CN107698622A

CN107698622A - Include the organic electronic device of the layer containing at least one metallo-organic compound and at least one metal oxide

Info

Publication number: CN107698622A
Application number: CN201610649460.6A
Authority: CN
Inventors: 渡部惣; 渡部惣一; C·席尔德克内希特; G·瓦根布拉斯特; C·伦纳茨; E·弗茨; O·莫尔特; T·格博纳; K·多尔曼; N·兰格尔; 田边润; 田边润一
Original assignee: Udc Ireland LLC
Current assignee: Udc Ireland LLC
Priority date: 2010-06-18
Filing date: 2011-06-16
Publication date: 2018-02-16
Anticipated expiration: 2031-06-16
Also published as: CN107698622B; CN103068950A; EP2582770A4; CN103068950B; KR20130118858A; JP6408519B2; KR101806586B1; JP2013537701A; JP6014938B2; EP2582770A1; WO2011158204A1; JP2016197744A

Abstract

The present invention relates to a kind of organic electronic device, the device includes first electrode, second electrode and the first organic layer being placed between first electrode and second electrode, wherein the first organic layer includes at least one metallo-organic compound and at least one metal oxide.The invention further relates to a kind of equipment for including organic electronic device of the present invention.

Description

Comprising containing at least one metallo-organic compound and at least one metal oxide The organic electronic device of layer

The application is Application No. 201180039004.5, the applying date to be on June 16th, 2011, entitled " include The patent application of the organic electronic device of layer containing at least one metallo-organic compound and at least one metal oxide " Divisional application.

The present invention relates to a kind of organic electronic device, it includes first electrode, second electrode and is placed in first electrode and the The first organic layer between two electrodes, wherein the first organic layer includes at least one metallo-organic compound and at least one metal Oxide.The invention further relates to a kind of equipment for including organic electronic device of the present invention.

Organic electronic is the subdomain of electronics, and uses the electronic circuit comprising polymer or smaller organic compound.Have Electromechanical son is the use of polymer or smaller organic compound in Organic Light Emitting Diode (OLED) using field, organic In solar cell (organic photo cell), and in switch element, such as make in organic transistor such as organic FET and organic tft With.

Therefore the use of suitable new organic materials allows to provide the various novel components based on organic electronic, such as show Device, sensor, transistor, data storage or photocell.This allows to thin, light, flexible and can produce with low cost development New opplication.

The preferred of the application using field is use of the smaller organic compound in Organic Light Emitting Diode.

The performance to be lighted when Organic Light Emitting Diode (OLED) is excited using material by electric current.OLED is as cathode-ray tube It is especially significant with the substitute production plane video frequency display device of liquid crystal display.Due to very closely knit design and inherently Low-power consumption, the device comprising OLED are particularly suited for Mobile solution, for example, for the application in radio telephone, laptop computer etc. and Lighting device.

The general principle of OLED method of works and suitable OLED structure (layer) are for example described in the Hes of WO 2005/113704 In document cited therein.

In addition to fluorescent material (fluorescent emitter), luminescent material (emitter) used can be phosphor material (phosphorescent emissions Body).With showing the fluorescent emitter of singlet emission on the contrary, phosphorescent emitters usually show organic gold of triplet transmitting Metal complex (M.A.Baldow et al., Appl.Phys.Lett.1999,75,4-6).Due to quantum-mechanical reason, work as use During phosphorescent emitters, at most 4 times of quantum efficiencies, energy efficiency and power efficiency are possible.

Of particular interest are with long service live, good efficiencies, high stability and low use and work to thermal stress Make the Organic Light Emitting Diode of voltage.

In practice to realize above-mentioned performance, suitable emitter material is not needed only provide for, but also must make OLED Other components (supplementary material) mutually balanced in suitable combination of devices thing.This kind of combination of devices thing can be for example comprising reality The particular substrate material that illuminator is contained therein with distribution form.In addition, composition is also comprising blocking agent material, hole blocking Agent, exciton blocking agent and/or electron-block agent may be present in combination of devices thing.Additionally or as selection, combination of devices thing is also Hole-injecting material and/or electron injection material and/or charge transport materials such as hole mobile material can be included and/or electronics passes Defeated material.The selection for the above-mentioned material being applied in combination with actual illuminator is to OLED parameter, including efficiency and life-span and use Have with operating voltage and significantly affect.

Especially with respect to the lower power consumption for including organic electronic device, the especially equipment of Organic Light Emitting Diode (OLED) Demand improve.To reduce power consumption, it is intended to reduce the driving voltage of organic electronic device.It is important in addition to driving voltage is reduced Also extend organic electronic device, especially OLED life-span.In the prior art, light-emitting component has been developed to overcome the above Problem.

The A1 of US 2006/0180812 disclose the light-emitting component with the layer containing organic material and inorganic material, wherein The activation energy of the electric conductivity of the layer is big for 0.01eV or more and is less than 0.30eV.Suitable organic material is to include arylamine bone Frame and the organic compound with hole transport performance, such as 4,4 '-bis- (N- { 4- [N, N '-bis- (3- aminomethyl phenyls) amino] benzene Base }-N- phenyl aminos] biphenyl (DNTPD) and N, N '-bis- (spiral shell -9,9 '-bis- fluorenes -2- bases)-N, N '-diphenylbenzidines (BSPB).Suitable inorganic material is metal oxide, especially molybdenum oxide, vanadium oxide, ruthenium-oxide and tungsten oxide.US 2006/ The concentration that molybdenum oxide is mentioned in 0180812 A1 improves more, and resistance reduces more, and when the concentration of molybdenum oxide is more than 80 During weight %, resistance improves more.

The A1 of US 2008/0008905 are disclosed with pixel or the electrode of pixel portion with light transmission conductive membranes, its The metal oxide of electron acceptor energy is shown containing hole transport organic compound and relative to hole transport organic compound. Organic compound is aromatic amine compound, carbazole derivates, aromatic hydrocarbon and high-molecular weight compounds.Inorganic compound is transition gold Belong to oxide, thus particularly preferred molybdenum oxide.

The A1 of DE 10 2,008 051 132 disclose the organic electronic device with specific layer order.The device includes bag Charge transport layer containing matrix material, described matrix material include dopant, and wherein matrix material and dopant forms electric charge and passed Transmission ＆ distribution compound.In the A1 of DE 10 2,008 051 132, the suitable basic materials for hole transmission layer are mentioned.It is described all Material is organic material, especially aromatic amido compound.Suitable dopant is, for example, metal oxide.

The A1 of US 2006/0008740 disclose the organic assembly for including the organic compound with charge transport ability.Should Device includes the layer containing electric charge transmission complex, and the layer has to work as transmits chemical combination by lamination or hybrid mode with organic hole The electric charge transmission complex that thing and molybdenum trioxide are formed when contacting；Wherein organic hole transport compound is matched somebody with somebody containing electric charge transmission It is radical cation state in the layer of compound.Suitable organic hole transport compound is novel arylamine compound.

In the above prior art, the reduction of power consumption is by using comprising organic compound, especially novel arylamine compound, And metal oxide, especially the hole transmission layer of molybdenum oxide is realized (as a rule).

However, further improved space be present in terms of the reduction and organic electronic device life-time dilatation of power consumption.

Low-work voltage, works fine life-span and good efficiencies and right are shown it is therefore an object of the present invention to provide The organic electronic device of the high stability of thermal stress, especially Organic Light Emitting Diode (OLED).

The purpose by it is a kind of comprising first electrode, second electrode and be placed between first electrode and second electrode first The organic electronic device of organic layer solves, wherein the first organic layer includes at least one metallo-organic compound and at least one gold Belong to oxide.

With this hair comprising at least one metallo-organic compound and the first organic layer of at least one metal oxide Bright organic electronic device shows outstanding power efficiency, life-span, quantum efficiency and/or low-work voltage.

Metal oxide

First organic layer includes at least one metal oxide, and preferably one or two kinds of metal oxides are more preferably a kind of Metal oxide.

Metal oxide is preferably transition metal oxide, even preferably belongs to periodic table the 4th, 5,6,7 or the metal of 8 races Oxide.Even more preferably metal oxide is selected from rheium oxide, molybdenum oxide, vanadium oxide, tungsten oxide, niobium oxide, tantalum oxide, oxidation Chromium and manganese oxide.Metal can be present in the oxide with every kind of suitable oxidation state.Most preferred metal oxide is oxygen Change molybdenum (MoO_x) or rheium oxide (ReO_x), especially MoO₃Or ReO₃.Especially, particularly preferred ReO₃.Inventor, which has found, to be passed through Use ReO₃, obtain the electronic device with outstanding working life.

Metal oxide be typically based on the total amount (for 100 weight %) of the first organic layer with 0.1 to<10 weight %, preferably 1-8 weight %, more preferably 3-5 weight % amount are used in the first organic layer.Inventor, which has found, has optimal metal oxidation The amount of thing.If more than optimised quantity, then the working life of electronic device is high, but the obvious reduction compared with optimised quantity.

Metallo-organic compound

First organic layer includes at least one metallo-organic compound, preferably one or two kinds of metallo-organic compounds, more A kind of it is preferred that metallo-organic compound.

Term " metallo-organic compound " (or organo-metallic compound) is what technical staff was commonly understood by.According to this hair Bright, the term should be understood such as Inorganic Chemistry (second edition), Gary L.Miesler and Donald A.Tarr, Prentice-Hall (1998), page 422, the 13rd chapter, the 1st section is defined.

Preferable metallo-organic compound is the metallo-organic compound with hole transport performance.In OLED situation Under, at least one metal-organic band gap with hole transport performance is typically larger than the band of emitter material used Gap.In the context of this application, " band gap " should be understood that means triplet energy.

Particularly preferred metallo-organic compound is arbine complex.Suitable arbine complex is, for example, such as WO 2005/ 019373rd, WO 2006/056418, WO 2005/113704, WO2007/115970, WO 2007/115981 and WO 2008/ 000727 arbine complex.

The example of particularly preferred arbine complex is the compound of lower formula (I)：

Wherein symbol has following implication：

M¹For the metal raw selected from Co, Rh, Ir, Nb, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re, Cu, Ag and Au Son, it is possible any oxidation state for respective metal atom；

Cabbeen is carbenes, and it can be not charged or single anion and monodentate, two teeth or three teeth, and wherein Cabbeen is matched somebody with somebody Body can also be double card guest or three carbenes；

L is single anion or two anion ligands, and it can be monodentate or two teeth；

K is selected from following not charged monodentate or bidentate ligand：Phosphine；Phosphonate and its derivative, arsenate and its derivative Thing；Phosphite；CO；Pyridine；Nitrile and and M¹Form the conjugated diene of π complexs；

N is the number of carbenes, and wherein n is at least 1, and works as n>When 1, the carbenes in Formulas I complex can be Identical or different；

M is the number of ligand L, and wherein m can be 0 or >=1 and work as m>When 1, ligand L can be identical or different；

O is part K number, and wherein o can be 0 or >=1, and work as o>When 1, part K can be identical or different；

Wherein n+m+o sums depend on the oxidation state and ligancy of metallic atom, and the ratcheting degree of part Cabbeen, L and K, And the electric charge on part, Cabbeen and L, condition are that n is at least 1.

The arbine complex is described in WO 2005/19373.

One example of suitable arbine complex is face formula-iridium-three (1,3- diphenyl benzimidazoles with formula (Ia) Quinoline -2- subunits-C, C2 ') (Ir (dpbic)₃)：

It is disclosed in WO 2005/19373.

At least one metallo-organic compound, preferably arbine complex generally using based on the first organic layer total amount (its as 100 weight %)>90 to 99.9 weight %, preferably 92-99 weight %, more preferably 95-97 weight % amount are used for the first organic layer In.

First organic layer

First organic layer includes at least one metallo-organic compound and at least one metal oxide.Preferable metal has Machine compound and preferable metal oxide and the appropriate amount of metallo-organic compound and metal oxide are previously described.

First organic layer is preferably hole transmission layer or hole injection layer, more preferably hole transmission layer.

First organic layer preferably comprises：

I) 0.1 to<10 weight %, preferably 1-8 weight %, more preferably 3-5 weight % metal oxide, be preferably selected from as Under metal oxide：The rheium oxide of every kind of appropriate oxidation state, molybdenum oxide, vanadium oxide, tungsten oxide, niobium oxide, tantalum oxide, oxidation Chromium and manganese oxide, more preferably molybdenum oxide (MoO_x) or rheium oxide (ReO_x), especially MoO₃Or ReO₃, most preferably ReO₃；With

ii)>90 to 99.9 weight %, preferably 92-99 weight %, more preferably 95-97 weight % metallo-organic compound, It is preferred that arbine complex, more preferably formula (I) arbine complex, most preferably formula (Ia) arbine complex,

Wherein metal oxide and metal-organic total amount are 100 weight %.

In a more preferred embodiment, the first organic layer includes：

I) 0.1 to<10 weight %, preferably 1-8 weight %, more preferably 3-5 weight % ReO₃；With

ii)>90 to 99.9 weight %, preferably 92-99 weight %, more preferably 95-97 weight % arbine complex, preferably Formula (I) arbine complex, more preferably formula (Ia) arbine complex,

Wherein the total amount of metal oxide and arbine complex is 100 weight %.

