(151)을, 발광층(150)과 전자수송층(160) 사이에 전자수송보조층을 추가로 더 형성할 수 있다.The organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. It may be manufactured using a deposition method such as PVD or CVD, for example, by depositing a metal or conductive metal oxide or an alloy thereof on a substrate to form the anode 120, and a hole injection layer 130 thereon , After forming an organic material layer including the hole transport layer 140, the light emitting layer 150, the electron transport layer 160 and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon. have. In addition, the light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150, and the electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160.
또한, 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스, 예컨대 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정, 롤투롤 공정, 닥터 블레이딩 공정, 스크린 프린팅 공정, 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다. 본 발명에 따른 유기물층은 다양한 방법으로 형성될 수 있으므로, 그 형성방법에 의해 본 발명의 권리범위가 제한되는 것은 아니다.In addition, the organic material layer is a solution process or a solvent process that is not a deposition method 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, a screen It can be produced with fewer layers by a printing process or a method such as thermal transfer. Since the organic material layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the formation method.
본 발명의 일 실시예에 따른 유기전기소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electric device according to an embodiment of the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.
또한, 본 발명의 일 실시예에 따른 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 단색 조명용 소자 및 퀀텀닷 디스플레이용 소자로 이루어진 군에서 선택될 수 있다.In addition, the organic electroluminescent device according to an embodiment of the present invention may be selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a monochromatic lighting device, and a quantum dot display device.
본 발명의 다른 실시예는 상술한 본 발명의 유기전기소자를 포함하는 디스플레이장치와, 이 디스플레이장치를 제어하는 제어부를 포함하는 전자장치를 포함할 수 있다. 이때, 전자장치는 현재 또는 장래의 유무선 통신단말일 수 있으며, 휴대폰 등의 이동 통신 단말기, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 전자장치를 포함한다.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 for controlling the display device. At this time, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game machines, various TVs, and various computers.
이하, 본 발명의 일 측면에 따른 유기전기소자에 대하여 설명한다.Hereinafter, an organic electric device according to an aspect of the present invention will be described.
본 발명의 일측면에 따른 유기전기소자는 제 1전극, 제 2 전극 및 상기 제 1전극과 상기 제 2전극 사이에 형성된 유기물층을 포함하며, 상기 유기물층은 인광성 발광층을 포함하고, 상기 인광성 발광층의 호스트는 하기 화학식 1로 표시되는 제 1화합물과 하기 화학식 2로 표시되는 제 2화합물을 포함한다.The organic electric device according to an aspect of the present invention 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 a phosphorescent emission layer, and the phosphorescent emission layer The host of the first compound represented by the following formula (1) and the second compound represented by the following formula (2).
<화학식 1> <화학식 2> <Formula 1> <Formula 2>
먼저, 화학식 1에 대하여 설명한다.First, Formula 1 will be described.
상기 화학식 1에서 각 기호는 아래와 같이 정의될 수 있다.In Chemical Formula 1, each symbol may be defined as follows.
X1은 O 또는 S이다.X 1 is O or S.
Ar1 및 Ar2는 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕시기; 및 C6~C30의 아릴옥시기로 이루어진 군에서 선택될 수 있다. Ar 1 and Ar 2 are independently of each other C 6 ~ C 60 aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 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; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 30 Alkoxy group; And C 6 ~ C 30 It may be selected from the group consisting of an aryloxy group.
Ar1 및 Ar2가 아릴기인 경우, 바람직하게는 C6~C30의 아릴기, 더욱 바람직하게는 C6~C18의 아릴기, 예컨대 페닐, 바이페닐, 나프틸, 터페닐, 페난트렌, 파이렌, 트리페닐렌 등일 수 있다. Ar1 및 Ar2가 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더욱 바람직하게는 C2~C18의 헤테로고리기, 예컨대 피리딘, 퀴놀린, 아이소퀴놀린, 카바졸, 페닐카바졸, 다이벤조싸이오펜, 다이벤조퓨란, 다이벤조다이옥신 등일 수 있다. Ar1 및 Ar2가 플루오렌일기인 경우, 9,9-다이페닐플루오렌, 9,9-다이메틸플루오렌 등일수 있다. Ar1 및 Ar2가 지방족고리기인 경우, 바람직하게는 C3~C30의 지방족고리, 더욱 바람직하게는 C3~C12의 지방족고리, 예컨대 사이클로헥산, 사이클로헥실사이클로헥산 등일 수 있다. Ar1 및 Ar2가 알킬기인 경우, 바람직하게는 C2~C10의 알킬기, 예컨대 메틸, t-부틸 등일 수 있다. Ar1 및 Ar2가 알켄일기인 경우, 바람직하게는 C2~C10의 알켄일기일 수 있고 예컨대 에텐, 프로펜 등일 수 있다.When Ar 1 and Ar 2 are aryl groups, preferably C 6 to C 30 aryl groups, more preferably C 6 to C 18 aryl groups, such as phenyl, biphenyl, naphthyl, terphenyl, phenanthrene, Pyrene, triphenylene, and the like. When Ar 1 and Ar 2 are heterocyclic groups, preferably C 2 to C 30 heterocyclic groups, more preferably C 2 to C 18 heterocyclic groups, such as pyridine, quinoline, isoquinoline, carbazole, phenyl Carbazole, dibenzothiophene, dibenzofuran, dibenzodioxin, and the like. When Ar 1 and Ar 2 are fluorenyl groups, it may be 9,9-diphenylfluorene, 9,9-dimethylfluorene, and the like. When Ar 1 and Ar 2 are an aliphatic ring group, preferably an aliphatic ring of C 3 to C 30 , more preferably an aliphatic ring of C 3 to C 12 , such as cyclohexane, cyclohexylcyclohexane, and the like. When Ar 1 and Ar 2 are alkyl groups, preferably C 2 to C 10 alkyl groups, such as methyl, t-butyl, and the like. When Ar 1 and Ar 2 are alkenyl groups, preferably a C 2 to C 10 alkenyl group, for example, ethene, propene, or the like.
L1 내지 L3은 서로 독립적으로 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; 및 C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기로 이루어진 군에서 선택될 수 있다.L 1 to L 3 are each independently a single bond; C 6 ~ C 60 Arylene group; Fluorylene group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring group; And it may be selected from the group consisting of a fused ring of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60.
L1 내지 L3이 아릴렌기인 경우, 바람직하게는 C6~C30의 아릴렌기, 더욱 바람직하게는 C6~C18의 아릴렌기, 예컨대 페닐, 바이페닐, 나프틸, 터페닐 등일 수 있다. L1 내지 L3이 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더욱 바람직하게는 C2~C18의 헤테로고리기, 예컨대 카바졸, 페닐카바졸, 다이벤조퓨란, 다이벤조싸이오펜 등일 수 있다.When L 1 to L 3 are arylene groups, preferably an arylene group of C 6 to C 30 , more preferably an arylene group of C 6 to C 18 , such as phenyl, biphenyl, naphthyl, terphenyl, etc. . When L 1 to L 3 are heterocyclic groups, preferably C 2 to C 30 heterocyclic groups, more preferably C 2 to C 18 heterocyclic groups, such as carbazole, phenylcarbazole, dibenzofuran, Dibenzothiophene, and the like.
R1은 수소; 중수소; 할로겐; 시아노기; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕시기; C6~C30의 아릴옥시기; 및 -L'-N(Ra)(Rb);로 이루어진 군에서 선택되며, 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있다.R 1 is hydrogen; heavy hydrogen; halogen; Cyano group; C 6 ~ C 60 Aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 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; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 30 Alkoxy group; C 6 ~ C 30 Aryloxy group; And -L'-N (R a ) (R b ); is selected from the group consisting of, adjacent groups may be bonded to each other to form a ring.
a는 0~9의 정수이고, a가 2 이상의 정수인 경우, 복수의 R1은 서로 같거나 상이하다.a is an integer of 0-9, and when a is an integer of 2 or more, a plurality of R 1 s are the same as or different from each other.
이웃한 R1끼리 서로 결합하여 형성된 고리는 C6~C60의 방향족고리기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; 또는 C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기 등일 수 있다. 이웃한 R1끼리 서로 결합하여 방향족고리를 형성할 경우, 바람직하게는 C6~C30의 방향족고리, 더욱 바람직하게는 C6~C14의 방향족고리, 예컨대 벤젠, 나프탈렌, 페난트렌 등과 같과 같은 방향족고리를 형성할 수 있다.Rings formed by bonding adjacent R 1 to each other include an aromatic ring group of C 6 to C 60 ; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring group; Or it may be a fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60. When adjacent R 1 is bonded to each other to form an aromatic ring, preferably an aromatic ring of C 6 ~ C 30 , more preferably an aromatic ring of C 6 ~ C 14 , such as benzene, naphthalene, phenanthrene, etc. The same aromatic ring can be formed.
R1이 아릴기인 경우, 바람직하게는 C6~C30의 아릴기, 더욱 바람직하게는 C6~C18의 아릴기, 예컨대, 페닐, 나프틸, 바이페닐, 터페닐, 페난트렌 등일 수 있다.When R 1 is an aryl group, preferably an aryl group of C 6 to C 30 , more preferably an aryl group of C 6 to C 18 , such as phenyl, naphthyl, biphenyl, terphenyl, phenanthrene, etc. .
상기 L'은 서로 독립적으로 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; 및 C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기;로 이루어진 군에서 선택될 수 있다.L'is independently of each other a single bond; C 6 ~ C 60 Arylene group; Fluorylene group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring group; And fused ring groups of the aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; may be selected from the group consisting of.
상기 Ra 및 Rb는 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; 및 C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기;로 이루어진 군에서 선택될 수 있다.R a and R b are independently of each other C 6 ~ C 60 aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring group; And fused ring groups of the aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; may be selected from the group consisting of.
바람직하게는, 상기 화학식 1에서 하기 화학식 1-1로부터 도출되는 화합물은 제외될 수 있다.Preferably, the compound derived from Formula 1-1 below in Formula 1 may be excluded.
<화학식 1-1><Formula 1-1>
상기 화학식 1-1에서, 각 기호는 상기 화학식 1에서 정의된 것과 같다. 바람직하게는, Ar1 및 Ar2는 서로 독립적으로 C6~C18의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C16의 헤테로고리기; C3~C60의 지방족고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕시기; 및 C6~C30의 아릴옥시기로 이루어진 군에서 선택된다.In Chemical Formula 1-1, each symbol is the same as defined in Chemical Formula 1. Preferably, Ar 1 and Ar 2 are independently of each other C 6 ~ C 18 aryl group; Fluorenyl group; C 2 ~ C 16 heterocyclic group containing at least one heteroatom of 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; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 30 Alkoxy group; And C 6 ~ C 30 It is selected from the group consisting of an aryloxy group.
바람직하게는, 상기 화학식 1은 하기 화학식 1-A 내지 화학식 1-E 중에서 하나로 표시될 수 있다.Preferably, the Chemical Formula 1 may be represented by one of the following Chemical Formulas 1-A to 1-E.
<화학식 1-A> <화학식 1-B><Formula 1-A> <Formula 1-B>
<화학식 1-C> <화학식 1-D><Formula 1-C> <Formula 1-D>
<화학식 1-E><Formula 1-E>
상기 화학식 1-A 내지 1-E에서, 각 기호는 아래와 같이 정의될 수 있다.In Chemical Formulas 1-A to 1-E, each symbol may be defined as follows.
Ar1, Ar2, L1 내지 L3, X1, R1, a는 화학식 1에서 정의된 것과 같다.Ar 1 , Ar 2 , L 1 to L 3 , X 1 , R 1 , a are as defined in Formula 1.
X2 및 X3은 서로 독립적으로 O 또는 S이다.X 2 and X 3 are each independently O or S.
R4, R8 및 R9는 서로 독립적으로 수소; 중수소; 할로겐; 시아노기; 니트로기; C6~C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; C3~C20의 지방족고리와 C6~C20의 방향족고리의 융합고리기; C1~C20의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C20의 알콕시기; C6~C30의 아릴옥시기; 및 -La-N(Ra)(Rb);로 이루어진 군에서 선택되며, 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있다.R 4 , R 8 and R 9 are independently of each other hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; C 6 ~ C 20 aryl group; Fluorenyl group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; C 3 ~ C 20 aliphatic ring and C 6 ~ C 20 aromatic ring fused ring group; C 1 ~ C 20 alkyl group; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 20 Alkoxy group; C 6 ~ C 30 Aryloxy group; And -L a -N(R a )(R b ); and adjacent groups may combine with each other to form a ring.
d1는 0~7의 정수이고, i 및 j는 각각 0~6의 정수이고, 이들 각각이 2 이상의 정수인 경우 복수의 R4 각각, 복수의 R8 각각, 복수의 R9 각각은 서로 같거나 상이하다.d1 is an integer from 0 to 7, i and j are integers from 0 to 6, and when each of them is an integer of 2 or more, each of a plurality of R 4, each of a plurality of R 8, and each of a plurality of R 9 are the same or different from each other Do.
