CN104838514A - Material for organic electroluminescent elements and organic electroluminescent element using same - Google Patents
Material for organic electroluminescent elements and organic electroluminescent element using same Download PDFInfo
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- CN104838514A CN104838514A CN201380064544.8A CN201380064544A CN104838514A CN 104838514 A CN104838514 A CN 104838514A CN 201380064544 A CN201380064544 A CN 201380064544A CN 104838514 A CN104838514 A CN 104838514A
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
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- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000000434 field desorption mass spectrometry Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 1
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- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- QSQIGGCOCHABAP-UHFFFAOYSA-N hexacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC6=CC=CC=C6C=C5C=C4C=C3C=C21 QSQIGGCOCHABAP-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ACIUFBMENRNYHI-UHFFFAOYSA-N naphtho[2,1-f]isoquinoline Chemical compound C1=CN=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 ACIUFBMENRNYHI-UHFFFAOYSA-N 0.000 description 1
- 150000005054 naphthyridines Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical class C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910000065 phosphene Inorganic materials 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-M picolinate Chemical compound [O-]C(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-M 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Chemical class 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical class C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 150000005255 pyrrolopyridines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- QEVBPWGFJKJQHA-UHFFFAOYSA-N quinolino[6,5-f]quinoline Chemical compound C1=CC=NC2=CC=C(C=3C(=NC=CC=3)C=C3)C3=C21 QEVBPWGFJKJQHA-UHFFFAOYSA-N 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- ZRIUSVITVGWLSQ-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1.C=1C=CC=CC=1C=CC1=CC=CC=C1 ZRIUSVITVGWLSQ-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 1
- OVTCUIZCVUGJHS-VQHVLOKHSA-N trans-dipyrrin Chemical class C=1C=CNC=1/C=C1\C=CC=N1 OVTCUIZCVUGJHS-VQHVLOKHSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
-
- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- 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
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
-
- 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
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
Abstract
Provided are: an organic electroluminescent element (organic EL element) having improved element light emission efficiency, ensuring sufficient drive stability, and having a simple configuration; and a material for organic EL elements, used in same. The material for organic EL elements comprises a carborane compound having a structure wherein a silyl group is bonded to a carborane ring via an aromatic group. This carborane compound is indicated by [Si(R)3]p-L-(A)r-L-[Si(R)3]q. In the formula, A indicates the carborane ring, L indicates the aromatic group, p indicates 1-5, q indicates 0-5, and r indicates 1-4. The organic EL element has a plurality of organic layers including a light-emitting layer, between a positive electrode and a negative electrode layered upon a substrate. One of these organic layers contains the carborane compound.
Description
Technical field
The present invention relates to a kind of organic electric-field light-emitting element containing caborane compounds, specifically relate to a kind of luminescent layer to including organic compounds and apply electric field and release the film-type device (device) of light.
Background technology
Generally, organic electric-field light-emitting element (hereinafter referred to as organic electroluminescent (electrofluorescence, EL) element), its simplest structure comprises luminescent layer and clamps a pair counter electrode of this layer.That is, in organic EL element, utilize following phenomenon: if apply electric field between two electrodes, then inject electronics from negative electrode, from anode injected hole, these combine again and release light in luminescent layer.
In recent years, the exploitation carrying out the organic EL element using organic film is started.Particularly in order to improve luminous efficiency, for the purpose of the efficiency improving self-electrode injection carrier, carry out the optimization of type of electrodes, comprise the hole transmission layer of aromatic diamine by exploitation setting between electrode and comprise oxine aluminium complex (hereinafter referred to as Alq
3) luminescent layer as the element of film, comparatively speaking carry out the significantly improvement of luminous efficiency with the element of the monocrystalline such as existing use anthracene, therefore developed to turn to target to the practicality of the high performance flat with the feature such as self-luminous, high-speed response.
And, as the trial of luminous efficiency improving element, be investigated and non-usage fluorescence but use phosphorescence.Be provided with the hole transmission layer that comprises aromatic diamine with above-mentioned and comprise Alq
3the element of luminescent layer be that numerous elements of representative make use of fluorescence radiation, by use phosphorescence luminous, namely utilize luminescence from triplet excited state (triplet excited state), the efficiency Comparatively speaking improving 3 times ~ about 4 times with the element of existing use fluorescence (singlet state (singlet)) can be expected.Begin one's study in order to this object with coumarin derivative or benzophenone derivates for luminescent layer, but only obtain extremely low brightness.And as the trial utilizing triplet, begin one's study use europium complex, but itself and unrealized high efficiency luminescence.In recent years, as cited by patent documentation 1, for the purpose of the high efficiency of luminescence or long lifetime, numerous research centered by the metal-organic complexs such as iridium complex is carried out.
[prior art document]
[patent documentation]
[patent documentation 1] WO01/041512A
[patent documentation 2] Japanese Patent Laid-Open 2001-313178 publication
[patent documentation 3] Japanese Patent Laid-Open 2005-162709 publication
[patent documentation 4] Japanese Patent Laid-Open 2005-166574 publication
In order to obtain high luminous efficiency, the material of main part importantly simultaneously used with above-mentioned dopant material.The representative materials proposed as material of main part can be set forth in two (9-carbazyl) biphenyl (hereinafter referred to as CBP) of carbazole compound 4,4'-introduced in patent documentation 2.CBP is being used as with three (2-phenylpyridine) iridium complex (hereinafter referred to as Ir (ppy)
3) material of main part for the green phosphorescent luminescent material of representative when, CBP except easily flow out hole and be difficult to flow out electronics characteristic except, charge injection balance is broken, and superfluous hole flows out to electron transfer layer side, and its result is from Ir (ppy)
3luminous efficiency reduce.
As mentioned above, in order to obtain high luminous efficiency with organic EL element, need that there are high triple excitation energy (tripletexcitation energy), and need to inject at two electric charges (hole, electronics) material of main part that transmission characteristic obtains balance.Further expectation electrochemistry (electrochemistry) is stablized, have high thermal endurance and the compound of excellent amorphous state (amorphous) stability, requires further to improve.
Caborane compounds shown below is disclosed in patent documentation 3 and patent documentation 4.
But above-claimed cpd is the compound that bond has phenyl, fluorenyl or carbazyl phenyl on the carbon atom of Carborane skeleton, do not disclose the compound of the bond silylation on the carbon atom of Carborane skeleton via concatenating group.
Summary of the invention
In order to organic EL element being applied in the display elements such as flat-panel monitor, need while the luminous efficiency improving element, guarantee stability when driving fully.The present invention, in view of above-mentioned present situation, its object is to provide high efficiency and useful organic EL element and be suitable for the compound of this organic EL element in the practicality with high driving stability.
The result that the people such as the present inventor carry out active research is: find by by bond has the caborane compounds of silylation to be used for can demonstrating in organic EL element excellent characteristic via aromatic hydrocarbyl or aromatic heterocycle, thus complete the present invention.
The present invention relates to a kind of organic electric-field light-emitting element material, it comprises the caborane compounds represented by general formula (1).
Herein, the C represented by any formula of ring A expression (1a) or formula (1b)
2b
10h
8the carborane radical of 4 valencys, when molecular memory at multiple ring A, can identical also can be different.L
1the base of p+1 valency, L
2the base of q+1 valency, L
1, L
2represent that the carbon number that is substituted or is unsubstituted is the aromatic hydrocarbyl of 6 ~ 30 independently of one another, the carbon number that is substituted or is unsubstituted be 3 ~ 30 aromatic heterocycle or 2 ~ 6 the aromatic series bases being selected from this aromatic heterocycle and this aromatic heterocycle link the link aromatic series base formed, can be straight-chain also can be branch-like when linking aromatic series base, the aromatic rings linked can identical also can be different.R
1, R
2, R
3, R
4, R
5, R
6represent that carbon number is the aliphatic alkyl of 1 ~ 12 independently, the carbon number that is substituted or is unsubstituted be 6 ~ 18 aromatic hydrocarbyl or the carbon number that is substituted or is unsubstituted be the aromatic heterocycle of 3 ~ 17, R
7, R
8represent that hydrogen, carbon number are the aliphatic alkyl of 1 ~ 12 independently, the carbon number that is substituted or is unsubstituted be 6 ~ 18 aromatic hydrocarbyl or the carbon number that is substituted or is unsubstituted be the aromatic heterocycle of 3 ~ 17.P represents the integer of 1 ~ 5, and q represents the integer of 0 ~ 5, and r represents the integer of 1 ~ 4.