First organic layer by any method, such as by wet method or drying method is prepared.First organic layer can for example lead to It is prepared by the coevaporation for crossing above-mentioned metallo-organic compound and metal oxide.It is particularly due to ReO₃Easily evaporation in a vacuum, The coevaporation being initially mentioned is preferable method.However, it is also possible to the first organic layer is prepared in this way：Coat and dry The roasting solution comprising above-mentioned metallo-organic compound and metal alkoxide.As painting method, such as ink ejecting method or rotation can be used Coating method.The other organic layers for the present invention electronic device being mentioned below can be prepared in a manner of with the first organic layer identical.

First organic layer generally has 5-100nm, preferably 20-80nm thickness.

In another embodiment, the present invention relates to include at least one metallo-organic compound and at least one metal oxygen The organic layer of compound, preferably hole transmission layer or hole injection layer.Suitable metallo-organic compound and metal oxide and Suitable amount is previously mentioned.It is preferred that hole transmission layer or hole injection layer are the hole in Organic Light Emitting Diode (OLED) Transport layer or hole injection layer.

In one embodiment of the invention, organic electronic device also includes the containing at least one formula (II) compound Two organic layers：

Wherein：

R¹And R²Independently of one another F, C₁-C₈Alkyl can be optionally by one or more C₁-C₈Alkyl-substituted C₆-C₁₄Virtue Base, or

Two substituent Rs¹And/or R²Combining formation can be optionally by one or more C₁-C₈Alkyl-substituted fused benzene rings base Group,

A and b is independently of one another 0, or 1-3 integer,

M is alkali metal atom or alkaline earth metal atom,

If M is alkali metal atom, n 1, if M is alkaline earth metal atom, n 2.

Most preferred metal complex is(Liq), it can be used as single species or exist in other forms, example Such as LigQg, wherein g is integer, such as Li6Q6.Q represents the derivative of 8-hydroxyquinoline part or 8-hydroxyquinoline.

It is preferred that the second organic layer also includes the compound of at least one formula (III), (IVa) and/or (IVb)：

Wherein：

R⁸¹、R⁸²、R⁸³、R⁸⁴、R^81’、R^82’、R^83’And R^84’Independently of one another H, C₁-C₁₈Alkyl, substituted and/or by D by E The C at interval₁-C₁₈Alkyl, C₆-C₂₄Aryl, the C substituted by G₆-C₂₄Aryl, C₂-C₂₀Heteroaryl, or the C substituted by G₂-C₂₀Heteroaryl Base,

Q is arlydene or heteroarylidene, and it optionally can each be substituted by G；

D is-CO-；-COO-；-S-；-SO-；-SO₂-；-O-；-NR²⁵-；-SiR³⁰R³¹-；-POR³²-；-CR²³=CR²⁴-； Or-C ≡ C-；And

E is-OR²⁹；-SR²⁹；-NR²⁵R²⁶；-COR²⁸；-COOR²⁷；-CONR²⁵R²⁶；-CN；Or F；G is E, C₁-C₁₈Alkyl, By the C at D intervals₁-C₁₈Alkyl, C₁-C₁₈Perfluoroalkyl, C₁-C₁₈Alkoxy, or substituted by E and/or the C by D intervals₁-C₁₈Alcoxyl Base, wherein：

R²³And R²⁴Independently of one another H, C₆-C₁₈Aryl；By C₁-C₁₈Alkyl or C₁-C₁₈The C of alkoxy substitution₆-C₁₈Virtue Base；C₁-C₁₈Alkyl；Or the C by-O- intervals₁-C₁₈Alkyl；

R²⁵And R²⁶Independently of one another C₆-C₁₈Aryl；By C₁-C₁₈Alkyl or C₁-C₁₈The C of alkoxy substitution₆-C₁₈Aryl； C₁-C₁₈Alkyl；Or the C by-O- intervals₁-C₁₈Alkyl；Or

R²⁵And R²⁶5 or 6 yuan of rings are formed together,

R²⁷And R²⁸Independently of one another C₆-C₁₈Aryl；By C₁-C₁₈Alkyl or C₁-C₁₈The C of alkoxy substitution₆-C₁₈Aryl； C₁-C₁₈Alkyl；Or the C by-O- intervals₁-C₁₈Alkyl,

R²⁹For C₆-C₁₈Aryl；By C₁-C₁₈Alkyl or C₁-C₁₈The C of alkoxy substitution₆-C₁₈Aryl；C₁-C₁₈Alkyl；Or by- The C at O- intervals₁-C₁₈Alkyl,

R³⁰And R³¹Independently of one another C₁-C₁₈Alkyl, C₆-C₁₈Aryl, or by C₁-C₁₈Alkyl-substituted C₆-C₁₈Aryl,

R³²For C₁-C₁₈Alkyl, C₆-C₁₈Aryl, or by C₁-C₁₈Alkyl-substituted C₆-C₁₈Aryl.Preferable formula (III) is changed Compound is formula (IIIa) compound：

Wherein Q is：

R⁸⁵For H or C₁-C₁₈Alkyl, and

R^85’For H, C₁-C₁₈Alkyl or

Most preferably formula (IIIaa) compound：

Wherein：

R⁸⁹For phenanthryl, pyrenyl, Sanya phenyl, 1,10- phenanthrolines, triazine radical, dibenzothiophenes base or pyrimidine radicals, its Each can be optionally by one or more C₁-C₁₈Alkyl, C₆-C₁₄Aryl or C₂-C₂₀Heteroaryl substitutes,

R⁹⁰For phenanthryl, pyrenyl, Sanya phenyl, 1,10- phenanthrolines, triazine radical, dibenzothiophenes base or pyrimidine radicals, its Each can be optionally by one or more C₁-C₁₈Alkyl, C₆-C₁₄Aryl or C₂-C₂₀Heteroaryl substitutes,

R⁹¹For phenanthryl, pyrenyl, Sanya phenyl, 1,10- phenanthrolines, triazine radical, dibenzothiophenes base, pyrimidine radicals or hexichol And furyl, it each can be optionally by one or more C₁-C₁₈Alkyl, C₆-C₁₄Aryl or C₂-C₂₀Heteroaryl substitutes,

R⁹²For H, phenanthryl, pyrenyl, Sanya phenyl, 1,10- phenanthrolines, triazine radical, dibenzothiophenes base or pyrimidine radicals, It each can be optionally by one or more C₁-C₁₈Alkyl, C₆-C₁₄Aryl or C₂-C₂₀Heteroaryl substitutes,

A is singly-bound, arlydene or heteroarylidene, and it each can be optionally by one or more C₁-C₁₈Alkyl substitutes；Or- SiR⁸⁷R⁸⁸-, wherein R⁸⁷And R⁸⁸Independently of one another C₁-C₁₈Alkyl, or can be optionally by one or more C₁-C₁₈It is alkyl-substituted C₆-C₁₄Aryl.

Preferable formula (IVa) and (IVb) compound are：

Wherein A, R⁸⁹、R⁹⁰、R⁹¹And R⁹²As defined above.

Most preferably formula (IVaaa) compound：

If it would be possible, C₁-C₁₈Alkyl is usually linear or branched.Example is methyl, ethyl, n-propyl, isopropyl Base, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, 2- amyl groups, 3- amyl groups, 2,2- dimethyl propyls, 1,1,3,3- tetra- Methyl amyl, n-hexyl, 1- methylhexyls, 1,1,3,3,5,5- hexamethyls hexyl, n-heptyl, different heptyl, 1,1,3,3- tetramethyls Base butyl, 1- methylheptyls, 3- methylheptyls, n-octyl, 1,1,3,3- tetramethyl butyls and 2- ethylhexyls, n-nonyl, the last of the ten Heavenly stems Base, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl or octadecyl. C₁-C₈Alkyl is usually methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, 2- penta Base, 3- amyl groups, 2,2- Dimethyl-propyls, n-hexyl, n-heptyl, n-octyl, 1,1,3,3- tetramethyl butyls and 2- ethyl hexyls Base.C₁-C₄Alkyl is usually methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group.

Can optionally substituted C₆-C₁₄Aryl is usually phenyl, 4- aminomethyl phenyls, 4- methoxyphenyls, naphthyl, especially 1- naphthyls or 2- naphthyls, xenyl, terphenyl base, pyrenyl, 2- or 9- fluorenyls, phenanthryl or anthryl, its can with it is unsubstituted or by Substitution.

C_2-C₂₀Heteroaryl basis representation has the ring or fused ring system of 5-7 annular atom, and wherein nitrogen, oxygen or sulphur is possible miscellaneous Atom, and be usually with 5-30 atom and with the heterocyclic group of at least six conjugated pi-electronics, such as thienyl, benzo Thienyl, dibenzothiophenes base, thianthrene group, furyl, furfuryl group, 2H- pyranoses, benzofuranyl, isobenzofuran-base, hexichol And furyl, phenoxy group thienyl, pyrrole radicals, imidazole radicals, pyrazolyl, pyridine radicals, bipyridyl, triazine radical, pyrimidine radicals, pyrazine Base, pyridazinyl, indolizine base, isoindolyl, indyl, indazolyl, purine radicals, quinolizine base, quinolyl, isoquinolyl, phthalazines Base, naphthyridines base, quinoxalinyl, quinazolyl, cinnolines base, pteridyl, carbazyl, carboline base, BTA base, benzoAzoles It is base, phenanthridinyl, acridinyl, pyrimidine radicals, phenanthroline, phenazinyl, isothiazolyl, phenothiazinyl, differentOxazolyl, furazanyl or FenPiperazine base, it can be with unsubstituted or substituted.

C₆-C₁₄Aryl and C_2-C₂₀Heteroaryl is preferably by one or more C₁-C₈Alkyl substitutes.

The example of arlydene is phenylene, naphthylene, Ya Fu bases (phenalenylene), anthrylene and phenanthrylene, and it can Optionally by one or more C₁-C₁₈Alkyl substitutes.Preferable arlydene is 1,3- phenylenes, 3,6- naphthylenes and 4,9- Ya Fu Base, it can be optionally by one or more C₁-C₁₈Alkyl substitutes.

The example of heteroarylidene is 1,3,4- thiadiazoles -2,5- subunits, 1,3- thiazole -2,4- subunits, 1,3- thiazoles -2,5- Subunit, 2,4- Asias thienyl, 2,5- Asias thienyl, 1,3-Azoles -2,4- subunits, 1,3-Azoles -2,5- subunits and 1,3,4-Diazole -2,5- subunit, 2,5- sub-indenyls, 2,6- sub-indenyls, especially sub- pyrazinyl, sub- pyridine radicals, sub- pyrimidine radicals and Asia three Oxazolyl, it can be optionally by one or more C₁-C₁₈Alkyl substitutes.Preferable heteroarylidene is 2,6- Asias pyrazinyl, 2,6- Asias pyrrole Piperidinyl, 4,6- Asias pyrimidine radicals and 2,6- Asia triazolyl, it can be optionally by one or more C₁-C₁₈Alkyl substitutes.

In particularly preferred embodiments, the second organic layer includes formula(Liq) compound and formulaThe mixture of compound.

In another particularly preferred embodiment, the second organic layer includes formula(Liq) compound and formulaThe mixture of compound.

Formula (II) organometallic complex is with 99-1 weight %, preferably 75-25 weight %, more preferably from about 50 weight % amount Included in the second organic layer, wherein formula (II) and the amount of (III) or (IVa) or (IVb) compound add up to 100 weight %.

The synthesis of formula (III) compound is described in J.Kido et al., Chem.Commun. (2008) 5821-5823, In J.Kido et al., Chem.Mater.20 (2008) 5951-5953 and JP2008-127326, or it can be similar to wherein described side Method is carried out.

The synthesis of formula (VIa) and (VIb) compound is described in WO2006128800, or can be similar to wherein methods described Carry out.

The synthesis of formula (II) compound is for example described in Christoph Schmitz et al., Chem.Mater.12 (2000) In 3012-3019 and WO00/32717, or it can be similar to wherein methods described progress.

Second organic layer is preferably electron transfer layer.

Organic electronic device

Organic electronic device of the present invention includes first electrode, second electrode and is placed between first electrode and second electrode First organic layer, wherein the first organic layer includes at least one metallo-organic compound and at least one metal oxide.Above Mention the preferred embodiment of the first organic layer.

Suitable first and second electrode is well known by persons skilled in the art.

Organic electronic device of the present invention is, for example, organic solar batteries (organic photo cell), switch element such as organic crystal Pipe, such as organic field effect tube (FET) or OTFT (TFT), organic field-effect transistor of giving out light (OLEFET) or Organic Light Emitting Diode (OLED), preferably OLED.

