CN110088110B - Novel compound and organic light-emitting element comprising same - Google Patents
Novel compound and organic light-emitting element comprising same Download PDFInfo
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Abstract
The present invention provides a novel compound containing two carbazolyl groups in a molecule, and an organic light-emitting element containing the same.
Description
Technical Field
Cross reference to related applications
The present application claims priority based on korean patent application No. 10-2017-0075026, 14.6.2017, the entire contents of which are incorporated herein by reference.
The present invention relates to a novel compound including two carbazolyl groups in a molecule, and an organic light-emitting element including the same.
Background
In general, the organic light emission phenomenon refers to a phenomenon in which electric energy is converted into light energy by using an organic substance. An organic light emitting element using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, a fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus a great deal of research is being conducted.
An organic light-emitting element generally has a structure including an anode and a cathode, and an organic layer located between the anode and the cathode. In order to improve the efficiency and stability of the organic light-emitting device, the organic layer is often formed of a multilayer structure formed of different materials, and may be formed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, or the like. With the structure of such an organic light emitting element, if a voltage is applied between both electrodes, holes are injected from the anode into the organic layer, electrons are injected from the cathode into the organic layer, excitons (exiton) are formed when the injected holes and electrons meet, and light is emitted when the excitons are transitioned again to the ground state.
As for organic materials used for the organic light emitting element as described above, development of new materials is continuously demanded.
Disclosure of Invention
The present invention relates to a novel compound containing two carbazolyl groups (carbazolyl groups) in a molecule, and an organic light-emitting device containing the same.
The present invention provides a compound of the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1 as described above,
r is substituted or unsubstituted C 6-60 An aryl group which is a radical of an aromatic group,
R 1 and R 2 Each independently is deuterium; halogen; a cyano group; a nitro group; an amino group; substituted or unsubstituted C 1-60 An alkyl group; substituted or unsubstituted C 1-60 A haloalkyl group; substituted or unsubstituted C 1-60 An alkoxy group; substituted or unsubstituted C 1-60 A haloalkoxy group; substituted or unsubstituted C 3-60 A cycloalkyl group; substituted or unsubstitutedC of (A) 2-60 An alkenyl group; substituted or unsubstituted C 6-60 An aryl group; substituted or unsubstituted C 6-60 An aryloxy group; substituted or unsubstituted C 7-60 Aralkyl group; substituted or unsubstituted C 7-60 An alkylaryl group; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-60 (ii) a heteroaryl group, wherein,
a1 and a2 are each independently an integer from 0 to 3,
cy is a multiple condensed ring of the following chemical formula 2,
[ chemical formula 2]
In the above chemical formula 2, X 1 Is O, S or NR 3 ，
A is a benzene ring of the following chemical formula 3 condensed with adjacent 2 rings,
b is C in common with A 1 And C 2 The ring of the following chemical formula 4,
[ chemical formula 3]
[ chemical formula 4]
In the above chemical formulae 3 and 4, X 2 Is O, S or NR 3 ，X 1 And X 2 Not simultaneously NR 3 ，
R 3 Is hydrogen; deuterium; a halogen; a cyano group; a nitro group; an amino group; substituted or unsubstituted C 1-60 An alkyl group; substituted or unsubstituted C 1-60 A haloalkyl group; substituted or unsubstituted C 1-60 An alkoxy group; substituted or unsubstituted C 1-60 A haloalkoxy group; substituted or unsubstituted C 3-60 A cycloalkyl group; substituted or unsubstituted C 2-60 An alkenyl group; substituted or unsubstituted C 6-60 An aryl group; substituted or unsubstituted C 6-60 An aryloxy group; substituted or unsubstituted C 7-60 Aralkyl group; substituted or unsubstituted C 7-60 An alkylaryl group; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-60 (ii) a heteroaryl group, wherein,
Ar 1 and Ar 2 Each independently is substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C containing one or more heteroatoms selected from O, N, Si and S 2-60 (ii) a heteroaryl group, wherein,
b1 and b2 are each independently an integer from 0 to 2.
In addition, the present invention provides an organic light emitting element including: the organic light emitting device includes a first electrode, a second electrode provided to face the first electrode, and one or more organic layers provided between the first electrode and the second electrode, wherein one or more of the organic layers include the compound of chemical formula 1.
The compound of chemical formula 1 described above can be used as a material for an organic layer of an organic light emitting element in which improvement in efficiency, lower driving voltage, and/or improvement in lifetime characteristics can be achieved. In particular, the above-described compound represented by chemical formula 1 may be used as a light emitting, electron transporting, or electron injecting material.
Drawings
Fig. 1 shows an example of an organic light-emitting element including a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
Fig. 2 illustrates an example of an organic light-emitting element composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4.
Description of the symbols
1: substrate 2: anode
3: light-emitting layer 4: cathode electrode
5: hole injection layer 6: hole transport layer
7: light-emitting layer 8: electron transport layer
Detailed Description
Hereinafter, the present invention will be described in more detail to assist understanding thereof.
In the context of the present specification,
represents a bond to other substituents.
In the present specification, the term "substituted or unsubstituted" means that the substituent is selected from deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio(s) of (A), (B) and (C)
Alkyl thio xy); arylthio radicals (A), (B) and (C)
Aryl thio); alkylsulfonyl (
Alkyl sulfo); arylsulfonyl (
Aryl sulfoxy); a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamino group; an aralkylamino group; a heteroaryl amino group; an arylamine group; an aryl phosphine group; or1 or more substituents in the heterocyclic group containing 1 or more of N, O and S atoms, or a substituent formed by connecting 2 or more substituents among the above-exemplified substituents. For example, the "substituent in which 2 or more substituents are bonded" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which 2 phenyl groups are linked.
In the present specification, the carbon number of the carbonyl group is not particularly limited, but the carbon number is preferably 1 to 40 (C) 1-40 ). Specifically, the compound may have the following structure, but is not limited thereto.
In the ester group, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, the compound may be a compound of the following structural formula, but is not limited thereto.
In the present specification, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the compound may have the following structure, but is not limited thereto.
In the present specification, specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.
In the present specification, the boron group includes specifically a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group and the like, but is not limited thereto.
In the present specification, examples of the halogen group include fluorine, chlorine, bromine, and iodine.
In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methylbutyl group, a 1-ethylbutyl group, a pentyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, a n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a 3, 3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, a n-heptyl group, a 1-methylhexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, an octyl group, a n-octyl group, a tert-octyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 2-propylpentyl group, a n-nonyl group, a2, 2-dimethylheptyl group, a 1-ethyl-propyl group, a1, 1-dimethyl-propyl group, a, Isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but the invention is not limited thereto.
In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms of the alkenyl group is 2 to 20. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 10. According to another embodiment, the number of carbon atoms of the above alkenyl group is 2 to 6. Specific examples thereof include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylethen-1-yl, 2-diphenylethen-1-yl, 2-phenyl-2- (naphthalen-1-yl) ethen-1-yl, 2-bis (biphenyl-1-yl) ethen-1-yl, stilbenyl, styryl and the like.