상기 La는 서로 독립적으로 단일결합; C6~C20의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.L a is a single bond independently of each other; C 6 ~ C 20 Arylene group; Fluorylene group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; And combinations thereof.
상기 Ra 및 Rb는 서로 독립적으로 C6~C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.R a and R b are independently of each other C 6 ~ C 20 aryl group; Fluorenyl group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; And combinations thereof.
바람직하게는, 상기 화학식 1-A는 하기 화학식 1-A-1 내지 화학식 1-A-6 중에서 하나로 표시될 수 있다.Preferably, the formula 1-A may be represented by one of the following formulas 1-A-1 to 1-A-6.
<화학식 1-A-1> <화학식 1-A-2> <화학식 1-A-3><Formula 1-A-1> <Formula 1-A-2> <Formula 1-A-3>
<화학식 1-A-4> <화학식 1-A-5> <화학식 1-A-6><Formula 1-A-4> <Formula 1-A-5> <Formula 1-A-6>
상기 화학식 1-A-1 내지 1-A-6에서, Ar1, Ar2, L1~L3, X1, R1, a는 화학식 1-A에서 정의된 것과 같다.In Chemical Formulas 1-A-1 to 1-A-6, Ar 1 , Ar 2 , L 1 to L 3 , X 1 , R 1 , a are as defined in Chemical Formula 1-A.
상기 화학식 1, 화학식 1-A 내지 1-E, 화학식 1-A-1 내지 1-A-6에서 각 기호는 더 치환될 수 있다. 예컨대, Ar1, Ar2, L1~L3, L', La, R1, R4, R8, R9, Ra, Rb, Ra, Rb, 및 이웃한 기끼리 결합하여 형성된 고리 등은 각각 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕시기; C6-C20의 아릴옥시기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 지방족고리기; C7-C20의 아릴알킬기; 및 C8-C20의 아릴알켄일기;로 이루어진 군에서 선택된 하나 이상의 치환기로 더 치환될 수 있다.Each symbol in Formula 1, Formula 1-A to 1-E, and Formula 1-A-1 to 1-A-6 may be further substituted. For example, Ar 1 , Ar 2 , L 1 ~L 3 , L', L a , R 1 , R 4 , R 8 , R 9 , R a , R b , R a , R b , and adjacent groups are bonded to each other Rings formed by deuterium, respectively; halogen; A silane group unsubstituted or substituted with an alkyl group of C 1 -C 20 or an aryl group of C 6 -C 20 ; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C 1 -C 20 alkylthio; C 1 -C 20 Alkoxy group; C 6 -C 20 Aryloxy group; C 1 -C 20 alkyl group; Alkenyl group of C 2 -C 20 ; Alkynyl group of C 2 -C 20 ; C 6 -C 20 Aryl group; A C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; A C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; C 3 -C 20 aliphatic ring group; C 7 -C 20 Arylalkyl group; And C 8 -C 20 Aryl alkenyl group; It may be further substituted with one or more substituents selected from the group consisting of.
구체적으로, 상기 화학식 1로 표시되는 화합물은 하기 화합물 중 하나일 수 있으나, 이에 한정되는 것은 아니다.Specifically, the compound represented by Formula 1 may be one of the following compounds, but is not limited thereto.
다음으로, 하기 화학식 2에 대하여 설명한다.Next, the following Chemical Formula 2 will be described.
<화학식 2><Formula 2>
상기 화학식 2에서 각 기호는 아래와 같이 정의될 수 있다.In Chemical Formula 2, each symbol may be defined as follows.
Ar4 내지 Ar6은 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕시기; 및 C6~C30의 아릴옥시기로 이루어진 군에서 선택될 수 있다.Ar 4 to Ar 6 are independently of each other C 6 ~ C 60 aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 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; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 30 Alkoxy group; And C 6 ~ C 30 It may be selected from the group consisting of an aryloxy group.
Ar4 내지 Ar6이 아릴기인 경우, 바람직하게는 C6~C30의 아릴기, 더욱 바람직하게는 C6~C18의 아릴기, 예컨대, 페닐, 바이페닐, 나프틸, 터페닐, 페난트렌 등일 수 있다. When Ar 4 to Ar 6 are aryl groups, preferably, C 6 to C 30 aryl groups, more preferably C 6 to C 18 aryl groups, such as phenyl, biphenyl, naphthyl, terphenyl, phenanthrene Etc.
Ar4 내지 Ar6이 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더욱 바람직하게는 C2~C20의 헤테로고리기, 예컨대, 다이벤조싸이오펜, 다이벤조퓨란, 벤조싸이에노피리미딘, 카바졸, 페닐카바졸, 벤조나프토싸이오펜, 벤조퓨로싸이오펜, 다이나프토싸이오펜, 다이나프토퓨란 등일 수 있다.When Ar 4 to Ar 6 are heterocyclic groups, preferably C 2 to C 30 heterocyclic groups, more preferably C 2 to C 20 heterocyclic groups, such as dibenzothiophene, dibenzofuran, benzo Thienopyrimidine, carbazole, phenylcarbazole, benzonaphthothiophene, benzofurothiophene, dynaphthothiophene, dynaphthofuran, and the like.
Ar4 내지 Ar6이 플루오렌일기인 경우, 9,9-다이메틸-9H-플루오렌, 9,9-다이페닐-9H-플루오렌, 9,9'-스파이로바이플루오렌 등일 수 있다.When Ar 4 to Ar 6 are fluorenyl groups, it may be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spirobifluorene, or the like.
L4 내지 L6은 서로 독립적으로 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.L 4 to L 6 are each independently a single bond; C 6 ~ C 60 Arylene group; Fluorylene group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring group; And combinations thereof.
L4 내지 L6이 아릴렌기인 경우, 바람직하게는 C6~C30의 아릴렌기, 더욱 바람직하게는 C6~C18의 아릴렌기, 예컨대, 페닐렌, 바이페닐, 나프틸, 터페닐 등일 수 있다.When L 4 to L 6 are arylene groups, preferably C 6 to C 30 arylene groups, more preferably C 6 to C 18 arylene groups, such as phenylene, biphenyl, naphthyl, terphenyl, etc. Can.
L4 내지 L6이 플루오렌일기인 경우, 9,9-다이메틸-9H-플루오렌, 9,9-다이페닐-9H-플루오렌, 9,9'-스파이로바이플루오렌 등일 수 있다.When L 4 to L 6 are fluorenyl groups, 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spyrobifluorene, and the like may be used.
상기 화학식 2는 하기 화학식 2-A 내지 화학식 2-I 중에서 하나로 표시될 수 있다.The Chemical Formula 2 may be represented by one of the following Chemical Formulas 2-A to 2-I.
<화학식 2-A> <화학식 2-B><Formula 2-A> <Formula 2-B>
<화학식 2-C><Formula 2-C>
<화학식 2-D> <화학식 2-E> <화학식 2-F><Formula 2-D> <Formula 2-E> <Formula 2-F>
<화학식 2-G> <화학식 2-H> <화학식 2-I><Formula 2-G> <Formula 2-H> <Formula 2-I>
<화학식 2-G> <화학식 2-H> <화학식 2-I><Formula 2-G> <Formula 2-H> <Formula 2-I>
상기 화학식 2-A 내지 화학식 2-I에서, Ar5, Ar6, L4~L6은 화학식 2에서 정의된 것과 같고, Y1~Y3은 서로 독립적으로 O, S, C(R')(R")이다.In Formulas 2-A to 2-I, Ar 5 , Ar 6 , L 4 to L 6 are the same as defined in Formula 2, and Y 1 to Y 3 are each independently O, S, C(R') (R").
R11~R16, R' 및 R"은 서로 독립적으로 수소; 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 시아노기; 니트로기; C1-C20의 알콕시기; C6-C20의 아릴옥시기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; 및 C3-C20의 지방족고리기;로 이루어진 군에서 선택되고, 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있고, R'과 R"끼리 서로 결합하여 고리를 형성할 수 있다. R'과 R"끼리 서로 결합하여 고리를 형성할 경우 스파이로 화합물이 형성될 수 있다.R 11 to R 16 , R'and R" are independently of each other hydrogen; deuterium; halogen; C 1 -C 20 alkyl group or C 6 -C 20 aryl group unsubstituted or substituted silane group; cyano group; nitro group ; C 1 -C 20 alkoxy group; C 6 -C 20 aryloxy group; C 1 -C 20 alkyl group; C 2 -C 20 alkenyl group; C 2 -C 20 alkynyl group; C 6 -C Aryl group of 20 ; fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; and aliphatic ring of C 3 -C 20 Group; selected from the group consisting of, adjacent groups can be bonded to each other to form a ring, R'and R" can be bonded to each other to form a ring. When R'and R" combine with each other to form a ring, a spy compound may be formed.
이웃한 기끼리 서로 결합하여 형성된 고리는 C6~C60의 방향족고리기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; 또는 C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기 등일 수 있다. 예컨대, 이웃한 R1끼리, 이웃한 R12끼리, 이웃한 R13끼리, 이웃한 R14끼리, 이웃한 R15끼리, 이웃한 R16끼리 또는 R'과 R"끼리 서로 결합하여 방향족 고리를 형성할 경우, 바람직하게는 C6~C30의 방향족고리, 더욱 바람직하게는 C6~C14의 방향족고리, 예컨대 벤젠, 나프탈렌, 페난트렌 등과 같과 같은 방향족고리를 형성할 수 있다. Rings formed by bonding adjacent groups to each other include an aromatic ring group of C 6 ~C 60 ; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring group; Or it may be a fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60. For example, neighboring R 1 , neighboring R 12 , neighboring R 13 , neighboring R 14 , neighboring R 15 , neighboring R 16, or R'and R" are bonded to each other to form an aromatic ring. When forming, preferably, an aromatic ring of C 6 to C 30 , more preferably an aromatic ring of C 6 to C 14 , for example, an aromatic ring such as benzene, naphthalene, and phenanthrene can be formed.
b는 0~4의 정수이고, b가 2 이상의 정수인 경우 복수의 R11 각각, 복수의 R13 각각, 복수의 R15 각각은 서로 같거나 상이하며, c는 0~3의 정수이고, c가 2 이상의 정수인 경우 복수의 R12 각각, 복수의 R14 각각, 복수의 R16 각각은 서로 같거나 상이하다.b is an integer from 0 to 4, and when b is an integer of 2 or more, each of a plurality of R 11, each of a plurality of R 13, and each of a plurality of R 15 are the same or different from each other, c is an integer from 0 to 3, c is In the case of an integer of 2 or more, each of the plurality of R 12, each of the plurality of R 14, and each of the plurality of R 16 are the same or different from each other.
상기 Ar4~Ar6, L4~L6, R11~R16, R', R" 및 이웃한 기끼리 결합하여 형성된 고리는 각각 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕시기; C6-C20의 아릴옥시기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 지방족고리기; C7-C20의 아릴알킬기; 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 더 치환될 수 있다.The Ar 4 ~ Ar 6 , L 4 ~ L 6 , R 11 ~ R 16 , R', R" and the ring formed by bonding adjacent groups are each deuterium; halogen; C 1 -C 20 alkyl group or C 6- Silane group unsubstituted or substituted with C 20 aryl group; siloxane group; boron group; germanium group; cyano group; nitro group; C 1 -C 20 alkylthio group; C 1 -C 20 alkoxy group; C 6- C 20 -C20 aryloxy 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 substituted with deuterium Aryl group of 20 ; fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; aliphatic ring group of C 3 -C 20 C 7 -C 20 arylalkyl group; and C 8 -C 20 arylalkenyl group may be further substituted with one or more substituents selected from the group consisting of.
구체적으로, 상기 화학식 2로 표시되는 화합물은 하기 화합물 중 하나일 수 있으나, 이에 한정되는 것은 아니다.Specifically, the compound represented by Formula 2 may be one of the following compounds, but is not limited thereto.