The structure of suitable organic electronic device is well known by persons skilled in the art and is described below.Organic transistor

Organic transistor generally comprises half formed by the organic layer with cavity transmission ability and/or electron transport ability Conductor layer；The gate electrode formed by conductive layer；And the insulating barrier introduced between semiconductor layer and conductive layer.Source electrode and drain electrode are installed With therefore generation transistor unit in the configuration.In addition, other layers well known by persons skilled in the art may be present in organic crystalline In body pipe.In preferred embodiments, with cavity transmission ability organic layer include at least one metallo-organic compound and At least one metal oxide.Suitable metallo-organic compound and metal oxide and suitable amount are previously mentioned.

Organic solar batteries

Organic solar batteries (components of photo-electric conversion) are generally comprised between the two template electrodes for being present in and being arranged in parallel Organic layer.Organic layer is configurable on comb-type electrode.On in the absence of the specifically limited of organic layer position, and in the absence of on Electrode material it is specifically limited.However, when using template electrode in parallel, at least one electrode preferably by transparency electrode such as The tin oxide electrode of ITO electrode or Fluorin doped is formed.Organic layer is passed by two sublayers with p-type semiconductor performance or hole The layer of Movement Capabilities and the forming layer with n-type semiconductor performance or electron transport ability are formed.In addition, those skilled in the art are The other layers known may be present in organic solar batteries.In preferred embodiments, the layer with cavity transmission ability includes At least one metallo-organic compound and at least one metal oxide.Suitable metallo-organic compound and metal oxide with And suitable amount is previously mentioned.

Organic Light Emitting Diode (OLED)

The invention further relates to a kind of Organic Light Emitting Diode, its include anode A n and negative electrode Ka, be placed in anode A n with Luminescent layer E between negative electrode Ka, the hole transmission layer and/or hole injection layer being placed between luminescent layer E and anode A n, and if It is properly at least one layer of selected from following other layers：At least one layer of hole/exciton barrier-layer, at least one layer of electronics/exciton resistance Barrier, at least one layer of electron transfer layer and at least one layer of electron injecting layer, its hole-transporting layer and/or hole injection layer include At least one metallo-organic compound and at least one metal oxide.Suitable metallo-organic compound and metal oxide with And suitable amount is previously mentioned.

OLED of the present invention structure

Organic Light Emitting Diode (OLED) of the present invention therefore generally there is following structure：

Anode (An) and negative electrode (Ka) and the luminescent layer E being placed between anode (An) and negative electrode (Ka) and it is placed in luminescent layer E Hole transmission layer and/or hole injection layer between anode A n.

In preferred embodiments, OLED of the present invention can be for example by being formed with lower floor：

1. anode

2. hole transmission layer

3. luminescent layer

4. hole/exciton barrier-layer

5. electron transfer layer

6. negative electrode

Layer order different from said structure is also possible, and is well known by persons skilled in the art.For example, OLED can Without all layers；Such as the OLED with layer (1), (2), (3), (4) and (6) is equally possible.In addition, OLED can have Electronics/exciton barrier-layer between hole transmission layer (2) and luminescent layer (3).In addition, OLED can have in hole transmission layer (2) hole injection layer between luminescent layer.

In addition, multiple above-mentioned functions (electronics/exciton blocking agent, hole/exciton blocking agent, hole injection, hole transport, Electron injection, electric transmission) it can be combined in one layer and homogenous material is presented for example present in the layer.For example, at one In embodiment, material therefor can block exciton and/or electronics simultaneously in hole transmission layer.

In addition, in those described above, OLED each layer can be formed by two layers or more layer again.For example, hole transmission layer It can be formed by hole by electrode injection one layer and the layer that is delivered in hole in luminescent layer from hole injection layer therein.Electronics passes Defeated layer by electron injection layer therein and electronics of the receiving from electron injecting layer and can equally incite somebody to action by multilayer, such as by electrode They are delivered to the layer composition in luminescent layer.These described layers each according to factor such as energy level, thermal resistance and charge carrier mobility, And the layer selects with the energy difference of organic layer or metal electrode.Those skilled in the art can select OLED structure to cause it Most preferably match the organic compound for being used as emitter substance according to the present invention.

To obtain particularly effective OLED, such as the HOMO (highest occupied molecular orbital) of hole transmission layer should match anode Work content, and the LUMO (lowest unoccupied molecular orbital) of electron transfer layer should match the work content of negative electrode, and condition is that above-mentioned layer is present In OLED of the present invention.

Anode (1) is the electrode for providing positive charge carrier.It can be for example by including metal, the mixture of different metal, gold The material of the mixture of category alloy, metal oxide or different metal oxides is formed.Alternatively, anode can be conducting polymer Thing.Suitable metal includes the metal and alloy of following metal：Main group metal, transition metal and lanthanide series, especially element Periodic table I b, IVa, Va and VIa races metal, and VIII a group 4 transition metals.When anode by for it is transparent when, it is usually used The mixed-metal oxides of the periodic table of elements (IUPAC versions) II b, IIIb and IVb races, such as tin indium oxide (ITO).Anode (1) organic material, such as polyaniline can be equally included, for example, such as Nature, volume 357, the 477-479 pages (June 11 in 1992 Day) described in.At least male or female should be at least partly transparent to launch formed light.For anode (1) Material is preferably ITO.

In the case where hole transmission layer does not include at least one metallo-organic compound and at least one metal oxide Or in addition at least one metallo-organic compound and at least one metal oxide, the hole suitable for oled layer of the present invention (2) passes Defeated material is e.g., as disclosed in Kirk-Othmer Encyclopedia of Chemical Technology, the 4th edition, volume 18, The 837-860 pages, in 1996.Hole transporting molecules or polymer can be used as hole mobile material.Usually used hole transport Molecule is selected from double [N- (1- the naphthyls)-N- benzene of three [N- (1- naphthyls)-N- (phenyl amino)] triphenylamines (1-NaphDATA), 4,4'- Base amino] biphenyl (α-NPD), N, N '-diphenyl-N, N '-bis- (3- aminomethyl phenyls)-[1,1 '-biphenyl] -4,4 '-diamines (TPD), 1,1- double [(two -4- Tolylaminos) phenyl] hexamethylene (TAPC), N, N '-bis- (4- aminomethyl phenyls)-N, N '-bis- (4- ethylphenyls)-[1,1 '-(3,3 '-dimethyl) biphenyl] -4,4 '-diamines (ETPD), four (3- aminomethyl phenyls)-N, N, N ', N ' -2,5- phenylenediamines (PDA), α-phenyl -4-N, N- diphenylaminostyrene (TPS), p- (diethylamino) benzaldehyde two Phenylhydrazone (DEH), triphenylamine (TPA), it is double [4- (N, N- diethylamino) -2- aminomethyl phenyls) (4- aminomethyl phenyls) methane (MPMP), 1- phenyl -3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazoline (PPR or DEASP), 1,2- trans- double (9H- carbazole -9- bases) cyclobutane (DCZB), N, N, N ', N '-four (4- aminomethyl phenyls)-(1,1 '-connection Benzene) -4,4 '-diamines (TTB), 4,4 ', 4 "-three (N, N- diphenyl amino) triphenylamines (TDTA), 4,4 ', 4 "-three (N- carbazoles Base) triphenylamine (TCTA), double (phenyl) benzidine (β-NPB) of double (naphthalene -2- the bases)-N, N'- of N, N'-, double (the 3- methylbenzenes of N, N'- Base) the double fluorenes (Spiro-TPD) of (phenyl) -9,9- spiral shells two of-N, N'-, double (the phenyl) -9,9- spiral shells of double (naphthalene -1- the bases)-N, N'- of N, N'- Two fluorenes (Spiro-NPB), double (3- the aminomethyl phenyls)-N, N'- of N, N'- double (phenyl) -9,9- dimethyl fluorenes (DMFL-TPD), two [4- (N, N- xylyl amino) phenyl] hexamethylene, double (the phenyl) -9,9- dimethyl fluorenes of double (naphthalene -1- the bases)-N, N'- of N, N'-, Double (the phenyl) -2,2- dimethylbenzidines of double (naphthalene -1- the bases)-N, N'- of N, N'-, the double (benzene of double (naphthalene -1- the bases)-N, N'- of N, N'- Base) benzidine, double (3- the aminomethyl phenyls)-N, N'- of N, N'- double (phenyl) benzidine, the fluoro- 7,7,8,8- four cyanos of 2,3,5,6- tetra- Quinone bismethane (F4-TCNQ), 4,4', 4 "-three (N-3- methylphenyl-N-phenyls amino) triphenylamines, 4,4', 4 "-three (N- (2- Naphthyl)-N- phenyl-aminos) triphenylamine, pyrazine simultaneously [2,3-f] [1,10] phenanthroline -2,3- dintrile (PPDN), N, N, N', N'- The double fluorenes of [double (4- methoxyphenyls) amino of N, N-] -9,9- spiral shells two of four (4- methoxyphenyls) benzidine (MeO-TPD), 2,7- (MeO-Spiro-TPD), the double fluorenes (2,2'-MeO-Spiro- of [double (4- methoxyphenyls) amino of N, N-] -9,9- spiral shells two of 2,2'- TPD), N, N'- diphenyl-N, N'- bis- [4- (N, N- xylyl amino) phenyl] benzidine (NTNPB), N, N'- diphenyl- N, N'- bis- [4- (N, N- diphenyl amino) phenyl] benzidine (NPNPB), N, N'- bis- (naphthalene -2- bases)-N, N'- terphenyl -1, 4- diamines (β-NPP), double (3- the aminomethyl phenyls)-N, N'- of N, N'- double (phenyl) -9,9- diphenylfluorenes (DPFL-TPD), N, N'- Double (naphthalene -1- bases)-N, N'- double (phenyl) -9,9- diphenylfluorenes (DPFL-NPB), (N, N- the diphenyl ammonia of 2,2', 7,7'- tetra- Base) two fluorenes (Spiro-TAD) of -9,9'- spiral shells, double [4- (double (biphenyl -4- bases) amino of N, N-) the phenyl] -9H- fluorenes of 9,9- (BPAPF), double [4- (double (naphthalene -2- bases) amino of N, N-) the phenyl] -9H- fluorenes (NPAPF) of 9,9-, 9,9- it is double [4- (and N, N- it is double (naphthalene - 2- yls) the double phenyl aminos of-N, N'-) phenyl] -9H- fluorenes (NPBAPF), 2,2', 7,7'- tetra- [N- naphthyls (phenyl) amino] -9, The fluorenes of 9'- spiral shells two (Spiro-2NPB), double (phenyl) benzidine (PAPB) of double (phenanthrene -9- the bases)-N, N'- of N, N'-, 2,7- double [N, N- Double (fluorenes -2- bases of 9,9- spiral shells two) amino] two fluorenes (Spiro-5) of -9,9- spiral shells, 2,2'- double [double (biphenyl -4- bases) amino of N, N-] - The double fluorenes (Spiro-BPA) of (N, N- diphenyl amino) -9.9- spiral shells two of the fluorenes of 9,9- spiral shells two (2,2'-Spiro-DBP), 2,2'-, 2, The fluorenes (Spiro-TTB) of 2', 7,7'- tetra- (N, N- xylyl) amino spiral shell two, N, N, the naphthalene -2- bases benzidine (TNB) of N', N'- tetra-, Porphyrin compound and phthalocyanine such as CuPc and TiOPc.Conventional hole mobile material is selected from PVK, (phenyl first Base) polysilane and polyaniline.Equally can be by the way that hole transporting molecules be entrained in polymer such as polystyrene and polycarbonate And obtain hole transport polymer.Suitable hole transporting molecules are molecule already mentioned above.

In addition, in one embodiment, it can be used arbine complex empty as hole mobile material, wherein at least one The band gap of hole transport materials is generally higher than the band gap of emitter material used.Suitable arbine complex is mentioned above.

In the preferred embodiment of the invention, hole transmission layer (2) is comprising at least one metallo-organic compound and at least A kind of metal oxide, wherein suitable metallo-organic compound and suitable metal oxide and suitable Organometallic close The amount of thing and suitable metal oxide is mentioned above.

Luminescent layer (3) includes at least one emitter material.It can be fluorescence or phosphorescence dispersion in principle.Suitably Emitter material is well known by persons skilled in the art.At least one emitter material is preferably phosphorescent emitters.It is preferred that use Phosphorescent emitters compound be based on the complex of metal complex, especially metal Ru, Rh, Ir, Pd and Pt, particularly Ir's Complex obtains importance.

Suitable metal complex for OLED of the present invention is for example described in A1, the US 2001/ of file WO 02/60910 0015432 A1、US 2001/0019782 A1、US 2002/0055014 A1、US 2002/0024293 A1、US 2002/ 0048689 A1、EP 1 191 612 A2、EP 1 191 613 A2、EP 1 211 257 A2、US 2002/0094453 A1、WO 02/02714 A2、WO 00/70655 A2、WO 01/41512 A1、WO 02/15645 A1、WO 2005/019373 A2、WO 2005/113704 A2、WO 2006/115301 A1、WO 2006/067074 A1、WO 2006/056418、WO 2006121811 2007095118 A2, WO 2007/115970 of A1, WO, WO 2007/115981 and WO 2008/000727 In.