In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specifically, there are mentioned, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like.
In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aromatic group may be a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a perylene group,
And a fluorenyl group, but is not limited thereto.
In the present specification, the fluorenyl group may be substituted, and 2 substituents may be combined with each other to form a spiro structure. When the fluorenyl group is substituted, the compound may be
And so on. But is not limited thereto.
In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N, Si and S as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, and the like,
Azolyl group,
Oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzobenzoxazinyl
Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophenePhenyl, dibenzothienyl, benzofuranyl, phenanthrolinyl, isoquinonyl
Oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but is not limited thereto.
In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the above-mentioned aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamino group is the same as the above-mentioned examples of the alkyl group. In the present specification, the heteroaryl group in the heteroarylamine can be applied to the above description about the heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the above-mentioned examples of the alkenyl group. In the present specification, the arylene group is a 2-valent group, and the above description of the aryl group can be applied thereto. In the present specification, a heteroarylene group is a 2-valent group, and in addition to this, the above description about a heterocyclic group can be applied. In the present specification, the hydrocarbon ring is not a 1-valent group but is formed by combining 2 substituents, and in addition to this, the above description about the aryl group or the cycloalkyl group can be applied. In the present specification, the heterocyclic group is not a 1-valent group but a combination of 2 substituents, and the above description of the heterocyclic group can be applied.
In addition, the present invention provides a compound of the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1 as described above,
r is substituted or unsubstituted C 6-60 An aryl group which is a radical of an aromatic group,
R 1 and R 2 Each independently is deuterium; halogen; a cyano group; a nitro group; an amino group; substituted or unsubstituted C 1-60 An alkyl group; substituted or unsubstituted C 1-60 A haloalkyl group; substituted or unsubstituted C 1-60 An alkoxy group; substituted or unsubstituted C 1-60 A haloalkoxy group; substituted or unsubstituted C 3-60 A cycloalkyl group;substituted or unsubstituted C 2-60 An alkenyl group; substituted or unsubstituted C 6-60 An aryl group; substituted or unsubstituted C 6-60 An aryloxy group; substituted or unsubstituted C 7-60 Aralkyl group; substituted or unsubstituted C 7-60 An alkylaryl group; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-60 (ii) a heteroaryl group, wherein,
a1 and a2 are each independently an integer from 0 to 3,
cy is a multiple condensed ring of the following chemical formula 2,
[ chemical formula 2]
In the above chemical formula 2, X 1 Is O, S or NR 3 ，
A is a benzene ring of the following chemical formula 3 condensed with adjacent 2 rings,
b is C in common with A 1 Carbon and C of 2 The carbon of (3) is a ring of the following chemical formula 4,
[ chemical formula 3]
[ chemical formula 4]
In the above chemical formulas 3 and 4, X 2 Is O, S or NR 3 ，X 1 And X 2 Not simultaneously being NR 3 ，
R 3 Is hydrogen; deuterium; halogen; a cyano group; a nitro group; an amino group; substituted or unsubstituted C 1-60 An alkyl group; substituted or unsubstituted C 1-60 A haloalkyl group; substituted or unsubstituted C 1-60 An alkoxy group; substituted or unsubstituted C 1-60 A haloalkoxy group; substituted or unsubstituted C 3-60 A cycloalkyl group; getSubstituted or unsubstituted C 2-60 An alkenyl group; substituted or unsubstituted C 6-60 An aryl group; substituted or unsubstituted C 6-60 An aryloxy group; substituted or unsubstituted C 7-60 Aralkyl group; substituted or unsubstituted C 7-60 An alkylaryl group; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O and S 2-60 (ii) a heteroaryl group, wherein,
Ar 1 and Ar 2 Each independently is substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C containing one or more heteroatoms selected from O, N, Si and S 2-60 (ii) a heteroaryl group, wherein,
b1 and b2 are each independently an integer from 0 to 2.
Specifically, in chemical formula 1, Cy is a multiple condensed ring in which 2 five-membered rings containing O or S and 3 benzene rings are alternately condensed, such as furan or thiophene, and may be represented by the following chemical formula 5 according to the condensed position:
[ chemical formula 5]
In the chemical formula 5 described above,
cy' is a benzene ring condensed with two adjacent five-membered rings,
X 1 and X 2 Each independently O, S or NR 3 ，X 1 And X 2 Not simultaneously NR 3 ，
R 3 Selected from hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 7-20 Aralkyl group, and substituted or unsubstituted C 7-20 An alkylaryl group.
More specifically, in the above chemical formula 1, Cy may be represented by any one of the following chemical formulas 5-1 to 5-6:
[ chemical formula 5-1]
[ chemical formula 5-2]
[ chemical formulas 5-3]
[ chemical formulas 5-4]
[ chemical formulas 5 to 5]
[ chemical formulas 5 to 6]
In the above chemical formulas 5-1 to 5-6,
X 1 and X 2 Each independently O, S or NR 3 ，X 1 And X 2 Not simultaneously being NR 3 ，
R 3 May be selected from hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 7-20 Aralkyl group, and substituted or unsubstituted C 7-20 An alkylaryl group.
More specifically, in the above chemical formula 1, Cy may be represented by any one functional group selected from the following functional groups:
in the above-mentioned chemical structural formula, the compound,
X 1 and X 2 Each independently O, S or NR 3 ，X 1 And X 2 Not simultaneously being NR 3 ，
R 3 May be selected from hydrogen, substituted or unsubstituted C 1-12 Alkyl, substituted or unsubstituted C 3-12 Cycloalkyl, substituted or unsubstituted C 2-12 Alkenyl, substituted or unsubstituted C 6-12 Aryl, substituted or unsubstituted C 7-13 Aralkyl group, and substituted or unsubstituted C 7-13 An alkylaryl group.
More specifically, among the functional groups of the above chemical formulas 5-1 to 5-6,
X 1 is O or S, and is a compound of,
X 2 is O, S or NR 3 ，
R 3 Can be selected from hydrogen, C 1-12 Alkyl radical, C 3-12 Cycloalkyl, C 6-12 Aryl radical, C 7-13 Aralkyl and C 7-13 The alkylaryl group, more specifically, may be hydrogen, methyl or phenyl.
In addition, the functional groups of the above chemical formula 5 and chemical formulae 5-1 to 5-6 may be substituted with Ar as shown in the above chemical formulae 3 and 4 1 And Ar 2 At least one of the functional groups of (a) is substituted for 1 or 2.
At this time, Ar is 1 And Ar 2 As defined above, more specifically, it may be any one of functional groups selected from the following:
in addition, in the above chemical formula 1, the two carbazolyl groups may be substituted or unsubstituted, and when substituted, may be each substituted with R 1 And R 2 Substituted 1 to 3, moreSpecifically, 1 or 2 may be substituted.