바람직하게는, 상기 화학식 1 및 2에서 L1 내지 L6은 서로 독립적으로 하기 화학식 b-1 내지 b-13 중에서 하나일 수 있다.Preferably, in Formulas 1 and 2, L 1 to L 6 may be each independently one of the following Formulas b-1 to b-13.
<화학식 b-1> <화학식 b-2> <화학식 b-3> <화학식 b-4><Formula b-1> <Formula b-2> <Formula b-3> <Formula b-4>
<화학식 b-5> <화학식 b-6> <화학식 b-7> <화학식 b-8><Formula b-5> <Formula b-6> <Formula b-7> <Formula b-8>
<화학식 b-9> <화학식 b-10><Formula b-9> <Formula b-10>
<화학식 b-11> <화학식 b-12> <화학식 b-13><Formula b-11> <Formula b-12> <Formula b-13>
상기 화학식 b-1 내지 b-13에서, 각 기호는 아래와 같이 정의될 수 있다.In the formulas b-1 to b-13, each symbol may be defined as follows.
R5 내지 R7은 서로 독립적으로 수소; 중수소; 할로겐; 시아노기; 니트로기; C6~C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; C3~C20의 지방족고리와 C6~C20의 방향족고리의 융합고리기; C1~C20의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C20의 알콕시기; C6~C30의 아릴옥시기; 및 -La-N(Ra)(Rb);로 이루어진 군에서 선택되며, 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있다.R 5 to R 7 are independently of each other hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; C 6 ~ C 20 aryl group; Fluorenyl group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; C 3 ~ C 20 aliphatic ring and C 6 ~ C 20 aromatic ring fused ring group; C 1 ~ C 20 alkyl group; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 20 Alkoxy group; C 6 ~ C 30 Aryloxy group; And -L a -N(R a )(R b ); and adjacent groups may combine with each other to form a ring.
이웃한 R5끼리, 이웃한 R6끼리, 또는 이웃한 R7끼리 서로 결합하여 방향족고리를 형성할 경우, 바람직하게는 C6~C30의 방향족고리, 더욱 바람직하게는 C6~C14의 방향족고리, 예컨대 벤젠, 나프탈렌, 페난트렌 등과 같과 같은 방향족고리를 형성할 수 있다.When neighboring R 5 , neighboring R 6 , or neighboring R 7 are bonded to each other to form an aromatic ring, preferably C 6 ~ C 30 aromatic ring, more preferably C 6 ~ C 14 Aromatic rings such as benzene, naphthalene, and phenanthrene can be formed.
Y는 N-(La-Ara), O, S 또는 C(R')(R")이다.Y is N-(L a -Ar a ), O, S or C(R')(R").
Z1 내지 Z3은 서로 독립적으로 C, C(R') 또는 N이고, Z1 내지 Z3 중에서 적어도 하나는 N이다.Z 1 to Z 3 are each independently C, C(R') or N, and at least one of Z 1 to Z 3 is N.
f는 0 내지 6의 정수이고, e, g, h, i는 각각 0 내지 4의 정수이고, j, k는 각각 0 내지 3의 정수이고, l은 0 내지 2의 정수이고, m은 0 내지 3의 정수이며, 이들 각각이 2 이상의 정수인 경우 복수의 R5 각각, 복수의 R6 각각, 복수의 R7 각각은 서로 동일하거나 상이할 수 있다.f is an integer from 0 to 6, e, g, h, and i are integers from 0 to 4, j, k are integers from 0 to 3, l is an integer from 0 to 2, and m is from 0 to It is an integer of 3, and when each of these is an integer of 2 or more, each of the plurality of R 5, each of the plurality of R 6, and each of the plurality of R 7 may be the same or different from each other.
상기 R' 및 R"는 서로 독립적으로 수소; 중수소; 할로겐; 시아노기; 니트로기; C6~C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; C3~C20의 지방족고리와 C6~C20의 방향족고리의 융합고리기; C1~C20의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C20의 알콕시기; C6~C30의 아릴옥시기; 및 -La-N(Ra)(Rb);로 이루어진 군에서 선택될 수 있다.R'and R" are independently of each other hydrogen; deuterium; halogen; cyano group; nitro group; C 6 ~ C 20 aryl group; fluorenyl group; O, N, S, Si and P at least one heteroatom C 2 ~ C 20 heterocyclic group containing; C 3 ~ C 20 aliphatic ring group; C 3 ~ C 20 aliphatic ring and C 6 ~ C 20 aromatic ring fused ring group; C 1 ~ C 20 Alkyl group of; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 20 alkoxy group; C 6 ~ C 30 aryloxy group; and -L a -N (R a ) (R b ); may be selected from the group consisting of.
C(R')(R")에서 R'와 R"끼리 서로 결합하여 고리를 형성할 수 있고, C(R')에서 이웃한 R'끼리 서로 결합하여 고리를 형성할 수 있다.In C(R')(R"), R'and R" may combine with each other to form a ring, and in C(R'), adjacent R's may combine with each other to form a ring.
상기 Ara는 C6~C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.The Ar a is C 6 ~ C 20 aryl group; Fluorenyl group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; And combinations thereof.
상기 La는 서로 독립적으로 단일결합; C6~C20의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.L a is a single bond independently of each other; C 6 ~ C 20 Arylene group; Fluorylene group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; And combinations thereof.
상기 Ra 및 Rb는 서로 독립적으로 C6~C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.R a and R b are independently of each other C 6 ~ C 20 aryl group; Fluorenyl group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; And combinations thereof.
상기 R5 내지 R7, La, Ara, R', R", Ra, Rb, 이웃한 기끼리 결합하여 형성된 고리, R'과 R"끼리 서로 결합하여 형성된 고리 등은 각각 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕시기; C6-C20의 아릴옥시기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 지방족고리기; C7-C20의 아릴알킬기; 및 C8-C20의 아릴알켄일기;로 이루어진 군에서 선택된 하나 이상의 치환기로 더 치환될 수 있다.The R 5 to R 7 , L a , Ar a , R', R", R a , R b , rings formed by bonding adjacent groups, rings formed by bonding R'and R" to each other, are deuterium; halogen; A silane group unsubstituted or substituted with an alkyl group of C 1 -C 20 or an aryl group of C 6 -C 20 ; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C 1 -C 20 alkylthio; C 1 -C 20 Alkoxy group; C 6 -C 20 Aryloxy group; C 1 -C 20 alkyl group; Alkenyl group of C 2 -C 20 ; Alkynyl group of C 2 -C 20 ; C 6 -C 20 Aryl group; A C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; A C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; C 3 -C 20 aliphatic ring group; C 7 -C 20 Arylalkyl group; And C 8 -C 20 Aryl alkenyl group; It may be further substituted with one or more substituents selected from the group consisting of.
상기 제 1화합물과 제2화합물의 중량비는 1:9 내지 9:1, 바람직하게는 3:7 내지 7:3, 더욱 바람직하게는 3:7 내지 5:5이다.The weight ratio of the first compound and the second compound is 1:9 to 9:1, preferably 3:7 to 7:3, and more preferably 3:7 to 5:5.
이하에서, 본 발명에 따른 화학식 1 및 화학식 2로 표시되는 화합물의 합성예 및 유기전기소자의 제조예에 관하여 실시예를 들어 구체적으로 설명하지만, 본 발명이 하기의 실시예로 한정되는 것은 아니다.Hereinafter, examples of the synthesis of the compounds represented by Chemical Formulas 1 and 2 according to the present invention and manufacturing examples of the organic electric device will be specifically described with reference to Examples, but the present invention is not limited to the following Examples.
[합성예 1] 화학식 1[Synthesis Example 1] Formula 1
본 발명에 따른 화학식 1로 표시되는 화합물(final product)은 하기 반응식 1과 같이 Sub 1과 Sub 2를 반응시켜 제조될 수 있으나, 이에 한정되는 것은 아니다.The compound represented by Chemical Formula 1 according to the present invention may be prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below, but is not limited thereto.
<반응식 1><Scheme 1>
1. Sub 1의 예시 화합물 및 합성예1. Exemplary compounds and synthetic examples of Sub 1
상기 반응식 1의 Sub 1에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니다.The compound belonging to Sub 1 of Reaction Scheme 1 may be the following compound, but is not limited thereto.
Sub 1에 속하는 상기 화합물의 FD-MS 값은 하기 표 1과 같다.The FD-MS values of the compounds belonging to Sub 1 are shown in Table 1 below.
[표 1][Table 1]
상기 반응식 1의 Sub 1은 하기 반응식 2의 반응경로에 의해 합성될 수 있으나, 이에 한정되는 것은 아니다.Sub 1 of Reaction Scheme 1 may be synthesized by the reaction route of Reaction Scheme 2 below, but is not limited thereto.
<반응식 2><Reaction Scheme 2>
Sub 1-7의 합성예Synthesis Example of Sub 1-7
2,4-dichloro-6-phenyl-1,3,5-triazine (30 g, 132.71 mmol)에 2-(9,9-diphenyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (70.77 g, 159.25 mmol), Pd(PPh3)4 (7.67 g, 6.64 mmol), K2CO3 (55.02 g, 398.12 mmol), THF (600 ml), 물 (300 ml)을 첨가한 후, 교반 환류시킨다. 반응이 완료되면, ether와 물로 추출한 후 유기층을 농축시킨 다음, MgSO4로 건조하고 농축시켰다. 이후, 농축물을 실리카겔 칼럼으로 분리 후 재결정하여 생성물 51.24 g (수율: 76%)를 얻었다.2-(9,9-diphenyl-9H-fluoren-2-yl)-4,4,5,5 to 2,4-dichloro-6-phenyl-1,3,5-triazine (30 g, 132.71 mmol) -tetramethyl-1,3,2-dioxaborolane (70.77 g, 159.25 mmol), Pd(PPh 3 ) 4 (7.67 g, 6.64 mmol), K 2 CO 3 (55.02 g, 398.12 mmol), THF (600 ml), Water (300 ml) was added, followed by reflux with stirring. After the reaction was completed, the organic layer was concentrated after extraction with ether and water, and then dried over MgSO 4 and concentrated. Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 51.24 g (yield: 76%) of the product.
Sub 1-29의 합성예Synthesis Example of Sub 1-29
2,4-dichloro-6-(dibenzo[b,d]furan-4-yl)-1,3,5-triazine (20 g, 63.26 mmol)를 둥근바닥플라스크에 넣고 THF 450 mL로 녹인 후에, 2-(4-(dibenzo[b,d]furan-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (28.11 g, 75.92 mmol), Pd(PPh3)4 (3.66 g, 3.16 mmol), K2CO3 (26.23 g, 189.79 mmol), 물 150 mL을 넣고 상기 Sub 1-7의 합성법과 같이 진행하여 생성물 69.7g (수율: 73%)를 얻었다.After adding 2,4-dichloro-6-(dibenzo[b,d]furan-4-yl)-1,3,5-triazine (20 g, 63.26 mmol) to a round bottom flask and dissolving in 450 mL of THF, 2 -(4-(dibenzo[b,d]furan-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (28.11 g, 75.92 mmol), Pd(PPh 3 ) 4 (3.66 g, 3.16 mmol), K 2 CO 3 (26.23 g, 189.79 mmol), 150 mL of water was added, and the same procedure as in Sub 1-7 was performed to obtain 69.7 g of product (yield: 73%).
Sub 1-39의 합성예Synthesis Example of Sub 1-39
2-([1,1':3',1''-terphenyl]-5'-yl)-4,6-dichloro-1,3,5-triazine (17 g, 44.94 mmol)를 둥근바닥플라스크에 넣고 THF 340 mL로 녹인 후에, 2-(dibenzo[b,d]thiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (16.73 g, 53.93 mmol), Pd(PPh3)4 (2.6 g, 2.25 mmol), K2CO3 (18.63 g, 134.83 mmol), 물 170 mL을 넣고 상기 Sub 1-7의 합성법과 같이 진행하여 생성물 69.7g (수율: 73%)를 얻었다.2-([1,1':3',1''-terphenyl]-5'-yl)-4,6-dichloro-1,3,5-triazine (17 g, 44.94 mmol) in a round bottom flask And dissolved in 340 mL of THF, 2-(dibenzo[b,d]thiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (16.73 g, 53.93 mmol), Pd (PPh 3 ) 4 (2.6 g, 2.25 mmol), K 2 CO 3 (18.63 g, 134.83 mmol), 170 mL of water was added and proceeded in the same manner as in the synthesis method of Sub 1-7 to obtain 69.7 g of product (yield: 73%) Got
2. Sub 2의 예시 화합물 및 합성예2. Exemplary compounds and synthetic examples of Sub 2
상기 반응식 1의 Sub 2에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니다The compound belonging to Sub 2 of Reaction Scheme 1 may be the following compound, but is not limited thereto.