Preferably following general formula (2) in caborane compounds represented by general formula (1), can enumerate general formula (3), caborane compounds represented by general formula (4) further as preferred compound.
In general formula (2), L
1, L
2, R
1~ R
8, p, q and r and general formula (1) synonym.The C represented by any formula of ring A expression (2a) or formula (2b)
2b
10h
8the carborane radical of 4 valencys, when molecular memory at multiple ring A, can identical also can be different.
In general formula (3), general formula (4), L
1, L
2, R
1~ R
8, p ~ r and general formula (1) these synonyms.
In general formula (3), general formula (4), preferably L
1, L
2carbon number independently of one another for being substituted or being unsubstituted is the aromatic hydrocarbyl of 6 ~ 18, the carbon number that is substituted or is unsubstituted is 3 ~ 17 aromatic heterocycle or 2 ~ 5 aromatic series bases being selected from this aromatic heterocycle and this aromatic heterocycle link aromatic series base of linking and forming.
In general formula (3), general formula (4), preferably R
1~ R
6independently of one another for carbon number be 1 ~ 10 aliphatic alkyl or the carbon number that is substituted or is unsubstituted be the aromatic hydrocarbyl of 6 ~ 12.
And the present invention relates to a kind of organic electric-field light-emitting element, it is the organic electric-field light-emitting element of stacked anode, organic layer and negative electrode on substrate, and it comprises organic layer, above-mentioned organic layer comprises above-mentioned organic electric-field light-emitting element material.
In addition, the organic layer that the present invention preferably comprises above-mentioned organic electric-field light-emitting element material contains phosphorescence light-emitting dopant.And the emission wavelength that it is desirable to phosphorescence light-emitting dopant has luminous greatly wavelength at below 550nm.
The caborane compounds that uses in the present invention to adopt via aromatic hydrocarbyl or aromatic heterocycle bond on Carborane skeleton to have the structure of silylation.Bond has two charge injection transmittabilities of the Carborane skeleton of aromatic hydrocarbyl or aromatic heterocycle high, but needs the optimization of charge injection transporting in order to the improvement of further element characteristic.But, if only import other substituting groups on aromatic hydrocarbyl, aromatic heterocycle or carborane ring, be then difficult to control the MO distribution dark with the relation of charge injection transporting.Therefore, by importing containing can the substituting group of silicon atom of the MO expansion of disjunction, the injection transporting of two electric charges can be controlled in better scope.Due to above effect, by using it in organic EL element, element drive voltage can be lowered.
And when comprising this caborane compounds in luminescent layer, the balance of electric charge becomes good, and therefore join probability improves again.In addition, this caborane compounds has wide band gap (band gap) due to the effect of the suppression Conjugate extended of silicon atom.Because the size of the width of band gap and minimum triple excitation energy (T1 energy) exists relation, therefore there is wide band gap and mean, when enclosing the T1 energy of dopant, there is sufficiently high T1 energy.Due to above reason, can effectively inhibition of self-doped agent to the movement of the T1 energy of host molecule.Consider from above aspect, high luminous efficiency can be reached.
Carborane skeleton and silylation link via aromatic hydrocarbyl or aromatic heterocycle by this caborane compounds, therefore can control the molecular orbit distribution on each substituting group due to the effect of the MO expansion of the disjunction of silicon atom.Electrochemical stability (resistance to oxidation/Reductive stability) (if be oxidized, is then highest occupied molecular orbital (HighestOccupied Molecular Orbital, HOMO) with the molecular orbit contributing to these; If reduction, be then lowest unoccupied molecular orbital (Lowest UnoccupiedMolecular Orbital, LUMO)) closely related, in order to make the stability for two electric charges of molecule self improve, must obligatoly be resistance to oxidation stability high position distribution HOMO, resistance to Reductive stability high position distribution LUMO MOLECULE DESIGN.This caborane compounds, by controlling above-mentioned MO expansion, can make molecular orbit be distributed in the position high to oxidation/reduction durability, can have good resistance to charge stability.In addition, the base that silicon atom links is not in the same plane, is therefore difficult to fill (packing) or interact, and crystallinity is low, and therefore this phosphorescent element material demonstrates good amorphous character and high thermal stability.That is, the element of this phosphorescent element material is used can to realize driving the organic EL element that the life-span is long, durability is high.
Accompanying drawing explanation
Fig. 1 is the profile of the structure example representing organic EL element.
Fig. 2 is the NMR figure of caborane compounds 1.
Fig. 3 is the NMR figure of caborane compounds 4.
Embodiment
Organic electric-field light-emitting element material of the present invention is the caborane compounds represented by above-mentioned general formula (1).This caborane compounds has the structure replaced by the aromatic hydrocarbyl of silylation institute bond or heteroaromatic, therefore can bring excellent effect as above.
In general formula (1), L
1or L
2separately represent that the carbon number that is substituted or is unsubstituted is the aromatic hydrocarbyl of 6 ~ 30, the carbon number that is substituted or is unsubstituted be 3 ~ 30 aromatic heterocycle or 2 ~ 6 aromatic rings being selected from the aromatic series base of these aromatic hydrocarbyls and aromatic heterocycle link the link aromatic series base formed, can be straight-chain also can be branch-like when linking, the aromatic rings of link can identical also can be different.The carbon number be preferably substituted or be unsubstituted is the aromatic hydrocarbyl of 6 ~ 18, the carbon number that is substituted or is unsubstituted is that the aromatic heterocycle of 3 ~ 17 or the aromatic ring of 2 ~ 5 these aromatic hydrocarbyls and aromatic heterocycle link the link aromatic series base formed.In addition, L
1for the base of p+1 valency, L
2for the base of q+1 valency.
The concrete example of the aromatic hydrocarbyl be unsubstituted can enumerate the base generated except dehydrogenation from benzene, naphthalene, fluorenes, anthracene, phenanthrene, fluoranthene, pyrene, the aromatic hydrocarbon compound such as (chrysene), triphenylene in the wrong or these multiple aromatic hydrocarbon compounds linked, preferably from the base that benzene, naphthalene, anthracene, phenanthrene, triphenylene generate except dehydrogenation.
The concrete example of the aromatic heterocycle be unsubstituted can be enumerated from pyridine, pyrimidine, triazine, quinoline, isoquinolin, quinoxaline, naphthyridines (naphthyridine), carbazole, dibenzofurans, dibenzothiophenes, acridine, azacyclo-heptantriene (azepine), three benzo azacyclo-heptantrienes, azophenlyene, phenoxazine, phenthazine, dibenzo phosphene (dibenzophosphole), the aromatic heterocyclic compounds such as dibenzo boron heterocyclic pentylene (dibenzoborole), or the concatenating group that these multiple aromatic heterocyclic compounds linked generate except dehydrogenation, preferably from pyridine, pyrimidine, triazine, carbazole, dibenzofurans, the base that dibenzothiophenes generates except dehydrogenation.
Aromatic series base is linked by being called from the base making the aromatic compound of the multiple structure linked of the aromatic ring of aromatic hydrocarbon compound or aromatic heterocyclic compounds generate except dehydrogenation.Linking aromatic series base is that 2 ~ 6 aromatic rings link and the base that forms, the aromatic ring linked can identical also can be different, also can comprise aromatic hydrocarbyl and aromatic heterocycle both this.The number of the aromatic ring linked preferably 2 ~ 5, more preferably 2 or 3.