At this time, R 1 And R 2 As defined above, more specifically, each independently may be deuterium, halogen, cyano, nitro, C 1-20 Alkyl radical, C 6-20 Aryl radical, C 7-20 Aralkyl, or C 7-20 Alkylaryl, more specifically, R 1 And R 2 Each independently may be deuterium, halogen, cyano, nitro, methyl, or phenyl.
In the chemical formula 1, R may be substituted or unsubstituted C 6-20 The aryl group may be, more specifically, a substituted or unsubstituted phenyl group.
When R is substituted, it may be selected from deuterium, halogen, cyano, nitro, amino, C 1-20 Alkyl radical, C 1-20 Haloalkyl, C 1-20 Alkoxy radical, C 1-20 Haloalkoxy, C 3-20 Cycloalkyl radical, C 2-20 Alkenyl radical, C 6-20 Aryl radical, C 6-20 Aryloxy group, C 7-20 Aralkyl radical, C 7-20 Alkylaryl, or C containing one or more heteroatoms selected from N, O and S 2-60 Heteroaryl is substituted, more particularly, by one or more substituents selected from C 1-12 Alkyl radical, C 3-12 Cycloalkyl radical, C 6-12 Aryl radical, C 7-12 Aralkyl radical and C 7-12 More than 1 functional group in the alkylaryl group.
Specifically, R may be selected from the following functional groups.
In view of the fact that the vapor deposition temperature increases and the thermal stability is lowered when the molecular weight is too large, the R may be a phenyl group, a biphenyl group or a naphthyl group among the functional groups of the above structure in order to secure an appropriate molecular weight.
Representative examples of the compound represented by the above chemical formula 1 are as follows:
the compound of the above chemical formula 1 has a structure advantageous to transport holes and electrons by having a structure of a multiple condensed ring group (Cy) in which 2 five-membered rings containing a heteroatom of O, S or N and 3 benzene rings are alternately condensed at the position of No. 3, and the other carbazolyl group is substituted at the position of No. 3 of one carbazolyl group as a core, and the position of No. 9 is substituted. Further, since the carbazole substituted at the 3-position contains an aryl group and the condensed ring group contains a heteroatom of O, S or N, the electron density is increased by utilizing an unshared electron pair of these atoms, and the hole transporting ability is increased. Among these, in the case of O, since the electronegativity is larger than that of C, and the effect of increasing the electron transport ability is obtained, when it is applied to a light-emitting layer, a light-emitting layer having a suitable balance between the hole transport ability and the electron transport ability can be formed. Therefore, an organic light emitting element using the same can have high efficiency, low driving voltage, high luminance, long life, and the like.
On the other hand, the compound of chemical formula 1 can be produced by a production method including a step of reacting a dicarbazole-based compound (II) with a halide (III) containing multiple condensed rings (Cy), as shown in the following reaction formula, as an example. The above-described production method can be further embodied in synthesis examples to be described later.
[ reaction formula 1]
R, R in the above reaction scheme 1 1 、R 2 A1, a2 and Cy are as defined above, and Z is a halogen group such as fluorine, chlorine, bromine or iodine.
Specifically, the reaction of the dicarbazole compound (II) and the halide (III) containing multiple condensed rings (Cy) can be carried out in the presence of a platinum catalyst compound such as Pd (P-tBu3) 2.
The reaction may be carried out in 1 or more organic solvents such as dichloromethane, ethyl acetate, diethyl ether, acetonitrile, isopropanol, acetone, Tetrahydrofuran (THF), Ν -Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or toluene, and an alkoxide reactant such as NaOtBu may be added to the reaction.
On the other hand, the dicarbazole-based compound (II) and the halide (III) containing multiple condensed rings (Cy) used as starting materials in the production of the compound of chemical formula 1 can be produced directly or purchased commercially. When the substrate is directly manufactured, the manufacturing method thereof can be further embodied in the manufacturing examples described later.
The compound of chemical formula 1 can be produced by referring to the reaction formula 1, and appropriately substituting the starting material according to the structure of the compound to be produced.
In another aspect, the present invention provides an organic light emitting device comprising the compound of chemical formula 1. As an example, the present invention provides an organic light emitting element including: the organic light emitting device includes a first electrode, a second electrode provided to face the first electrode, and one or more organic layers provided between the first electrode and the second electrode, wherein one or more of the organic layers include a compound represented by the chemical formula 1.
The organic layer of the organic light-emitting device of the present invention may be formed of a single layer structure, or may be formed of a multilayer structure in which two or more organic layers are stacked. For example, the organic light-emitting element of the present invention may have a structure including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and the like as an organic layer. At least one of an electron blocking layer and a hole blocking layer may be included between the hole transport layer and the light-emitting layer and between the light-emitting layer and the electron transport layer. However, the structure of the organic light emitting element is not limited thereto, and a smaller number of organic layers may be included.
In addition, the organic layer may include a hole injection layer, a hole transport layer, or a layer simultaneously performing hole injection and transport, and the hole injection layer, the hole transport layer, or the layer simultaneously performing hole injection and transport includes the compound represented by the chemical formula 1.
In addition, the organic layer may include a light emitting layer including the compound represented by the chemical formula 1.
In addition, the organic layer may include an electron transport layer or an electron injection layer including the compound represented by the chemical formula 1.
In addition, the electron transport layer, the electron injection layer, or the layer simultaneously performing electron injection and electron transport includes the compound represented by the above chemical formula 1. In particular, the compound represented by chemical formula 1 according to the present invention is excellent in thermal stability, having a deep HOMO level of 6.0eV or more, a high triplet level (ET), and hole stability. In addition, when the compound represented by the above chemical formula 1 is used for an organic layer that can simultaneously perform electron injection and electron transport, an n-type dopant used in this field may be mixed for use.
In addition, the organic layer may include a light emitting layer and an electron transport layer, and the electron transport layer may include the compound represented by the chemical formula 1.
In addition, the organic light emitting element according to the present invention may be an organic light emitting element having a structure (normal type) in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting element according to the present invention may be an inverted (inverted) type organic light emitting element in which a cathode, one or more organic layers, and an anode are sequentially stacked on a substrate. For example, a structure of an organic light emitting element according to an embodiment of the present invention is illustrated in fig. 1 and 2.
Fig. 1 shows an example of an organic light-emitting element including a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In the structure as described above, the compound represented by the above chemical formula 1 may be included in the above light emitting layer.
Fig. 2 illustrates an example of an organic light-emitting element composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4. In the structure as described above, the compound represented by the above chemical formula 1 may be included in one or more layers among the above hole injection layer, hole transport layer, light emitting layer, and electron transport layer.
In addition, the organic light emitting element according to an embodiment of the present invention may be composed of a substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode, and in the structure as described above, the compound represented by the above chemical formula 1 may be included in the above light emitting layer.
The organic light emitting element according to the present invention may be manufactured using materials and methods well known in the art, except that one or more of the organic layers include the compound represented by the above chemical formula 1. In addition, when the organic light emitting element includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.