Sub 2에 속하는 상기 화합물의 FD-MS 값은 하기 표 2와 같다.The FD-MS value of the compound belonging to Sub 2 is shown in Table 2 below.
[표 2][Table 2]
상기 반응식 1의 Sub 2는 하기 반응식 3의 반응경로에 의해 합성될 수 있으나, 이에 한정되는 것은 아니다.Sub 2 of Reaction Scheme 1 may be synthesized by the reaction route of Reaction Scheme 3 below, but is not limited thereto.
<반응식 3><Scheme 3>
Sub 2-4 합성예Sub 2-4 Synthesis Example
6-(4-bromonaphthalen-2-yl)naphtho[1,2-b]benzofuran (15 g, 35.44 mmol)에 bis(pinacolato)diboron (CAS Registry Number: 73183-34-3) (11.7 g, 46.07 mmol), PdCl2(dppf) (1.3 g, 1.77 mmol), KOAc (10.4 g, 106.31 mmol), DMF (300 ml)을 첨가한 후, 교반 환류시킨다. 반응이 완료되면, CH2Cl2와 물을 이용하여 유기층을 추출한 다음, MgSO4로 건조하고 농축한다. 이후, 농축물을 실리카겔 칼럼으로 분리 후 재결정하여 생성물 12.83 g (수율: 77%)를 얻었다.Bis(pinacolato)diboron (CAS Registry Number: 73183-34-3) (11.7 g, 46.07 mmol) in 6-(4-bromonaphthalen-2-yl)naphtho[1,2-b]benzofuran (15 g, 35.44 mmol) ), PdCl 2 (dppf) (1.3 g, 1.77 mmol), KOAc (10.4 g, 106.31 mmol), DMF (300 ml) was added, followed by reflux with stirring. When the reaction is completed, the organic layer is extracted with CH 2 Cl 2 and water, then dried over MgSO 4 and concentrated. Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 12.83 g of product (yield: 77%).
Sub 2-25 합성예Sub 2-25 Synthesis Example
8-bromobenzo[b]naphtho[2,1-d]thiophene (25 g, 79.82 mmol)에 bis(pinacolato)diboron (CAS registry number, 73183-34-3) (26.35 g, 103.76 mmol), PdCl2(dppf) (3.08 g, 4.21 mmol), KOAc (24.77 g, 252.4 mmol), DMF (500 ml)을 첨가한 후, 교반 환류시킨다. 반응이 완료되면, CH2Cl2와 물을 이용하여 유기층을 추출한 다음, MgSO4로 건조하고 농축한다. 이후, 농축물을 실리카겔 칼럼으로 분리 후 재결정하여 생성물 24 g (수율: 83%)를 얻었다.8-bromobenzo[b]naphtho[2,1-d]thiophene (25 g, 79.82 mmol) with bis(pinacolato)diboron (CAS registry number, 73183-34-3) (26.35 g, 103.76 mmol), PdCl 2 ( dppf) (3.08 g, 4.21 mmol), KOAc (24.77 g, 252.4 mmol), DMF (500 ml) was added, followed by reflux with stirring. When the reaction is completed, the organic layer is extracted with CH 2 Cl 2 and water, then dried over MgSO 4 and concentrated. Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 24 g of the product (yield: 83%).
3. 최종 화합물 합성예3. Final compound synthesis example
1-13의 합성예Synthesis example of 1-13
Sub 1-11 (34.7g, 80 mmol), Sub 2-25 (30.9g, 80 mmol), K2CO3 (19.3 g, 140 mmol), Pd(PPh3)4 (2.8 g, 2.4 mmol)를 둥근바닥플라스크에 넣고 THF와 물을 넣어서 녹인 후 80 ℃에서 12시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 실리카겔 칼럼으로 분리하여 생성물을 (37.4g, 71%)를 얻었다.Sub 1-11 (34.7 g, 80 mmol), Sub 2-25 (30.9 g, 80 mmol), K 2 CO 3 (19.3 g, 140 mmol), Pd(PPh 3 ) 4 (2.8 g, 2.4 mmol) It was put in a round bottom flask, dissolved in THF and water, and refluxed at 80°C for 12 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. The organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was separated by a silica gel column to obtain the product (37.4 g, 71%).
1-27의 합성예Synthesis example of 1-27
Sub 1-11 대신 Sub 1-13 (44.6g, 80 mmol)을, Sub 2-25 대신 Sub 2-43 (30.9g, 80 mmol)을 사용하여 상기 1-13의 합성방법과 같은 방법으로 진행시켜서 생성물(43.2g, 69%)를 얻었다.Sub 1-13 (44.6 g, 80 mmol) instead of Sub 1-11 and Sub 2-43 (30.9 g, 80 mmol) instead of Sub 2-25 were used to proceed in the same manner as in the synthesis method of 1-13 above. Product (43.2 g, 69%) was obtained.
1-34의 합성예Synthesis example of 1-34
Sub 1-11 대신 Sub 1-34 (42.7g, 80 mmol)을, Sub 2-25 대신 Sub 2-18 (34.9g, 80 mmol)을 사용하여 상기 1-13의 합성방법과 같은 방법으로 진행시켜서 생성물(42.7g, 66%)를 얻었다.Sub 1-34 (42.7 g, 80 mmol) instead of Sub 1-11 and Sub 2-18 (34.9 g, 80 mmol) instead of Sub 2-25 were used to proceed in the same manner as in the synthesis method of 1-13 above. Product (42.7 g, 66%) was obtained.
1-45의 합성예Synthesis example of 1-45
Sub 1-11 대신 Sub 1-37 (40.8g, 80 mmol)을, Sub 2-25 대신 Sub 2-49 (43.1g, 80 mmol)을 사용하여 상기 1-13의 합성방법과 같은 방법으로 진행시켜서 생성물(51.0g, 72%)를 얻었다.Sub 1-37 (40.8 g, 80 mmol) instead of Sub 1-11, Sub 2-49 (43.1 g, 80 mmol) instead of Sub 2-25 was used to proceed in the same manner as in the synthesis method of 1-13 above. Product (51.0 g, 72%) was obtained.
1-53의 합성예Synthesis example of 1-53
Sub 1-11 대신 Sub 1-1 (40.8g, 80 mmol)을, Sub 2-25 대신 Sub 2-51 (37.0g, 80 mmol)을 사용하여 상기 1-13의 합성방법과 같은 방법으로 진행시켜서 생성물(45.4g, 70%)를 얻었다.Sub 1-1 (40.8 g, 80 mmol) was used instead of Sub 1-11, and Sub 2-51 (37.0 g, 80 mmol) was used instead of Sub 2-25 to proceed in the same manner as the synthesis method of 1-13 above. Product (45.4 g, 70%) was obtained.
1-88의 합성예Synthesis example of 1-88
Sub 1-11 대신 Sub 1-4 (44.0g, 80 mmol)을, Sub 2-25 대신 Sub 2-16 (29.6g, 80 mmol)을 사용하여 상기 1-13의 합성방법과 같은 방법으로 진행시켜서 생성물(41.2g, 68%)를 얻었다.Sub 1-4 (44.0 g, 80 mmol) was used instead of Sub 1-11, and Sub 2-16 (29.6 g, 80 mmol) was used instead of Sub 2-25. Product (41.2 g, 68%) was obtained.
상기 합성예와 같은 방법으로 합성된 본 발명의 화합물 1-1 내지 1-124의 FD-MS 값은 하기 표 3과 같다.FD-MS values of the compounds 1-1 to 1-124 of the present invention synthesized in the same manner as in the synthesis example are shown in Table 3 below.
[표 3][Table 3]
[합성예 2] 화학식 2[Synthesis Example 2] Formula 2
본 발명의 화학식 2로 표시되는 화합물(Final product 2)은 하기 반응식 4와 같이 Sub 3과 Sub 4를 반응시켜 제조될 수 있으나, 이에 한정되는 것은 아니다.The compound represented by Formula 2 of the present invention (Final product 2) may be prepared by reacting Sub 3 and Sub 4 as shown in Reaction Scheme 4 below, but is not limited thereto.
<반응식 4><Reaction Scheme 4>
1. Sub 3의 예시 화합물1. Exemplary compounds of Sub 3
상기 반응식 4의 Sub 3은 하기 반응식 5와 같이 합성할 수 있으나, 이에 한정되는 것은 아니다.Sub 3 of Reaction Scheme 4 may be synthesized as in Reaction Scheme 5 below, but is not limited thereto.
<반응식 5><Reaction Scheme 5>
상기 반응식 4의 Sub 3에 속하는 화합물은 아래와 같으나, 이에 한정되는 것은 아니다.The compounds belonging to Sub 3 of Scheme 4 are as follows, but are not limited thereto.
Sub 3에 속하는 상기 화합물의 FD-MS 값은 하기 표 4와 같다.The FD-MS values of the compounds belonging to Sub 3 are shown in Table 4 below.
[표 4][Table 4]
2. Sub 4의 예시 화합물 및 합성예2. Exemplary compounds and synthetic examples of Sub 4
Sub 4에 속하는 상기 화합물의 FD-MS 값은 하기 표 5와 같다.The FD-MS values of the compounds belonging to Sub 4 are shown in Table 5 below.
