CN109153871A

CN109153871A - The preparation of organic functional material

Info

Publication number: CN109153871A
Application number: CN201780031667.XA
Authority: CN
Inventors: 菲利普·梅; 帕维尔·麦斯凯万茨; 丹尼尔·瓦尔克
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2016-06-16
Filing date: 2017-06-13
Publication date: 2019-01-04
Also published as: WO2017216129A1; KR20190019138A; JP2019523997A

Abstract

The present invention relates to the preparations for containing at least one organic functional material and at least the first organic solvent, wherein first organic solvent is 1,1- diphenylethlene derivative, and are related to the electronic device prepared by using these preparations.

Description

The preparation of organic functional material

Technical field

The present invention relates to containing preparation of 1, the 1- diphenylethlene derivative as the first solvent, and be related to by using The electroluminescent device of these preparations preparation.

Background technique

Through a long time is manufactured organic luminescent device (OLED) by vacuum deposition process.Such as ink-jet of other technologies is beaten Print has been well studied recently the advantages of such as being saved cost due to it and expanded scale feasibility.Multilayer prints main Challenge first is that determining relevant parameter to obtain the uniform ink in substrate and deposit.In order to trigger these parameters, such as surface Some additives can be added to preparation in tension, viscosity or boiling point.

Technical problem and goal of the invention

Many solvents have been proposed in the organic electronic device for inkjet printing.However, deposition and it is dried The quantity of the important parameter to work in journey makes the selection of solvent very challenging.Therefore, containing for being beaten by ink-jet There is still a need for improve for the organic semi-conductor preparation of print deposition.It is an object of the present invention to provide a kind of organic semi-conductor systems Agent, can controlled deposition to form the organic semiconductor layer with good layer property and efficiency performance.Of the invention is another A purpose is to provide a kind of organic semi-conductor preparation, when for example in inkjet printing methods in use, it can be in substrate Uniformly applied ink droplet, to provide good layer property and efficiency performance.

Technical solution

By provide realized comprising 1,1- diphenylethlene derivative as the preparation of the first solvent it is of the invention above-mentioned Purpose.

Beneficial effect

Inventor surprisingly, it is found that, using containing 1,1- diphenylethlene derivative as the organic molten of the first solvent Agent can fully control surface tension and effective ink is induced to deposit, to form the highly uniform and boundary of functional material Clearly demarcated organic layer, the organic layer have good layer property and performance.

Detailed description of the invention

Fig. 1 is shown comprising substrate, ito anode, hole injection layer (HIL), hole transmission layer (HTL), green light emitting layer (G-EML), the exemplary layer structure of the device of hole blocking layer (HBL), electron transfer layer (ETL) and Al cathode.

Fig. 2 shows the device performances of the OLED prepared according to embodiment 1.

Specific embodiment

The present invention relates to a kind of preparation, the preparation contains at least one organic functional material and as the 1 of the first solvent, 1- diphenylethlene derivative.

Preferred embodiment

In the first preferred embodiment, first organic solvent is spread out according to 1, the 1- diphenylethlene for leading to formula (I) Biology

Wherein

R¹And R²It is identical or different at each occurrence, and be F, Cl, Br, I, NO₂, CN, with 1 to 20 carbon atom Straight chain alkyl or alkoxy base or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, The non-adjacent CH of middle one or more₂Group can be by-O- ,-S- ,-NR⁵-、-CONR⁵,-CO-O- ,-C=O- ,-CH=CH- or- C ≡ C- replacement, and wherein one or more hydrogen atoms can be replaced by F, or have 4 to 14 carbon atoms and can by one or Multiple non-aromatic R⁵The aryl or heteroaryl group that group replaces, and multiple on same ring or on two different rings take For base R⁵Can be formed together again can be by multiple substituent Rs⁵Substituted monocycle or polycyclic aliphatic series, aromatics or heteroaromatic ring system；

R³And R⁴It is identical or different at each occurrence, and be H, F, Cl, Br, I, NO₂, CN, with 1 to 20 carbon original The alkyl or alkoxy base of the straight chain of son or the branch or cricoid alkyl with 3 to 20 carbon atoms or alkoxy base, Wherein one or more non-adjacent CH₂Group can be by-O- ,-S- ,-NR⁵-、-CONR⁵,-CO-O- ,-C=O- ,-CH=CH- Or-C ≡ C- replacement, and wherein one or more hydrogen atoms can be replaced by F, or have 4 to 14 carbon atoms and can be by one A or multiple non-aromatic R⁵The aryl or heteroaryl group that group replaces, and it is more on same ring or on two different rings A substituent R⁵Can be formed together again can be by multiple substituent Rs⁵Substituted monocycle or polycyclic aliphatic series, aromatics or heteroaromatic ring system；

R⁵It is identical or different in each case, and be the alkyl or alkoxy of the straight chain with 1 to 20 carbon atom Group or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, wherein one or more are non-adjacent CH₂Group can be replaced by-O- ,-S- ,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C-, and wherein one or more hydrogen are former Son can be replaced by F, or have 4 to 14 carbon atoms and can be by one or more non-aromatic R⁵The aryl or heteroaryl that group replaces Base group, and

M and n is 0,1,2 or 3, preferably 0 or 1, more preferably 0 identical or differently at each occurrence.

In the first preferred embodiment, first solvent is spread out according to 1, the 1- diphenylethlene for leading to formula (I) Biology, wherein

R¹And R²It is identical or different at each occurrence, and be the alkyl or alcoxyl of the straight chain with 1 to 20 carbon atom Base group or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, wherein one or more are non-adjacent CH₂Group can be by-O- ,-S- ,-NR⁵-、-CONR⁵,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replacement；

R³And R⁴It is identical or different at each occurrence, and be H, the alkyl or alkane of the straight chain with 1 to 20 carbon atom Oxygroup group or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, wherein one or more non-phases Adjacent CH₂Group can be by-O- ,-S- ,-NR⁵-、-CONR⁵,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replacement；

R⁵It is identical or different in each case, and be the alkyl or alkoxy of the straight chain with 1 to 20 carbon atom Group or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, wherein one or more are non-adjacent CH₂Group can be replaced by-O- ,-S- ,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C-；

M and n is 0 or 1, preferably 0 identical or differently at each occurrence.

In the second preferred embodiment, first solvent is spread out according to 1, the 1- diphenylethlene for leading to formula (I) Biology, wherein

R³And R⁴It is H；

M and n is 0 or 1, preferably 0 identical or differently at each occurrence.

In the first most preferred embodiment, first solvent is spread out according to 1, the 1- diphenylethlene for leading to formula (I) Biology, wherein

R¹And R²It is identical or different at each occurrence, and be linear alkyl groups or tool with 1 to 20 carbon atom There are the branch or cricoid alkyl group of 3 to 20 carbon atoms；

R³And R⁴It is H；And

M and n is 0 or 1, preferably 0 identical or differently at each occurrence.

In the second most preferred embodiment, first organic solvent is according to 1, the 1- diphenyl second for leading to formula (II) Alkene

The example and its boiling point (BP) of most preferred 1,1- diphenylethlene derivative are shown in the following table 1.