The concrete example of above-mentioned link aromatic series base can be enumerated from biphenyl, terphenyl, phenylnaphthalene, diphenyl naphthalene, phenylanthracene, diphenylanthrancene, diphenylfluorene, bipyridine, connection pyrimidine, connection triazine, two carbazole, two dibenzofurans, two dibenzothiophenes, phenylpyridine, phenyl pyrimidine, phenyl triazine, phenyl carbazole, phenyl dibenzofurans, phenyl dibenzothiophenes, diphenyl pyridine, diphenyl triazine, two carbazyl benzene, two dibenzofuran group benzene, the base that two dibenzo thiophenyl benzene etc. generate except dehydrogenation.
Above-mentioned aromatic hydrocarbyl, aromatic heterocycle or link aromatic series base and also can have substituting group, have in substituent situation, preferred substituting group to be carbon number be 1 ~ 12 alkyl, carbon number be 1 ~ 12 alkoxyl, cyano group or acetyl group.More preferably carbon number to be alkyl, the carbon number of 1 ~ 4 be 1 ~ 2 alkoxyl or acetyl group.
, when above-mentioned link aromatic series base is divalent base, such as, represent with following formula herein, also can straight-chain or branch-like and link.
(Ar
1~ Ar
6for the aromatic hydrocarbon ring that is unsubstituted or heteroaromatic)
In general formula (1), p represents the integer of 1 ~ 5, preferably 1 ~ 2.Q is the integer of 0 ~ 5, preferably 0 ~ 2.R is the integer of 1 ~ 4, preferably 1 ~ 2.
In general formula (1), R
1~ R
6separately represent carbon number be 1 ~ 12 aliphatic alkyl, carbon number be 6 ~ 18 aromatic hydrocarbyl or carbon number be the aromatic heterocycle of 3 ~ 17.Preferably carbon number be 1 ~ 10 aliphatic alkyl or carbon number be the aromatic hydrocarbyl of 6 ~ 12.In addition, aliphatic alkyl can be and saturatedly also can be unsaturated, also can be straight-chain, branch-like or ring-type.
R
1~ R
6concrete example can enumerate the alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, amyl group, hexyl, octyl group, the cycloalkyl such as cyclopenta, cyclohexyl, aromatic hydrocarbyl or the aromatic heterocycles such as phenyl, pyridine radicals, pyrimidine radicals, triazine radical, naphthyl, quinolyl, isoquinolyl, quinazolyl, phthalazinyl (phthalazinyl), fluorenyl, carbazyl, dibenzofuran group, dibenzo thiophenyl.Preferably enumerate phenyl, pyridine radicals, pyrimidine radicals, triazine radical, naphthyl, quinolyl, isoquinolyl, fluorenyl or carbazyl.
These also can have substituting group further; preferred substituting group to be carbon number be 1 ~ 4 alkyl, carbon number be 1 ~ 2 alkoxyl, acetyl group, cyano group, carbon number be 6 ~ 12 aromatic hydrocarbyl, carbon number be the aromatic heterocycle of 3 ~ 12, concrete example can enumerate methyl, ethyl, isopropyl, butyl, methoxyl group, ethyoxyl, acetyl group, phenyl, pyridine radicals, pyrimidine radicals, triazine radical, naphthyl, quinolyl, isoquinolyl, fluorenyl, carbazyl, dibenzofuran group, dibenzo thiophenyl, cyano group.
In general formula (1), R
7, R
8separately represent hydrogen, carbon number be 1 ~ 12 aliphatic alkyl, carbon number be 6 ~ 18 aromatic hydrocarbyl or carbon number be the aromatic heterocycle of 3 ~ 17.Preferably hydrogen, carbon number to be aliphatic alkyl, the carbon number of 1 ~ 8 be 6 ~ 12 aromatic hydrocarbyl or carbon number be the aromatic heterocycle of 3 ~ 12, except comprising hydrogen, other and above-mentioned R
1~ R
6in illustrated identical.
In general formula (1), the C represented by any formula of ring A expression (1a) or formula (1b)
2b
10h
8the carborane radical of 4 valencys, when molecular memory at multiple ring A, can identical also can be different.4 associative keys that formula (1a) or formula (1b) have can produce from C, also can produce from B, preferably with L
1or L
2the associative key of bond produces from C.
In caborane compounds represented by general formula (1), caborane compounds represented by above-mentioned general formula (2) can be enumerated as preferred compound, preferably can enumerate above-mentioned general formula (3) or general formula (4), caborane compounds represented by more preferably above-mentioned general formula (3).
In general formula (1) ~ general formula (4), except ring A, mark identical respectively and formula are then interpreted as having identical implication unless otherwise noted.Ring A in the implication of general formula (2) limited by general formula (1) in different.
Caborane compounds represented by general formula (1) ~ general formula (4) can select raw material according to the structure of target compound, uses known gimmick and synthesizes.
Can with " organometallic chemistry magazine (Journal of Organometallic Chemistry) ", the synthesis example shown in the 1993,462, the 19th page ~ the 29th page is reference and synthesizes (A-1) by following reaction equation.
Can with " organic chemistry magazine (Journal of Organic Chemistry) ", the synthesis example shown in the 2007,72, the 6241st page ~ the 6246th page is reference and synthesizes (A-2) by following reaction equation.
Can with " European inorganic chemistry magazine (European Journal of Inorganic Chemistry) ", 2010,2012nd page ~ the 2024th page and " inorganic chemistry (Inorganic Chemistry) ", 1995, synthesis example shown in 34,2095th page ~ the 2100th page is reference and synthesizes (A-3) by following reaction equation.
Can with " Chinese Journal of Inorganic Chemistry (Inorganica Chimica Acta) ", the synthesis example shown in the 1995,240, the 371st page ~ the 378th page is reference and synthesizes (A-4) by following reaction equation.
Below represent the concrete example of the caborane compounds represented by general formula (1) ~ general formula (4), but organic electric-field light-emitting element material of the present invention is not limited to these compounds.
Organic electric-field light-emitting element material of the present invention contains at least one organic layer of the organic EL element of anode stacked on substrate, multiple organic layer and negative electrode, can provide excellent organic electric-field light-emitting element thus.As contained organic layer, applicable is luminescent layer, electron transfer layer or hole blocking layer.Herein, when using in luminescent layer, can be used as the material of main part of the luminescent layer of or phosphorescence photism dopant luminous containing fluorescence radiation, delayed fluorescence, compound of the present invention can be used as the luminous organic material of radiofluorescence and delayed fluorescence in addition.When being used as the luminous organic material of radiofluorescence and delayed fluorescence, preferably at least any one party of use excited singlet state energy, excited triplet state energy has other organic compounds of the value higher than compound of the present invention as material of main part.Especially preferred is containing the material of main part of compound of the present invention as the luminescent layer containing phosphorescence light-emitting dopant.
Secondly, to using the organic EL element of organic electric-field light-emitting element material of the present invention to be illustrated.
Comprise the organic layer that at least one contains luminescent layer between the anode that organic EL element of the present invention is stacked on substrate and negative electrode, and at least one organic layer comprises organic electric-field light-emitting element material of the present invention.In luminescent layer, advantageously comprise phosphorescence light-emitting dopant and organic electric-field light-emitting element material of the present invention.
Secondly, one side is illustrated with reference to the structure of accompanying drawing one in the face of organic EL element of the present invention, but the structure of organic EL element of the present invention is not subject to any restriction of accompanying drawing.