[표 5][Table 5]
<반응식 6><Scheme 6>
Sub 4-1의 합성예Synthesis Example of Sub 4-1
둥근바닥플라스크에 aniline (15 g, 161.1 mmol), 1-bromonaphthalene (36.7 g, 177.2 mmol), Pd2(dba)3 (7.37 g, 8.05 mmol), P(t-Bu)3 (3.26 g, 16.1 mmol), NaOt-Bu (51.08 g, 531.5 mmol), toluene (1690 mL)을 넣은 후에 100 ℃에서 반응을 진행시킨다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하여 생성된 유기물을 실리카겔 칼럼으로 분리 후 재결정하여 Sub 4-1을 25.4 g 얻었다. (수율: 72%)Round bottom flask with aniline (15 g, 161.1 mmol), 1-bromonaphthalene (36.7 g, 177.2 mmol), Pd 2 (dba) 3 (7.37 g, 8.05 mmol), P(t-Bu) 3 (3.26 g, 16.1 mmol), NaOt-Bu (51.08 g, 531.5 mmol), toluene (1690 mL) was added and the reaction proceeded at 100°C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated to separate the produced organic material with a silica gel column and recrystallized to obtain 25.4 g of Sub 4-1. (Yield: 72%)
Sub 4-30의 합성예Synthesis Example of Sub 4-30
둥근바닥플라스크에 [1,1'-biphenyl]-4-amine (15 g, 88.6 mmol), 2-(4-bromophenyl)-9,9-diphenyl-9H-fluorene (46.2 g, 97.5 mmol), Pd2(dba)3 (4.06 g, 4.43 mmol), P(t-Bu)3 (1.8 g, 8.86 mmol), NaOt-Bu (28.1 g, 292.5 mmol), toluene (931 mL)을 넣은 후 상기 Sub 4-1의 합성법과 같은 방법으로 진행시켜서 Sub 4-30을 34.9 g 얻었다. (수율 : 70%)Round bottom flask [1,1'-biphenyl]-4-amine (15 g, 88.6 mmol), 2-(4-bromophenyl)-9,9-diphenyl-9H-fluorene (46.2 g, 97.5 mmol), Pd 2 (dba) 3 (4.06 g, 4.43 mmol), P(t-Bu) 3 (1.8 g, 8.86 mmol), NaOt-Bu (28.1 g, 292.5 mmol), toluene (931 mL), and Sub 4 By proceeding in the same manner as in the synthesis method of -1, Sub 4-30 was obtained 34.9 g. (Yield: 70%)
Sub 4-46의 합성예Synthesis Example of Sub 4-46
둥근바닥플라스크에 naphthalen-1-amine (15 g, 104.8 mmol), 2-bromodibenzo[b,d]thiophene (30.3 g, 115.2 mmol), Pd2(dba)3 (4.8 g, 5.24 mmol), P(t-Bu)3 (2.12 g, 10.48 mmol), NaOt-Bu (33.22 g, 345.7 mmol), toluene (1100 mL)을 넣은 후 상기 Sub 4-1의 합성법과 같은 방법으로 진행시켜서 Sub 4-46을 24.9 g 얻었다. (수율 : 73%)Naphthalen-1-amine (15 g, 104.8 mmol), 2-bromodibenzo[b,d]thiophene (30.3 g, 115.2 mmol), Pd 2 (dba) 3 (4.8 g, 5.24 mmol), P( After adding t-Bu) 3 (2.12 g, 10.48 mmol), NaOt-Bu (33.22 g, 345.7 mmol), toluene (1100 mL), proceed in the same way as in the synthesis method for Sub 4-1 to perform Sub 4-46. 24.9 g. (Yield: 73%)
Sub 4-49의 합성예Synthesis Example of Sub 4-49
둥근바닥플라스크에 [1,1'-biphenyl]-4-amine (15 g, 88.64 mmol), 2-bromodibenzo[b,d]thiophene (23.32 g, 88.64 mmol), Pd2(dba)3 (2.43 g, 2.66 mmol), P(t-Bu)3 (17.93 g, 88.64 mmol), NaOt-Bu (17.04 g, 177.27 mmol), toluene (886 mL)을 넣은 후 상기 Sub 4-1의 합성법과 같은 방법으로 진행시켜서 Sub 4-49을 24.61 g 얻었다. (수율 : 79%)[1,1'-biphenyl]-4-amine (15 g, 88.64 mmol), 2-bromodibenzo[b,d]thiophene (23.32 g, 88.64 mmol), Pd 2 (dba) 3 (2.43 g) , 2.66 mmol), P(t-Bu) 3 (17.93 g, 88.64 mmol), NaOt-Bu (17.04 g, 177.27 mmol), toluene (886 mL), and then in the same manner as in the synthesis method of Sub 4-1. Advances to obtain 24.61 g of Sub 4-49. (Yield: 79%)
Sub 4-56의 합성예Synthesis Example of Sub 4-56
둥근바닥플라스크에 4-(dibenzo[b,d]furan-2-yl)aniline (15 g, 57.85 mmol), 2-bromodibenzo[b,d]furan (15.7 g, 63.63 mmol), Pd2(dba)3 (2.65 g, 2.89 mmol), P(t-Bu)3 (1.17 g, 5.78 mmol), NaOt-Bu (18.35 g, 190.9 mmol), toluene (607 mL)을 넣은 후 상기 Sub 4-1의 합성법과 같은 방법으로 진행시켜서 Sub 4-56을 17.2 g 얻었다. (수율 : 70%)4-(dibenzo[b,d]furan-2-yl)aniline (15 g, 57.85 mmol), 2-bromodibenzo[b,d]furan (15.7 g, 63.63 mmol), Pd 2 (dba) in a round bottom flask Synthesis of Sub 4-1 after adding 3 (2.65 g, 2.89 mmol), P(t-Bu) 3 (1.17 g, 5.78 mmol), NaOt-Bu (18.35 g, 190.9 mmol), toluene (607 mL) It proceeded in the same way to obtain Sub 4-56 17.2 g. (Yield: 70%)
3. 최종 화합물의 합성예3. Synthesis Example of Final Compound
2-1 의 합성Synthesis of 2-1
둥근바닥플라스크에 sub 3-1 (10 g, 42.9 mmol), Sub 4-21 (13.79 g, 42.9 mmol), Pd2(dba)3 (1.18 g, 1.29 mmol), P(t-Bu)3 (8.68 g, 42.9 mmol), NaOt-Bu (8.25 g, 85.80 mmol), toluene (429 mL)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 실리카겔 칼럼으로 분리 후 재결정하여 생성물 2-1 를 15.6 g 얻었다. (수율: 77%)Round bottom flask sub 3-1 (10 g, 42.9 mmol), Sub 4-21 (13.79 g, 42.9 mmol), Pd 2 (dba) 3 (1.18 g, 1.29 mmol), P(t-Bu) 3 ( 8.68 g, 42.9 mmol), NaOt-Bu (8.25 g, 85.80 mmol) and toluene (429 mL) were added and then the reaction was carried out at 100°C. After the reaction was completed, the organic layer was extracted with CH 2 Cl 2 and water, dried over MgSO 4 and concentrated, and the resulting organic material was separated by a silica gel column and recrystallized to obtain 15.6 g of product 2-1. (Yield: 77%)
2-4 의 합성Synthesis of 2-4
둥근바닥플라스크에 Sub 3-2 (10 g, 35.3 mmol), Sub 4-27 (14.8 g, 35.31 mmol), Pd2(dba)3 (0.97 g, 1.06 mmol), P(t-Bu)3 (7.14 g, 35.31 mmol), NaOt-Bu (6.79 g, 70.63 mmol), toluene (353 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 2-4를 16.9 g 얻었다. (수율 : 78%)In a round bottom flask, Sub 3-2 (10 g, 35.3 mmol), Sub 4-27 (14.8 g, 35.31 mmol), Pd 2 (dba) 3 (0.97 g, 1.06 mmol), P(t-Bu) 3 ( 7.14 g, 35.31 mmol), NaOt-Bu (6.79 g, 70.63 mmol), and toluene (353 mL) were added, followed by the same method as in the synthesis of 2-1 to obtain 16.9 g of product 2-4. (Yield: 78%)
2-10의 합성Synthesis of 2-10
둥근바닥플라스크에 Sub 3-6 (10 g, 32.34 mmol), Sub 4-12 (12.86 g, 32.34 mmol), Pd2(dba)3 (0.89 g, 0.97 mmol), P(t-Bu)3 (6.54 g, 32.34 mmol), NaOt-Bu (6.22 g, 64.68 mmol), toluene (323 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 2-10을 15.1 g 얻었다. (수율 : 75%)In a round bottom flask, Sub 3-6 (10 g, 32.34 mmol), Sub 4-12 (12.86 g, 32.34 mmol), Pd 2 (dba) 3 (0.89 g, 0.97 mmol), P(t-Bu) 3 ( 6.54 g, 32.34 mmol), NaOt-Bu (6.22 g, 64.68 mmol) and toluene (323 mL) were added and then proceeded in the same manner as in the synthesis method of 2-1 to obtain 15.1 g of product 2-10. (Yield: 75%)
2-19의 합성Synthesis of 2-19
둥근바닥플라스크에 Sub 3-10 (10 g, 38 mmol), Sub 4-16 (11.23 g, 38 mmol), Pd2(dba)3 (1.04 g, 1.14 mmol), P(t-Bu)3 (7.69 g, 38 mmol), NaOt-Bu (7.3 g, 76 mmol), toluene (380 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 2-19을 13.7 g 얻었다. (수율 : 76%)In a round bottom flask, Sub 3-10 (10 g, 38 mmol), Sub 4-16 (11.23 g, 38 mmol), Pd 2 (dba) 3 (1.04 g, 1.14 mmol), P(t-Bu) 3 ( 7.69 g, 38 mmol), NaOt-Bu (7.3 g, 76 mmol) and toluene (380 mL) were added and then proceeded in the same manner as in the synthesis method of 2-1 to obtain 13.7 g of product 2-19. (Yield: 76%)
2-68의 합성Synthesis of 2-68
둥근바닥플라스크에 Sub 3-38 (10 g, 33.65 mmol), Sub 4-49 (11.83 g, 33.65 mmol), Pd2(dba)3 (0.92 g, 1.01 mmol), P(t-Bu)3 (6.81 g, 33.65 mmol), NaOt-Bu (6.47 g, 67.31 mmol), toluene (337 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 2-68을 15.28 g 얻었다. (수율 : 80%)In a round bottom flask, Sub 3-38 (10 g, 33.65 mmol), Sub 4-49 (11.83 g, 33.65 mmol), Pd 2 (dba) 3 (0.92 g, 1.01 mmol), P(t-Bu) 3 ( 6.81 g, 33.65 mmol), NaOt-Bu (6.47 g, 67.31 mmol), and toluene (337 mL) were added, followed by the same method as the synthesis method of 2-1 to obtain 15.28 g of product 2-68. (Yield: 80%)
2-24 의 합성Synthesis of 2-24
둥근바닥플라스크에 Sub 3-10 (10 g, 38 mmol), Sub 4-33 (18.38 g, 38 mmol), Pd2(dba)3 (1.04 g, 1.14 mmol), P(t-Bu)3 (7.69 g, 38 mmol), NaOt-Bu (7.3 g, 76 mmol), toluene (380 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 18.72 g 얻었다. (수율 : 74%)In a round bottom flask, Sub 3-10 (10 g, 38 mmol), Sub 4-33 (18.38 g, 38 mmol), Pd 2 (dba) 3 (1.04 g, 1.14 mmol), P(t-Bu) 3 ( 7.69 g, 38 mmol), NaOt-Bu (7.3 g, 76 mmol) and toluene (380 mL) were added, followed by the same method as in the synthesis method of 2-1 to obtain 18.72 g of product. (Yield: 74%)
2-29의 합성Synthesis of 2-29
둥근바닥플라스크에 Sub 3-11 (10 g, 29.48 mmol), Sub 4-46 (9.59 g, 29.48 mmol), Pd2(dba)3 (0.81 g, 0.88 mmol), P(t-Bu)3 (5.96 g, 29.48 mmol), NaOt-Bu (5.67 g, 58.95 mmol), toluene (295 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 2-29을 12.39 g 얻었다. (수율 : 72%)In a round bottom flask, Sub 3-11 (10 g, 29.48 mmol), Sub 4-46 (9.59 g, 29.48 mmol), Pd 2 (dba) 3 (0.81 g, 0.88 mmol), P(t-Bu) 3 ( 5.96 g, 29.48 mmol), NaOt-Bu (5.67 g, 58.95 mmol), and toluene (295 mL) were added, followed by the same method as in the synthesis method of 2-1 to obtain 12.39 g of product 2-29. (Yield: 72%)
2-30의 합성Synthesis of 2-30
둥근바닥플라스크에 Sub 3-14 (10 g, 29.48 mmol), Sub 4-20 (9.47 g, 29.48 mmol), Pd2(dba)3 (0.81 g, 0.88 mmol), P(t-Bu)3 (5.96 g, 29.48 mmol), NaOt-Bu (5.67 g, 58.95 mmol), toluene (295 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 2-30을 12.13 g 얻었다. (수율 : 71%)In a round bottom flask, Sub 3-14 (10 g, 29.48 mmol), Sub 4-20 (9.47 g, 29.48 mmol), Pd 2 (dba) 3 (0.81 g, 0.88 mmol), P(t-Bu) 3 ( 5.96 g, 29.48 mmol), NaOt-Bu (5.67 g, 58.95 mmol) and toluene (295 mL) were added and then proceeded in the same manner as in the synthesis method of 2-1 to obtain 12.13 g of product 2-30. (Yield: 71%)
2-36의 합성Synthesis of 2-36
둥근바닥플라스크에 Sub 3-10 (10 g, 38 mmol), Sub 4-51 (14.5 g, 38 mmol), Pd2(dba)3 (1.04 g, 1.14 mmol), P(t-Bu)3 (7.69 g, 38 mmol), NaOt-Bu (7.30 g, 76 mmol), toluene (380 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 2-36을 16.5 g 얻었다. (수율 : 77%)In a round bottom flask, Sub 3-10 (10 g, 38 mmol), Sub 4-51 (14.5 g, 38 mmol), Pd 2 (dba) 3 (1.04 g, 1.14 mmol), P(t-Bu) 3 ( 7.69 g, 38 mmol), NaOt-Bu (7.30 g, 76 mmol) and toluene (380 mL) were added and then proceeded in the same manner as in the synthesis method of 2-1 to obtain 16.5 g of product 2-36. (Yield: 77%)
2-50의 합성Synthesis of 2-50