Other suitable metal complexs are commercially available metal complex three (2- phenylpyridines) iridium (III), three (2- (4- Tolyl) pyridine-N, C²') iridium (III), double (2- phenylpyridines) (acetylacetone,2,4-pentanedione) iridium (III), three (1- phenyl isoquinolins quinoline) iridium (III), double (2,2 '-benzothiophene) pyridine-N, C³') (acetylacetone,2,4-pentanedione) iridium (III), three (2- phenylchinolines) iridium (III), double (2- (4,6- difluorophenyls) pyridines-N, C²) picoline iridium (III), double (1- phenyl isoquinolins quinoline) (acetylacetone,2,4-pentanedione) iridium (III), double (2- phenylchinolines) (acetylacetone,2,4-pentanedione) iridium (III), double (two-benzo [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) iridium (III), double (2- first Two-benzo of base [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) iridium (III) and three (3- methyl isophthalic acids-phenyl -4- pivaloyl group -5- pyrroles Oxazoline) terbium (III), double [1- (9,9- dimethyl -9H- fluorenes -2- bases) isoquinolin] (acetylacetone,2,4-pentanedione) iridium (III), double (2- phenyl benzene And thiazole) (acetylacetone,2,4-pentanedione) iridium (III), double (2- (9,9- dihexyls fluorenyl) -1- pyridines) (acetylacetone,2,4-pentanedione) iridium (III), double (2- Benzo [b] thiophene -2- bases-pyridine) (acetylacetone,2,4-pentanedione) iridium (III).

In addition, following commercially available material is suitable：Single (phenanthroline) europium (III) of three (dibenzoyl acetone), three (biphenyl first Acyl methane)-mono- (phenanthroline) europium (III), single (5- amino the phenanthroline)-europium (III) of three (dibenzoyl methanes), three (two -2- naphthalenes Acyl methane) single (phenanthroline) europium (III), single (phenanthroline) europium (III) of three (4- Bromophenacyls methane), three (two (biphenyl) methane) Single (phenanthroline) europium (III), single (the 4,7- diphenyl phenanthroline) europium (III) of three (dibenzoyl methanes), three (dibenzoyl first Alkane) single (bis--methyl of 4,7- phenanthroline) europium (III), single (the 4,7- dimethyl phenanthroline disulfonic acid) europium of three (dibenzoyl methanes) (III) single (phenanthroline) europium (III) of disodium salt, three [two (4- (2- (2- ethoxy ethoxies) ethyoxyl) benzoyl methane)] and Single (the 5- amino phenanthroline) europium (III) of three [two [4- (2- (2- ethoxy ethoxies) ethyoxyl) benzoyl methane)], osmium (II) Double (3- (trifluoromethyl) -5- (4- tert .-butylpyridines base) -1,2,4- triazoles) diphenyl methyl phosphines, the double (3- (fluoroforms of osmium (II) Base) -5- (2- pyridine radicals) -1,2,4- triazoles) dimethylphenylphosphine, double (3- (trifluoromethyl) -5- (the 4- tert-butyl group pyrroles of osmium (II) Piperidinyl) -1,2,4- triazoles) dimethylphenylphosphine, double (3- (trifluoromethyl) -5- (2- pyridine radicals) pyrazoles) dimethyl benzenes of osmium (II) Base phosphine, three [4,4'- di-t-butyls (2,2')-bipyridyl] rutheniums (III), osmium (II) are double, and (2- (9,9- dibutylfluorenyls) -1- is different Quinoline (acetylacetone,2,4-pentanedione).

Preferable triplet emitters are arbine complex.Suitable arbine complex is known to those skilled in the art , and for example it is described in 2006/056418 A2, the WO 2005/113704 of A2, WO of WO 2005/019373, WO 2007/ 115970th, in WO 2007/115981 and WO 2008/000727.Preferable arbine complex is above-mentioned formula (I) carbene complex Thing.Particularly preferred arbine complex is above-mentioned formula (Ia) and (Ib) arbine complex.

In addition to emitter material, luminescent layer can include other components.

For example, fluorescent dye may be present in luminescent layer to change the transmitting color of emitter material.In addition, preferred real Apply in scheme, matrix material can be used.The matrix material can be polymer, such as poly- (N- vinyl carbazoles) or polysilane. However, matrix material can be small molecule, such as 4,4 '-N, N '-two carbazole biphenyl (CDP=CBP) or tertiary aromatic amine such as TCTA.

In addition to above-mentioned matrix material, suitable matrix material is to be hereinafter described as hole and electron transporting materials in principle The arbine complex referred in material, and carbon complex, such as WO 2005/019373.It is specially suitable to have carbazole derivative Thing, such as double (carbazole -9- bases) biphenyl (CBP) of 4,4'- pairs of (carbazole -9- bases) -2,2'- dimethyl diphenyls (CDBP), 4,4'-, 1,3- double (N- carbazyls) benzene (mCP), and the matrix material that following application is described：WO2008/034758、WO2009/003919.

In addition, dibenzofurans is suitable for matrix material, such as dibenzofurans disclosed in the A1 of US 2007/0224446, Such as those dibenzofurans that wherein at least one group R1-R8 is heterocyclic group, such as compound A-15, and WO 2009/ 069442 dibenzofurans disclosed in the A1 and A of JP 2006/321750 of A1, WO 2010/090077.

Other matrix materials based on dibenzofurans be for example described in US2009066226, EP1885818B1, In EP1970976, EP1998388 and EP2034538.

Following publication can be described in for other suitable basic materials of small molecule or the (co) polymer of the small molecule In thing：

WO2007108459 (H-1 to H-37), preferably H-20 to H-22 and H-32 to H-37, most preferably H-20, H-32, H- 36th, (compound 1 to 46 and Host-1 are extremely by H-37, WO2008035571 A1 (Host 1 to Host 6), JP2010135467 Host-39 and Host-43), WO2009008100 compound Ns o.1 to No.67, preferably No.3, No.4, No.7 to No.12, No.55, No.59, No.63 to No.67, more preferably No.4, No.8 to No.12, No.55, No.59, No.64, No.65 and No.67, WO2009008099 compound N are o.1 to No.110, WO2008140114 compounds 1-1 to 1-50, WO2008090912 Compound OC-7 to OC-36, and Mo-42 to Mo-51 polymer, JP2008084913H-1 to H-70, WO2007077810ization Compound 1 to 44, preferably 1,2,4-6,8,19-22,26,28-30,32,36,39-44, WO201001830 monomers 1-1 to 1-9, it is excellent Select 1-3,1-7 and 1-9 polymer, WO2008029729 compounds 1-1 to 1-36 (polymer), WO20100443342HS- 1 to HS-101 and BH-1 to BH-17, the (co) polymer of preferably BH-1 to BH-17, JP2009182298 based on monomer 1 to 75, The (co) polymer of JP2009170764, JP2009135183 based on monomer 1-14, WO2009063757 are preferably based on monomer 1-1 To 1-26 (co) polymer, WO2008146838 compound as -1 to a-43 and 1-1 to 1-46, JP2008207520 are based on list Body 1-1 to 1-26 (co) polymer, (co) polymers of the JP2008066569 based on monomer 1-1 to 1-16, (co) polymers of the WO2008029652 based on monomer 1-1 to 1-52, (common) of the WO2007114244 based on monomer 1-1 to 1-18 Polymer, JP2010040830 compounds HA-1 to HA-20, HB-1 to HB-16, HC-1 to HC-23 and based on monomer HD-1 extremely HD-12 (co) polymer, JP2009021336, WO2010090077 compounds 1 to 55, WO2010079678 compounds H1 is extremely H42, WO2010067746, WO2010044342 compound HS-1 to HS-101 and Poly-1 to Poly-4, JP2010114180 Compound PH-1 to PH-36, US2009284138 compound 1 to 111 and H1 to H71, WO2008072596 compound 1 to 45, JP2010021336 compounds H-1 to H-38, preferably H-1, WO2010004877 compounds H-1 to H-60, JP2009267255 Compound 1-1 to 1-105, WO2009104488 compound 1-1 to 1-38, WO2009086028, US2009153034, US2009134784, WO2009084413 compound 2-1 to 2-56, JP2009114369 compound 2-1 to 2-40, JP2009114370 compounds 1 to 67, WO2009060742 compounds 2-1 to 2-56, WO2009060757 compounds 1-1 to 1- 76, WO2009060780 compound 1-1 to 1-70, WO2009060779 compounds 1-1 to 1-42, WO2008156105 compounds 1 to 54, JP2009059767 compound 1 to 20, JP2008074939 compounds 1 to 256, JP2008021687 compounds 1 to 50, WO2007119816 compounds 1 to 37, WO2010087222 compounds H-1 to H-31, WO2010095564 compounds HOST-1 to HOST-61, WO2007108362, WO2009003898, WO2009003919, WO2010040777, US2007224446 and WO06128800.

In particularly preferred embodiments, one or more logical formula (X) compounds described below are used as matrix material.It is logical During the preferred embodiment of formula (X) compound is equally described below.

In preferred embodiments, present invention is accordingly directed to organic electronic device of the present invention, preferably OLED, it is included at least A kind of logical formula (X) compound, is particularly preferably combined with the arbine complex as triplet emitters：

Wherein：

T is NR⁵⁷, S, O or PR⁵⁷, preferably S or O, more preferably O；

R⁵⁷For aryl, heteroaryl, alkyl, cycloalkyl or Heterocyclylalkyl；

Q ' is-NR⁵⁸R⁵⁹、-SiR⁷⁰R⁷¹R⁷²、-P(O)R⁶⁰R⁶¹、-PR⁶²R⁶³、-S(O)₂R⁶⁴、-S(O)R⁶⁵、-SR⁶⁶Or- OR⁶⁷, preferably-NR⁵⁸R⁵⁹；More preferably

Wherein：

R⁶⁸、R⁶⁹It is each independently alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl；It is preferred that methyl, carbazyl, Dibenzofuran group or dibenzothiophenes base；

Y, z is each independently 0,1,2,3 or 4, preferably 0 or 1；

R⁵⁵、R⁵⁶It is each independently alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, SiR⁷⁰R⁷¹R⁷², group Q ' or Group with donor or receptor acting；

A " is 0,1,2,3 or 4；

B ' is 0,1,2 or 3；

R⁵⁸、R⁵⁹With forming the cyclic group with 3-10 annular atom together with nitrogen-atoms, it can be with unsubstituted or by one Individual or multiple substitutions selected from alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and the group with donor or acceptor property Base substitutes；And/or one or more other cyclic groups with 3-10 annular atom can be condensed, wherein condensed group can be not It is substituted or alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl is selected from by one or more and there is donor or acceptor property Group substituent substitution；

R⁷⁰、R⁷¹、R⁷²、R⁶⁰、R⁶¹、R⁶²、R⁶³、R⁶⁴、R⁶⁵、R⁶⁶、R⁶⁷It is each independently aryl, heteroaryl, alkyl, cycloalkanes Base or Heterocyclylalkyl,

Or

Two logical formula (X) units are by optionally by least one the linear or branched of hetero atom interval, saturation or unsaturation Bridge, by key or by the mutual bridgings of O.

It is preferred that formula (X) compound, wherein：

T is S or O, preferably O, and

Q ' is

Wherein：

Y, z is each independently 0,1,2,3 or 4, preferably 0 or 1.

Particularly preferred formula (X) compound has following formula (Xa)：

Wherein symbol and index Q ', T, R⁵⁵、R⁵⁶, a " and b ' each as defined above.

Formula (X) compound very particularly preferably has formula (Xaa)：

Wherein symbol and index R⁶⁸、R⁶⁹、y、z、T、R⁵⁵、R⁵⁶, a " and b ' each as defined above.

In embodiment very particularly preferably, in formula (Xaa)：

T is O or S, preferably O；

A " is 1；

B ' is 0；

Y, z is each independently 0 or 1；And

R⁶⁸、R⁶⁹Methyl, carbazyl, dibenzofuran group or dibenzothiophenes base are each independently,

R⁵⁵For substituted phenyl, carbazyl, dibenzofuran group or dibenzothiophenes base.

Another formula (X) compound very particularly preferably has formula (Xab)：

Wherein symbol and index R⁶⁸、R⁶⁹y、z、T、R⁵⁵、R⁵⁶, a " and b ' there is implication described previously independently of one another.

In particularly preferred embodiments, the symbol in formula (Xab) and index have following implication：T is O or S, preferably O；

A " is 0；

B ' is 0；

Y, z independently is 0 or 1；And

R⁶⁸、R⁶⁹It independently is methyl, carbazyl, dibenzofuran group or dibenzothiophenes base.

Particularly preferred formula (Xab) compound is following compound：

Wherein T is O or S, preferably O.

Formula (X) compound can be for example such as WO2010079051, WO2007/077810, JP2009267255, correspondingly US20090017331 A1) and WO2009/003898 described in or prepare similar to preparation method described in above-mentioned file.