Table 1: preferred 1,1- diphenylethlene derivative and its boiling point (BP).

Preferably, first solvent has the >=surface tension of 20mN/m.It is highly preferred that the surface of first solvent Tension is in the range of 25mN/m to 40mN/m, most preferably in the range of 28mN/m to 37.5mN/m.

Based on the total amount of the solvent in preparation, the content of first solvent is preferably in 50 volume % to 100 volume %'s In range, more preferably in the range of 75 volume % to 100 volume %, most preferably in 90 volume % to the range of 100 volume % It is interior.

Therefore, the total amount based on the solvent in preparation, the content of second solvent is preferably in 0 volume % to 50 volume % In the range of, more preferably in the range of 0 volume % to 25 volume %, most preferably in the range of 0 volume % to 10 volume %.

Preferably, the boiling point of first solvent is in the range of 100 DEG C to 400 DEG C, more preferably at 150 DEG C to 350 DEG C In the range of.

Preparation according to the present invention includes at least one different from the second of first solvent in one embodiment Solvent.Second solvent is used together with first solvent.

Suitable second solvent is preferably organic solvent, especially includes alcohol, aldehyde, ketone, ether, ester, amide such as two-C_1-2Alkane Base formamide, sulphur compound, nitro compound, hydrocarbon, halogenated hydrocarbons (such as chlorohydrocarbon), aromatics or heteroaromatic hydrocarbon and halogenated aromatics Or heteroaromatic hydrocarbon.

Preferably, second solvent can be selected from one kind in following classification: replacing and unsubstituted aromatics or straight chain Ester, such as ethyl benzoate, butyl benzoate；Substitution and unsubstituted aromatics or linear, such as 3- phenoxytoluene or benzene first Ether；Substituted or unsubstituted arene derivatives, such as dimethylbenzene；Indan derivative such as hexamethyl indane；Replace and unsubstituted virtue Race or straight chain ketone；Replace and unsubstituted heterocyclic compound, such as pyrrolidones, pyridine, pyrazine；Other fluoro or chlorinated aromatic hydrocarbons.

Particularly preferred second organic solvent is, for example, 1,2,3,4- durols, 1,2,3,5- durol, and 1,2,3- Trimethylbenzene, 1,2,4,5- durol, 1,2,4- trichloro-benzenes, 1,2,4- trimethylbenzene, 1,2- dihydronaphthalene, 1,2- dimethyl Naphthalene, 1,3- benzodioxolane, 1,3- diisopropyl benzene, 1,3- dimethylnaphthalene, Isosorbide-5-Nitrae-benzo twoAlkane, Isosorbide-5-Nitrae-diisopropyl Benzene, Isosorbide-5-Nitrae-dimethylnaphthalene, 1,5- dimethyltetralin, 1- benzothiophene, thio naphthalene, 1- bromonaphthalene, the chloro- methyl naphthalene of 1-, 1-ethylnaphthalene, 1- methoxynaphthalene, 1- methyl naphthalene, 1- methyl indol, 2,3- benzofurans, 2,3- Dihydrobenzofuranes, 2,3- dimethyl benzene first Ether, 2,4- dimethylanisoles, 2,5- dimethylanisoles, 2,6- dimethylanisoles, 2,6- dimethylnaphthalenes, the bromo- 3- bromine of 2- Methyl naphthalene, 2- bromomethyl naphthalene, 2- bromonaphthalene, 2- ethyoxyl naphthalene, 2-ethylnaphthalene, 2- cumene methyl ether, 2- methylanisole, 2- first Base indoles, 3,4- dimethylanisoles, 3,5- dimethylanisoles, 3- bromoquinoline, 3- methylanisole, 4- methylanisole, 5- decalactone, 5- methoxyindan, 5- methoxy-Indole, 5- tert-butyl-meta-xylene, 6- methylquinoline, 8- methylquinoline, benzene Ethyl ketone, methyl phenyl ethers anisole, benzonitrile, benzothiazole, benzyl acetate, bromobenzene, butyl benzoate, butyl phenylate, cyclohexyl benzene, decahydro Naphthols, dimethoxy-p, 3- phenoxytoluene, diphenyl ether, propiophenone, ethylo benzene, ethyl benzoate, hexyl benzene, indane, Hexamethyl indane, indenes is heterochromatic full, isopropylbenzene, m- cymol, mesitylene, methyl benzoate, ortho-xylene, two Toluene, paraxylene, propyl benzoate, propylbenzene, o-dichlorobenzene, amylbenzene, phenetole, ethoxybenzene, phenylacetate are p- Cymol, propiophenone, sec-butylbenzene, tert-butyl benzene, thiophene, toluene, veratrole, monochloro-benzene, o-dichlorobenzene, pyridine, The mixing of pyrazine, pyrimidine, pyrrolidones, morpholine, dimethyl acetamide, dimethyl sulfoxide, decahydronaphthalenes and/or these compounds Object.

These solvents can be used alone or the mixture as two kinds, three or more solvents uses, described in formation Second solvent.

Preferably, the boiling point of second solvent is in the range of 100 DEG C to 400 DEG C, more preferably at 150 DEG C to 350 DEG C In the range of.

It is described at least one organic functional material first solvent and in second solvent have solubility, The solubility is preferably in the range of 1g/l to 250g/l, more preferably in the range of 1g/l to 50g/l.

Total weight based on preparation, the content of at least one organic functional material in the formulation is in 0.001 weight % To 20 weight %, preferably in the range of 0.01 weight % to 15 weight %, more preferably in 0.1 weight % to 10 weights In the range of measuring %, most preferably in the range of 0.3 weight % to 10 weight %.

The surface tension of preparation according to the present invention is preferably in the range of 10mN/m to 50mN/m, more preferably in 25mN/m To 40mN/m.

In addition, the viscosity of preparation according to the present invention preferably in the range of 1mPa.s to 50mPa.s, more preferably exists 2mPa.s to 40mPa.s, most preferably in the range of 2mPa.s to 20mPa.s.

Preferably, the surface tension of the blend of the organic solvent is in the range of 15mN/m to 80mN/m, more preferably In the range of 20mN/m to 60mN/m, most preferably in the range of 25mN/m to 40mN/m.FTA can be used in surface tension (First Ten Angstrom) 1000 contact angle angular instruments measure at 20 DEG C.The details of this method can be from First Ten Angstrom is obtained, " the Surface Tension Measurements Using as published by Roger doctor P.Woodward The Drop Shape Method (using drop shape method surface tension) ".Preferably, sessile drop method can be used for determining surface Power.The measuring technique distributes drop in a large amount of liquid or gaseous state phase from syringe needle.The shape of drop is by surface tension, gravity and close The relationship spent between difference generates.Using sessile drop method, http://www.kruss.de/services/education- is used Shadow image gauging surface tension of the theory/glossary/drop-shape-analys is from hanging drop.One kind is common and can Commercially available high-precision Drop Shape Analysis tool comes from First TenFTA1000, be used to carry out institute There is stalagmometry.Surface tension is determined by software FTA1000.It is all to measure within the scope of 20 DEG C to 22 DEG C at room temperature It carries out.S.O.P. includes determining every kind of preparation using new disposable drop distribution system (syringe and syringe needle) Surface tension.Each drop measured within one minute duration, carries out 60 measurements, is averaged later to measured value Value.For every kind of preparation, three drops are measured.The measurement is averaged to obtain end value.For with known surface The plurality of liquid of power periodically mutually verifies the tool.