Fig. 1 is the profile of the structure example representing the general organic EL element used in the present invention, and 1 represents that substrate, 2 represents that anode, 3 represents that hole injection layer, 4 represents that hole transmission layer, 5 represents that luminescent layer, 6 represents that electron transfer layer, 7 represents negative electrode.In organic EL element of the present invention, also can adjoin with luminescent layer and comprise exciton barrier-layer, and also can comprise electronic barrier layer between luminescent layer and hole injection layer.Exciton barrier-layer can be inserted into the anode-side of luminescent layer, any side of cathode side, also can be inserted into both sides simultaneously.In organic EL element of the present invention, comprise substrate, anode, luminescent layer and negative electrode as require layers, as for the layer beyond require layers, hole injection/transport layer, electron injection transport layer can be comprised, hole blocking layer can be comprised further between luminescent layer and electron injection transport layer.In addition, hole injection/transport layer represent any person of hole injection layer and hole transmission layer or both, electron injection transport layer represent any person of electron injecting layer and electron transfer layer or both.
In addition, also can be the structure contrary with Fig. 1, that is, also can sequentially stacked negative electrode 7, electron transfer layer 6, luminescent layer 5, hole transmission layer 4, anode 2 on substrate 1, in this case, also optionally can add layer or omit layer.
-substrate-
Organic EL element of the present invention is preferably supported on substrate.About this substrate, there is no particular restriction, if all the time just usual in organic EL element substrate, such as, can use the substrate comprising glass, transparent plastic, quartz etc.
-anode-
It is the anode of electrode substance that anode in organic EL element can preferably use with the metal of work function large (more than 4eV), alloy, conductive compound and these mixture.The concrete example of this kind of electrode substance can enumerate the metals such as Au, CuI, tin indium oxide (ITO), SnO
2, the conductive clear material such as ZnO.And, also can use IDIXO (In
2o
3-ZnO) etc. noncrystalline and the material of nesa coating can be made.As for anode, these electrode substances can be utilized the method such as evaporation or sputter to form film, utilize photoetching process and form the pattern of desired shape; Or when pattern accuracy is not very necessary (about more than 100 μm), when evaporation or the above-mentioned electrode substance of sputter, pattern can be formed via the mask of desired shape.Or, when use can carry out the material be coated with as organic conductive compound, the wet type such as mode of printing, coating method membrane formation process also can be used.When taking out luminous from this anode, it is desirable to make penetrance be greater than 10%, and as electrical sheet resistance (sheet resistance) preferably hundreds of Ω/below of anode.In addition, thickness also depends on material, usually selects in the scope of 10nm ~ 1000nm, preferably 10nm ~ 200nm.
-negative electrode-
On the other hand, negative electrode can use with the metal of work function little (below 4eV) (being called electron injection metal), alloy, conductive compound and these mixture is electrode substance person.The concrete example of this kind of electrode substance can enumerate sodium, sodium-potassium-sodium alloy, magnesium, lithium, magnesium/copper mixture, magnesium/silver-colored mixture, magnesium/aluminium mixture, magnesium/indium mixture, aluminium/aluminium oxide (Al
2o
3) mixture, indium, lithium/aluminium mixture, rare earth metal etc.Consider from electron injection and for the aspect of the durability of oxidation etc., desirably electron injection metal and the bimetallic mixture as the work function value metal large and more stable than it in these, such as magnesium/silver-colored mixture, magnesium/aluminium mixture, magnesium/indium mixture, aluminium/aluminium oxide (Al
2o
3) mixture, lithium/aluminium mixture, aluminium etc.Negative electrode makes by being utilized by these electrode substances the method such as evaporation or sputter to form film.And as electrical sheet resistance preferably hundreds of Ω/below of negative electrode, thickness is selected usually in the scope of 10nm ~ 5 μm, preferably 50nm ~ 200nm.In addition, in order to make luminous light transmission, if any one party of the male or female of organic EL element is transparent or semitransparent, then luminosity improves and is suitable for.
And, using the thickness of 1nm ~ 20nm by above-mentioned metal as after negative electrode, conductive clear material cited in the explanation of anode is made thereon, transparent or semitransparent negative electrode can be made thus, apply it and can make the element making anode and negative electrode both sides have permeability.
-luminescent layer-
Luminescent layer is layer luminous after generating exciton by combining again from each injected holes of anode and negative electrode and electronics, comprises luminous organic material and material of main part in luminescent layer.
When luminescent layer is fluorescent light-emitting layer, fluorescence luminescent material can be used alone at least one fluorescence luminescent material, preferably fluorescence luminescent material is used as fluorescence radiation dopant, comprises material of main part.
Fluorescence luminescent material in luminescent layer can use the caborane compounds represented by general formula (1), can know, therefore also can be selected from these according to numerous patent documentations etc.Include, for example benzoxazole derivative, benzothiazole derivant, benzimidizole derivatives, styryl benzene derivative, polyphenylene (polyphenyl) derivative, diphenylbutadiene derivatives, tetraphenylbutadiene derivative, Naphthalamide derivatives, coumarin derivative, condensation aromatic compound, purple cyclic ketones (perinone) derivative, oxadiazole derivative, oxazine derivatives, aldazine (aldazine) derivative, pyrrolidin derivatives, cyclopentadiene derivant, bisstyryl anthracene derivant, quinacridone derivative, Pyrrolopyridine derivatives, thiadiazoles pyridine derivate, styryl amine derivative, diketopyrrolopyrrolecocrystals derivative, aromatic series two methylidyne compound, the metal complex of oxine derivative or the metal complex of pyrroles's methylene (pyrromethene) derivative, rare earth complex, various metal complexs etc. representated by transition metal complex, polythiophene, polyphenyl (polyphenylene), the polymer compounds such as polyphenylacetylene (polyphenylenevinylene), organic silane derivative etc.Preferably can enumerate condensation aromatic compound, compound of styryl, Diketopyrrolo-pyrrole compounds, oxazine compounds, pyrroles's methylene metal complex, transition metal complex, Lanthanide Complexes, more preferably can enumerate aphthacene (naphthacene), pyrene, bend, triphenylene, benzo [c] is luxuriant and rich with fragrance, benzo [a] anthracene, pentacene (pentacene), perylene, fluoranthene, acenaphthene fluoranthene (acenaphtofluoranthene), dibenzo [a, j] anthracene, dibenzo [a, h] anthracene, benzo [a] aphthacene, hexacene, anthanthrene (anthanthrene), naphtho-[2, 1-f] isoquinolin, α-naphthalene phenanthridines (α-naphthaphenanthridine), Fei Bing oxazole (phenanthroxazole), quino [6, 5-f] quinoline, benzo aphthothiophenes (benzothiophanthrene) etc.These also can have alkyl, aryl, aromatic heterocycle, ammonia diaryl base alternatively base.
Fluorescent host material in luminescent layer can use the caborane compounds represented by general formula (1), can know, therefore also can be selected from these according to numerous patent documentations etc.Such as using naphthalene, anthracene, phenanthrene, pyrene, flexion, and four benzene, benzene, sanya), fluoranthene, fluorene and indene or its derivatives with condensation of aromatic ring compounds, N, N '- 2 naphthyl - N, N' - diphenyl - 4, 4 '- diphenyl - 1, 1' - diamine derivatives, aromatic amine with three (8 - hydroxyquinoline), aluminum (III) as a representative of metal chelate e symplectic compound (metal chelated oxinoid compound), two styryl benzene derivatives such as double styryl derivatives, tetraphenyl butadiene derivatives, indene derivatives, coumarin derivatives, oxadiazoles derivatives, pyrrole and pyridine derivatives, ZiHuan ketone derivatives, cyclopentadiene derivatives, pyrrole and pyrrole derivatives, thiamethoxam 1 and pyridine derivatives, diphenyl and furan derivatives, carbazole derivatives, indole carbazole derivatives, triazine derivatives, polymer polystyrene acetylene in derivatives, poly benzene derivatives, poly fluorene derivatives, polyethylene carbazole derivatives, poly (thiophene derivatives, etc., there is no special limits.