For example, the organic light emitting element according to the present invention can be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. In this case, the following production can be performed: the organic el display device is manufactured by depositing a metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a PVD (Physical Vapor Deposition) method such as a sputtering method or an electron beam evaporation method (e-beam evaporation) method to form an anode, forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer on the anode, and then depositing a substance that can be used as a cathode on the organic layer. In addition, when the organic layer further includes an electron blocking layer and a hole blocking layer between the hole transport layer and the light emitting layer and between the light emitting layer and the electron transport layer, respectively, a step of forming the layers may be further included. In addition to this method, a cathode material, an organic layer, and an anode material may be sequentially deposited on a substrate to manufacture an organic light-emitting element.
In addition, when the compound represented by the above chemical formula 1 is used to manufacture an organic light emitting device, the organic layer may be formed not only by a vacuum deposition method but also by a solution coating method. Here, the solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.
In addition to these methods, an organic light-emitting element can be manufactured by depositing a cathode material, an organic material layer, and an anode material on a substrate in this order (WO 2003/012890). However, the production method is not limited thereto.
In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.
The anode material is preferably a material having a large work function so that holes can be smoothly injected into the organic layer. Specific examples of the above-mentioned anode material include metals such as vanadium, chromium, copper, zinc, gold, etc., or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and the like; such as ZnO, Al or SnO 2 A combination of a metal such as Sb and an oxide; such as poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]Conductive polymers such as (PEDOT), polypyrrole, and polyaniline, but the present invention is not limited thereto.
The cathode material is preferably a material having a small work function so that electrons can be easily injected into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof; such as LiF/Al or LiO 2 And a multilayer structure material such as Al, but not limited thereto.
The hole injection layer is a layer for injecting holes from the electrode, and the following compounds are preferable as the hole injection substance: has an ability to transport holes, has a hole injection effect from the anode, has an excellent hole injection effect with respect to the light-emitting layer or the light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the electron injection layer or the electron injection material, and has excellent thin film-forming ability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injecting substance is between the work function of the anode substance and the HOMO of the surrounding organic layer. Specific examples of the hole injecting substance include, but are not limited to, metalloporphyrin (porphyrin), oligothiophene, arylamine-based organic substances, hexanitrile-hexaazatriphenylene-based organic substances, quinacridone-based organic substances, perylene-based organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers.
The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer, and the hole transport material is a material that can receive holes from the anode or the hole injection layer and transport the holes to the light-emitting layer. Specific examples thereof include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers in which a conjugated portion and a non-conjugated portion are present simultaneously.
The light-emitting substance is a substance that can receive holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and combine them to emit light in the visible light range, and is preferably a substance having high quantum efficiency with respect to fluorescence or phosphorescence. As a specific example, there is an 8-hydroxyquinoline aluminum complex (Alq) 3 ) (ii) a A carbazole-based compound; dimeric styryl (dimerized styryl) compounds; BAlq; 10-hydroxybenzoquinoline metal compounds; benzo (b) is
Azole, benzothiazole and benzimidazole-based compounds; poly (p-phenylene vinylene) (PPV) polymers; spiro (spiro) compounds; polyfluorene, rubrene, and the like, but are not limited thereto.
The light emitting layer may include a host material and a dopant material. The host material includes a fused aromatic ring derivative, a heterocyclic ring-containing compound, and the like. Specifically, the fused aromatic ring derivative includes an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, a fluoranthene compound, and the like, and the heterocyclic ring-containing compound includes a carbazole derivative, a dibenzofuran derivative, a ladder-type furan compound
And pyrimidine derivatives, but are not limited thereto.
As the dopant material, there are an aromatic amine derivative, a styryl amine compound, a boron complex, a fluoranthene compound, a boron-containing compound, and a metal oxide,Metal complexes, and the like. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and examples thereof include pyrene, anthracene, perylene, and the like having an arylamino group,
Diindenoperene (Periflanthene) and the like, as the styrylamine compound, a compound in which at least one arylvinyl group is substituted on a substituted or unsubstituted arylamine, and which is substituted or unsubstituted with one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltrimethylamine, and styryltretramine. The metal complex includes, but is not limited to, iridium complexes and platinum complexes. The dopant content may be 1% to 99% with respect to the amount of the host material of the light emitting layer.
The electron transporting layer is a layer that receives electrons from the electron injecting layer and transports the electrons to the light emitting layer, and the electron transporting substance is a substance that can inject electrons from the cathode well and transfer the electrons to the light emitting layer, and a substance having a high electron mobility is preferable. Specific examples thereof include an Al complex of 8-hydroxyquinoline and an Al complex containing Alq 3 The complex of (a), an organic radical compound, a hydroxyflavone-metal complex, etc., but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in the art. Examples of suitable cathode substances are, in particular, the customary substances having a low work function and associated with an aluminum layer or a silver layer. In particular cesium, barium, calcium, ytterbium and samarium, in each case accompanied by an aluminum or silver layer.
The electron injection layer is a layer for injecting electrons from the electrode, and is preferably a compound of: has an ability to transport electrons, an electron injection effect from a cathode, an excellent electron injection effect with respect to a light-emitting layer or a light-emitting material, prevents excitons generated in the light-emitting layer from migrating to a hole-injecting layer, and is excellent in thin film-forming ability. Specifically, there are fluorenone, anthraquinone dimethane (Anthraquinodimethane),Diphenoquinone, thiopyran dioxide,
Azole,
Oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives thereof, metal complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.
Examples of the metal complex include lithium 8-quinolinolate, zinc bis (8-quinolinolate), copper bis (8-quinolinolate), manganese bis (8-quinolinolate), aluminum tris (2-methyl-8-quinolinolate), and gallium tris (8-quinolinolate), bis (10-hydroxybenzo [ h ] quinoline) beryllium, bis (10-hydroxybenzo [ h ] quinoline) zinc, bis (2-methyl-8-quinoline) gallium chloride, bis (2-methyl-8-quinoline) (o-cresol) gallium, bis (2-methyl-8-quinoline) (1-naphthol) aluminum, bis (2-methyl-8-quinoline) (2-naphthol) gallium, and the like, but are not limited thereto.
In the case where the organic light-emitting element further includes one or more of an electron blocking layer and a hole blocking layer between the hole transport layer and the light-emitting layer and between the light-emitting layer and the electron transport layer, the electron blocking layer is a layer that blocks electrons from reaching the anode and can be formed under the same conditions as the electron injection layer. The electron blocking layer is made of a material having a function of transporting holes and a significantly small ability to transport electrons, and can increase the probability of recombination of electrons and holes by transporting holes and blocking electrons.
The hole-blocking layer is a layer that prevents injected holes from entering the electron-transporting layer through the light-emitting layer, and can improve the life and efficiency of the device, and includes
Nitrogen-containing heterocyclic derivatives such as oxadiazole derivatives and triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes (aluminum complexes), and the like, but the present invention is not limited thereto. Specifically, the hole blocking layer may comprise Korean patent laid-open No. 10-1052973 and korean patent laid-open No. 10-1317495.