In another preferred embodiment of the present invention, at least one formula (V) compound is used as matrix material, particularly preferably with Arbine complex as triplet emitters is together：

Wherein：

X is NR, S, O or PR；

R is aryl, heteroaryl, alkyl, cycloalkyl or Heterocyclylalkyl；

A is-NR⁶R⁷、-P(O)R⁸R⁹、-PR¹⁰R¹¹、-S(O)₂R¹²、-S(O)R¹³、-SR¹⁴Or-OR¹⁵；R¹、R²And R³Mutually solely It is on the spot aryl, heteroaryl, alkyl, cycloalkyl or Heterocyclylalkyl, wherein group R¹、R²Or R³In it is at least one be aryl or miscellaneous Aryl；

R⁴And R⁵Independently of one another alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, group A or with donor or by The group of bulk properties；

N and m is independently of one another 0,1,2 or 3；

R⁶、R⁷With forming the cyclic group with 3-10 annular atom together with nitrogen-atoms, it can be with unsubstituted or can be by one Individual or multiple substitutions selected from alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and the group with donor or acceptor property Base substitutes；And/or it can condense one or more other cyclic groups with 3-10 annular atom, wherein condensed group can be with It is unsubstituted or can by one or more selected from alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and have donor or acceptor The substituent substitution of the group of characteristic；And

R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴And R¹⁵Independently of one another aryl, heteroaryl, alkyl, cycloalkyl or heterocycle alkane Base.

Formula (V) compound is described in WO2010079051 (PCT/EP2009/067120).

For logical formula (X) compound, especially for R⁵⁵-R⁷⁷Group, and for logical formula (V) compound, it is especially right In R¹-R¹⁵Group：

Term aryl or group, heteroaryl or group, alkyl or group, cycloalkyl or group, Heterocyclylalkyl or group, chain Alkenyl or group, alkynyl or group and group with donor and/or receptor acting each as defined below：

Aryl (or group) should be understood that means with 6-30 carbon atom, the basic bone of preferably 6-18 carbon atom Frame, and the group formed by aromatic ring or multiple fused aromatic rings.Suitable basic skeleton be, for example, phenyl, naphthyl, anthryl or phenanthryl, Indenyl or fluorenyl.The basic skeleton can be undersaturated (this means that all commutable carbon atoms carry hydrogen atom), or can To be substituted in the one of basic skeleton, more than one or all may replace on position.

Suitable substituent be, for example, deuterium, alkoxy, aryloxy group, alkyl amino, arylamino, carbazyl, silicyl, SiR⁷⁸R⁷⁹R⁸⁰, suitable silicyl SiR⁷⁸R⁷⁹R⁸⁰In being described below, alkyl, the preferably alkyl with 1-8 carbon atom, More preferably methyl, ethyl or isopropyl, preferably aryl, C₆Aryl, it can substituted or unsubstituted again, heteroaryl, preferably wrap Heteroaryl containing at least one nitrogen-atoms, more preferably pyridine radicals and carbazyl, preferably alkenyl, the alkene with a double bond Base, the alkenyl more preferably with a double bond and 1-8 carbon atom, alkynyl, the preferably alkynyl with three keys, more preferably Alkynyl with three keys and 1-8 carbon atom, or the group with donor or receptor acting.Suitably have donor or by During the group of body effect is described below.Substituted aryl is most preferably carried selected from methyl, ethyl, isopropyl, alkoxy, miscellaneous Aryl, halogen, the substituent of pseudohalogen and amino, preferred aryl groups amino.Aryl or aromatic yl group are preferably C₆-C₁₈Aryl, more It is preferred that C₆Aryl, it is optionally substituted by least one or more than one above-mentioned substituent.C₆-C₁₈Aryl, preferably C₆Aryl is more preferably With 0,1,2,3 or 4, most preferably with 0,1 or 2 above-mentioned substituent.

Heteroaryl or heteroaryl groups should be understood that means different from being the basic skeleton in aryl in place of above-mentioned aryl In the basic skeleton of the group that is exchanged for heteroatoms of at least one carbon atom and heteroaryl preferably there is 5-18 annular atom.It is preferred that Hetero atom be N, O and S.Particularly preferably suitable heteroaryl is nitrogenous heteroaryl.Most preferably one or two of basic skeleton Carbon atom is substituted by hetero atom, preferably nitrogen.Particularly preferred basic skeleton is selected from system such as pyridine, pyrimidine and 5 yuan of heteroaromatic chemical combination Thing for example pyrroles, furans, pyrazoles, imidazoles, thiophene,Azoles, thiazole, triazole.In addition, heteroaryl can be fused ring system, such as benzene And furyl, benzothienyl, benzopyrrole base, dibenzofuran group, dibenzothiophenes base, phenanthroline, carbazyl, azepine Carbazyl or diaza carbazyl.Basic skeleton can one of basic skeleton, it is more than one or all may replace quilt on position Substitution.Suitable substituent is identical with having been described on aryl.

Alkyl or alkyl group are understood to mean with 1-20 carbon atom, preferably 1-10 carbon atom, more preferably 1-8 carbon atom, the group of most preferably 1-4 carbon atom.Alkyl can be branched or non-branching and can be optionally by one or more Individual hetero atom, preferably Si, N, O or S, more preferably N, O or S interval.In addition, the alkyl can be by one or more on described in aryl Substituent substitution.In addition, the alkyl according to existing for the present invention can have at least one halogen atom, such as F, Cl, Br or I, especially It is F.In another embodiment, the alkyl according to existing for the present invention can be fully fluorinated.Same alkyl can carry one Individual or multiple (miscellaneous) aryl.In the present context, such as benzyl is therefore substituted alkyl.Herein, Suo Youshang It is suitable to arrange (miscellaneous) aryl.Alkyl is more preferably selected from methyl, ethyl, isopropyl, n-propyl, normal-butyl, isobutyl group and tertiary fourth Base, very particularly preferably methyl and ethyl.

Cycloalkyl or group of naphthene base are understood to mean with 3-20 carbon atom, preferably 3-10 carbon atom, more It is preferred that the group of 3-8 carbon atom.The basic skeleton can be that unsubstituted (this means that all commutable carbon atoms are former with hydrogen Son) or can be substituted in one of basic skeleton, more than one or all may replace on position.Suitable substituent closes for more than In the group that aryl has described.Same cycloalkyl can carry one or more (miscellaneous) aryl.The example of suitable cycloalkyl is ring third Base, cyclopenta and cyclohexyl.

Heterocyclylalkyl or heterocycloalkyl should be understood that means different from being in place of above-mentioned cycloalkyl in cycloalkyl The group that at least one carbon atom is exchanged for heteroatoms in basic skeleton.Preferable hetero atom is N, O and S.Most preferably cycloalkyl One or two carbon atom of basic skeleton is exchanged for heteroatoms.The example of Suitable heterocyclic rings alkyl be derived from pyrrolidines, piperidines, Piperazine, tetrahydrofuran, twoThe group of alkane.

Alkenyl or kiki alkenyl group should be understood that means the base corresponding to the above-mentioned alkyl with least two carbon atoms Group, difference are that at least one C -- C single bond of alkyl is substituted by C-C double bond.Alkenyl preferably has one or two double Key.

Alkynyl or alkynyl group should be understood that means the group corresponding to the above-mentioned alkyl with least two carbon atoms, no At least one C -- C single bond for being alkyl with part is substituted by the keys of C-C tri-.Alkynyl preferably has one or two three key.

SiR⁷⁸R⁷⁹R⁸⁰Group should be understood that means silicyl, wherein：R⁷⁸、R⁷⁹And R⁸⁰It is each independently alkyl, ring Alkyl, Heterocyclylalkyl, aryl, heteroaryl or OR⁷³。

SiR⁷⁴R⁷⁵R⁷⁶Group should be understood that means silicyl, wherein：R⁷⁴、R⁷⁵And R⁷⁶It is each independently alkyl, ring Alkyl, Heterocyclylalkyl, aryl, heteroaryl or OR⁷³。

In the present context, the group or substituent for having donor or receptor acting should be understood that means following base Group：

Group with donor effect should be understood that means the group with+I and/or+M effects, have receptor acting Group should be understood that means the group with-I and/or-M effects.Preferable proper group is selected from C₁-C₂₀Alkoxy, C₆-C₃₀Virtue Epoxide, C₁-C₂₀Alkylthio group, C₆-C₃₀Arylthio, SiR81 " R82 " R83 ", OR⁷³, halogen group, halo C₁-C₂₀Alkyl, carbonyl (- CO (R81 ")), carbonyl sulfenyl (- C=O (SR81 ")), carbonyloxy group (- C=O (OR81 ")), Epoxide carbonyl (- OC=O (R81 ")), sulphur For carbonyl (- SC=O (R81 ")), amino (- NR81 " R82 "), pseudohalide groups, acylamino- (- C=O (NR81 ")) ,-NR81 " C =O (R83 "), phosphonate ester (- P (O) (OR81 ")₂, phosphate (- OP (O) (OR81 ")₂), phosphine (- PR81 " R82 "), phosphine oxide (- P (O)R81”₂), sulfuric ester (- OS (O)₂OR81 "), sulfoxide (- S (O) R81 "), sulphonic acid ester (- S (O)₂OR81 "), sulfo group (- S (O)₂R81 ", sulfonamide (- S (O)₂NR81”R82”)、NO₂, borate (- OB (OR81 ")₂), imino group (- C=NR81 " R82 ")), Boryl, stannane base, diazanyl, hydrazone group, oximido, nitroso, two azo groups, vinyl, sulfoximide, aluminium alkane, germane, ring boron oxygen Alkane and boron azine.

Group R81 ", R82 " and the R83 " referred in the above-mentioned group with donor or receptor acting is each independently：

Substitution or unsubstituted C₁-C₂₀Alkyl or substitution or unsubstituted C₆-C₃₀Aryl, or OR⁷⁶, it is suitable and preferred Alkyl and aryl to be above-described.Group R81 ", R82 " and R83 " are more preferably C₁-C₆Alkyl, for example, methyl, ethyl or Isopropyl, or phenyl.In preferred embodiments, in the case of SiR81 " R82 " R83 ", R81 ", R82 " and R83 " are preferably each From independently be substitution or unsubstituted C₁-C₂₀Alkyl or substitution or unsubstituted aryl, preferably phenyl.

The preferable substituent with donor or receptor acting is selected from：

C₁-C₂₀Alkoxy, preferably C₁-C₆Alkoxy, more preferably ethyoxyl or methoxyl group；C₆-C₃₀Aryloxy group, preferably C₆-C₁₀ Aryloxy group, more preferably phenoxy group；SiR81 " R82 " R83 ", its R81 ", R82 " and R83 " are preferably each independently substitution or not Substituted alkyl or substitution or unsubstituted aryl, preferably phenyl；More preferably at least group R81 ", a R82 " and R83 " For substitution or unsubstituted phenyl, suitable substituent is above-mentioned；Halogen group, preferably F, Cl, more preferably F, halo C₁- C₂₀Alkyl, preferably halo C₁-C₆Alkyl, most preferably it is fluorinated C₁-C₆Alkyl, such as CF₃、CH₂F、CHF₂Or C₂F₅；Amino, preferably two Methylamino, diethylamino or ammonia diaryl base, more preferably ammonia diaryl base；Pseudohalide groups, preferably CN ,-C (O) OC₁-C₄ Alkyl, preferably-C (O) OMe, P (O) R₂, preferably P (O) Ph₂。

The substituent with donor or receptor acting very particularly preferably is selected from methoxyl group, phenoxy group, halo C₁-C₄Alkane Base, preferably CF₃、CH₂F、CHF₂、C₂F₅, halogen, preferably F, CN, SiR81 " R82 " R83 ", suitable group R81 ", R82 " and R83 " has been described, and (NR84 " R85 ", wherein R84 ", R85 " are respectively C to ammonia diaryl base₆-C₃₀Aryl) ,-C (O) OC₁-C₄ Alkyl, preferably-C (O) OMe, P (O) Ph₂。

Halogen group preferably should be understood that means F, Cl and Br, more preferably F and Cl, most preferably F.

Pseudohalide groups preferably should be understood that means CN, SCN and OCN, more preferably CN.

The above-mentioned group with donor or receptor acting is not excluded for mentioned by the application but is not included in above-listed with donor Or the other groups and substituent in the group of receptor acting have donor or the possibility of receptor acting.

Aryl or group, heteroaryl or group, alkyl or group, cycloalkyl or group, Heterocyclylalkyl or base as described above Group, alkenyl or group and the group with donor and/or receptor acting can be substituted or unsubstituted.In the application In context, unsubstituted group should be understood that means the group that may replace atom and carry hydrogen atom of wherein group.At this Apply in context, substituted radical should be understood that means that wherein one or more may replace atom and carry at least on a position Instead of the group of the substituent of hydrogen atom.Suitable substituent is the substituent described in above with respect to aryl or group.

When the group with identical numbering occurs more than once in the application compound, these groups can be each independent Ground has the definition.

Group T in formula (X) compound is NR⁵⁷, S, O or PR⁵⁷, preferably NR⁵⁷, S or O, more preferably O or S, most preferably O. Group X in formula (V) is NR, S, O or PR, more preferably O or S, most preferably O.