둥근바닥플라스크에 Sub 3-40 (10 g, 30.94 mmol), Sub 4-21 (9.95 g, 30.94 mmol), Pd2(dba)3 (0.85 g, 0.93 mmol), P(t-Bu)3 (6.26 g, 30.94 mmol), NaOt-Bu (5.95 g, 61.88 mmol), toluene (309 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 2-50을 13.26 g 얻었다. (수율 : 76%)In a round bottom flask, Sub 3-40 (10 g, 30.94 mmol), Sub 4-21 (9.95 g, 30.94 mmol), Pd 2 (dba) 3 (0.85 g, 0.93 mmol), P(t-Bu) 3 ( 6.26 g, 30.94 mmol), NaOt-Bu (5.95 g, 61.88 mmol) and toluene (309 mL) were added and then proceeded in the same manner as in the synthesis method of 2-1 to obtain 13.26 g of product 2-50. (Yield: 76%)
2-52의 합성Synthesis of 2-52
둥근바닥플라스크에 Sub 3-33 (10 g, 22.76 mmol), Sub 4-9 (7.86 g, 22.76 mmol), Pd2(dba)3 (0.63 g, 0.68 mmol), P(t-Bu)3 (4.60 g, 22.76 mmol), NaOt-Bu (4.38 g, 45.52 mmol), toluene (228 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 2-52을 11.38 g 얻었다. (수율 : 71%)In a round bottom flask, Sub 3-33 (10 g, 22.76 mmol), Sub 4-9 (7.86 g, 22.76 mmol), Pd 2 (dba) 3 (0.63 g, 0.68 mmol), P(t-Bu) 3 ( 4.60 g, 22.76 mmol), NaOt-Bu (4.38 g, 45.52 mmol), and toluene (228 mL) were added, followed by the same method as the synthesis method of 2-1 to obtain 11.38 g of product 2-52. (Yield: 71%)
2-60의 합성Synthesis of 2-60
둥근바닥플라스크에 Sub 3-35 (10 g, 30.94 mmol), Sub 4-59 (10.94 g, 30.94 mmol), Pd2(dba)3 (0.85 g, 0.93 mmol), P(t-Bu)3 (6.26 g, 30.94 mmol), NaOt-Bu (5.95 g, 61.88 mmol), toluene (309 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 2-60을 13.46 g 얻었다. (수율 : 73%)In a round bottom flask, Sub 3-35 (10 g, 30.94 mmol), Sub 4-59 (10.94 g, 30.94 mmol), Pd 2 (dba) 3 (0.85 g, 0.93 mmol), P(t-Bu) 3 ( 6.26 g, 30.94 mmol), NaOt-Bu (5.95 g, 61.88 mmol) and toluene (309 mL) were added and then proceeded in the same manner as in the synthesis method of 2-1 to obtain 13.46 g of product 2-60. (Yield: 73%)
2-85의 합성Synthesis of 2-85
둥근바닥플라스크에 Sub 3-49 (10 g, 21.21 mmol), Sub 4-21 (6.82 g, 21.21 mmol), Pd2(dba)3 (0.58 g, 0.64 mmol), P(t-Bu)3 (4.29 g, 21.21 mmol), NaOt-Bu (4.08 g, 42.43 mmol), toluene (212 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 2-85을 10.57 g 얻었다. (수율 : 70%)In a round bottom flask, Sub 3-49 (10 g, 21.21 mmol), Sub 4-21 (6.82 g, 21.21 mmol), Pd 2 (dba) 3 (0.58 g, 0.64 mmol), P(t-Bu) 3 ( 4.29 g, 21.21 mmol), NaOt-Bu (4.08 g, 42.43 mmol) and toluene (212 mL) were added and then proceeded in the same manner as in the synthesis method of 2-1 to obtain 10.57 g of product 2-85. (Yield: 70%)
2-89 의 합성Synthesis of 2-89
둥근바닥플라스크에 Sub 3-50 (10 g, 25.17 mmol), Sub 4-30 (14.14 g, 25.17 mmol), Pd2(dba)3 (0.69 g, 0.76 mmol), P(t-Bu)3 (5.09 g, 25.17 mmol), NaOt-Bu (4.84 g, 50.34 mmol), toluene (252 mL)을 넣은 후 상기 2-1의 합성법과 같은 방법으로 진행시켜서 생성물 2-89을 15.91 g 얻었다. (수율 : 72%)In a round bottom flask, Sub 3-50 (10 g, 25.17 mmol), Sub 4-30 (14.14 g, 25.17 mmol), Pd 2 (dba) 3 (0.69 g, 0.76 mmol), P(t-Bu) 3 ( After adding 5.09 g, 25.17 mmol), NaOt-Bu (4.84 g, 50.34 mmol), toluene (252 mL), and proceeding in the same manner as in the synthesis method of 2-1, 15.91 g of product 2-89 was obtained. (Yield: 72%)
상기와 같은 합성예에 따라 제조된 화합물 2-1 내지 2-97의 FD-MS 값은 하기 표 6과 같다.The FD-MS values of compounds 2-1 to 2-97 prepared according to the above synthesis example are shown in Table 6 below.
[표 6][Table 6]
유기전기소자의 제조평가Manufacturing evaluation of organic electric devices
[실시예 1] 내지 [실시예 90] 적색유기발광소자(발광층 혼합 인광호스트)[Example 1] to [Example 90] Red organic light emitting device (light-emitting layer mixed phosphorescent host)
유리 기판에 형성된 ITO층(양극) 상에 4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine (이하 "2-TNATA"로 약기함)막을 진공증착하여 60 nm 두께의 정공주입층을 형성한 후, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (이하 "NPD"로 약기함) 막을 55 nm 두께로 진공증착하여 정공수송층을 형성하였다. A 60 nm thick hole is deposited by vacuum depositing a 4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as "2-TNATA") film on an ITO layer (anode) formed on a glass substrate. After forming the injection layer, a 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter abbreviated as "NPD") film was vacuum-deposited to a thickness of 55 nm to form a hole transport layer.
다음으로, 상기 정공수송층 상에 30nm 두께의 발광층을 형성하였는데, 이때 하기 표 5에서와 같이 본 발명의 화학식 1로 표시되는 화합물(제1호스트)과 본 발명의 화학식 2로 표시되는 화합물(제2호스트)를 3:7의 중량비로 혼합한 혼합물을 호스트로, bis-(1-phenylisoquinolyl)iridium(Ⅲ)acetylacetonate(이하 "(piq)2Ir(acac)"로 약기함)를 도펀트로 사용하되, 호스트와 도펀트를 95:5 중량비가 되도록 사용하였다.Next, a light emitting layer having a thickness of 30 nm was formed on the hole transport layer. At this time, as shown in Table 5 below, the compound represented by Chemical Formula 1 (first host) and the compound represented by Chemical Formula 2 of the present invention (second) The mixture of the host) in a weight ratio of 3:7 is used as a host, and bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter abbreviated as "(piq) 2 Ir(acac)") is used as a dopant. The host and dopant were used in a 95:5 weight ratio.
다음으로, 상기 발광층 상에 (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (이하 "BAlq"로 약기함)을 10 nm 두께로 진공증착하여 정공저지층을 형성하였다.Next, a hole blocking layer by vacuum-depositing (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as "BAlq") on the light emitting layer to a thickness of 10 nm Formed.
이어서, 상기 정공저지층 상에 tris-(8-hydroxyquinoline)aluminum (이하 "Alq3"로 약기함)와 bis(10-hydroxybenzo[h]quinolinato)beryllium (이하 BeBq2로 약칭함)를 1:1로 혼합하여 45 nm 두께로 성막하여 전자수송층을 형성하였다. 이후, 전자수송층 상에 LiF를 0.2 nm 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 음극을 형성함으로써 유기전기발광소자를 제조하였다.Subsequently, tris-(8-hydroxyquinoline)aluminum (hereinafter abbreviated as “Alq 3 ”) and bis (10-hydroxybenzo[h]quinolinato)beryllium (hereinafter abbreviated as BeBq 2 ) on the hole blocking layer 1:1. It was mixed to form a film with a thickness of 45 nm to form an electron transport layer. Subsequently, an organic electroluminescent device was manufactured by depositing LiF on the electron transport layer to a thickness of 0.2 nm, and then depositing Al on a thickness of 150 nm to form a cathode.
[비교예 1] 내지 [비교예 4][Comparative Example 1] to [Comparative Example 4]
발광층의 호스트 물질로 하기 표 5에 기재된 것과 같이 본 발명의 화학식 1로 표시되는 화합물을 단독으로 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound represented by Formula 1 of the present invention was used alone as the host material of the light emitting layer.
[비교예 5] 및 [비교예 6][Comparative Example 5] and [Comparative Example 6]
발광층의 호스트 물질로 하기 표 5에 기재된 것과 같이 비교화합물 1과 비교화합물 2의 혼합물, 비교화합물 1과 비교화합물 3의 혼합물을 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescent device in the same manner as in Example 1, except that a mixture of Comparative Compound 1 and Comparative Compound 2 and a mixture of Comparative Compound 1 and Comparative Compound 3 were used as the host material of the light emitting layer, as shown in Table 5 below. Was produced.
<비교화합물 1> <비교화합물 2> <비교화합물 3> <Comparative compound 1> <Comparative compound 2> <Comparative compound 3>
본 발명의 실시예 1 내지 실시예 90 및 비교예 1 내지 비교예 6에 의해 제조된 유기전기발광소자에 순바이어스 직류전압을 가하여 포토리서치 (photoresearch) 사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 2500cd/m2 기준휘도에서 맥사이언스사의 수명측정장비를 통해 T95 수명을 측정하였으며, 그 측정 결과는 하기 표 7과 같다.Electro-luminescence (EL) characteristics of the organic electroluminescent device manufactured by Examples 1 to 90 and Comparative Examples 1 to 6 of the present invention were applied to a PR-650 manufactured by Photoresearch by applying a direct bias DC voltage. The T95 lifespan was measured through the life measurement equipment of Mac Science at a reference luminance of 2500 cd/m 2 , and the measurement results are shown in Table 7 below.
[표 7][Table 7]
상기 표 7의 결과로부터 알 수 있듯이, 본 발명의 화학식 1 및 화학식 2로 표시되는 화합물을 혼합하여 인광 호스트로 사용할 경우 (실시예1~90), 화학식 1로 표시되는 화합물을 단독으로 사용하거나(비교예1~4)나 비교화합물을 혼합하여 사용한 경우(비교예 5~6)에 비해 소자의 구동전압, 효율 및 수명이 현저하게 개선되는 것을 확인할 수 있다. As can be seen from the results of Table 7, when the compounds represented by Formula 1 and Formula 2 of the present invention are mixed and used as a phosphorescent host (Examples 1 to 90), the compounds represented by Formula 1 may be used alone ( It can be seen that the driving voltage, efficiency and lifespan of the device are significantly improved compared to Comparative Examples 1 to 4) or when the compounds are used in combination (Comparative Examples 5 to 6).
비교예 1 내지 6을 비교해보면, 본 발명의 화합물을 단독으로 사용한 경우(비교예 1~4)보다 비교화합물을 두 종류 혼합하여 사용한 경우(비교예 5~6)에 소자의 특성이 더 향상되었다.Comparing Comparative Examples 1 to 6, the properties of the device were further improved when the compounds of the present invention were used by mixing two types of comparative compounds (Comparative Examples 5 to 6) than when the compounds of the present invention were used alone (Comparative Examples 1 to 4). .
또한, 비교예 5~6과 본 발명의 실시예를 비교해보면, 비교화합물을 두 종류 혼합한 것보다는 본 발명의 화학식 1에 따른 화합물과 화학식 2에 따른 화합물을 혼합한 호스트를 사용할 경우 구동전압이 낮아지고 효율과 수명이 현저히 향상되었다.In addition, when comparing Examples 5 to 6 and Examples of the present invention, when using a host in which a compound according to Formula 1 and a compound according to Formula 2 of the present invention are mixed, rather than two kinds of comparative compounds, the driving voltage is It was lowered and efficiency and lifespan were significantly improved.
본 발명의 발명자들은 이러한 결과로부터 화학식 1의 물질과 화학식 2의 물질을 혼합한 혼합물의 경우 각각의 물질이 갖는 특성 이외의 다른 신규한 특성을 갖는다고 판단하여, 이들 각 물질 및 혼합물을 사용하여 PL lifetime을 측정하였다. 그 결과 본 발명 화학식 1 및 화학식 2를 혼합한 혼합물의 경우 단독 화합물일 때와 달리 새로운 PL 파장이 형성되는 것을 확인할 수 있었다.From the results, the inventors of the present invention determined that, in the case of a mixture of the substance of Formula 1 and the substance of Formula 2, it has novel characteristics other than those of each substance, and uses each of these substances and mixtures to PL The lifetime was measured. As a result, in the case of the mixture of the present invention formula 1 and formula 2, it was confirmed that a new PL wavelength was formed unlike the single compound.