The organic light emitting element of the present invention may be a top emission type, a bottom emission type, or a bidirectional emission type depending on the material used.
In addition, the compound represented by the above chemical formula 1 may be included in an organic solar cell or an organic transistor, in addition to the organic light emitting element.
The production of the compound represented by the above chemical formula 1 and the organic light emitting device comprising the same is specifically described in the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.
[ Synthesis examples ]
< Synthesis example 1> (Synthesis of Compound 1)
1-1) Synthesis of Compound 1-1
3-Hydroxydibenzo [ b, d ] in a two-neck flask]Furan (3-Hydroxydibenzo [ b, d ]]Furan) (15.0g,81.4mmol) was dissolved in 200ml of CH 2 Cl 2 Stirring was carried out at 0 ℃ under nitrogen atmosphere. In the resulting reaction solution, Br was added 2 (5ml,97.7mmol) was dissolved in 20ml CH 2 Cl 2 After dropwise addition over 40 minutes, the mixture was stirred at room temperature for 12 hours. After the reaction, Na was added to the obtained reaction solution 2 S 2 O 3 The aqueous solution was transferred to a separatory funnel and CH was used 2 Cl 2 Extraction is carried out. With MgSO 4 The extract was dried, and the resultant sample was purified by silica gel column chromatography to obtain 17.1g of compound 1-1 as a solid. (yield 80%, MS [ M + H ]] + ＝263)
1-2) Synthesis of Compound 1-2
In a three-neck flask, the mixture is put into a vacuum flask,compound 1-1(17.0g,64.6mmol) and (4-chloro-2-fluorophenyl) boronic acid ((4-chloro-2-fluorophenyl) boronic acid) (11.8g,67.8mmol) were dissolved in 650ml of THF, to which K was added 2 CO 3 (35.7g,258.5mmol) was dissolved in 320ml of H 2 O is added. Pd (PPh) was added to the resulting mixed solution 3 ) 4 (0.7g,0.6mmol) was stirred under reflux for 8 hours under an argon atmosphere. After the reaction was completed, the obtained reaction solution was cooled to normal temperature, transferred to a separatory funnel, and CH was added 2 Cl 2 Extraction is carried out. The resulting extract was extracted with MgSO 4 After drying, filtration and concentration, the resulting sample was purified by silica gel column chromatography to obtain 15.8g of compound 1-2 as a solid. (yield 78%, MS [ M + H ]] + ＝313)
1-3) Synthesis of Compounds 1-3
A two-necked flask was charged with 1-2(15.0g,48.0mmol) and K 2 CO 3 (9.9g,71.9mmol) and 200mL of NMP were stirred at 150 ℃ for 8 hours under an argon atmosphere. After the reaction was completed, the obtained reaction solution was cooled to normal temperature, transferred to a separatory funnel, and 200mL of H was added 2 O, extraction with ethyl acetate. The obtained extract was purified by silica gel column chromatography to obtain 12.5g of compound 1-3 as a solid. (yield 89%, MS [ M + H ]] + ＝293)
1-4) Synthesis of Compounds 1-4
In a three-necked flask, 3-bromo-9H-carbazole (3-bromo-9H-carbazole) (10.0g,40.6mmol) and 9-phenyl-3- (4,4,5,5-tetramethyl-1,3, 2-dioxaborolan-2-yl) -9H-carbazole (9-phenyl-3- (4,4,5, 5-tetramethy-1, 3, 2-dioxaborono 1an-2-y1) -9H-carbazole) (15.8g,42.7mmol) were dissolved in 400ml THF, and K was added thereto 2 CO 3 (22.5g,162.5mmol) of a solutionDissolved in 200ml of H 2 O is added. Pd (PPh) was added to the resulting mixed solution 3 ) 4 (0.5g,0.4mmol) was stirred under reflux for 8 hours under an argon atmosphere. After the reaction was completed, the obtained reaction solution was cooled to room temperature, transferred to a separatory funnel, and used with CH 2 Cl 2 Extraction is carried out. The resulting extract was extracted with MgSO 4 After drying, filtration and concentration, the resulting sample was purified by silica gel column chromatography to obtain 12.4g of compound 1 to 4 as a solid. (yield 75%, MS [ M + H ]] + ＝409)
1-5) Synthesis of Compound 1
In a three-necked flask, compounds 1 to 4(8.0g,19.6mmol) and compounds 1 to 3(6.3g,21.5mmol) were dissolved in 200ml of toluene, and sodium tert-butoxide (sodium tert-butoxide; NaOtBu) (2.8g,29.4mmol) and Bis (tri-tert-butylphosphine) palladium (0) (Bis (tri-tert-butylphosphine) palladium (0); Pd (P-tBu 3 ) 2 ) (0.2g,0.4mmol), and then stirred under reflux for 6 hours under argon atmosphere. After the reaction was completed, the obtained reaction solution was cooled to normal temperature, and 200ml of H was added 2 And O, transferring to a separating funnel for extraction. The obtained extract was extracted with MgSO 4 After drying and concentration, the sample obtained as a result was purified by silica gel column chromatography and then purified by sublimation to obtain 5.9g of compound 1. (yield 45%, MS [ M + H ]] + ＝665)
< Synthesis example 2> (Synthesis of Compound 2)
2-1) Synthesis of Compound 2-1
In a three-neck flask, 2-hydroxy dibenzo [ b, d ]]Furan (2-hydroxydibenzo [ b, d)]furan) (15.0g,81.4mmol) was dissolved in 100ml of acetic acid, and iodine monochloride (iododine monochlride; ICl) (4.48ml,89.6mmol) and 55mlAfter a solution of concentrated hydrochloric acid (conc. hcl) and 35ml of acetic acid, it was stirred at room temperature for 24 hours. At the end of the reaction, 300ml of H was added to the resulting reaction solution 2 O, filtering the resulting precipitate with H 2 And O, washing. The solid obtained as a result was washed with MeOH, thereby obtaining 18.9g of Compound 2-1 as a solid. (yield 75%, MS [ M + H ]] + ＝310)
2-2) Synthesis of Compound 2-2
In a three-necked flask, compound 2-1(18.0g,58.0mmol) and (4-chloro-2-fluorophenyl) boronic acid (10.6g,61.0mmol) were dissolved in 600ml of THF, and K was added thereto 2 CO 3 (32.1g,232.2mmol) was dissolved in 300ml of H 2 O is added. Pd (PPh) was added to the resulting mixed solution 3 ) 4 (0.7g,0.6mmol), and stirred under reflux for 8 hours under argon atmosphere. After the reaction, the obtained reaction solution was cooled to room temperature, transferred to a separatory funnel, and used with CH 2 Cl 2 Extraction is carried out. The obtained extract was extracted with MgSO 4 After drying, filtration and concentration, the resulting sample was purified by silica gel column chromatography to obtain 14.5g of compound 2-2 as a solid. (yield 80%, MS [ M + H ]] + ＝313)
2-3) Synthesis of Compound 2-3