R⁵⁷Group is aryl, heteroaryl, alkyl, cycloalkyl or Heterocyclylalkyl, and preferred aryl groups, heteroaryl or alkyl are more excellent Aryl is selected, wherein above-mentioned group can be unsubstituted or substituted.Suitable substituent is above-mentioned.R⁵⁷More preferably may be used It is substituted with such substituents as described above or unsubstituted phenyl.R⁵⁷Most preferably unsubstituted phenyl.

R group is aryl, heteroaryl, alkyl, cycloalkyl or Heterocyclylalkyl, wherein above-mentioned group can be it is unsubstituted or Substituted.Suitable substituent is above-mentioned.R can be more preferably substituted with such substituents as described above or unsubstituted phenyl.R is most Preferably unsubstituted phenyl.

Group Q ' in formula (X) compound is-NR⁵⁸R⁵⁹、-P(O)R⁶⁰R⁶¹、-PR⁶²R⁶³、-S(O)₂R⁶⁴、-S(O)R⁶⁵、- SR⁶⁶Or-OR⁶⁷；It is preferred that NR⁵⁸R⁵⁹、-P(O)R⁶⁰R⁶¹Or-OR⁶⁷, more preferably-NR⁵⁸R⁵⁹。

A groups in formula (V) compound are-NR⁶R⁷、-P(O)R⁸R⁹、-PR¹⁰R¹¹、-S(O)₂R¹²、-S(O)R¹³、-SR¹⁴ Or-OR¹⁵, preferably-NR⁶R⁷、-P(O)R⁸R⁹Or-OR¹⁵, more preferably-NR⁶R⁷。

R⁵⁸-R⁶⁷And R⁷⁴-R⁷⁶And R⁶-R¹⁵Group each as defined below：

R⁵⁸、R⁵⁹、R⁶、R⁷With forming the cyclic group with 3-10 annular atom together with nitrogen-atoms, it can be with unsubstituted Or by one or more selected from alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and the group with donor or acceptor property Substituent substitution；And/or one or more other cyclic groups with 3-10 annular atom, wherein condensed group can be condensed Can with it is unsubstituted or by one or more selected from alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and with donor or by The substituent substitution of the group of bulk properties；

R⁶⁰、R⁶¹、R⁶²、R⁶³、R⁶⁴、R⁶⁵、R⁶⁶、R⁶⁷、R⁷⁴、R⁷⁵、R⁷⁶、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵It is each independent Ground is aryl, heteroaryl, alkyl, cycloalkyl or Heterocyclylalkyl, preferred aryl groups or heteroaryl, wherein group can with unsubstituted or Substituted by one or more selected from following group：Alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and with donor or by The group of body effect, more preferably unsubstituted or substitution phenyl, suitable substituent is above-mentioned, such as tolyl or following formula Group：

Wherein group T and R⁷⁰、R⁷¹And R⁷²Group on formula (X) compound independently of one another as defined.

R⁶⁰、R⁶¹、R⁶²、R⁶³、R⁶⁴、R⁶⁵、R⁶⁶And R⁶⁷And R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵Most preferably independently of one another For phenyl, tolyl or following formula group：

Wherein T is NPh, S or O.

Preferable suitable-NR⁵⁸R⁵⁹Group and-NR⁶R⁷The example of group is selected from pyrrole radicals, 2,5- dihydro -1- pyrrole radicals, pyrrole Cough up alkyl, indyl, indoline base, isoindoline base, carbazyl, azepine carbazyl, diaza carbazyl, imidazole radicals, imidazoles Quinoline base, benzimidazolyl, pyrazolyl, indazolyl, 1,2,3- triazolyls, BTA base, 1,2,4- triazolyls, tetrazole radical, 1, 3-Oxazolyl, 1,3- thiazolyls, piperidyl, morpholinyl, acridan base and 1,4-Piperazine base, wherein above-mentioned group Can with it is unsubstituted or by one or more selected from alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and with donor or by The substituent substitution of the group of body effect；–NR⁶R⁷Group and-NR⁵⁸R⁵⁹Group is independently preferably selected from carbazyl, pyrrole radicals, Yin Diindyl base, imidazole radicals, benzimidazolyl, azepine carbazyl and diaza carbazyl, wherein above-mentioned group can with it is unsubstituted or by One or more is selected from taking for alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and the group with donor or receptor acting Substitute for base；-NR⁵⁸R⁵⁹Group and-NR⁶R⁷Group independently more preferably is carbazyl, its can with it is unsubstituted or by one or Multiple substituents selected from alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and the group with donor or receptor acting take Generation.

Particularly preferred-NR⁵⁸R⁵⁹With-NR⁶R⁷Group is：

Wherein：

Y, z is each independently 0,1,2,3 or 4, preferably 0 or 1；

Such as：

Wherein X and T independently are NPh, S or O；

Wherein T is NPh, S or O,

R in formula (X) compound⁵⁵、R⁵⁶With the R in formula (V) compound⁴、R⁵It is each independently alkyl, cycloalkyl, miscellaneous Cycloalkyl, aryl, heteroaryl, other A groups or the group with donor or receptor acting；It is preferred that be each independently alkyl, Aryl, heteroaryl or the group with donor or receptor acting.Such as R⁵⁵Or R⁵⁶Or R⁴Or R⁵It can be each independently：

Wherein T is NPh, S or O.

In formula (X) compound, the individual R of a " may be present⁵⁵Group and/or the individual R of b '⁵⁶Group, wherein a " and b ' are：

A " is 0,1,2,3 or 4；It is preferably independently 0,1 or 2；

B ' is 0,1,2 or 3；It is preferably independently 0,1 or 2.

Most preferably at least a " or b ' is 0, and it is that 1 and b ' is 0 that very particularly preferred a " and b ', which is respectively 0 or a ",.

In formula (V) compound, m R may be present⁴Group and/or the individual R of n '⁵Group, wherein m and n are：

M is 0,1,2,3 or 4；It is preferably independently 0,1 or 2；

N is 0,1,2 or 3；It is preferably independently 0,1 or 2.

Most preferably at least m or n is 0, and very particularly preferred m and n is respectively that 0 or m is 1 and n is 0.

Other preferably logical formula (V) compounds are equivalent to following formula (XI)：

Wherein：

R⁷⁰、R⁷¹、R⁷²It is each independently aryl, heteroaryl, alkyl, cycloalkyl or Heterocyclylalkyl.

The preferred embodiment of formula (V) compound is：

The compound is described in WO2010079051 (PCT/EP2009/067120；Particularly the 19-26 pages, Yi Ji 27-34, the 35-37 pages and the 42-43 pages table) in.

The example of particularly preferred matrix material is shown in following：

In above-claimed cpd, T is O or S, preferably O.If T occurs being more than 1 time in the molecule, all group T have Identical meanings.

In addition, luminescent layer can include other arbine complexes as other or unique matrix material and/or as in addition Emitter material.Suitable other arbine complexes are arbine complex same as described above, especially formula (I) carbene complex Thing.

In preferred embodiments, luminescent layer is by 2-70 weight %, preferably 5-40 weight % at least one above-mentioned transmitting At least one formula of body material and 30-98 weight %, preferably 60-95 weight % above-mentioned matrix material-in one embodiment (V) summation of compound-formation, wherein emitter material and matrix material adds up to 100 weight %.

In preferred embodiments, luminescent layer includes the formula of at least one above-mentioned matrix material-in one embodiment (V) compound-such as

With two kinds of arbine complexes, preferably following formula：

In the embodiment described in which, luminescent layer is by 2-40 weight %, preferably 5-35 weight %'sWith Formula (V) chemical combination of 60-98 weight %, preferably 65-95 weight % at least one above-mentioned matrix material-in one embodiment Thing-withFormation, wherein arbine complex and at least one above-mentioned matrix material-in an embodiment Middle formula (V) compound-summation add up to 100 weight %.

In preferred embodiments, luminescent layer includes at least one above-mentioned matrix material-as described below in an implementation Formula (V) compound is as matrix material and one or two kinds of arbine complexes in scheme, preferred formula (Ia) and/or (Ib's).

In another embodiment, at least one above-mentioned matrix material-formula in one embodiment as described below (V) compound-be used as hole/exciton blocks agent material, preferably together with the arbine complex as triplet emitters.Extremely A kind of few above-mentioned matrix material-formula (V) compound in one embodiment as described below-also can be with sending out as triplet The arbine complex of beam is used as matrix material together and hole/exciton blocks agent material.

Hole/exciton barrier-layer if (4) do not include any above-mentioned matrix material-as described below in an implementation In scheme any formula (V) compound-or except any above-mentioned matrix material-as described below it is any in one embodiment Formula (V) compound-outer, OLED has the hole blocking agent material being usually used in OLED-if there is hole blocking layer- Material, such as 2,6- double (N- carbazyls) pyridine (mCPy), 2,9- dimethyl -4,7- diphenyl -1,10- phenanthroline (bathocuproin, (BCP)), double (2- methyl -8- quinoline) -4- phenyls) aluminium (III) (BAIq), phenthazine S, S- bis- Oxide derivative and 1,3,5- tri- (N- phenyl -2- benzyl imidazoles base) benzene) (TPBI), TPBI, which is also suitable, makees electronics conduction material Material.Other suitable hole blocking agent and/or electron transport material are 2,2', 2 "-(base of 1,3,5- benzene three) three (1- phenyl -1- H- benzimidazoles), 2- (4- xenyls) -5- (4- tert-butyl-phenyls) -1,3,4-Diazole, 8-hydroxyquinoline lithium, 4- (naphthalene -1- Base) -3,5- diphenyl -4H-1,2,4- triazoles, double [2- (2,2'- bipyridyl -6- the bases) -1,3,4- of 1,3-Diazole -5- bases] Benzene, 4,7- diphenyl -1,10- phenanthroline, 3- (4- xenyls) -4- phenyl -5- tert-butyl-phenyl -1,2,4- triazoles, 6,6'- are double [5- (biphenyl -4- bases) -1,3,4-Diazole -2- bases] -2,2'- bipyridyls, 2- phenyl -9,10- two (naphthalene -2- bases) anthracene, 2,7- Double [2- (2,2'- bipyridyl -6- bases) -1,3,4-Diazole -5- bases] -9,9- dimethyl fluorenes, double [2- (the 4- tert-butyl benzenes of 1,3- Base) -1,3,4-Diazole -5- bases] benzene, 2- (naphthalene -2- bases) -4,7- diphenyl -1,10- phenanthroline, three (2,4,6- trimethyls - 3- (pyridin-3-yl) phenyl) borine, double (naphthalene -2- the bases) -4,7- diphenyl -1,10- phenanthroline of 2,9-, 1- methyl -2- (4- (naphthalene -2- bases) phenyl) -1H- imidazoles [4,5-f] [1,10] phenanthroline.In another embodiment, such as WO2006/ can be used The compound of 100298 aromatics included by carbonyl group-containing groups connection or heteroaromatic rings, selected from following dimethyl silanyl Compound：Dimethyl silanyl carbazole, dimethyl silanyl benzofuran, dimethyl silanyl benzothiophene, dimethyl silanyl benzo phosphorus Heterocyclic pentylene, dimethyl silanyl benzothiophene S- oxides and dimethyl silanyl benzothiophene S, S- dioxide, such as example WO2009003919 (PCT/EP2008/058207) and WO2009003898 (PCT/EP2008/058106) is described, and such as Dimethylamino silane based compound described in WO2008/034758 is as hole/exciton barrier-layer (4) or as the base in luminescent layer (3) Body material.

In preferred embodiments, the present invention relates to OLED of the present invention, it includes layer：(1) anode, (2) hole transmission layer, (3) luminescent layer, (4) hole/exciton barrier-layer, (5) electron transfer layer and (6) negative electrode, and other layers if appropriate, wherein Hole transmission layer includes at least one metallo-organic compound and at least one metal oxide.Suitable metallo-organic compound It is previously mentioned with metal oxide and suitable amount.