Using 40mm parallel-plate geometry and using TA instrument ARG2 rheometer in 10s^-1To 1000s^-1Shear rate Range measures the preparation of embodiment and the viscosity of solvent.In 200s^-1To 800s^-1Between measurement is averaged, in 200s^-1It arrives 800s^-1Between temperature and shear rate accurately control.The viscosity provided in table 3 be every kind of preparation 25 DEG C temperature and 500s^-1Shear rate under the viscosity that measures.Every kind of solvent measurement is three times.Shown viscosity number is averaged to what the measured value took Value.

Preparation according to the present invention includes the organic functional material of at least one functional layer that can be used for producing electronic device. Functional material is usually the organic material introduced between the anode and cathode of electronic device.

Term organic functional material especially indicates, organic conductor, organic semiconductor, organic fluorescent compounds, Phosphorescent Compound, organic light-absorbing compound, organic photosensitive chemical combination object, organic photosensitive agent and other organic light-activated compounds. Term organic functional material further includes the metal-organic complex of transition metal, rare earth metal, lanthanide series and actinides.

The organic functional material is selected from fluorescent illuminant, phosphorescent emitter, material of main part, host material, exciton blocking Material, electron transport material, electron injection material, hole conductor material, hole-injecting material, n-type dopant, p-type dopant, Wide bandgap material, electron-blocking materials and hole barrier materials.

The preferred embodiment of organic functional material is disclosed in detail in 2011/076314 A1 of WO, wherein by the document It is incorporated by reference into the application.

In a preferred embodiment, organic functional material is selected from hole injection, hole transport, shines, electronics biography Defeated and electron injection material organic semiconductor.

It is highly preferred that organic functional material is the organic semiconductor selected from hole injection and hole mobile material.

Organic functional material can be the compound with low molecular weight, polymer, oligomer or dendritic macromole, Middle organic functional material is also possible to the form of mixture.Therefore, preparation according to the present invention may include two different tools There are the compound of low molecular weight, a kind of compound with low molecular weight and a kind of polymer or two kinds of polymer (blend).

Organic functional material is usually described via the property of frontal orbital, and frontal orbital will be retouched in further detail below It states.The molecular orbit of material, and especially up to occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), it Energy level and minimum triplet T₁Energy or lowest excited singlet state S₁Energy determined via quantum chemistry calculation. In order to calculate the organic substance of not metal, the " ground state/semiempirical/default spin/spin substance of AM1/ charge 0/ is used first State " method carries out Geometrical optimization.Then, it is made energy calculation on the basis of the geometry of the optimization.It uses herein " TD-SCF/DFT/ defaults spin/B3PW91 " method and " 6-31G (d) " base group (charge 0, spin singlet state).For containing metal Compound, optimized by " ground state/Hartree-Fock/ default that spin/LanL2MB/ charge 0/ spin singlet state " method several What structure.It is made energy calculation similar to the above method for organic substance, the difference is that making for metallic atom With " LanL2DZ " base group, and " 6-31G (d) " base group is used for ligand.The energy balane is obtained as unit of hartree HOMO energy level HEh or lumo energy LEh.Referring to HOMO the and LUMO energy of cyclic voltammetry measurement calibration measured with electron-volt Grade is following to be determined:

HOMO (eV)=((HEh*27.212) -0.9899)/1.1206

LUMO (eV)=((LEh*27.212) -2.0041)/1.385

For the purpose of the application, these values be considered be respectively material HOMO and lumo energy.

Minimum triplet T₁It is defined as, there is the energy of the triplet of the minimum energy generated by the quantum chemistry calculation Amount.

Lowest excited singlet state S₁It is defined as, there is the excitation list of the minimum energy generated by the quantum chemistry calculation The energy of weight state.

Method described herein is unrelated with used software package, and always provides identical result.It is commonly used The example of the program for this purpose be that (Q-Chem is public by " Gaussian09W " (Gaussian company) and Q-Chem 4.1 Department).

Compound with hole injection property, also referred herein as hole-injecting material are simplifying or are promoting hole i.e. just Charge is transferred in organic layer from anode.In general, hole-injecting material has the region for being in anode energy level or is higher than anode energy The HOMO energy level of grade, i.e. the HOMO energy level of typically at least -5.3eV.

Compound with hole transporting property, also referred herein as hole mobile material, being capable of transporting holes, that is, positive electricity Lotus, the positive charge are usually injected from anode or adjacent layer such as hole injection layer.Hole mobile material usually has preferably extremely The high HOMO energy level of few -5.4eV.Depending on the structure of electronic device, hole mobile material also can be used and injected as hole Material.

Preferred compound with hole injection and/or hole transporting property is for example including triarylamine, benzidine, four virtues Base-p-phenylenediamine, triaryl phosphine, phenthazine, phenoPiperazine, dihydrophenazine, thianthrene, dibenzo is to twoEnglish, phenoThiophene, carbazole,, thiophene, pyrroles and furan derivatives and it is other with high HOMO (HOMO=highest occupied molecular orbital) containing O, S or The heterocyclic compound of N.

It, can be it is especially mentioned that phenylenediamine be derivative as the compound with hole injection and/or hole transporting property Object (US 3615404), arylamine derivatives (US 3567450), the chalcone derivative (US 3526501) that amino replaces, benzene Vinyl anthracene derivative (JP-A-56-46234), polynuclear aromatic compound (EP 1009041), polyaryl alkane derivatives (US 3615402), fluorenone derivatives (JP-A-54-110837), hydazone derivative (US 3717462), acylhydrazone, stilbene derivative (JP-A- 61-210363), silazane derivatives (US 4950950), polysilane (JP-A-2-204996), aniline (JP-A-2- 282263), thiophene oligomers (JP Heisei 1 (1989) 211399), polythiophene is poly- (N- vinyl carbazole) (PVK), polypyrrole, Polyaniline and other conductive macromolecules, porphyrin compound (JP-A-63-2956965, US 4720432), aromatics diformazan subunit Type compound, carbazole compound, such as CDBP, CBP, mCP, aromatic uncle amine and styrylamine compound (US 4127412), example Such as the triphenylamine of benzidine-type, the triphenylamine of the triphenylamine of styrylamine type and two amine type.Arylamine dendroid can also be used Macromolecular (JP Heisei 8 (1996) 193191), monomelic triarylamines (US 3180730) contain one or more vinyl groups And/or the triarylamine (US 3567450 and US 3658520) or four aryl two of at least one functional group for containing reactive hydrogen Amine (two tertiary amine units are connected by aryl group).There may also be more triaryl amino groups in molecule.Phthalein Cyanines derivative, naphthalocyanine derivative, butadiene derivatives and quinoline, such as two pyrazines simultaneously [2,3-f:2 ', 3 '-h]-quinoline Quinoline pregnancy nitrile, and it is suitable.