In a two-necked flask, compound 2-2(14.0g,44.8mmol) and K were placed 2 CO 3 (9.3g,67.2mmol) and 180mL of NMP were stirred at 150 ℃ for 8 hours under an argon atmosphere. After completion of the reaction, the obtained reaction solution was cooled to normal temperature, the resulting sample was transferred to a separatory funnel, and 200mL of H was added 2 O, extraction with ethyl acetate. The extract was purified by silica gel column chromatography to obtain 10.6g of compound 2-3 as a solid. (yield 81%，MS[M+H] + ＝293)
2-4) Synthesis of Compounds 2-4
In a three-necked flask, 3-bromo-9H-carbazole (5.0g,20.3mmol) and 9- ([1,1' -biphenyl ] were added]-3-yl) -3- (4,4,5,5-tetramethyl-1,3, 2-dioxaborolan-2-yl) -9H-carbazole (9- ([1,1' -bipheny 1)]-3-y1) -3- (4,4,5,5-tetramethy1-1,3,2-dioxabor1an-2-y1) -9H-carbazo1e) (9.5g,21.3mmol) was dissolved in 200ml of THF, to which K was added 2 CO 3 (11.2g,81.3mmol) was dissolved in 100ml of H 2 O is added. Pd (PPh) was added to the resulting mixed solution 3 ) 4 (0.2g,0.2mmol), and stirred under reflux for 8 hours under argon atmosphere. After the reaction was completed, the obtained reaction solution was cooled to room temperature, transferred to a separatory funnel, and used with CH 2 Cl 2 Extraction is carried out. The resulting extract was extracted with MgSO 4 After drying, filtration and concentration, the sample obtained as a result was purified by silica gel column chromatography to obtain 7.6g of compound 2-4 as a solid. (yield 77%, MS [ M + H ]] + ＝485)
2-5) Synthesis of Compound 2
In a three-necked flask, the compound 2-4(7.0g,14.4mmol) and the compound 2-3(4.7g,15.9mmol) were dissolved in 140ml of toluene, and NaOtBu (2.1g,21.7mmol) and Pd (P-tBu) were added 3 ) 2 (0.1g,0.3mmol) and then stirred under reflux for 6 hours under argon atmosphere. After the reaction was completed, the obtained reaction solution was cooled to room temperature, transferred to a separatory funnel, and 200ml of H was added 2 And extracting after O. The resulting extract was extracted with MgSO 4 The resulting sample was purified by silica gel column chromatography after drying and concentration, and then purified by sublimation to obtain 5.0g of compound 2. (yield 47%, MS [ M + H ]] + ＝665)
< Synthesis example 3> (Synthesis of Compound 3)
3-1) Synthesis of Compound 3-1
3-fluorodibenzo [ b, d ] is added into a three-neck flask]Furan (15.0g,80.6mmol) and 400mL of THF, cooled to-78 ℃. N-butyllithium (n-BuLi) (1.6M n-hexane solution, 55mL,88.6mmol) was added dropwise thereto, and the mixture was stirred at-78 ℃ for 20 minutes. Triisopropyl borate (45.5g,241.7mmol) was added to the resulting mixed solution, and the mixture was stirred at-78 ℃ for 1 hour and then further stirred at room temperature for 4 hours. 130mL of 1N HCI was added to the resulting reaction solution, and after stirring at room temperature for 1 hour, the mixture was concentrated, transferred to a separatory funnel, added with 200mL of water, and then washed with CH 2 Cl 2 Extraction is carried out. The obtained extract was extracted with MgSO 4 After drying, filtration, concentration and recrystallization from toluene-hexane, 11.1g of compound 3-1 was obtained. (yield 60%, MS [ M + H ]] + ＝230)。
3-2) Synthesis of Compound 3-2
In a three-necked flask, compound 3-1(10.0g,43.5mmol) and 5-chloro-2-iodophenol (5-chloro-2-iodophenol) (11.6g,45.7mmol) were dissolved in 430ml of THF, to which K was added 2 CO 3 (24.0g,173.9mmol) was dissolved in 220ml of H 2 O is added. Pd (PPh) was added to the resulting mixed solution 3 ) 4 (0.5g,0.4mmol) was stirred under reflux for 8 hours under an argon atmosphere. After the reaction was completed, the obtained reaction solution was cooled to normal temperature, transferred to a separatory funnel, and used with CH 2 Cl 2 Extraction is carried out. The resulting extract was extracted with MgSO 4 After drying, filtration and concentration, the resulting sample was purified by silica gel column chromatography to obtain 10.5g of Compound 3-2 as a solid (yield 77%, MS [ M + H ]] + ＝313)。
3-3) Synthesis of Compound 3-3
In a two-necked flask, compound 3-2(10.0g,32.0mmol) and K were placed 2 CO 3 (6.6g,48.0mmol) and 130mL of NMP were stirred at 150 ℃ for 8 hours under an argon atmosphere. After the reaction was completed, the obtained reaction solution was cooled to room temperature, transferred to a separatory funnel, and 100mL of H was added 2 After O, extraction was performed with ethyl acetate. The obtained extract was purified by silica gel column chromatography to obtain 6.2g of Compound 3-3 as a solid (yield 66%, MS [ M + H ]] + ＝293)。
3-4) Synthesis of Compound 3-4
In a three-necked flask, 3-bromo-9H-carbazole (5.0g,20.3mmol) and 9- ([1,1' -biphenyl ] were added]-4-yl) -3- (4,4,5,5-tetramethyl-1,3, 2-dioxaborolan-2-yl) -9H-carbazole (9.5g,21.3mmol) is dissolved in 200ml of THF, to which K is added 2 CO 3 (11.2g,81.3mmol) was dissolved in 100ml of H 2 O is added. Pd (PPh) was added to the resulting mixed solution 3 ) 4 (0.2g,0.2mmol), and stirred under reflux for 8 hours under argon atmosphere. After the reaction, the obtained reaction solution was cooled to room temperature, transferred to a separatory funnel, and used with CH 2 Cl 2 Extraction is carried out. The resulting extract was extracted with MgSO 4 After drying, filtration and concentration, the resulting sample was purified by silica gel column chromatography to obtain 7.4g of Compound 3-4 as a solid (yield 74%, MS [ M + H ]] + ＝485)。
3-5) Synthesis of Compound 3
In a three-necked flask, compound 3-4(7.0g,14.4mmol) and compound 3-3(4.7g,15.9mmol) were dissolved in 140ml of toluene, and NaOtBu (2.1g,21.7mmol), Pd (P-tBu) and NaOtBu (2.1g,21.7mmol) were added 3 ) 2 ) (0.1g,0.3mmol), and then stirred under reflux for 6 hours under argon atmosphere. At the end of the reaction, the resulting reaction solution was cooled to room temperature, and 200ml of H was added 2 And O, transferring to a separating funnel for extraction. The resulting extract was extracted with MgSO 4 The resulting sample was purified by silica gel column chromatography after drying and concentration, and then purified by sublimation to obtain 4.7g of Compound 3 (yield 44%, MS [ M + H ]] + ＝741)。
< Synthesis example 4> (Synthesis of Compound 4)