Appropriate electronic transmission material for OLED of the present invention layer (5) includes the metal for being chelated with the pungent compounds of Class e, Such as 2,2 ', 2 "-(1,3,5- phenylenes) three [1- phenyl -1H- benzimidazoles] (TPBI), three (8-hydroxyquinoline) aluminium (Alq₃), such as 2,9- dimethyl -4,7- diphenyl -1, the 10- phenanthroline of the compound based on phenanthroline (DDPA=BCP) or 4,7- Diphenyl -1,10- phenanthroline (DPA), and azole compounds, such as 2- (4- xenyls) -5- (4- tert-butyl-phenyls) -1,3,4-Diazole (PBD) and 3- (4- xenyls) -4- phenyl -5- (4- tert-butyl-phenyls) -1,2,4- triazoles (TAZ), 8-hydroxyquinoline Lithium (Liq), 4,7- diphenyl -1,10- phenanthroline (BPhen), double (2- methyl -8- quinoline) -4- (phenylphenol) aluminium (BAlq), Double [2- (2,2 '-bipyridyl -6- bases) -1,3,4- of 1,3-Diazole -5- bases] benzene (Bpy-OXD), 6,6 '-bis- [5- (biphenyl -4- Base) -1,3,4-Diazole -2- bases] -2,2 '-bipyridyl (BP-OXD-Bpy), 4- (naphthalene -1- bases) -3,5- diphenyl -4H-1, Double (naphthalene -2- the bases) -4,7- diphenyl -1,10- phenanthroline (NBphen) of 2,4- triazoles (NTAZ), 2,9-, 2,7- it is double [2- (2,2 ' - Bipyridyl -6- bases) -1,3,4-Diazole -5- bases] -9,9- dimethyl fluorenes (Bby-FOXD), double [2- (the 4- tert-butyl benzenes of 1,3- Base) -1,3,4-Diazole -5- bases] benzene (OXD-7), three (2,4,6- trimethyls -3- (pyridin-3-yl) phenyl) borines (3TPYMB), 1- methyl -2- (4- (naphthalene -2- bases) phenyl) -1H- imidazos [4,5-f] [1,10] phenanthroline (2-NPIP), 2- benzene Base -9,10- two (naphthalene -2- bases) anthracene (PADN), 2- (naphthalene -2- bases) -4,7- diphenyl -1,10- phenanthroline (HNBphen).Layer (5) Available for promoting electric transmission and as cushion or barrier layer to prevent exciton to be quenched on OLED bed boundary.Layer (5) is excellent Choosing improves the mobility of electronics and reduces exciton quenching.In preferred embodiments, TPBI is used as electron conductor material.In principle Electronic conductor layer can include at least one formula (V) compound as electron conductor material.

In preferred embodiments, OLED of the present invention electron transfer layer (5) include formula (II) organometallic complex with And preferably formula (III), (IVa) or (IVb) compound.The mobility of layer (5) advantageous embodiment electronics.Formula (II), (III), (IVa) (IVb) compound and the compound are mentioned above in organic layer, the appropriate amount especially in electron transfer layer.

It is above-mentioned as the material of hole mobile material and electron transport material in, some can perform multiple functions.Such as When they have low HOMO, then some electron transport materials are simultaneously hole barrier materials.These can for example be used for hole/swash In sub- barrier layer (4).

Charge transport layer also can be electron adulterated to improve the transmission performance of material therefor, first so that thickness degree is denseer (avoiding aperture/short circuit), secondly so that the operating voltage of device minimizes.For example, can be by hole mobile material electron acceptor Doping；Such as by phthalocyanine or the arylamine such as quinhydrones bismethane (F4-TCNQ) of TPD or TDTA tetrafluoros four or MoO can be used₃Or WO₃Mix It is miscellaneous.Electron adulterated is well known by persons skilled in the art and e.g., as disclosed in W.Gao, A.Kahn, J.Appl.Phys., the 94th Volume, No.1, on July 1st, 2003 (p-doping organic layer)；A.G.Werner, F.Li, K.Harada, M.Pfeiffer, T.Fritz, K.Leo.Appl.Phys.Lett., on June 23rd, volume 82, No.25 1 and Pfeiffer et al., In Organic Electronics 2003,4,89-103.

Negative electrode (6) is the electrode for introducing electronics or negative charge carrier.Suitable for the material of negative electrode, to be selected from element the (old IUPAC versions) Ia races alkali metal such as Li, Cs, alkaline-earth metal such as calcium, barium or magnesium, group iib metal, including the group of the lanthanides of IIa races Element and actinides, such as samarium.In addition, it is possible to use metal such as aluminium or indium, and the combination of all metals.In addition, contain Lithium organo-metallic compound or potassium fluoride (KF) can be applicable between organic layer and negative electrode to reduce operating voltage.

OLED of the present invention can also include other layers well known by persons skilled in the art.Such as promote positive charge transport and/or The layer for being mutually matched the band gap of layer can be applicable between layer (2) and luminescent layer (3).Alternatively, other layers are available goes bail for Sheath.Other layers can be present between luminescent layer (3) and layer (4) in a similar manner, to promote negative charge transport and/or make layer Between band gap be mutually matched.Alternatively, the layer can be used as protective layer.

In preferred embodiments, in addition to layer (1)-(6), OLED of the present invention also includes at least one layer mentioned below such as Lower floor：

Hole injection layer between-anode (1) and hole transmission layer (2)；

Electronic barrier layer between-hole transmission layer (2) and luminescent layer (3)；

Electron injecting layer between-electron transfer layer (5) and negative electrode (6).

Material for hole injection layer may be selected from CuPc, 4,4', 4 "-three (N-3- methylphenyl-N-phenyls amino) Triphenylamine (m-MTDATA), 4,4', 4 "-three (N- (2- naphthyls)-N- phenyl aminos) triphenylamines (2T-NATA), 4,4', 4 "-three (N- (1- naphthyls)-N- phenyl aminos) triphenylamine (1T-NATA), 4,4', 4 "-three (N, N- diphenyl amino) triphenylamines (NATA), TiOPc, the fluoro- TCNQs (F4-TCNQ) of 2,3,5,6- tetra-, pyrazine simultaneously [2,3-f] [1, 10] phenanthroline -2,3- dintrile (PPDN), N, N, N', N'- tetra- (4- methoxyphenyls) benzidine (MeO-TPD), 2,7- pairs [N, Double (4- methoxyphenyls) amino of N-] two fluorenes (MeO-Spiro-TPD) of -9,9- spiral shells, double [double (the 4- methoxybenzenes of N, N- of 2,2'- Base) amino] two fluorenes (2,2'-MeO-Spiro-TPD) of -9,9- spiral shells, N, N'- diphenyl-N, N'- bis--[4- (N, N- xylyls Amino) phenyl] benzidine (NTNPB), N, N'- diphenyl-N, N'- bis--[4- (N, N- diphenyl amino) phenyl] benzidine (NPNPB), N, N'- bis- (naphthalene -2- bases)-N, N'- terphenyl -1,4- diamines (α-NPP).In principle, hole injection layer can include At least one metallo-organic compound and at least one metal oxide.Suitable metallo-organic compound and suitable metal oxygen Compound and the appropriate amount of the metallo-organic compound and the metal oxide are mentioned above.

As the material for electron injecting layer, KF or Liq can be for example selected.KF is than Liq more preferably.

It is known to those skilled in the art how to select suitable material (such as based on electrochemical research).Material suitable for each layer Material is well known by persons skilled in the art, e.g., as disclosed in WO 00/70655.

In addition, it will can be handled for some layer surfaces in OLED of the present invention, to improve charge carrier transport efficiency.For The selection of the material of each layer is preferably by obtaining that there is the OLED in high efficiency and life-span to determine.

OLED of the present invention can be produced by method known to those skilled in the art.In general, OLED of the present invention passes through It is vapor-deposited each layer successively on suitable base material and produces.Suitable base material be, for example, glass, inorganic semiconductor such as ITO or IZO or polymer film.For vapour deposition, routine techniques, such as thermal evaporation, chemical vapor deposition (CVD), physics gas can be used Mutually deposition (PVD) and other technologies.In alternative, coating well known by persons skilled in the art can be used in OLED organic layer Technology is by the solution in suitable solvent or dispersion application.

In general, different layers has following thickness：Anode (1) 50-500nm, preferably 100-200nm；Hole-conductive Layer (2) 5-100nm, preferably 20-80nm, luminescent layer (3) 1-100nm, preferably 10-80nm, hole/exciton barrier-layer (4) 2- 100nm, preferably 5-50nm, electronic conductive layer (5) 5-100nm, preferably 20-80nm, negative electrode (6) 20-1000nm, preferably 30- 500nm.In OLED of the present invention hole and the recombination zone of electronics relative to negative electrode relative position and therefore OLED emission spectrum It can be influenceed by the relative thickness of each layer together with other factorses.This means the thickness that should preferably select electron transfer layer so that recombinating The optical cavity performance of the position in area and diode and therefore matched with the launch wavelength of emitter.The thickness of each layer in OLED The ratio between degree depends on material used.The thickness degree of any other layer used is well known by persons skilled in the art.Electronics conducts Layer and/or hole-conductive layer have than by them when electrically doped described in the bigger thickness of thickness degree.

Using the first organic layer of the application, especially hole transmission layer or hole injection layer, can obtain with high efficiency And the OLED with low-work voltage.Generally by using the first organic layer of the application, especially hole transmission layer or hole The OLED that implanted layer obtains also has the high life.OLED efficiency can be also optimized to improve by making other layers of OLED.Lead The formed substance and new electron transport material for causing operating voltage reduction or quantum efficiency raising can also be used in OLED of the present invention.This Outside, other layers may be present in OLED to adjust the energy level of different layers and promote electroluminescent.

OLED can further include at least one layer of second luminescent layer.OLED total transmitting can be by the hair of at least two-layer luminescent layer Composition is penetrated, and can also include white light.

OLED can be used in the useful all devices of electroluminescent.Suitable device is preferably selected from fixed and mobile video and shown Showing device and lighting device.Fixed video display device is, for example, the video display devices of computer, television set, printing machine, kitchen Video display devices, lighting device and information board in room household electrical appliances and billboard.Mobile video display device is, for example, radio Video display devices in words, laptop computer, digital camera, MP3 player, vehicle, and the mesh on bus and train Ground display.The other devices that OLED of the present invention can be used are, for example, keyboard；The part of clothes；Furniture；Wallpaper.

In addition, the electron transfer layer of the application can be used in the OLED with reverse geometry.Reverse OLED structure and logical It is well known by persons skilled in the art to be usually used in material therein.

Moreover, it relates to include organic electronic device of the present invention or organic layer of the present invention, especially electron transfer layer Equipment, the equipment be selected from fixed video display device such as computer, television set video display devices, printing machine, kitchen Video display devices, lighting device, information board in household electrical appliances and billboard, and mobile video display device such as radio telephone, knee Video display devices in laptop, digital camera, MP3 player, vehicle, and destination on bus and train show Show device；Lighting device；Keyboard；Clothing；Furniture；Wallpaper.

It is for illustration purposes only including following examples, and does not limit the scope of claims.Unless otherwise indicated, institute There is part and percentage is attached most importance to gauge.

Embodiment

I conductances

Conductance comparative example 1

Will act as the ITO base materials of anode first be used for LCD productions commercial laundering agent (20NS, and 25Nertralizer), then cleaned in ultra sonic bath in acetone/isopropanol.It is any possible to eliminate Organic remains, base material is exposed under continuous flow of ozone other 25 minutes in ozone baking oven.The processing further improves ITO's Hole injection efficiency.

Thereafter, by organic material described below by being vapor-deposited about 10^-8With about 0.5-5nm/min speed under millibar Applied on cleaning base material.By Ir (dpbic)₃(V1) it is applied to 80nm thickness on base material.

Ir(dpbic)₃

(on preparing, referring to the Ir complexs (7) in application WO 2005/019373)

100nm thickness Al electrodes are applied finally by vapour deposition.

Conductance embodiment 1

In the preparation and construction such as conductance comparative example 1 of device, difference is to replace single Ir (dpbic)₃ (V1), will be doped with 5 weight %MoO₃Ir (dpbic)₃(V1) it is applied on base material.Conductance embodiment 2

In the preparation and construction such as conductance comparative example 1 of device, difference is to replace single Ir (dpbic)₃ (V1), will be doped with 5 weight %ReO₃Ir (dpbic)₃(V1) it is applied on base material.

The A under 2V, the mA/cm under 2V on the measurement of the device of conductance embodiment and conductance comparative example², electricity Resistance rate Ω cm and conductance S/m are shown in table 1 below.

¹⁾Ir(dpbic)₃

Doped with metal oxide, especially doped with ReO₃V1 conductance it is more much higher than independent V1 conductance.

II Application Examples

Comparison study example 1

Will act as the ITO base materials of anode first be used for LCD productions commercial laundering agent (20NS, and 25Nertralizer), then cleaned in ultra sonic bath in acetone/isopropanol.It is any possible to eliminate Organic remains, base material is exposed under continuous flow of ozone other 25 minutes in ozone baking oven.The processing further improves ITO's Hole injection efficiency.Then by AJ20-1000 (purchased in market by Plexcore) spin coatings and dry with formed hole injection layer (~ 40nm)。

Thereafter, by organic material described below by being vapor-deposited about 10^-8With about 0.5-5nm/min speed under millibar Applied on cleaning base material.As hole transport and exciton blocking agent, by Ir (dpbic)₃(V1) it is applied to 40nm thickness On base material.

Ir(dpbic)₃

(on preparing, referring to the Ir complexs (7) in application WO 2005/019373)

Then, by 30 weight % compound(V2), 35 weight % compound (V1) and 35 weights Measure % compound(described in V3, PCT/EP2009/067120's) For mixture by being vapor-deposited with 40nm thickness application, wherein compound V2 serves as emitter material, and compound V1 and V3 fill Work as matrix material.

Then by material(V3) exciton and hole blocking are used as Agent is by being vapor-deposited with 5nm thickness application.

Then, by 25 weight %'s(8-hydroxyquinoline-lithium (Liq)) and 75 weight %'s(V4) mixture is as electron transfer layer by being vapor-deposited with 40nm's Thickness application, similarly, 2nm thickness potassium fluoride layers (electron injecting layer) and last 100nm thickness Al electrodes.