Above-mentioned fluorescence luminescent material is being used as fluorescence radiation dopant, and when comprising material of main part, the amount of fluorescence radiation dopant contained by luminescent layer can be the scope of 0.01 % by weight ~ 20 % by weight, preferably 0.1 % by weight ~ 10 % by weight.
Under normal circumstances, organic EL element from anode, negative electrode two electrodes by charge injection to luminescent substance, generate the luminescent substance of excitation state and make it luminous.When the organic EL element of charge-injection type, in the exciton generated, 25% is activated into singlet excited, and residue 75% is activated into triplet excited state.As " advanced material (Advanced Materials) " 2009, 21, shown in 4802-4806, known specific fluorescence radiation material is due to intersystem crossing (intersystem crossing) etc. and after making energy jump (transition) to triplet excited state, due to the absorption of triplet-triplet annihilation (triplet-triplet annihilation) or heat energy, inverse intersystem crossing (inverse intersystem crossing) is singlet excited and radiofluorescence, show thermal activation (thermal activation) delayed fluorescence.Organic EL element of the present invention also can show delayed fluorescence.In this case, fluorescence radiation and delayed fluorescence can also be comprised luminous both this.Wherein, also can be a luminous part or the partial luminescence from material of main part.
When luminescent layer is delayed fluorescence luminescent layer, delayed luminescence material can be used alone at least one delayed luminescence material, preferably delayed fluorescence material is used as delayed fluorescence light-emitting dopant, comprises material of main part.
As the delayed fluorescence luminescent material in luminescent layer, the caborane compounds represented by general formula (1) can be used, also can be selected from known delayed fluorescence luminescent material.Include, for example tin complex, indole carbazole derivative, copper complex, carbazole derivates etc.Specifically, compound described in following non-patent literature, patent documentation can be enumerated, but be not limited to these compounds.
1) " advanced material (Adv.Mater.) " 2009,21,4802-4806,2) " Applied Physics bulletin (Appl.Phys.Lett.) " 98,083302 (2011), 3) Japanese Patent Laid-Open 2011-213643 publication, 4) " American Chemical Society's proceedings (J.Am.Chem.Soc.) " 2012,134,14706-14709.
The concrete example of delayed luminescence material is shown, but is not limited to following compound.
Above-mentioned delayed fluorescence luminescent material is being used as delayed fluorescence light-emitting dopant, when comprising material of main part, the amount of delayed fluorescence light-emitting dopant contained by luminescent layer can be the scope of 0.01 % by weight ~ 50 % by weight, preferably 0.1 % by weight ~ 20 % by weight, more preferably 0.01% ~ 10%.
Delayed fluorescence material of main part in luminescent layer can use the caborane compounds represented by general formula (1), also can be selected from the compound beyond carborane.Such as using naphthalene, anthracene, phenanthrene, pyrene, flexion, and four benzene, benzene, sanya), fluoranthene, fluorene and indene or its derivatives with condensation of aromatic ring compounds, N, N '- 2 naphthyl - N, N' - diphenyl - 4, 4 '- diphenyl - 1, 1' - diamine derivatives, aromatic amine with three (8 - hydroxyquinoline), aluminum (III) as a representative of metal chelate class e compounds, two styryl benzene derivatives such as double styryl derivatives, tetraphenyl butadiene derivatives, indene derivatives, coumarin derivatives, oxadiazoles derivatives, pyrrole and pyridine derivatives, ZiHuan ketone derivatives, cyclopentadiene derivatives, pyrrole and pyrrole derivatives, thiamethoxam 1 and pyridine derivatives, diphenyl and furan derivatives, carbazole derivatives, indole carbazole derivatives, triazine derivatives, polymer polystyrene acetylene in derivatives, poly benzene derivatives, poly fluorene derivatives, polyethylene carbazole derivatives, poly (thiophene derivatives, aromatic silane derivate, etc., but there is no special limits.
When luminescent layer is phosphorescence luminescent layer, luminescent layer comprises phosphorescence light-emitting dopant and material of main part.Phosphorescence luminescent dopant agent material can be the material containing metal-organic complex, and above-mentioned metal-organic complex comprises at least one metal being selected from ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold.Specifically can enumerate compound described in following patent documentation, but be not limited to these compounds.
WO2009/073245 publication, WO2009/046266 publication, WO2007/095118 publication, WO2008/156879 publication, WO2008/140657 publication, US2008/261076 publication etc.
Preferred phosphorescence light-emitting dopant can enumerate the Ir (ppy) as central metal such as the precious metal element that has Ir
3deng complex compound class, Ir (bt)
2acac
3deng complex compound class, PtOEt
3deng complex compound class.Below represent the concrete example of these complex compound classes, but be not limited to following compound.
The amount contained in luminescent layer of above-mentioned phosphorescence light-emitting dopant preferably 2 % by weight ~ 40 % by weight, preferably 5 % by weight ~ 30 % by weight scope.
When luminescent layer is phosphorescence luminescent layer, the material of main part in luminescent layer preferably uses the caborane compounds represented by above-mentioned general formula (1) of the present invention.Wherein, when using this caborane compounds in other any organic layers beyond luminescent layer, the material used in luminescent layer also can be other material of main parts beyond caborane compounds.And, also caborane compounds and other material of main parts can be used.In addition, also can by multiple for known material of main part and with and use.
As spendable known host compound, preferably there is cavity transmission ability, electron transport ability, and prevent luminous long wavelengthization, there is the compound of high vitrification point in addition.
Other material of main parts of this kind can be known by numerous patent documentations etc., therefore can be selected from these.The concrete example of material of main part is not particularly limited, and can enumerate indole derivatives, carbazole derivates, triazole derivative, oxazole derivative, oxadiazole derivative, imdazole derivatives, polyaryl alkane derivatives, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, arylamine derivatives, amino chalcones derivative, styrylanthracene derivatives, fluorenone derivatives, hydazone derivative, Stilbene (stilbene) derivative, silazane derivatives, aromatic series tertiary amine compounds, styrylamine compounds, aromatic series two methine based compound, porphyrin based compound, anthraquinone bismethane derivative, anthracyclinone derivatives, diphenoquinone, thiopyran dioxide (thiopyrandioxide) derivative, the heterocycle tetracarboxylic anhydride of Nai perylene etc., phthalocyanine derivates, the metal complex of oxine (8-quinolinol) derivative or metal phthalocyanine, various metal complexs representated by the metal complex of benzoxazole or benzothiazole derivant, polysilane based compound, poly-(N-vinylcarbazole) derivative, aniline based copolymer, thiophene oligomer, polythiofuran derivative, polyphenylene derivatives, polyphenylacetylene derivative, the macromolecular compounds etc. such as polyfluorene derivative.
Luminescent layer can be any person of fluorescent light-emitting layer, delayed fluorescence luminescent layer or phosphorescence luminescent layer, preferably phosphorescence luminescent layer.
-implanted layer-
So-called implanted layer is in order to the layer reducing driving voltage or improve luminosity and be arranged between electrode and organic layer, there is hole injection layer and electron injecting layer, can be present between anode and luminescent layer or hole transmission layer and between negative electrode and luminescent layer or electron transfer layer.Implanted layer can optionally be arranged.
-hole blocking layer-
So-called hole blocking layer, there is the function of electron transfer layer in a broad sense, comprise the function with transmission electronic and the obviously little hole barrier materials of the ability of transporting holes, by transmission electronic and blocking hole and improve the join probability again in electronics and hole.
In hole blocking layer, preferably using the caborane compounds represented by general formula of the present invention (1), when caborane compounds being used for other any organic layers, known hole barrier layer material can be used.And hole barrier layer material is visual needs the material using electron transfer layer described later.
-electronic barrier layer-
So-called electronic barrier layer, comprises the function with transporting holes and the obviously little material of the ability of transmission electronic, by transporting holes and block electrons and improve the probability that electronics is combined with hole again.