이는 본 발명의 화합물을 혼합하여 사용할 경우 각각의 물질이 갖는 에너지 준위를 통해 전자와 정공이 이동되는 것뿐만 아니라, 혼합으로 인하여 형성된 새로운 에너지 준위를 갖는 신규 영역(exciplex)에 의한 전자 및 정공의 이동 또는 에너지 전달로 인해 효율 및 수명이 증가한 것으로 판단된다. 이는 본 발명의 혼합물을 사용할 경우 혼합 박막이 exciplex 에너지 전달 및 발광 프로세스를 보이는 중요한 예라고 할 수 있다.When the compound of the present invention is used in combination, not only electrons and holes are moved through the energy level of each material, but also electrons and holes are moved by a new exciplex having a new energy level formed due to mixing. Or, it is judged that the efficiency and lifetime have increased due to energy transfer. This can be said to be an important example in which the mixed thin film shows an exciplex energy transfer and luminescence process when using the mixture of the present invention.
또한, 전자뿐만 아니라 정공에 대한 안정성이 높고, 높은 T1 값을 갖는 화학식 1로 표시되는 다환 화합물에 정공(hole) 특성이 강한 화학식 2로 표시되는 화합물을 혼합할 경우, 높은 T1과 높은 LUMO 에너지 값으로 인해 전자 블로킹 능력이 향상되고, 발광층에 더 많은 hole이 빠르고 쉽게 이동하게 된다. 이와 같이 정공이 발광층에 더 빨리 이동하고 전자 블로킹 능력이 향상되면 발광층 내에서 전하 균형이 증가하게 되어 정공수송층 계면이 아닌 발광층 내부에서 발광이 잘 이루어지고, 그로 인해 HTL 계면의 열화 또한 감소하여 소자 전체의 구동 전압, 효율 그리고 수명이 극대화된다. 따라서, 화학식 1 및 화학식 2로 표시되는 화합물을 혼합하여 호스트로 사용할 경우 전기 화학적 시너지 작용으로 소자 전체의 성능이 크게 향상된 결과를 보였다.In addition, when a compound represented by Chemical Formula 2 having high hole characteristics is mixed with a polycyclic compound represented by Chemical Formula 1 having high stability against holes as well as a high T1 value, high T1 and high LUMO energy values Due to this, the electron blocking ability is improved, and more holes in the light emitting layer are moved quickly and easily. As described above, when the hole moves faster to the light emitting layer and the electron blocking ability is improved, the charge balance in the light emitting layer increases, so that the light emission is performed well inside the light emitting layer rather than the hole transport layer interface, thereby reducing the deterioration of the HTL interface, thereby reducing the entire device. The driving voltage, efficiency and lifetime are maximized. Accordingly, when a compound represented by Chemical Formula 1 and Chemical Formula 2 is used as a mixture, the overall performance of the device is greatly improved due to the electrochemical synergy effect.
[실시예 91] 내지 [실시예 94][Example 91] to [Example 94]
하기 표 7에 기재된 것과 같이 제1호스트와 제2호스트를 일정 비율별로 혼합하여 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the first host and the second host were mixed by a certain ratio as described in Table 7 below.
본 발명의 실시예 91 내지 실시예 94에 의해 제조된 유기전기발광소자에 순바이어스 직류전압을 가하여 포토리서치 (photoresearch) 사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 2500cd/m2 기준휘도에서 맥사이언스사의 수명측정장비를 통해 T95 수명을 측정하였다. 그 결과는 하기 표 8과 같다. 실시예 3 및 실시예 80은 표 6에서와 동일하게 제1호스트와 제2호스트를 3:7로 혼합하여 사용한 경우의 소자 특성 측정 결과이다.Electroluminescence (EL) characteristics were measured by PR-650 of photoresearch by applying a net bias DC voltage to the organic electroluminescent devices manufactured in Examples 91 to 94 of the present invention, and based on 2500 cd/m 2 The T95 life was measured at a luminance through a life measurement equipment of Max Science. The results are shown in Table 8 below. Example 3 and Example 80 is the result of measuring the device characteristics when the first host and the second host are mixed in a ratio of 3:7 as in Table 6.
[표 8][Table 8]
상기 표 8을 참조하면, 제1호스트와 제2호스트를 3:7로 혼합할 경우 구동전압, 효율 및 수명이 가장 우수하며, 제1호스트의 비율이 많아질수록 소자 특성이 저하되는 것을 확인할 수 있다. 이는 화학식 1로 표시되는 화합물보다 상대적으로 hole 특성이 강한 화학식 2로 표시되는 화합물의 양이 많아짐에 따라 발광층 내 전하균형이 극대화되기 때문으로 보인다.Referring to Table 8, it can be seen that when the first host and the second host are mixed at 3:7, the driving voltage, efficiency, and life are the best, and the device characteristics decrease as the ratio of the first host increases. have. This is because the charge balance in the light emitting layer is maximized as the amount of the compound represented by the formula (2), which has a relatively higher hole property than the compound represented by the formula (1), increases.
이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명에 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내의 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains will be capable of various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention, but to explain the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be interpreted by the claims below, and all technologies within the equivalent range should be interpreted as being included in the scope of the present invention.
CROSS-REFERENCE TO RELATED APPLICATIONCROSS-REFERENCE TO RELATED APPLICATION
본 특허출원은 2018년 12월 20일 한국에 출원한 특허출원번호 제10-2018-0166495호에 대해 미국 특허법 119조 내지 121조, 365조 (35 U.S.C §19조 내지 §121조, §365조)에 따라 우선권을 주장하며, 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다. 아울러, 본 특허출원은 미국 이외에 국가에 대해서도 위와 동일한 이유로 우선권을 주장하면 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다.This patent application is filed in Korea on December 20, 2018 with respect to Patent Application No. 10-2018-0166495, U.S. Patent Acts 119 to 121, 365 (35 USC §19 to §121, §365) ), all contents of which are incorporated into this patent application by reference. In addition, if this patent application claims priority for the same reasons as above for countries other than the United States, all of the contents are incorporated into this patent application as a reference.
Claims (11)
- 제 1전극, 제 2 전극 및 상기 제 1전극과 상기 제 2전극 사이에 형성된 유기물층을 포함하는 유기전기소자에 있어서, In the organic electrical device including a first electrode, a second electrode and an organic material layer formed between the first electrode and the second electrode,상기 유기물층은 인광성 발광층을 포함하고, 상기 인광성 발광층의 호스트는 하기 화학식 1로 표시되는 제 1화합물과 하기 화학식 2로 표시되는 제 2화합물을 포함하는 것을 특징으로 하는 유기전기소자:The organic material layer includes a phosphorescent light-emitting layer, the host of the phosphorescent light-emitting layer is an organic electric device comprising a first compound represented by the following formula (1) and a second compound represented by the following formula (2):<화학식 1> <화학식 2> <Formula 1> <Formula 2>
상기 화학식에서,In the above formula,X1은 O 또는 S이고,X 1 is O or S,Ar1, Ar2, Ar4 내지 Ar6은 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕시기; 및 C6~C30의 아릴옥시기로 이루어진 군에서 선택되며,Ar 1 , Ar 2 , Ar 4 to Ar 6 are independently of each other C 6 ~ C 60 aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 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; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 30 Alkoxy group; And C 6 ~ C 30 It is selected from the group consisting of an aryloxy group,L1 내지 L6은 서로 독립적으로 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택되며,L 1 to L 6 are each independently a single bond; C 6 ~ C 60 Arylene group; Fluorylene group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring group; And combinations thereof,R1은 수소; 중수소; 할로겐; 시아노기; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕시기; C6~C30의 아릴옥시기; 및 -L'-N(Ra)(Rb);로 이루어진 군에서 선택되며, 이웃한 R1끼리 서로 결합하여 고리를 형성할 수 있고,R 1 is hydrogen; heavy hydrogen; halogen; Cyano group; C 6 ~ C 60 Aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 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; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 30 Alkoxy group; C 6 ~ C 30 Aryloxy group; And -L'-N (R a ) (R b ); is selected from the group consisting of, R 1 adjacent to each other may be bonded to each other to form a ring,a는 0~9의 정수이고, a가 2 이상의 정수인 경우 복수의 R1 각각은 서로 같거나 상이하며,a is an integer from 0 to 9, and when a is an integer of 2 or more, each of the plurality of R 1 is the same or different from each other,상기 L'은 서로 독립적으로 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택되며,L'is independently of each other a single bond; C 6 ~ C 60 Arylene group; Fluorylene group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring group; And combinations thereof,상기 Ra 및 Rb는 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택된다.R a and R b are independently of each other C 6 ~ C 60 aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring group; And combinations thereof. - 제 1항에 있어서,According to claim 1,상기 화학식 1에서 하기 화학식 1-1로부터 도출되는 화합물은 제외되는 것을 특징으로 하는 유기전기소자:An organic electrical device characterized in that the compound derived from the following Chemical Formula 1-1 in Chemical Formula 1 is excluded:<화학식 1-1><Formula 1-1>
상기 화학식 1-1에서, L1 내지 L3, X1, R1, a는 제1항에서 정의된 것과 같고, In Formula 1-1, L 1 to L 3 , X 1 , R 1 , a are the same as defined in claim 1,Ar1 및 Ar2는 서로 독립적으로 C6~C18의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C16의 헤테로고리기; C3~C60의 지방족고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕시기; 및 C6~C30의 아릴옥시기로 이루어진 군에서 선택된다.Ar 1 and Ar 2 are independently of each other C 6 ~ C 18 aryl group; Fluorenyl group; C 2 ~ C 16 heterocyclic group containing at least one heteroatom of 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; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 30 Alkoxy group; And C 6 ~ C 30 It is selected from the group consisting of an aryloxy group. - 제 1항에 있어서, According to claim 1,상기 L1 내지 L6은 서로 독립적으로 하기 화학식 b-1 내지 b-13 중에서 하나인 것을 특징으로 하는 유기전기소자:The L 1 to L 6 are each independently an organic electric device characterized in that one of the following formulas b-1 to b-13:<화학식 b-1> <화학식 b-2> <화학식 b-3> <화학식 b-4><Formula b-1> <Formula b-2> <Formula b-3> <Formula b-4>
<화학식 b-5> <화학식 b-6> <화학식 b-7> <화학식 b-8><Formula b-5> <Formula b-6> <Formula b-7> <Formula b-8>
<화학식 b-9> <화학식 b-10><Formula b-9> <Formula b-10>
<화학식 b-11> <화학식 b-12> <화학식 b-13><Formula b-11> <Formula b-12> <Formula b-13>
상기 화학식에서,In the above formula,R5 내지 R7은 서로 독립적으로 수소; 중수소; 할로겐; 시아노기; 니트로기; C6~C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; C3~C20의 지방족고리와 C6~C20의 방향족고리의 융합고리기; C1~C20의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C20의 알콕시기; C6~C30의 아릴옥시기; 및 -La-N(Ra)(Rb);로 이루어진 군에서 선택되며, 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있으며,R 5 to R 7 are independently of each other hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; C 6 ~ C 20 aryl group; Fluorenyl group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; C 3 ~ C 20 aliphatic ring and C 6 ~ C 20 aromatic ring fused ring group; C 1 ~ C 20 alkyl group; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 20 Alkoxy group; C 6 ~ C 30 Aryloxy group; And -L a -N (R a ) (R b ); is selected from the group consisting of, adjacent groups may be bonded to each other to form a ring,Y는 N-(La-Ara), O, S 또는 C(R')(R")이고,Y is N-(L a -Ar a ), O, S or C(R')(R"),Z1 내지 Z3은 서로 독립적으로 C, C(R') 또는 N이고, Z1 내지 Z3 중에서 적어도 하나는 N이며, Z 1 to Z 3 are each independently C, C(R') or N, and at least one of Z 1 to Z 3 is N,f는 0 내지 6의 정수이고, e, g, h, i는 각각 0 내지 4의 정수이고, j, k는 각각 0 내지 3의 정수이고, l은 각각 0 내지 2의 정수이고, m은 0 내지 3의 정수이며, 이들 각각이 2 이상의 정수인 경우 복수의 R5 각각, 복수의 R6 각각, 복수의 R7 각각은 서로 동일하거나 상이하며,f is an integer from 0 to 6, e, g, h, and i are integers from 0 to 4, j, k are integers from 0 to 3, l is an integer from 0 to 2, and m is 0, respectively. And an integer of 3 to 3, each of which is an integer of 2 or more, each of a plurality of R 5, each of a plurality of R 6, each of a plurality of R 7 is the same or different from each other,상기 R' 및 R"는 서로 독립적으로 수소; 중수소; 할로겐; 시아노기; 니트로기; C6~C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; C3~C20의 지방족고리와 C6~C20의 방향족고리의 