Preferably comprise aromatic uncle amine (US 2008/0102311 A1, US 4720432 and US of at least two tertiary amine units , such as NPD (α-NPD=4,4 '-bis- [N- (1- naphthalene)-N- phenyl amino] biphenyl) (US 5061569), TPD 5061569) 232 (=N, N '-be bis--(N, N '-diphenyl -4- aminophenyl)-N, N- diphenyl -4,4 '-diaminostilbene, 1 '-biphenyl) or MTDATA (MTDATA or m-MTDATA=4,4 ', 4 "-three [3- aminomethyl phenyl) phenyl amino] triphenylamine) (JP-A-4- 308688), TBDB (=N, N, N ', N '-four (4- biphenyl)-diamino phenylbenzene fork), (=1,1- are bis-, and (4- bis- is to toluene by TAPC Base aminophenyl) hexamethylene), TAPPP (bis- (4- di-p-tolyl the aminophenyl) -3- phenyl-propanes of=1,1-), BDTAPVB Bis- [2- [4- [N, N- bis- (p-methylphenyl) amino] phenyl] vinyl] benzene of (=Isosorbide-5-Nitrae -), and TTB (=N, N, N ' ,-four pairs of toluene of N ' 4,4 '-benzidine of base -), TPD (=4,4 '-bis- [N-3- methylphenyl]-N- phenyl aminos) biphenyl), N, N, N ' and, N '- 4,4 " '-diaminostilbene of tetraphenyl-, 1 ', 4 ', 1 ", 4 ", 1 " '-quaterphenyl, also, it is preferred that the tertiary amine containing carbazole unit, such as TCTA (bis- [4- (9H- carbazole -9- base) phenyl] aniline of=4- (9H- carbazole -9- base)-N, N-).Also, it is preferred that according to US The six azepine terphenyls fork compound and phthalocyanine derivates (such as H of 2007/0092755 A1₂Pc, CuPc (=copper phthalocyanine), CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl₂SiPc, (HO) AlPc, (HO) GaPc, VOPc, TiOPc, MoOPc, GaPc-O-GaPc).

The triarylamine compound of particularly preferred formula (TA-1) to (TA-12) below, they are disclosed in following documents: EP 1162193 B1, EP 650 955 B1, Synth.Metals1997,91 (1-3), 209, DE 19646119 A1, WO 2006/122630 A1, EP 1 860 097 A1, EP 1834945 A1, JP 08053397 A, US 6251531 B1, US 2005/0221124, JP 08292586 A, US 7399537 B2, US 2006/0061265 A1, EP 1 661 888 and WO 2009/041635.The compound of the formula (TA-1) to (TA-12) can also be substituted:

The other compounds that may be used as hole-injecting material are described in 1029909 A1 of EP 0891121 A1 and EP, Implanted layer general description is in 2004/0174116 A1 of US.

These arylamines and heterocyclic compound for being typically used as hole injection and/or hole mobile material preferably result in polymerization HOMO in object is greater than -5.8eV (relative to vacuum level), especially preferred more than -5.5eV.

Compound with electron injection and/or electronic transport property is, for example, pyridine, pyrimidine, pyridazine, pyrazine,Two Azoles, quinoline, quinoxaline, anthracene, benzanthracene, pyrene, benzimidazole, triazine, ketone, phosphine oxide and phenazene derivative, there are also triaryls Borine and the other heterocyclic compound containing O, S or N with low LUMO (LUMO=lowest unoccupied molecular orbital).

Specially suitable compound for electron-transport and electron injecting layer is the metallo-chelate (example of 8-hydroxyquinoline Such as LiQ, AlQ₃、GaQ₃、MgQ₂、ZnQ₂、InQ₃、ZrQ₄), BAlQ, Ga oxyquinoline complex compound, 4- aza-phenanthrenes -5- alcohol-Be complexing Object (5529853 A of US, referring to formula ET-1), butadiene derivatives (US 4356429), heterocyclic optical brighteners (US 4539507), benzimidizole derivatives (2007/0273272 A1 of US), such as TPBI (US 5766779, referring to formula ET-2), 1,3,5-triazines, such as two fluorenyl pyrrolotriazine derivatives (such as according to DE 102008064200) of spiral shell, pyrene, anthracene, aphthacene, fluorenes, spiral shell Fluorenes, dendritic macromole, aphthacene (such as rubrene derivative), 1,10- phenanthroline derivative (JP 2003-115387, JP 2004-311184, JP-2001-267080, WO 02/043449), Silole derivative (EP 1480280, EP 1478032, EP 1469533), borane derivative, such as containing Si triarylborane derivative (2007/0087219 A1 of US, Referring to formula ET-3), pyridine derivate (JP 2004-200162), phenanthroline, especially 1,10- phenanthroline derivative, such as BCP And Bphen, and a variety of phenanthroline (US 2007-0252517 A1) or and anthracene that are connected by biphenyl or other aromatic groups The phenanthroline (US 2007-0122656 A1, referring to formula ET-4 and ET-5) of connection.

Equally suitable is heterocyclic organic compounds, such as thiopyrandioxide,Azoles, triazole, imidazoles orDiazole.Make With the pentacyclic example containing N, such asAzoles, preferably 1,3,4-Diazole, such as the change of formula ET-6, ET-7, ET-8 and ET-9 Object is closed, is especially disclosed in 2007/0273272 A1 of US；Thiazole,Diazole, thiadiazoles, triazole, referring particularly to US 2008/ 0102311 A1 and Y.A.Levin, M.S.Skorobogatova, Khimiya Geterotsiklicheskikh Soedinenii 1967 (2), 339-341, the preferably compound of formula ET-10, Silole derivative.Preferredization Close the compound that object is formula below (ET-6) to (ET-10):

Also can be used organic compound, for example, Fluorenone, fluorenes subunit methane, tetra-carbonic, anthraquinone bismethane, diphenylquinone, The derivative of anthrone and anthraquinone diethylene triamine.

It is preferred that anthracene (with 1- or 2- naphthalene and 4- or 3- xenyl) that 2,9,10- replaces or containing there are two points of anthracene unit Son (2008/0193796 A1 of US, referring to formula ET-11).The connection of anthracene unit and benzimidizole derivatives that 9,10- replaces It is very favorable (US 1551206 A1 of 2006/147747 A and EP, referring to formula ET-12 and ET 13).

The compound that electron injection and/or electronic transport property can be generated is preferably resulted in less than -2.5eV (relative to true Unoccupied level), particularly preferably less than -2.7eV LUMO.

Preparation of the invention may include illuminator.The material that term illuminator is expressed as follows is passing through any type energy Transfer and after exciting, the material can radiation transistion to ground state and issue light.In general, it is known that two classes shine Body, i.e. fluorescence and phosphorescent emitter.Term fluorescent illuminant indicates, wherein the radiation transistion from excited singlet state to ground state occurs Material or compound.Term phosphorescent emitter preferably indicates, luminescent material or compound containing transition metal.