The material of electronic barrier layer optionally can use the material of hole transmission layer described later.The thickness preferably 3nm ~ 100nm of electronic barrier layer, more preferably 5nm ~ 30nm.
-exciton barrier-layer-
So-called exciton barrier-layer be blocked in hole in luminescent layer be combined again with electronics and the exciton diffusion that produces to the layer of charge transport layer, by insert this layer and can efficiently by exciton inclosure in luminescent layer, the luminous efficiency of element can be made to improve.Exciton barrier-layer can adjoin with luminescent layer and be inserted into any side of anode-side, cathode side, also can be inserted into both sides simultaneously.
The material of exciton barrier-layer can use the caborane compounds represented by general formula (1), other materials include, for example 1,3-bis-carbazyl benzene (mCP) or two (2-methyl-oxine)-4-phenylphenol aluminium (III) (BAlq).
-hole transmission layer-
So-called hole transmission layer, comprises the hole mobile material of the function with transporting holes, can arrange the hole transmission layer of single or multiple lift.
Any person of the barrier of the cuniculate injection of hole mobile material tool or transmission, electronics, can be any person of organic substance, inorganic matter.As spendable known hole mobile material, preferably use the caborane compounds represented by general formula (1), can in existing known compound, select any person and use.As spendable known hole mobile material, include, for example triazole derivative, oxadiazole derivative, imdazole derivatives, polyaryl alkane derivatives, pyrazoline derivative and pyrazolone derivative, phenylenediamine derivative, arylamine derivatives, amino chalcones derivative, oxazole derivative, styrylanthracene derivatives, fluorenone derivatives, hydazone derivative, stilbene derivative, silazane derivatives, aniline based copolymer, and electroconductive polymer oligomer, particularly thiophene oligomer etc., preferably use porphyrin compound, aromatic series tertiary amine compounds and styrylamine compounds, more preferably use aromatic series tertiary amine compounds.
-electron transfer layer-
So-called electron transfer layer, comprises the material of the function with transmission electronic, can arrange the electron transfer layer of single or multiple lift.
Electron transport material (also there is the situation doubling as hole barrier materials) is if having the function by being conveyed to luminescent layer from negative electrode injected electrons.In electron transfer layer, preferably use the carborane derivative represented by general formula of the present invention (1), can in existing known compound, select any person and use, include, for example nitro-substituted fluorene derivative, diphenoquinone, thiopyran dioxide derivative, carbodiimide (carbodiimide), fluorenylidenemethane derivatives, anthraquinone bismethane and anthracyclinone derivatives, oxadiazole derivative etc.In addition, in the Shang Shu oxadiazole derivative of ， the oxygen atom of oxadiazole rings is substituted by sulphur atom thiadiazoles derivative, have and be known as electron withdrawing group quinoxaline ring (quinoxaline ring) quinoxaline derivatices also can be used as electron transport material.Also can use further and these materials are directed in macromolecular chain or make these materials become the macromolecular material of high molecular main chain.
[embodiment]
Below, be described in more detail the present invention by embodiment, the present invention is not limited to these embodiments certainly, only otherwise exceed its purport, then and can various form and implementing.
In addition, in this specification, the value of so-called T1 energy is the value using the molecular computing software Gauss (Gaussian) 09 of U.S. Gauss (Gaussian) company manufacture and obtain, and is defined through B3LYP/6-31G
*the value that the structure optimization of level calculates and calculates.
The caborane compounds of organic electric-field light-emitting element material is become by path shown below.In addition, compound number is corresponding with the numbering appended by above-mentioned chemical formula.
Embodiment 1
Compound 1 is synthesized according to following reaction equation.
In a nitrogen environment, add a carborane 6.92g (0.0480mol), 1,2-dimethoxy-ethane (DME) 183mL, DME solution is cooled to 0 DEG C.Drip the lithium hexane solution 61.1mL of 1.65M, at room temperature carry out the stirring of 15 minutes.Add copper chloride (I) 9.5g (0.0960mol), after at room temperature carrying out stirring in 15 minutes, add pyridine 28.7mL.After at room temperature carrying out the stirring of 5 minutes, add bromo-iodobenzene 28.5g (0.101mol), at 95 DEG C, stir an evening.In the reactant liquor of gained, one side stirs and simultaneously adds carrene (500mL), 1N hydrochloric acid (500mL), is cleaned organic layer with distilled water (3 × 500mL).After carrying out drying with anhydrous magnesium sulfate to organic layer, by magnesium sulfate isolated by filtration, desolventizing is heated up in a steamer in decompression.By silicone tube column chromatography, purifying is carried out to the residue of gained, obtain 13.7g (30.2mmol, productive rate are 63%) intermediate A.
In a nitrogen environment, make intermediate A 8.6g (0.0189mol), oxolane (THF) 17mL is dissolved in diethyl ether 60mL and is cooled to-30 DEG C.Thereafter, drip the lithium hexane solution 25mL of 1.65M, at room temperature carry out the stirring of 1 hour.The tri-phenyl chloride 11.6g (0.0393mol) be dissolved in THF 34ml and diethyl ether 24ml is dripped in the white solution of gained.Thereafter, one side is slowly warming up to room temperature one side and stirs an evening, in the reactant liquor of gained, one side stirs and simultaneously adds carrene (300mL), 1N hydrochloric acid (200mL), utilizes distilled water (3 × 500mL) to be cleaned organic layer.After carrying out drying with anhydrous magnesium sulfate to organic layer, by magnesium sulfate isolated by filtration, desolventizing is heated up in a steamer in decompression.By partial crystallization, purifying is carried out to the residue of gained, obtain the compound 1 of 3.56g (4.38mmol, productive rate are 23%) as white solid.By FD-MS, m/z 813 [M]
+,
1h-NMR measurement result (measures solvent: CDCl
3) shown in Figure 2.
Embodiment 2
Compound 4 is synthesized according to following reaction equation.
In a nitrogen environment, add 2,6-dibromo pyridine 63.6g (0.268mol), THF 1080mL and be cooled to-50 DEG C.Thereafter, drip the lithium hexane solution of 2.69M, at-50 DEG C, carry out the stirring of 2 hours.The tri-phenyl chloride 78.4g (0.266mol) be dissolved in THF 240ml and diethyl ether 160ml is dripped in the dark solution of gained.Thereafter, one side is slowly warming up to room temperature one side and stirs an evening, in the reactant liquor of gained, one side stirs and simultaneously adds ethyl acetate (1000mL), 1N hydrochloric acid (1000mL), utilizes distilled water (3 × 500mL) to clean organic layer.After carrying out drying with anhydrous magnesium sulfate to organic layer, by magnesium sulfate isolated by filtration, desolventizing is heated up in a steamer in decompression.Utilize silicone tube column chromatography to carry out purifying to the residue of gained, obtain the intermediate B of 18.5g (44.4mmol, productive rate are 17%) as white solid.
In a nitrogen environment, add a carborane 2.6g (0.0185mol), 1,2-dimethoxy-ethane (DME) 80mL, at room temperature carry out the stirring of 5 minutes.Drip the lithium hexane solution 27.4mL of 1.59M, at room temperature carry out the stirring of 5 minutes.Thereafter, add pyridine 11mL, copper chloride (I) 5.9g (0.0592mol), stir 1 hour at 60 DEG C.In the dark solution of gained, drip the intermediate B 17.0g (0.0408mol) be dissolved in DME 40mL, at 90 DEG C, stir an evening.In the reactant liquor of gained, one side stirs and simultaneously adds carrene (500mL), 1N hydrochloric acid (500mL), utilizes distilled water (3 × 500mL) to clean organic layer.After carrying out drying with anhydrous magnesium sulfate to organic layer, by magnesium sulfate isolated by filtration, desolventizing is heated up in a steamer in decompression.By partial crystallization, silicone tube column chromatography, purifying is carried out to the residue of gained, obtain 1.9g (2.33mmol, productive rate are 13%) compound 4.By APCI-TOFMS, m/z 816 [M+H]
+,
1h-NMR measurement result (measures solvent: CDCl
3) shown in Figure 3.