In that<Synthesis example 3>In the reaction of 3-fluorodibenzo [ b, d]Transformation of furan into 3-fluorodibenzo [ b, d ]]Thiophene, coupling 9- ([1,1' -biphenyl)]Compound 4 (yield 10%, MS [ M + H ] M + H) was synthesized by the reaction formula described above, except that (E) -4-yl) -3- (4,4,5,5-tetramethyl-1,3, 2-dioxaborolan-2-yl) -9H-carbazole was changed to 9- (naphthalen-2-yl) -3- (4,4,5,5-tetramethyl-1,3, 2-dioxaborolan-2-yl) -9H-carbazole and used in the same manner as in Synthesis example 3] + ＝731)。
< Synthesis example 5> (Synthesis of Compound 5)
5-1) Synthesis of Compound 5-1
A three-necked flask was charged with 1, 2-difluoro-3, 6-diiodobenzene (20.0g,54.7mmol), 2-methoxyphenylboronic acid (19.9g,131.2mmol), and 2M Na 2 CO 3 Aqueous solution (110mL,218.6mmol), DME 110mL, toluene 110mL, Pd (PPh) 3 ) 4 (6.3g,5.5mmol), and stirred under reflux for 8 hours under an argon atmosphere. When the reaction is finished, cooling the obtained reaction solution to normal temperatureTransferred to a separatory funnel, and 200mL of H was added 2 O, with CH 2 Cl 2 Extraction is carried out. The resulting extract was extracted with MgSO 4 After drying, filtration and concentration, the resulting sample was purified by silica gel column chromatography to obtain 11.6g of Compound 5-1 as a solid (yield 65%, MS [ M + H ]] + ＝326)。
5-2) Synthesis of Compound 5-2
Compound 5-1(11.0g,33.7mmol), NBS (6.0,33.7mmol) and 340mL of DMF were charged in a two-necked flask and stirred at room temperature for 8 hours under an argon atmosphere. After completion of the reaction, the obtained reaction solution was transferred to a separatory funnel, water (300mL) was added thereto, and extraction was performed with ethyl acetate. The sample was purified by silica gel column chromatography to obtain 11.2g of Compound 5-2 as a solid. (yield 82%, MS [ M + H ]] + ＝405)
5-3) Synthesis of Compound 5-3
In a two-necked flask, compound 5-2(11.0g,27.1mmol) and 1M BBr were placed 3 CH (A) of 2 Cl 2 Solution (65mL,65.1mmol) and 163mL of CH 2 Cl 2 The temperature was set to 0 ℃ under argon atmosphere, and the mixture was stirred for 8 hours. Then, further stirred at room temperature for 4 hours with saturated NaHCO 3 The aqueous solution is neutralized. The resulting reaction solution was transferred to a separatory funnel and CH was used 2 Cl 2 Extraction was performed, and the obtained extract was purified by silica gel column chromatography to obtain 8.7g of compound 5-3 as a solid. (yield 85%, MS [ M + H ]] + ＝377)
5-4) Synthesis of Compound 5-4
In a two-necked flask, compound 5-3(8.7g,23.1mmol) and K were placed 2 CO 3 (7.0g,50.7mmol) and 96mL of NMP were stirred at 150 ℃ for 8 hours under an argon atmosphere. After the reaction was completed, the obtained reaction solution was cooled to room temperature, transferred to a separatory funnel, and 100mL of H was added 2 O, extraction with ethyl acetate. The obtained extract was purified by silica gel column chromatography to obtain 6.9g of compound 5-4. (yield 89%, MS [ M + H ]] + ＝337)
5-5) Synthesis of Compound 5
In a three-necked flask, the compound 1-4(7.0g,17.1mmol) and the compound 5-4(6.4g,18.8mmol) were dissolved in 170ml of toluene (toluene), and NaO (t-bu) (2.5g,25.7mmol), Pd (P-tBu) and the mixture were added 3 ) 2 (0.2g,0.3mmol), and then stirred under reflux for 6 hours under argon atmosphere. After the reaction was completed, after cooling to room temperature, 200ml of H was added 2 And O, transferring the reaction liquid to a separating funnel for extraction. With MgSO 4 The extract was dried and concentrated, and the sample was purified by silica gel column chromatography and then purified by sublimation to obtain 5.0g of Compound 5 (yield 44%, MS [ M + H ]] + ＝665)。
< Synthesis example 6> (Synthesis of Compound 6)
As described above<Synthesis example 5>Compound No. 6 was synthesized by the above reaction scheme (yield 15%, MS [ M + H ] in the same manner as in Synthesis example 5, except that 1, 2-difluoro-3, 6-diiodobenzene was used instead of 1, 4-dibromo-2, 5-difluorobenzene] + ＝665)。
< Synthesis example 7> (Synthesis of Compound 7)
7-1) Synthesis of Compound 7-1
In a three-neck flask, 2-bromo-4-chlorodibenzo [ b, d ]]After furan (30.0g,106.6mmol) and 2- (nitrophenyl) boronic acid (19.6g,117.2mmol) were dissolved in 450ml of THF, K was added 2 CO 3 (58.9g,426.2mmol) was dissolved in 225ml of H 2 O is added. Wherein Pd (PPh) is added 3 ) 4 (4.9g,4.3mmol), and the mixture was stirred under reflux for 8 hours under an argon atmosphere. After the reaction was completed, the reaction mixture was cooled to room temperature, and then transferred to a separatory funnel, followed by extraction with ethyl acetate. With MgSO 4 After drying the extract, it was filtered and concentrated, and then a sample was purified by silica gel column chromatography to obtain 30.4g of compound 7-1 (yield 88%, MS [ M + H ]] + ＝324)。
7-2) Synthesis of Compound 7-2
A two-necked flask was charged with compound 7-1(30.0g,92.7mmol), Triphenylphosphine (PPh) 3 ) (19.2g,139.0mmo1) and 300ml of o-dichlorobenzene (o-dichlorobenzene; o-DCB), stirred under reflux for 12 hours. Cooling to room temperature at the end of the reaction, distilling under reduced pressure to remove the solvent, adding water and CH 2 Cl 2 Extraction is carried out. With MgSO 4 The extract was dried, filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 16.5g of Compound 7-2 (yield 61%, MS [ M + H ]] + ＝292)。
7-3) Synthesis of Compound 7-3
In a three-necked flask, compound 7-2(15.0g,51.4mol) and bromobenzene (8.9g,56.6mmol) were dissolved in 510ml of toluene (toluene), and sodium tert-butoxide (sod) was addedAn ium tert-butoxide; NaO (t-bu)) (7.4g,77.1mmol), Bis (tri-tert-butylphosphine) palladium (0) (Bis (tri-tert-butylphosphine) palladium (0); pd (P-tBu) 3 ) 2 ) (0.5g,1.0mmol) and then stirred under reflux for 6 hours under argon atmosphere. After the reaction was completed, the reaction mixture was cooled to room temperature, and 200ml of H was added 2 And O, transferring the reaction liquid to a separating funnel for extraction. With MgSO 4 The extract was dried, filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 12.3g of compound 7-3 (yield 65%, MS [ M + H ]] + ＝368)。
7-4) Synthesis of Compound 7
In a three-necked flask, the compound 1-4(10.0g,24.5mmol) and the compound 7-3(9.9g,26.9mmol) were dissolved in 250ml of toluene, and sodium tert-butoxide (Na O (t-bu)) (3.5g,36.7mmol), bis (tri-tert-butylphosphine) palladium (0) (Pd (P-tBu) and the mixture were added 3 ) 2 ) (0.3g,0.5mmol) and then stirred under reflux for 6 hours under argon atmosphere. After the reaction was completed, after cooling to room temperature, 200ml of H was added 2 And O, transferring the reaction liquid to a separating funnel for extraction. With MgSO 4 After drying the extract, filtration and concentration were carried out, and then a sample was purified by silica gel column chromatography and then purified by sublimation to obtain 5.6g of Compound 7 (yield 31%, MS [ M + H ]] + ＝740)。