Application Example 1

OLED preparation and construction such as Comparison study example 1, difference are Ir (dpbic)₃(V1) with 40nm thickness Applied on base material, wherein originally 35nm is doped with MoO₃(50 weight %) is to form hole transport and exciton blocking agent.

Application Example 2

OLED preparation and construction such as Comparison study example 1, difference are Ir (dpbic)₃(V1) with 40nm thickness Applied on base material, wherein originally 35nm is doped with ReO₃(50 weight %) is to form hole transport and exciton blocking agent.

Application Example 3

OLED preparation and construction such as Comparison study example 1, difference are Ir (dpbic)₃(V1) with 40nm thickness Applied on base material, wherein originally 35nm is doped with ReO₃(3 weight %) is to form hole transport and exciton blocking agent.

Application Example 4

OLED preparation and construction such as Comparison study example 1, difference are Ir (dpbic)₃(V1) with 40nm thickness Applied on base material, wherein originally 35nm is doped with ReO₃(5 weight %) is to form hole transport and exciton blocking agent.

To characterize OLED, the electroluminescent spectrum under different electric currents and voltage is recorded.In addition, combined with the light output of transmitting Measure current-voltage characteristics.It can be demarcated by using photometer and light output is changed into photometric parameter.To determine life-span, OLED Operated under constant current density and record the reduction of light output.Life-span is defined as declining the half until initial value is down in brightness Time.

300cd/m on the measurement of the device of Application Example and Comparison study example²Under V, 300cd/m²Under lm/W, 300cd/m²Under EQE (%), 2000cd/m²Under life-span (hour), 300cd/m²Under life-span (hour) and color (CIE) It is shown in table 2 below, the measurement data of wherein Comparison study example is arranged to 100, and the data of Application Example are relative to application pair Those descriptions of ratio.

Table 2

¹⁾Ir(dpbic)₃

²⁾External quantum efficiency (EQE) is #HT layers=sky that the #a/ of photon as caused by material or device flows through its electronics Cave transport layer

Life-span, power efficiency and the quantum efficiency of the device of Application Example are outstanding compared with the device of Comparison study example.

Claims

1. a kind of organic electronic device, it includes first electrode, second electrode and is placed between first electrode and second electrode First organic layer, wherein the first organic layer includes at least one metallo-organic compound and at least one metal oxide.

2. organic electronic device according to claim 1, wherein the metal oxide is transition metal oxide, preferably belong to The oxide of periodic table the 4th, 5,6,7 or the metal of 8 races, more preferably described metal oxide are selected from rheium oxide, molybdenum oxide, oxidation Vanadium, tungsten oxide, niobium oxide, tantalum oxide, chromium oxide and manganese oxide, most preferably described metal oxide are rheium oxide or molybdenum oxide.

3. organic electronic device according to claim 2, wherein the transition metal oxide is MoO₃Or ReO₃, preferably ReO₃。

4. organic electronic device as claimed in one of claims 1-3, wherein the metal oxide is based on the first organic layer Gross weight with 0.1 to<10 weight %, preferably 1-8 weight %, more preferably 3-5 weight % amount are used in the first organic layer.

5. organic electronic device as claimed in one of claims 1-4, wherein the metallo-organic compound is metal carbene Complex.

6. organic electronic device according to claim 5, wherein the metal carbene complex is formula (I) compound：

Wherein symbol has following implication：

M¹For the metallic atom selected from Co, Rh, Ir, Nb, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re, Cu, Ag and Au, its For possible any oxidation state for respective metal atom；

Cabbeen is carbenes, its can be not charged or single anion and monodentate, two teeth or three teeth, wherein carbenes also Can be double card guest or three carbenes；

K is selected from following not charged monodentate or bidentate ligand：Phosphine；Phosphonate and its derivative, arsenate and its derivative；It is sub- Phosphate；CO；Pyridine；Nitrile and and M¹Form the conjugated diene of π complexs；

N is the number of carbenes, and wherein n is at least 1, and works as n>When 1, the carbenes in Formulas I complex can be identical It is or different；

Wherein n+m+o sums depend on the oxidation state and ligancy of metallic atom, and the ratcheting degree of part Cabbeen, L and K, and Electric charge on part, Cabbeen and L, condition are that n is at least 1.

7. organic electronic device according to claim 6, wherein the metal carbene complex has following formula：

8. organic electronic device as claimed in one of claims 1-7, wherein comprising at least one metallo-organic compound and First organic layer of at least one metal oxide is hole transmission layer or hole injection layer.

9. organic electronic device as claimed in one of claims 1-8, it also contains at least one formula (II) compound The second organic layer：

Wherein：

R¹And R²Independently of one another F, C₁-C₈Alkyl can be optionally by one or more C₁-C₈Alkyl-substituted C₆-C₁₄Aryl, Or

Two substituent Rs¹And/or R²Combining formation can be optionally by one or more C₁-C₈Alkyl-substituted fused benzene rings group,

A and b is independently of one another 0, or 1-3 integer,

M is alkali metal atom or alkaline earth metal atom,

If M is alkali metal atom, n 1, if M is alkaline earth metal atom, n 2.

10. organic electronic device according to claim 9, wherein second organic layer also comprising at least one formula (III), (IVa) and/or (IVb) compound：

Wherein：

R⁸¹、R⁸²、R⁸³、R⁸⁴、R^81’、R^82’、R^83’And R^84’Independently of one another H, C₁-C₁₈Alkyl, substituted and/or by D intervals by E C₁-C₁₈Alkyl, C₆-C₂₄Aryl, the C substituted by G₆-C₂₄Aryl, C₂-C₂₀Heteroaryl, or the C substituted by G₂-C₂₀Heteroaryl,

D is-CO-；-COO-；-S-；-SO-；-SO₂-；-O-；-NR²⁵-；-SiR³⁰R³¹-；-POR³²-；-CR²³=CR²⁴-；Or-C ≡ C-；And

E is-OR²⁹；-SR²⁹；-NR²⁵R²⁶；-COR²⁸；-COOR²⁷；-CONR²⁵R²⁶；-CN；Or F；G is E, C₁-C₁₈Alkyl, by between D Every C₁-C₁₈Alkyl, C₁-C₁₈Perfluoroalkyl, C₁-C₁₈Alkoxy, or substituted by E and/or the C by D intervals₁-C₁₈Alkoxy, its In：

R²³And R²⁴Independently of one another H, C₆-C₁₈Aryl；By C₁-C₁₈Alkyl or C₁-C₁₈The C of alkoxy substitution₆-C₁₈Aryl；C₁- C₁₈Alkyl；Or the C by-O- intervals₁-C₁₈Alkyl；

R²⁵And R²⁶Independently of one another C₆-C₁₈Aryl；By C₁-C₁₈Alkyl or C₁-C₁₈The C of alkoxy substitution₆-C₁₈Aryl；C₁-C₁₈ Alkyl；Or the C by-O- intervals₁-C₁₈Alkyl；Or

R²⁵And R²⁶5 or 6 yuan of rings are formed together,

R²⁷And R²⁸Independently of one another C₆-C₁₈Aryl；By C₁-C₁₈Alkyl or C₁-C₁₈The C of alkoxy substitution₆-C₁₈Aryl；C₁-C₁₈ Alkyl；Or the C by-O- intervals₁-C₁₈Alkyl,

R²⁹For C₆-C₁₈Aryl；By C₁-C₁₈Alkyl or C₁-C₁₈The C of alkoxy substitution₆-C₁₈Aryl；C₁-C₁₈Alkyl；Or by between-O- Every C₁-C₁₈Alkyl,

R³²For C₁-C₁₈Alkyl, C₆-C₁₈Aryl, or by C₁-C₁₈Alkyl-substituted C₆-C₁₈Aryl；

Wherein：

R⁸⁹For phenanthryl, pyrenyl, Sanya phenyl, 1,10- phenanthrolines, triazine radical, dibenzothiophenes base or pyrimidine radicals, its is each Can be optionally by one or more C₁-C₁₈Alkyl, C₆-C₁₄Aryl or C₂-C₂₀Heteroaryl substitutes,

R⁹⁰For phenanthryl, pyrenyl, Sanya phenyl, 1,10- phenanthrolines, triazine radical, dibenzothiophenes base or pyrimidine radicals, its is each Can be optionally by one or more C₁-C₁₈Alkyl, C₆-C₁₄Aryl or C₂-C₂₀Heteroaryl substitutes,

R⁹¹For phenanthryl, pyrenyl, Sanya phenyl, 1,10- phenanthrolines, triazine radical, dibenzothiophenes base, pyrimidine radicals or dibenzo furan Mutter base, it each can be optionally by one or more C₁-C₁₈Alkyl, C₆-C₁₄Aryl or C₂-C₂₀Heteroaryl substitutes,

R⁹²For H, phenanthryl, pyrenyl, Sanya phenyl, 1,10- phenanthrolines, triazine radical, dibenzothiophenes base or pyrimidine radicals, and each Can be optionally by one or more C₁-C₁₈Alkyl, C₆-C₁₄Aryl or C₂-C₂₀Heteroaryl substitutes,

11. organic electronic device as claimed in one of claims 1-10, wherein the organic electronic device be selected from it is organic too Positive energy battery, switch element and Organic Light Emitting Diode, preferably Organic Light Emitting Diode.

12. organic electronic device according to claim 11, wherein the organic electronic device is the OLED for also including luminescent layer, The luminescent layer includes at least one phosphorescent emissive material, preferably metal carbene complex.

13. organic electronic device according to claim 12, wherein the luminescent layer is also made comprising at least one formula (X) compound For material of main part：

Wherein：

T is NR⁵⁷, S, O or PR⁵⁷, preferably S or O, more preferably O；

R⁵⁷For aryl, heteroaryl, alkyl, cycloalkyl or Heterocyclylalkyl；

Q ' is-NR⁵⁸R⁵⁹、-SiR⁷⁰R⁷¹R⁷²、-P(O)R⁶⁰R⁶¹、-PR⁶²R⁶³、-S(O)₂R⁶⁴、-S(O)R⁶⁵、-SR⁶⁶Or-OR⁶⁷, it is excellent Choosing-NR⁵⁸R⁵⁹；More preferably

Wherein：

R⁶⁸、R⁶⁹It is each independently alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl；It is preferred that methyl, carbazyl, dibenzo Furyl or dibenzothiophenes base；

Y, z is each independently 0,1,2,3 or 4, preferably 0 or 1；

R⁵⁵、R⁵⁶It is each independently alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, SiR⁷⁰R⁷¹R⁷², group Q ' or have The group of donor or receptor acting；

A " is 0,1,2,3 or 4；

B ' is 0,1,2 or 3；

R⁵⁸、R⁵⁹With forming the cyclic group with 3-10 annular atom together with nitrogen-atoms, its can with it is unsubstituted or by one or Multiple substituents selected from alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and the group with donor or acceptor property take Generation；And/or one or more other cyclic groups with 3-10 annular atom can be condensed, wherein condensed group can not taken In generation, is selected from alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and the base with donor or acceptor property by one or more The substituent substitution of group；

R⁷⁰、R⁷¹、R⁷²、R⁶⁰、R⁶¹、R⁶²、R⁶³、R⁶⁴、R⁶⁵、R⁶⁶、R⁶⁷Be each independently aryl, heteroaryl, alkyl, cycloalkyl or Heterocyclylalkyl,

Or

Two logical formula (X) units are by optionally by least one the linear or branched of hetero atom interval, saturation or unsaturated bridge, borrowing Help key or by the mutual bridgings of O.

14. organic electronic device according to claim 12, wherein the luminescent layer is also made comprising at least one formula (V) compound For material of main part：

Wherein：

X is NR, S, O or PR；

R is aryl, heteroaryl, alkyl, cycloalkyl or Heterocyclylalkyl；

A is-NR⁶R⁷、-P(O)R⁸R⁹、-PR¹⁰R¹¹、-S(O)₂R¹²、-S(O)R¹³、-SR¹⁴Or-OR¹⁵；R¹、R²And R³Independently of each other For aryl, heteroaryl, alkyl, cycloalkyl or Heterocyclylalkyl, wherein group R¹、R²Or R³In it is at least one be aryl or heteroaryl；

R⁴And R⁵Independently of one another alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, group A, or there is donor or acceptor The group of characteristic；

N and m is independently of one another 0,1,2 or 3；

R⁶、R⁷With forming the cyclic group with 3-10 annular atom together with nitrogen-atoms, its can with it is unsubstituted or can by one or Multiple substituents selected from alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and the group with donor or acceptor property take Generation；And/or it can condense one or more other cyclic groups with 3-10 annular atom, wherein condensed group can not by Substitution selected from alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and can have donor or acceptor property by one or more Group substituent substitution；And

R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴And R¹⁵Independently of one another aryl, heteroaryl, alkyl, cycloalkyl or Heterocyclylalkyl.

15. include at least one metallo-organic compound and the hole transmission layer of at least one metal oxide or hole injection Layer.

16. include the organic electronic device according to any one of claim 1-14 or hole transmission layer according to claim 15 Or the equipment of implanted layer.