Reference example 1
The result calculating the T1 energy of caborane compounds by using Gauss (Gaussian) 09 is shown in Table 1.
Chemical formula in order to compound H-1 ~ compound H-3 compared is as follows.
[table 1]
Can confirm according to table 1: by via aromatic hydrocarbyl or aromatic heterocycle on Carborane skeleton bond silylation, T1 energy value can be made to become large.
And, use compound 1, compound 2, compound 4, compound 5, compound 6, compound 8, compound 13, compound 32 and compound H-1, compound H-2, compound H-3 and make organic EL element.
Embodiment 3
Be formed on the glass substrate comprising the anode of tin indium oxide (ITO) that thickness is 70nm, utilizing vacuum vapour deposition to be 2.0 × 10 in vacuum degree
-5stacked each film under Pa.First, copper phthalocyanine (CuPC) is formed as by ITO 30nm thickness and as hole injection layer.Secondly, N, N'-bis-(1-naphthyl)-N, N'-diphenylbenzidine (α-NPD) is formed as 15nm thickness and as hole transmission layer.Secondly, on hole transmission layer, common evaporation is carried out and using the compound 1 of the material of main part as luminescent layer and the iridium complex [two (4 as the blue phosphor materials of dopant from different vapor deposition source, 6-difluorophenyl)-pyridine-N, C2'] pyridine carboxylic acid iridium (III)] (iridium (III) [bis (4,6-difluorophenyl)-pyridinato-N, C2 '] picolinate) (FIrpic) be formed as the luminescent layer of the thickness of 30nm.The concentration of FIrpic is 10%.Secondly, by Alq
3be formed as 25nm thickness and as electron transfer layer.Further on the electron transport layer, lithium fluoride (LiF) is formed as 1.0nm thickness and as electron injecting layer.Finally, on electron injecting layer, aluminium (Al) is formed as 70nm thickness and as electrode.The organic EL element of gained has following layer and forms: in the organic EL element shown in Fig. 1, between negative electrode and electron transfer layer, add electron injecting layer.
The organic EL element of gained connects external power source and applies direct voltage, results verification is to having the characteristics of luminescence as shown in table 2.In table 2, brightness, voltage and luminous efficiency represent at 2.5mA/cm
2under value (initial characteristic).In addition, the very big wavelength of element emission spectrum (emission spectrum) is 475nm, and known acquisition is from the luminescence of FIrpic.
Embodiment 4 ~ embodiment 9
Use compound 2, compound 4, compound 5, compound 6, compound 8, compound 32 replace compound 1 and as the material of main part of the luminescent layer in embodiment 3, carry out similarly to Example 3 in addition and make organic EL element.
Comparative example 1
Use mCP as the material of main part of the luminescent layer in embodiment 3, carry out similarly to Example 3 in addition and make organic EL element.
Comparative example 2 ~ comparative example 4
Use compound H-1, compound H-2 or compound H-3 as the material of main part of the luminescent layer in embodiment 3, carry out similarly to Example 3 in addition and make organic EL element.
About the organic EL element of gained in embodiment 4 ~ embodiment 9 and comparative example 1 ~ comparative example 4, evaluate similarly to Example 3, results verification is to having the characteristics of luminescence as shown in table 2.In addition, in embodiment 4 ~ embodiment 9 and comparative example 1 ~ comparative example 4, the very big wavelength of the emission spectrum of the organic EL element of gained is 475nm, can be accredited as the luminescence obtained from FIrpic.
[table 2]
According to table 2, in embodiment 3 ~ embodiment 9, when using caborane compounds of the present invention in luminescent layer, Comparatively speaking luminous efficiency and comparative example 1 ~ comparative example 4, demonstrate good characteristic.
Embodiment 10
Be formed on the glass substrate comprising the anode of ITO that thickness is 70nm, utilizing vacuum vapour deposition to be 2.0 × 10 in vacuum degree
-5stacked each film under Pa.First, CuPC is formed as by ITO 30nm thickness and as hole injection layer.Secondly, α-NPD is formed as 15nm thickness and as hole transmission layer.Secondly, on hole transmission layer, carry out common evaporation and using the compound 1 of the material of main part as luminescent layer and the Ir (ppy) as dopant from different vapor deposition source
3be formed as the luminescent layer of the thickness of 30nm.Ir (ppy)
3concentration be 10%.Secondly, by Alq
3be formed as 25nm thickness and as electron transfer layer.Further on the electron transport layer, LiF is formed as 1nm thickness and as electron injecting layer.Finally, on electron injecting layer, Al is formed as the thickness of 70nm as electrode, makes organic EL element.
The organic EL element of gained connects external power source and applies direct voltage, results verification is to having the characteristics of luminescence as shown in table 3.In table 3, brightness, voltage and luminous efficiency represent at 20mA/cm
2value (initial characteristic) during lower driving.The very big wavelength of element emission spectrum is 530nm, and known acquisition is from Ir (ppy)
3luminescence.
Embodiment 11 ~ embodiment 17
Use compound 2, compound 4, compound 5, compound 6, compound 8, compound 13, compound 32 to replace compound 1 as the material of main part of the luminescent layer in embodiment 10, carry out similarly to Example 10 in addition and make organic EL element.
Comparative example 5 ~ comparative example 8
Use CBP, H-1, H-2 or H-3 as the material of main part of the luminescent layer in embodiment 10, carry out similarly to Example 10 in addition and make organic EL element.
About the organic EL element of gained in embodiment 11 ~ embodiment 17 and comparative example 5 ~ comparative example 8, evaluate similarly to Example 10, results verification is to having the characteristics of luminescence as shown in table 3.In addition, in embodiment 11 ~ embodiment 17 and comparative example 5 ~ comparative example 8, the very big wavelength of the emission spectrum of the organic EL element of gained is 530nm, can be accredited as and obtain from Ir (ppy)
3luminescence.
[table 3]
According to table 3, when being used in luminescent layer by caborane compounds of the present invention (embodiment 10 ~ embodiment 17), Comparatively speaking demonstrate good luminous efficiency with situation (comparative example 5 ~ comparative example 8) in addition.
Embodiment 18
Be formed on the glass substrate comprising the anode of ITO that thickness is 70nm, utilizing vacuum vapour deposition to be 2.0 × 10 in vacuum degree
-5stacked each film under Pa.First, CuPC is formed as by ITO 30nm thickness and as hole injection layer.Secondly, α-NPD is formed as 15nm thickness and as hole transmission layer.Secondly, on hole transmission layer, carry out common evaporation and using the CBP of the material of main part as luminescent layer and the Ir (ppy) as dopant from different vapor deposition source
3be formed as the luminescent layer of the thickness of 30nm.Ir (ppy)
3concentration be 10%.Secondly, on luminescent layer, compound 1 is formed as 5nm thickness and as hole blocking layer.Secondly, by Alq
3be formed as 20nm thickness and as electron transfer layer.Further on the electron transport layer, LiF is formed as 1.0nm thickness and as electron injecting layer.Finally, Al is formed as by electron injecting layer 70nm thickness and as electrode.The organic EL element of gained has following layer and forms: in the organic EL element shown in Fig. 1, and adding between negative electrode and electron transfer layer has electron injecting layer, and adds between luminescent layer and electron transfer layer and have hole blocking layer.
The organic EL element of gained connects external power source and applies direct voltage, results verification is to having the characteristics of luminescence as shown in table 4.In table 4, brightness, voltage and luminous efficiency represent at 20mA/cm
2value (initial characteristic) during lower driving.The very big wavelength of element emission spectrum is 530nm, and known acquisition is from Ir (ppy)
3luminescence.