[ element examples ]
< example 1>
Will be provided with
The glass substrate coated with ITO (Indium Tin Oxide) as a thin film of (b) was put in distilled water in which a detergent was dissolved, and washed by ultrasonic waves. In this case, Decon (Fischer Co.) from Phichel was used as a detergent TM The CON705 product used distilled water was filtered twice with a 0.22 μm sterilizing filter (sterilizing filter) manufactured by Millipore Co. Washing ITOAfter 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After the completion of the distilled water washing, ultrasonic washing was performed for 10 minutes using solvents such as isopropyl alcohol, acetone, and methanol, and the resultant was dried, and then the product was transferred to a plasma cleaning machine. After the substrate was cleaned with oxygen plasma for 5 minutes, the substrate was transported to a vacuum evaporator.
On the ITO transparent electrode thus prepared
The hole injection layer was formed by thermal vacuum evaporation of 95 wt% of HT-a described below and 5 wt% of P-dopant. On the hole injection layer
The hole transport layer is formed by vapor deposition of only the HT-A substance.
On the hole transport layer, the following HT-B and
the electron blocking layer is formed by thermal vacuum evaporation to a thickness.
Then, on the above-mentioned electron blocking layer to obtain
The light-emitting layer was formed by thermal vacuum deposition of compound 1 as a host material at a ratio of 95 wt% and GD as a dopant at a ratio of 5 wt%.
Then, the following ET-A is added on the light-emitting layer
The hole blocking layer is formed by thermal vacuum deposition.
Further, on the hole blocking layer, the following ET-B and Liq were added in a weight ratio of 2:1
Is subjected to thermal vacuum evaporation to form an electron transport layer, and then LiF and magnesium are added in a weight ratio of 1:1
The electron injection layer is formed by vacuum evaporation.
Magnesium and silver were added to the electron injection layer at a weight ratio of 1:4
The cathode is formed by vapor deposition to produce an organic light-emitting device.
Examples 2 to 7 and comparative examples 1 to 4
Organic light-emitting devices of examples 2 to 7 and comparative examples 1 to 4 were produced by the same method as in example 1, except that the host material was changed as shown in table 1 below.
[ TABLE 1]
| Host material | |
| Example 1 | |
| Example 2 | |
| Example 3 | |
| Example 4 | |
| Example 5 | |
| Example 6 | |
| Example 7 | |
| Comparative example 1 | GH-A |
| Comparative example 2 | GH-B |
| Comparative example 3 | GH-C |
| Comparative example 4 | GH-D |
When a current was applied to the organic light-emitting elements produced in examples 1 to 7 and comparative examples 1 to 4, the voltage, efficiency, and lifetime (T95) were measured, and the results are shown in table 2 below. In this case, the voltage and efficiency were adjusted by applying 10mA/cm 2 Measured at a current density of 20mA/cm, T95 2 Next, the time until the initial luminance was reduced to 95%.
[ TABLE 2]
The compound of formula 1 includes a chalcogen atom having higher electronegativity than a carbon atom and having an unshared electron pair, and thus is advantageous for the transport of both electrons and holes. As a result, it was confirmed from Table 2 that the host material of the light-emitting layer is more suitable than GH-A of comparative example 1 or GH-C of comparative example 3, which do not contain a chalcogen atom. Further, it is found that, when there is one oxygen atom such as GH-D in comparative example 4 or three oxygen atoms such as GH-B in comparative example 2, the electric charge in the light emitting layer is not balanced, and the device characteristics are rather degraded. Therefore, when the compound having the structure of chemical formula 1 is applied to a light-emitting layer of an organic light-emitting element, an organic light-emitting element with low voltage, high efficiency, and long lifetime can be realized.
Claims (5)
1. A compound of the following chemical formula 1:
chemical formula 1
In the chemical formula 1, the metal oxide is represented by,
r is C 6-60 An aryl group which is a radical of an aromatic group,
R 1 and R 2 Each independently is deuterium; or C 1-20 An alkyl group, a carboxyl group,
a1 and a2 are each independently an integer from 0 to 3,
cy is any one of the following functional groups:
in the chemical structural formula,
X 1 and X 2 Each independently is O or S.
2. The compound of claim 1, wherein R is any one of the following functional groups selected from:
3. the compound according to claim 1, wherein the compound is any one selected from the group consisting of,
4. an organic light-emitting element comprising: a first electrode, a second electrode provided so as to face the first electrode, and one or more organic material layers provided between the first electrode and the second electrode,
one or more of the organic layers comprising the compound of claim 1.
5. The organic light-emitting element according to claim 4, wherein the organic layer containing the compound is a light-emitting layer.
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| WO2016036171A1 (en) * | 2014-09-04 | 2016-03-10 | Rohm And Haas Electronic Materials Korea Ltd. | A plurality of host materials and organic electroluminescent devices comprising the same |
| WO2016153283A1 (en) * | 2015-03-24 | 2016-09-29 | 주식회사 엠비케이 | Organic light-emitting compound, ink composition, organic light-emitting diode, and electronic device |
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| WO2016036171A1 (en) * | 2014-09-04 | 2016-03-10 | Rohm And Haas Electronic Materials Korea Ltd. | A plurality of host materials and organic electroluminescent devices comprising the same |
| WO2016153283A1 (en) * | 2015-03-24 | 2016-09-29 | 주식회사 엠비케이 | Organic light-emitting compound, ink composition, organic light-emitting diode, and electronic device |
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