Illuminator is also commonly referred to as dopant, and the dopant causes above-mentioned property in system in this case.Include Dopant in the system of host material and dopant refers to the lesser component of ratio in the mixture.It correspondingly, include matrix Host material in the system of material and dopant refers to the component of large percentage in the mixture.Therefore, term phosphorescence shines Body can also for example refer to phosphorescent dopants.

The compound that can be shone especially includes fluorescent illuminant and phosphorescent emitter.These especially include containing Stilbene, Stilbene Amine, styrylamine, cumarin, rubrene, rhodamine, thiazole, thiadiazoles, cyanine, thiophene, to phenylene, phthalocyanine, porphyrin, Ketone, quinoline, imines, anthracene and/or pyrene structure compound.Particularly preferably following compound, can at room temperature It is shone with high efficiency from triplet, that is, shows the compound of electroluminescent phosphorescence rather than electroluminescent fluorescent, the compound usually draws Play the increase of energy efficiency.Be suitable for this purpose is the compound of the heavy atom containing atomic number greater than 36 first.It is preferred that Be the compound containing d the or f transition metal for meeting above-mentioned condition.Particularly preferably contain the 8th to 10 race's element herein The respective compound of (Ru, Os, Rh, Ir, Pd, Pt).Suitable functional compounds are, for example, a variety of complex compounds herein, such as example 02/,068,435 02/081488 A1, EP 1239526 described in A2 and 2004/026886 A2 of WO of A1, WO of WO.

The preferred compound that can be used as fluorescent illuminant is described by following instance.Preferred fluorescent illuminant is selected from as follows Classification: single styryl amine, diphenylethyllene amine, triphenylethylene base amine, tetraphenyl ethylene base amine, styryl phosphine, styryl Ether and arylamine.

Single styryl amine refers to, containing a substituted or unsubstituted styryl group and at least one amine, preferably The compound of aromatic amine.Diphenylethyllene amine refers to, containing there are two substituted or unsubstituted styryl groups and at least one The compound of amine, preferably aromatic amine.Triphenylethylene base amine refers to, containing there are three substituted or unsubstituted styryl group and extremely The compound of few amine, preferably aromatic amine.Tetraphenyl ethylene base amine refers to, containing there are four substituted or unsubstituted styryl bases The compound of group and at least one amine, preferably aromatic amine.The styryl group is particularly preferably Stilbene, can also be further Replace.To define corresponding phosphine and ether in a manner of as amine.Arylamine or aromatic amine in the sense of the present invention refers to, contains Three with the substituted or unsubstituted aromatics of nitrogen Direct Bonding or the compound of heteroaromatic ring system.These aromatics or heteroaromatic ring system At least one of preferably condensed ring system, preferably with the condensed ring system of at least 14 aromatic ring atoms.Its preferred embodiment is Aromatics anthranylamine, aromatics anthradiamine, aromatics pyrene amine, aromatics pyrene diamines, aromaticsAmine or aromaticsDiamines.Aromatics anthranylamine refers to, In diarylamino groups and anthryl group Direct Bonding, preferably in the compound of 9 Direct Bondings.Aromatics anthradiamine is Refer to, two of them diarylamino groups and anthryl group Direct Bonding, preferably at 2,6 or 9, the chemical combination of 10 Direct Bondings Object.Aromatics pyrene amine, aromatics pyrene diamines, aromatics are defined in similar modeAmine and aromaticsDiamines, wherein two virtue Base amino group is preferably bonded at 1 or at 1,6 with pyrene.

Other preferred fluorescent illuminants are selected from indeno fluorenamine or indeno fluorenediamine, are especially described in WO 2006/ In 122630；Benzo indeno fluorenamine or benzo indeno fluorenediamine, are especially described in WO 2008/006449；With dibenzo indenes And fluorenamine or dibenzo indeno fluorenediamine, it is especially described in WO 2007/140847.

Can be used as fluorescent illuminant from the example of the other compound of styryl amine be substituted or unsubstituted three Stilbene amine is described in WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549 and WO Dopant in 2007/115610.Diphenylethyllene benzene and distyrylbiphenyl derivatives are described in US 5121029.Its Its styryl amine is found in 2007/0122656 A1 of US.

Particularly preferred styrylamine compounds are the compounds and DE of formula EM-1 described in 7250532 B2 of US The compound of formula EM-2 described in 10 2,005 058557 A1:

Particularly preferred triarylamine compound be 1,583,691 08/053397 A and 6251531 B1 of US of A, JP of CN, 1,957,606 200,8/0,113,101 2006/210830 A, WO 2008/006449 and DE of A1, US of A1, US of EP Formula EM-3 disclosed in 102008035413 is to the compound of EM-15 and its derivative:

Can be used as fluorescent illuminant other preferred compounds be selected from following compound derivative: naphthalene, anthracene, aphthacene, Benzanthracene, benzophenanthrene (DE 10 2,009 005746), fluorenes, fluoranthene, two indeno pyrenes, indeno, phenanthrene, (US 2007/ 0252517 A1), pyrene,, it is decacyclene, coronene, tetraphenyl cyclopentadiene, Pentaphenylcyclopentadiene, fluorenes, spiro fluorene, red glimmering Alkene, cumarin (US 4769292, US 6020078,2007/0252517 A1 of US), pyrans,Azoles, benzoAzoles, benzo thiophene Azoles, benzimidazole, pyrazine, cinnamate, diketopyrrolo-pyrrole, acridone and quinacridone (US 2007/0252517 A1)。

In anthracene compound, the anthracene that particularly preferably 9,10- replaces, for example, 9,10- diphenylanthrancenes and 9, the bis- (benzene of 10- Ethyl-acetylene base) anthracene.Bis- (the 9 '-acetenyl anthryl) benzene of 1,4- are also preferred dopant.

It is also preferred that the derivative of following compound: rubrene, cumarin, rhodamine, quinacridone such as DMQA (=N, N'- dimethylquinacridone), dicyano first subunit pyrans such as DCM (=4- (dicyano second subunit) -6- (4- diformazan Base aminostyryl -2- methyl) -4H- pyrans), thiapyran, polymethine, pyransAnd thiapyranSalt, two indeno pyrenes and indeno .

Blue luminescence body is preferably polynuclear aromatic compound, for example, 9,10- bis- (2- naphthyl anthracenes) and other anthracenes are derivative Object, aphthacene, xanthene, derivative, such as 2,5,8,11- tetra-terts, benzene subunit such as 4,4 '-bis- (9- ethyl -3- Carbazole ethylene subunit) -1,1 '-biphenyl, fluorenes, fluoranthene, aryl pyrene (2006/0222886 A1 of US), fragrant subunit ethylene subunit (US 5121029, US 5130603), bis- (azine) imines-boron compounds (2007/0092753 A1 of US), bis- (azine) first Ylidene compounds and quinoline-2-one (carbostyryl) compound.

Other preferred blue luminescence bodies are described in C.H.Chen etc.: " Recent developments in Organic electroluminescent materials (latest development of electroluminescent organic material) " Macromol.Symp. (macromolecular seminar), 125, (1997) 1-48 and " Recent progress of molecular Organic electroluminescent materials and devices be (molecule organic electroluminescent material and device Latest developments) " Mat.Sci.and Eng.R (Materials Science and Engineering report), 39 (2002), in 143-222.