융합고리기; C1~C20의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C20의 알콕시기; C6~C30의 아릴옥시기; 및 -La-N(Ra)(Rb);로 이루어진 군에서 선택되며, R'and R" are independently of each other hydrogen; deuterium; halogen; cyano group; nitro group; C 6 ~ C 20 aryl group; fluorenyl group; O, N, S, Si and P at least one heteroatom C 2 ~ C 20 heterocyclic group containing; C 3 ~ C 20 aliphatic ring group; C 3 ~ C 20 aliphatic ring and C 6 ~ C 20 aromatic ring fused ring group; C 1 ~ C 20 Alkyl group of; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 20 alkoxy group; C 6 ~ C 30 aryloxy group; and -L a -N (R a ) (R b ); is selected from the group consisting of,C(R')(R")에서 R'와 R"끼리 서로 결합하여 고리를 형성할 수 있고, C(R')에서 이웃한 R'끼리 서로 결합하여 고리를 형성할 수 있으며,In C(R')(R"), R'and R" may combine with each other to form a ring, and in C(R'), adjacent R's may combine with each other to form a ring,상기 Ara는 C6~C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택되며,The Ar a is C 6 ~ C 20 aryl group; Fluorenyl group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; And combinations thereof,상기 La는 서로 독립적으로 단일결합; C6~C20의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택되며,L a is a single bond independently of each other; C 6 ~ C 20 Arylene group; Fluorylene group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; And combinations thereof,상기 Ra 및 Rb는 서로 독립적으로 C6~C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택된다.R a and R b are independently of each other C 6 ~ C 20 aryl group; Fluorenyl group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; And combinations thereof. - 제 1항에 있어서, According to claim 1,상기 화학식 1은 하기 화학식 1-A 내지 화학식 1-E 중에서 하나로 표시되는 것을 특징으로 하는 유기전기소자:The Formula 1 is an organic electric device characterized in that represented by one of the following Formula 1-A to Formula 1-E:<화학식 1-A> <화학식 1-B><Formula 1-A> <Formula 1-B>
<화학식 1-C> <화학식 1-D><Formula 1-C> <Formula 1-D>
<화학식 1-E><Formula 1-E>
상기 화학식에서, In the above formula,Ar1, Ar2, L1 내지 L3, X1, R1, a는 제1항에서 정의된 것과 같고,Ar 1 , Ar 2 , L 1 to L 3 , X 1 , R 1 , a are the same as defined in claim 1,X2 및 X3은 서로 독립적으로 O 또는 S이며,X 2 and X 3 are each independently O or S,R4, R8 및 R9는 서로 독립적으로 수소; 중수소; 할로겐; 시아노기; 니트로기; C6~C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; C3~C20의 지방족고리와 C6~C20의 방향족고리의 융합고리기; C1~C20의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C20의 알콕시기; C6~C30의 아릴옥시기; 및 -La-N(Ra)(Rb);로 이루어진 군에서 선택되며, 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있으며,R 4 , R 8 and R 9 are independently of each other hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; C 6 ~ C 20 aryl group; Fluorenyl group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; C 3 ~ C 20 aliphatic ring and C 6 ~ C 20 aromatic ring fused ring group; C 1 ~ C 20 alkyl group; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 20 Alkoxy group; C 6 ~ C 30 Aryloxy group; And -L a -N (R a ) (R b ); is selected from the group consisting of, adjacent groups may be bonded to each other to form a ring,d1은 0~7의 정수이고, i 및 j는 각각 0~6의 정수이고, 이들 각각이 2 이상의 정수인 경우 복수의 R4 각각, 복수의 R8 각각, 복수의 R9 각각은 서로 같거나 상이하며,d1 is an integer from 0 to 7, i and j are integers from 0 to 6, and when each of them is an integer of 2 or more, each of a plurality of R 4, each of a plurality of R 8, and each of a plurality of R 9 are the same or different from each other And상기 La는 서로 독립적으로 단일결합; C6~C20의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택되며,L a is a single bond independently of each other; C 6 ~ C 20 Arylene group; Fluorylene group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; And combinations thereof,상기 Ra 및 Rb는 서로 독립적으로 C6~C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리기; 및 이들의 조합으로 이루어진 군에서 선택된다.R a and R b are independently of each other C 6 ~ C 20 aryl group; Fluorenyl group; C 2 ~ C 20 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 20 aliphatic ring group; And combinations thereof. - 제 4항에 있어서,The method of claim 4,상기 화학식 1-A는 하기 화학식 1-A-1 내지 화학식 1-A-6 중에서 하나로 표시될 수 있는 것을 특징으로 하는 유기전기소자:The formula 1-A is an organic electric device characterized in that it can be represented by one of the following formula 1-A-1 to formula 1-A-6:<화학식 1-A-1> <화학식 1-A-2> <화학식 1-A-3><Formula 1-A-1> <Formula 1-A-2> <Formula 1-A-3>
<화학식 1-A-4> <화학식 1-A-5> <화학식 1-A-6><Formula 1-A-4> <Formula 1-A-5> <Formula 1-A-6>
상기 화학식에서, Ar1, Ar2, L1~L3, X1, R1, a는 제4항에서 정의된 것과 같다.In the above formula, Ar 1 , Ar 2 , L 1 ~L 3 , X 1 , R 1 , a are as defined in claim 4. - 제 1항에 있어서, According to claim 1,상기 화학식 2는 하기 화학식 2-A 내지 화학식 2-C 중에서 하나로 표시되는 것을 특징으로 하는 유기전기소자:The formula 2 is an organic electric device, characterized in that represented by one of the following formula 2-A to formula 2-C:<화학식 2-A> <화학식 2-B><Formula 2-A> <Formula 2-B>
<화학식 2-C><Formula 2-C>
상기 화학식에서, Ar5, Ar6, L4~L6은 제1항에서 정의된 것과 같고,In the above formula, Ar 5 , Ar 6 , L 4 ~L 6 is the same as defined in claim 1,Y1~Y3은 서로 독립적으로 O, S, C(R')(R")이고,Y 1 ~ Y 3 are independently of each other O, S, C(R')(R"),R11~R16, R' 및 R"은 서로 독립적으로 수소; 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 시아노기; 니트로기; C1-C20의 알콕시기; C6-C20의 아릴옥시기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; 및 C3-C20의 지방족고리기;로 이루어진 군에서 선택되고, 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있으며, R 11 to R 16 , R'and R" are independently of each other hydrogen; deuterium; halogen; C 1 -C 20 alkyl group or C 6 -C 20 aryl group unsubstituted or substituted silane group; cyano group; nitro group ; C 1 -C 20 alkoxy group; C 6 -C 20 aryloxy group; C 1 -C 20 alkyl group; C 2 -C 20 alkenyl group; C 2 -C 20 alkynyl group; C 6 -C Aryl group of 20 ; fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; and aliphatic ring of C 3 -C 20 Group; selected from the group consisting of, adjacent groups may combine with each other to form a ring,b는 0~4의 정수이고, b가 2 이상의 정수인 경우 복수의 R11 각각, 복수의 R13 각각, 복수의 R15 각각은 서로 같거나 상이하며,b is an integer from 0 to 4, and when b is an integer of 2 or more, each of the plurality of R 11, each of the plurality of R 13, and each of the plurality of R 15 are the same or different from each other,c는 0~3의 정수이고, c가 2 이상의 정수인 경우 복수의 R12 각각, 복수의 R14 각각, 복수의 R16 각각은 서로 같거나 상이하다.c is an integer of 0 to 3, and when c is an integer of 2 or more, each of the plurality of R 12, each of the plurality of R 14, and each of the plurality of R 16 are the same or different from each other. - 제 1항에 있어서,According to claim 1,상기 화학식 2는 하기 화학식 2-D 내지 화학식 2-I 중 하나로 표시되는 것을 특징으로 하는 유기전기소자:The formula 2 is an organic electric device, characterized in that represented by one of the following formula 2-D to formula 2-I:<화학식 2-D> <화학식 2-E> <화학식 2-F><Formula 2-D> <Formula 2-E> <Formula 2-F>
<화학식 2-G> <화학식 2-H> <화학식 2-I><Formula 2-G> <Formula 2-H> <Formula 2-I>
<화학식 2-G> <화학식 2-H> <화학식 2-I><Formula 2-G> <Formula 2-H> <Formula 2-I>
상기 화학식에서, Ar5, Ar6, L4~L6은 제1항에서 정의된 것과 같고,In the above formula, Ar 5 , Ar 6 , L 4 ~L 6 is the same as defined in claim 1,Y1은 서로 독립적으로 O, S, C(R')(R")이고,Y 1 is independently of each other O, S, C(R')(R"),R11, R12, R' 및 R"은 서로 독립적으로 수소; 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 시아노기; 니트로기; C1-C20의 알콕시기; C6-C20의 아릴옥시기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; 및 C3-C20의 지방족고리기;로 이루어진 군에서 선택되고, 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있으며, R 11 , R 12 , R'and R" are independently of each other hydrogen; deuterium; halogen; C 1 -C 20 alkyl group or C 6 -C 20 aryl group unsubstituted or substituted silane group; cyano group; nitro group ; C 1 -C 20 alkoxy group; C 6 -C 20 aryloxy group; C 1 -C 20 alkyl group; C 2 -C 20 alkenyl group; C 2 -C 20 alkynyl group; C 6 -C Aryl group of 20 ; fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; and aliphatic ring of C 3 -C 20 Group; selected from the group consisting of, adjacent groups may combine with each other to form a ring,b는 0~4의 정수이고, b가 2 이상의 정수인 경우 복수의 R11 각각은 서로 같거나 상이하며,b is an integer from 0 to 4, and when b is an integer of 2 or more, each of the plurality of R 11 is the same or different from each other,c는 0~3의 정수이고, c가 2 이상의 정수인 경우 복수의 R12 각각은 서로 같거나 상이하다.c is an integer of 0 to 3, and when c is an integer of 2 or more, each of the plurality of R 12 s are the same or different. - 제 1항에 있어서, According to claim 1,상기 화학식 1로 표시되는 화합물은 하기 화합물 중 하나인 것을 특징으로 하는 유기전기소자:The compound represented by Formula 1 is an organic electric device, characterized in that one of the following compounds:
.
. - 제 1항에 있어서, According to claim 1,상기 화학식 2로 표시되는 화합물은 하기 화합물 중 하나인 것을 특징으로 하는 유기전기소자:The compound represented by Formula 2 is an organic electric device, characterized in that one of the following compounds:
.
. - 제1항의 유기전기소자를 포함하는 디스플레이장치; 및 A display device comprising the organic electroluminescent device of claim 1; And상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치.An electronic device comprising; a control unit for driving the display device.
- 제 10항에 있어서,The method of claim 10,상기 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 단색 조명용 소자 및 퀀텀닷 디스플레이용 소자로 이루어진 군에서 선택되는 것을 특징으로 하는 전자장치.The organic electric device is an electronic device characterized in that it is selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a monochromatic lighting device, and a quantum dot display device.
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| KR1020180166495A KR102712988B1 (en) | 2018-12-20 | 2018-12-20 | An organic electronic element comprising compound for organic electronic element and an electronic device thereof |
| KR10-2018-0166495 | 2018-12-20 |
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| US11678569B2 (en) | 2020-03-31 | 2023-06-13 | Idemitsu Kosan Co., Ltd. | Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device |
| US11744149B2 (en) | 2019-05-31 | 2023-08-29 | Idemitsu Kosan Co., Ltd. | Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device |
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| KR20220050825A (en) * | 2020-10-16 | 2022-04-25 | 주식회사 엘지화학 | Organic light emitting device comprising organic compounds |
| US20240349605A1 (en) * | 2021-08-05 | 2024-10-17 | Lg Chem, Ltd. | Organic light emitting device |
| WO2023096318A1 (en) * | 2021-11-26 | 2023-06-01 | 주식회사 엘지화학 | Novel compound and organic light-emitting device comprising same |
| KR20230131696A (en) * | 2022-03-07 | 2023-09-14 | 엘티소재주식회사 | Heterocyclic compound, organic light emitting device comprising same, manufacturing method of same and composition for organic layer of organic light emitting device |
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| KR20170130737A (en) * | 2016-05-19 | 2017-11-29 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
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| KR101399636B1 (en) * | 2011-03-11 | 2014-05-28 | (주)씨에스엘쏠라 | Organic light compound and organic light device using the same |
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| KR20170083765A (en) * | 2016-01-11 | 2017-07-19 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| KR20170130737A (en) * | 2016-05-19 | 2017-11-29 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
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| US11678569B2 (en) | 2020-03-31 | 2023-06-13 | Idemitsu Kosan Co., Ltd. | Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device |
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