Embodiment 19 ~ embodiment 25
Compound 2, compound 4, compound 5, compound 6, compound 8, compound 13, compound 32 is used to replace compound 1 and as the hole barrier materials in embodiment 18, carry out similarly to Example 18 in addition and make organic EL element.
Comparative example 9
Using the Alq as electron transfer layer in embodiment 18
3thickness be set to 25nm, hole blocking layer is not set, carries out similarly to Example 18 in addition and make organic EL element.
Comparative example 10 ~ comparative example 12
Use compound H-1, compound H-2 or compound H-3 as the hole barrier materials in embodiment 18, carry out similarly to Example 18 in addition and make organic EL element.
About the organic EL element of gained in embodiment 19 ~ embodiment 25 and comparative example 9 ~ comparative example 12, evaluate similarly to Example 18, results verification is to having the characteristics of luminescence as shown in table 4.In addition, in embodiment 19 ~ embodiment 25 and comparative example 9 ~ comparative example 12, the very big wavelength of the emission spectrum of the organic EL element of gained is 530nm, is accredited as and obtains from Ir (ppy)
3luminescence.In addition, the material of main part of the luminescent layer used in embodiment 19 ~ embodiment 25 and comparative example 9 ~ comparative example 12 is CBP.
[table 4]
According to table 4, with the situation (not using the situation of hole barrier materials) beyond comparative example 9 Comparatively speaking, the improvement of visible initial characteristic in all systems.Wherein, when using caborane compounds of the present invention in hole blocking layer, with the situation (comparative example 10 ~ comparative example 12) beyond it Comparatively speaking, demonstrate good characteristic.
[utilizability in industry]
Organic EL element of the present invention has satiable level in practicality in the characteristics of luminescence, driving life-span and durability, at flat-panel monitor (mobile phone display element, car-mounted display element, office automation (Office Automation, OA) Computer display element or TV etc.), apply flexibly in the light source (back light of illumination, the light source of copying machines, liquid crystal display or scale (gauge) class) of the feature as planar luminous body, display panel or mark lamp etc. application, its technological value is large.
Claims (9)
1. an organic electric-field light-emitting element material, it comprises the caborane compounds represented by general formula (1):
Herein, the C represented by any formula of ring A expression (1a) or formula (1b)
2b
10h
8the carborane radical of 4 valencys, when molecular memory at multiple ring A, can identical also can be different; L
1the base of p+1 valency, L
2the base of q+1 valency, L
1, L
2represent that the carbon number that is substituted or is unsubstituted is the aromatic hydrocarbyl of 6 ~ 30 independently of one another, the carbon number that is substituted or is unsubstituted be 3 ~ 30 aromatic heterocycle or 2 ~ 6 the aromatic series bases being selected from described aromatic heterocycle and described aromatic heterocycle link the link aromatic series base formed, can be straight-chain also can be branch-like when linking aromatic series base, the aromatic rings linked can identical also can be different; R
1, R
2, R
3, R
4, R
5, R
6represent that carbon number is the aliphatic alkyl of 1 ~ 12 independently, the carbon number that is substituted or is unsubstituted be 6 ~ 18 aromatic hydrocarbyl or the carbon number that is substituted or is unsubstituted be the aromatic heterocycle of 3 ~ 17, R
7, R
8represent that hydrogen, carbon number are the aliphatic alkyl of 1 ~ 12 independently, the carbon number that is substituted or is unsubstituted be 6 ~ 18 aromatic hydrocarbyl or the carbon number that is substituted or is unsubstituted be the aromatic heterocycle of 3 ~ 17; P represents the integer of 1 ~ 5, and q represents the integer of 0 ~ 5, and r represents the integer of 1 ~ 4.
2. organic electric-field light-emitting element material according to claim 1, wherein, described caborane compounds is the caborane compounds represented by general formula (2):
Herein, L
1, L
2, R
1~ R
8, p, q and r and general formula (1) synonym; The C represented by any formula of ring A expression (2a) or formula (2b)
2b
10h
8the carborane radical of 4 valencys, when molecular memory at multiple ring A, can identical also can be different.
3. organic electric-field light-emitting element material according to claim 1, wherein, described caborane compounds is general formula (3) or the caborane compounds represented by general formula (4):
Herein, L
1, L
2, R
1~ R
8, p, q and r and general formula (1) synonym.
4. organic electric-field light-emitting element material according to claim 3, wherein, in general formula (3) or general formula (4), L
1, L
2carbon number independently of one another for being substituted or being unsubstituted is the aromatic hydrocarbyl of 6 ~ 18, the carbon number that is substituted or is unsubstituted is 3 ~ 17 aromatic heterocycle or 2 ~ 5 aromatic series bases being selected from described aromatic heterocycle and described aromatic heterocycle link aromatic series base of linking and forming.
5. organic electric-field light-emitting element material according to claim 3, wherein, in general formula (3) or general formula (4), R
1~ R
6independently of one another for carbon number be 1 ~ 10 aliphatic alkyl or carbon number be the aromatic hydrocarbyl of 6 ~ 12.
6. an organic electric-field light-emitting element, it is the organic electric-field light-emitting element of stacked anode, organic layer and negative electrode on substrate, the feature of described organic electric-field light-emitting element is to comprise organic layer, and described organic layer comprises organic electric-field light-emitting element material according to any one of claim 1 to 5.
7. organic electric-field light-emitting element according to claim 6, wherein, the described organic layer comprising described organic electric-field light-emitting element material is at least one layer being selected from the group be made up of luminescent layer, electron transfer layer and hole blocking layer.
8. organic electric-field light-emitting element according to claim 7, wherein, the described organic layer comprising described organic electric-field light-emitting element material is the luminescent layer containing phosphorescence light-emitting dopant.
9. organic electric-field light-emitting element according to claim 8, wherein, the emission wavelength of described phosphorescence light-emitting dopant has luminous greatly wavelength at below 550nm.
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| WO2015045705A1 (en) * | 2013-09-30 | 2015-04-02 | 新日鉄住金化学株式会社 | Material for organic electroluminescent element and organic electroluminescent element using the same |
| JP6402177B2 (en) * | 2014-03-28 | 2018-10-10 | 新日鉄住金化学株式会社 | Material for organic electroluminescence device and organic electroluminescence device using the same |
| JP6307332B2 (en) * | 2014-04-21 | 2018-04-04 | 新日鉄住金化学株式会社 | Organic electroluminescence device |
| JP6383623B2 (en) * | 2014-09-29 | 2018-08-29 | 新日鉄住金化学株式会社 | Organic electroluminescence device |
| JP6378993B2 (en) * | 2014-09-29 | 2018-08-22 | 新日鉄住金化学株式会社 | Organic electroluminescence device |
| KR20170132205A (en) * | 2015-03-30 | 2017-12-01 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Organic electroluminescent device material and organic electroluminescent device using the same |
| US10978647B2 (en) | 2017-02-15 | 2021-04-13 | Universal Display Corporation | Organic electroluminescent materials and devices |
| KR102345418B1 (en) | 2019-07-16 | 2021-12-30 | 한국재료연구원 | Method of manufacturing metal exterior material for smart device |
| KR20210136224A (en) | 2020-05-06 | 2021-11-17 | 삼성디스플레이 주식회사 | Llight emitting device and electronic apparatus comprising same |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6360796B2 (en) | 2018-07-18 |
| KR102111358B1 (en) | 2020-05-15 |
| WO2014103724A1 (en) | 2014-07-03 |
| KR20150100890A (en) | 2015-09-02 |
| JPWO2014103724A1 (en) | 2017-01-12 |
| TW201431867A (en) | 2014-08-16 |
| CN104838514B (en) | 2017-03-08 |
| TWI558718B (en) | 2016-11-21 |
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