Other preferred blue luminescence bodies are hydrocarbon disclosed in DE 102008035413.

The preferred compound that may be used as phosphorescent emitter is hereinafter illustrated description.

WO 00/70655、WO 01/41512、WO 02/02714、WO 02/15645、EP 1191613、EP 1191612, EP 1191614 and WO 2005/033244 disclose the example of phosphorescent emitter.In general, according to existing skill The art all phosphorescent complexes known to those skilled in the art in field of organic electroluminescence for the sum of phosphorescent OLED are all It is suitable, and those skilled in the art will be complexed using other phosphorescence without creative efforts Object.

Phosphorescent metal complex preferably comprises Ir, Ru, Pd, Pt, Os or Re, more preferable Ir.

Preferred ligand is 2- phenylpyridine derivative, 7,8- benzoquinoline derivative, 2- (2- thienyl) pyridine derived Object, 2- (1- naphthalene) pyridine derivate, 1- octaverine, 3- octaverine or 2- phenylchinoline are derivative Object.All these compounds can for example be replaced for the fluorine of blue light, cyano and/or trifluoromethyl substituent.Assistant ligand is excellent Choosing is acetylacetonate or pyridine carboxylic acid.

Particularly, the Pt or Pd of formula EM-16 and the complex compound of tetradentate ligands are suitable

The compound of formula EM-16 is described in greater detail in 2007/0087219 A1 of US, wherein in order to explain in above formula Substituent group and label, for disclosure purposes and refer to the specification.In addition, the Pt- porphyrin complex with widened ring system (2009/0061681 A1 of US) and Ir complex compound are also suitable, such as 2,3,7,8,12,13,17,18- octaethyl -21H, 23H- porphyrin-Pt (II), tetraphenyl-Pt (II) Tetrabenzoporphyrin (2009/0061681 A1 of US), cis--bis- (2- phenyl pyrazoline Pyridine root conjunction-N, C²') Pt (II), cis--bis- (2- (2 '-thienyl) pyridine root conjunction-N, C³') Pt (II), cis--bis- (2- (2 '- Thienyl) quinoline root conjunction-N, C⁵') Pt (II), (2- (4,6- difluorophenyl) pyridine root conjunction-N, C²') Pt (II) (acetylacetonate Object) or three (2- phenylpyridine root conjunction-N, C²') Ir (III) (=Ir (ppy)₃, green light), bis- (2- phenylpyridine root conjunction-N, C²) Ir (III) (acetylacetonate) (=Ir (ppy)₂Acetylacetonate, green light, US 2001/0053462 A1, Baldo, Thompson etc., Nature (nature), 403, (2000), 750-753), bis- (1- phenyl isoquinolin quinoline root conjunction-N, C²') (2- phenyl Pyridine root conjunction-N, C²') iridium (III), bis- (2- phenylpyridine root conjunction-N, C²') (1- phenyl isoquinolin quinoline root conjunction-N, C²') iridium (III), bis- (2- (2 '-benzothienyl) pyridine root conjunction-N, C³') iridium (III) (acetylacetonate), bis- (2- (4 ', 6 '-two Fluorophenyl) pyridine root conjunction-N, C²') iridium (III) (pyridine carboxylic acid salt) (FIrpic, blue light), bis- (2- (4 ', 6 '-difluorophenyl) Pyridine root conjunction-N, C²') Ir (III) (four (1- pyrazolyl) borates), three (2- (biphenyl -3- base) -4- tert .-butylpyridine) iridium (III)、(ppz)₂Ir(5phdpym)(US 2009/0061681 A1)、(45ooppz)₂Ir(5phdpym)(US 2009/ 0061681 A1), the derivative of 2- phenylpyridine-Ir complex compound, (=bis- (2- phenylchinoline base-N, C for example, PQIr²') second Acyl acetone iridium (III)), three (2- phenyl isoquinolin quinoline root conjunction-N, C) Ir (III) (feux rouges), bis- (2- (2 '-benzos [4,5-a] thiophene Base) pyridine root conjunction-N, C³) Ir (acetylacetonate) ([Btp₂Ir (acac)], feux rouges, Adachi etc., Appl.Phys.Lett. (applied physics flash report), 78 (2001), 1622-1624).

That equally suitable is trivalent lanthanide series such as Tb³⁺And Eu³⁺Complex compound (J.Kido etc., Appl.Phys.Lett. (applied physics flash report), 65 (1994), 2124；Kido etc., Chem.Lett. (Chemistry Letters), 657,1990；2007/0252517 A1 of US) or Pt (II), Ir (I), Rh (I) and two sulphur synthetic fibre of Maleic nitrile phosphorescent complexes (Johnson etc., JACS 105,1983,1795), Re (I) three carbonyls-diimine complex compound (especially Wrighton, JACS 96, 1974,998), complex compound (Ma etc., Synth.Metals (synthesis of Os (II) and cyano ligand and bipyridyl or phenanthroline ligand Metal), 94,1998,245).

Other phosphorescent emitters with tridentate ligand are described in US 6824895 and US 10/729238.It glows Phosphorescent complexes are seen in US 6835469 and US 6830828.

Particularly preferred compound as the phosphorescent dopants especially compound of formula EM-17, is especially described in US 2001/0053462 A1 and Inorg.Chem. (inorganic chemistry), 2001,40 (7), 1704-1711；JACS 2001,123 (18), in 4304-4312 and its derivative.

Derivative is described in 7378162 B2, US 6835469 of US in B2 and 2003/253145 A of JP.

In addition, the 7238437 formula EM-18 to EM- described in A1 and EP 1348711 of B2, US 2009/008607 of US 21 compound and its derivative may be used as illuminator.

Quantum dot may also serve as illuminator, these materials are disclosed in detail in 2011/076314 A1 of WO.

Being used as the compound of material of main part with being especially used together with luminophor includes the material from multiclass substance Material.

Material of main part usually has the biggish band gap between HOMO and LUMO compared to luminiferous material used.This Outside, preferred material of main part shows the property of hole transport or electron transport material.In addition, material of main part can have electronics Both transmission and hole transporting property.

Material of main part is also referred to as host material in some cases, especially if material of main part and phosphorescent emitter exist It is such when being applied in combination in OLED.

The preferred material of main part being especially used together with fluorescent dopants or total material of main part classification chosen from the followings: Oligomeric virtue subunit (such as 2,2 ', 7,7 '-tetraphenyl spiral shell, two fluorenes or dinaphthyl anthracene according to EP 676461), especially containing thick Close the oligomeric fragrant subunit of aromatic group, such as anthracene, benzanthracene, benzophenanthrene (DE 10 2,009 005746, WO 2009/ 069566), phenanthrene, aphthacene, coronene,, fluorenes, spiro fluorene, phthalein simultaneously, naphtho-, decacyclene, rubrene, oligomeric virtue is sub- Base ethylene subunit (such as DPVBi=4,4 '-bis- (2,2- diphenylacetylenes) -1,1 '-biphenyl or spiral shell-according to EP 676461 DPVBi), the metal complex of polypody metal complex (such as according to WO 04/081017), especially 8-hydroxyquinoline, such as AlQ₃(=tri- (8-hydroxyquinoline) aluminium (III)) or bis- (8- hydroxy-2-methylquinolines)-(4- phenylphenoxy) aluminium, Yi Jimi Azoles chelate (2007/0092753 A1 of US) and quinoline-metal complex, aminoquinoline-metal complex, benzoquinoline-gold Belong to complex compound, hole-conductive compound (such as according to WO 2004/058911), electronics conducting compound, especially ketone, oxidation Phosphine, sulfoxide etc. (such as according to WO 2005/084081 and WO 2005/084082), atropisomer (such as according to WO 2006/ 048268), boronic acid derivatives (such as according to WO 2006/117052) or benzanthracene (such as according to WO 2008/145239).

May be used as material of main part or altogether material of main part particularly preferred compound classification chosen from the followings: including anthracene, The atropisomer of the oligomeric fragrant subunit or these compounds of benzanthracene and/or pyrene.Oligomeric fragrant subunit in the sense of the present invention It is intended to refer to, the compound that wherein at least three aryl or fragrant subunit group bond together.

Preferred material of main part in particular selected from formula (H-1) compound,

Ar⁴-(Ar⁵)p-Ar⁶ (H-1)

Wherein Ar⁴、Ar⁵、Ar⁶Be identical or differently at each occurrence aryl with 5 to 30 aromatic ring atoms or Heteroaryl groups, the group are optionally substituted, and p indicates the integer in 1 to 5 range；If p=1, Ar⁴、Ar⁵ And Ar⁶In pi-electron summation be at least 30, the pi-electron summation is at least 36 if p=2, and if p=3 the π electricity Sub- summation is at least 42.

In the compound of formula (H-1), group Ar⁵Particularly preferably represent anthracene, and group Ar⁴And Ar⁶At 9 and 10 Position bonding, wherein these groups can be optionally substituted.Very particularly preferably, group Ar⁴And/or Ar⁶At least one of be choosing From 1- naphthalene or 2- naphthalene, 2- phenanthryl, 3- phenanthryl or 9- phenanthryl or 2- benzo anthryl, 3- benzo anthryl, 4- benzo anthryl, 5- Fused-aryl group in benzo anthryl, 6- benzo anthryl or 7- benzo anthryl.Anthracene-based compounds are described in US 2007/ In 2007/0252517 A1 of 0092753 A1 and US, such as 2- (4- aminomethyl phenyl) -9,10- bis- (2- naphthalene) anthracene, 9- (2- naphthalene Base) -10- (1,1 '-biphenyl) anthracene and 9,10- bis- [4- (2,2- diphenylacetylene) phenyl] anthracenes, 9,10- diphenylanthrancene, 9,10- Bis- (phenylene-ethynylene) anthracenes and bis- (the 9 '-acetenyl anthryl) benzene of 1,4-.Further preferably containing there are two the compound (US of anthracene unit 2008/0193796 A1), such as 10,10 '-base -9 bis- [1,1 ', 4 ', 1 "] terphenyl -2-, 9 '-dianthranides.

Other preferred compounds are the derivatives of following substance: arylamine, styryl amine, fluorescein, diphenyl fourth Diene, tetraphenylbutadiene, cyclopentadiene, tetraphenyl cyclopentadiene, Pentaphenylcyclopentadiene, cumarin,Diazole, double benzosOxazoline,Azoles, pyridine, pyrazine, imines, benzothiazole, benzoAzoles, benzimidazole (2007/0092753 A1 of US) (example Such as 2,2 ', 2 "-(1,3,5- benzene subunit) three [1- phenyl -1H- benzimidazole]), aldazine, Stilbene, styryl virtue subunit are derivative Object (such as 9, bis- [4- (2, the 2- diphenylacetylene) phenyl] anthracenes of 10-) and diphenylethyllene virtue ylidene derivatives (US 5121029), diphenylethlene, vinyl anthracene, diaminocarbazole, pyrans, thiapyran, diketopyrrolo-pyrrole, polymethine, cortex cinnamomi Acid esters and fluorescent dye.

The particularly preferably derivative of arylamine and styryl amine, such as TNB (=4,4 '-bis- [N- (1- naphthalene)- N- (2- naphthalene) amino] biphenyl).Metal-hydroxy group quinoline complexes, such as LiQ or AlQ₃, may be used as total main body.

The compound preferably with oligomeric fragrant subunit as matrix is disclosed in US 2003/0027016 A1, US 7326371 B2、US 2006/043858 A、WO 2007/114358、WO 2008/145239、JP 3148176 B2、EP 1009044、US 2004/018383、WO 2005/061656 A1、EP 0681019B1、WO 2004/013073A1、US 5077142, in WO 2007/065678 and DE 102009005746, wherein particularly preferred formula H-2 to H-8 is retouched It states.

In addition, the compound that can be used as main body or matrix includes the material being used together with phosphorescent emitter.

These compounds for also acting as the structural element in polymer include CBP (the bis- carbazyl biphenyl of N, N-), carbazole Derivative (such as according to WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851), azepine carbazole is (such as according to EP 1617710, EP 1617711, EP 1731584 or JP 2005/ 347160), ketone (such as according to WO 2004/093207 or according to DE 102008033943), phosphine oxide, sulfoxide and sulfone (such as According to WO 2005/003253), oligocene subunit, aromatic amine (such as according to US 2005/0069729), bipolarity host material (such as according to WO 2007/137725), silane (such as according to WO 2005/111172), 9,9- diaryl fluorene derivatives (such as According to DE 102008017591), azepine boron heterocyclic pentylene or borate (such as according to WO 2006/117052), triazine is spread out Biological (such as according to DE 102008036982), indolocarbazole derivatives (such as according to WO 2007/063754 or WO 2008/056746), indenocarbazole derivatives (such as according to DE 102009023155 and DE 102009031021), diaza Phosphene derivative (such as according to DE 102009022858), triazole derivative,Azoles andZole derivatives, imidazoles Derivative, poly- aromatic yl paraffin derivative, pyrazoline derivative, pyrazolone derivative, distyrylpyrazine derivatives, thiapyran Dioxide derivative, phenylenediamine derivative, aromatic uncle amine, styryl amine, the chalcone derivative that amino replaces, indoles, Hydazone derivative, stilbene derivative, silazane derivatives, aromatics diformazan ylidene compounds, carbodiimide derivative, 8-hydroxyquinoline The metal complex of derivative, such as AlQ₃, can also it contain triaryl amino-phenol ligand (2007/0134514 A1 of US), Metal complex/polysilane compound and thiophene, benzothiophene and dibenzothiophene derivatives.

The example of preferred carbazole derivates is mCP (bis- carbazyl benzene of=1,3-N, N- (=9,9 '-(1,3- benzene subunits) Double -9H- carbazoles)) (formula H-9), CDBP (=9,9 '-(2,2 '-dimethyl [1,1 '-biphenyl] -4,4 '-diyls) double -9H- clicks Azoles), bis- (N, N '-two carbazyl) benzene of 1,3- (bis- (carbazole -9- base) benzene of=1,3-), PVK (polyvinyl carbazole), 3,5- bis- (9H- carbazole -9- base) biphenyl and CMTTP (formula H-10).Particularly preferred compound be disclosed in 2007/0128467 A1 of US and In 2005/0249976 A1 of US (formula H-11 and H-13).

Preferred four aryl-Si compound is e.g., as disclosed in US 2004/0209115, US 2004/0209116, US In 2007/0087219 A1 and H.Gilman, E.A.Zuech, Chemistry&Industry (chemistry with industry) (London, Britain), in 1960,120.

Particularly preferred four aryl-Si formula H-14 to H-21 description.

The particularly preferred compound from the 4th class for being used to prepare the matrix of phosphorescent dopants is especially disclosed in DE 102009022858, in DE 102009023155, EP 652273 B1, WO 2007/063754 and WO 2008/056746, In particularly preferred formula H-22 to H-25 description.

About can functional compounds used according to the invention and can be used as material of main part, especially preferably containing extremely The substance of a few nitrogen-atoms.These substances preferably include aromatic amine, pyrrolotriazine derivatives and carbazole derivates.Therefore, carbazole spreads out Biology especially shows surprising high efficiency.Pyrrolotriazine derivatives lead to the unexpected long-life of electronic device.

Furthermore preferably using a variety of different host materials for being in form of mixtures, especially at least a kind of electronics conduction Host material and at least one hole-conductive host material.It is also preferred that transmitting host material and electrically inert base using charge The mixture of material will not largely participate in charge even if the electrically inert host material participates in charge transmission Transmission, as described in such as WO 2010/108579.

Furthermore following compound can be used, the compound improves the transition from singlet state to triplet, and works as and use The compound improves the phosphorescence of these compounds when in the carrier of the functional compounds with the volume property that shines.Especially Ground, be suitable for the purpose is the carbazole dimerization body unit of carbazole and bridge joint, such as in such as WO 2004/070772 A2 and WO Described in 2004/113468 A1.Be equally applicable to this purpose is ketone, phosphine oxide, sulfoxide, sulfone, silane derivative and similar Compound, as described in such as 2005/040302 A1 of WO.

N-type dopant herein refers to reducing agent, i.e. electron donor.The preferred embodiment of n-type dopant is W (hpp)₄And root According to other electron rich metal complexes of 2005/086251 A2 of WO, P=N compound (such as WO 2012/175535 A1, WO 2012/175219 A1), naphthylene carbodiimides (such as 2012/168358 A1 of WO), fluorenes (such as WO 2012/031735 A1), free radical and diradical (such as 1,837,926 2007/107306 A1 of A1, WO of EP), pyridine (such as EP 2452946 2463927 A1 of A1, EP), N- heterocyclic compound (such as 2009/000237 A1 of WO) and acridine and azophenlyene (such as US 2007/145355 A1)。

In addition, the preparation may include wide bandgap material as functional material.Wide bandgap material refers in US 7,294, Material in 849 disclosure meaning.These systems show particularly advantageous performance data in electroluminescent device.

Compound as wide bandgap material can preferably have 2.5eV or bigger, preferably 3.0eV or bigger, especially excellent Select 3.5eV or bigger band gap.Highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital can especially be passed through (LUMO) energy level calculates band gap.

In addition, the preparation may include hole barrier materials (HBM) as functional material.Hole barrier materials are indicated more The material penetrated in hole (positive charge) is prevented or minimized in coating systems, especially if the material with luminescent layer or hole It is even more so when the form arrangement of the adjacent layer of conducting shell.In general, hole barrier materials are compared to the hole in adjacent layer Transmission material has lower HOMO energy level.Hole blocking layer be usually placed in luminescent layer in OLED and electron transfer layer it Between.

Any of hole barrier materials substantially can be used.In addition to other holes resistance of the other place descriptions of the application Except obstructing material, advantageous hole barrier materials are metal complex (US 2003/0068528), for example, bis- (8- hydroxyl -2- Methylquinoline)-(4- phenylphenoxy) aluminium (III) (BAlQ).For this purpose, same-three (1- Phenylpyrazole root of using face formula Conjunction-N, C2) iridium (III) (Ir (ppz)₃)(US 2003/0175553 A1).It can also use phenanthroline derivative, such as BCP or phthalimide, such as TMPP.

In addition, advantageous hole barrier materials are described in WO 00/70655 A2, WO 01/41512 and WO 01/93642 In A1.

In addition, the preparation may include electron-blocking materials (EBM) as functional material.Electron-blocking materials are indicated more The material of electronics penetrated is prevented or minimized in coating systems, especially if the material with luminescent layer or electronic conductive layer phase It is even more so when the form arrangement of adjacent layer.In general, electron-blocking materials are compared to the electron transport material in adjacent layer With higher lumo energy.

Any of electron-blocking materials substantially can be used.In addition to other electronics resistance of the other place descriptions of the application Except obstructing material, advantageous electron-blocking materials are transition metal complexes, for example, Ir (ppz)₃(US 2003/0175553)。

The electron-blocking materials can be preferably selected from amine, triarylamine and its derivative.

In addition, can be used as the functional compounds of the organic functional material in the preparation, if it is low molecular weight compound, Then preferably there is≤3000g/mol, more preferably≤2000g/mol, most preferably≤1000g/mol molecular weight.

In addition, being especially envisaged that the functional compounds characterized by high glass-transition temperature.In this respect, can be used as The particularly preferred functional compounds of organic functional material in the preparation are those of following compounds, the compound tool With good grounds DIN 51005 is measured as >=70 DEG C, glass preferably >=100 DEG C, more preferably >=125 DEG C, most preferably >=150 DEG C Glass transition temperature.

The preparation also may include polymer as organic functional material.It is described above as the usual tool of organic functional material There is the compound of relatively low molecular weight can also be with mixed with polymers.Equally these compounds can be covalently incorporated in polymer. This especially for compound below be it is feasible, the compound by reactive leaving group for example bromine, iodine, chlorine, boric acid or Borate is replaced by reactive polymerizable groups such as alkene or oxetanes.These may be used as corresponding for producing The monomer of oligomer, dendritic macromole or polymer.Oligomeric or polymerization herein is preferably via halogen functional group or boric acid official It can roll into a ball or be carried out via polymerizable groups.In addition, crosslinked polymer can be made by such group.It is according to the present invention Compound and polymer can be used as crosslinking or uncrosslinked layer.

The polymer that can be used as organic functional material usually contains to be retouched in the context of the compound having been described above The unit or structural element stated, especially such as in 02/077060 A1 of WO, in 2005/014689 A2 of WO and in WO It those of lists disclosed in 2011/076314 A1 and extensively.These are incorporated by reference into the application.Functional material can be with From for example following classification:

1st class: the structural element of hole injection and/or hole transporting property can be generated；

2nd class: the structural element of electron injection and/or electronic transport property can be generated；

3rd class: by the structural element of the combination of properties described in the 1st class and the 2nd class；

4th class: the structural element with luminosity, particularly phosphorescence groups；

5th class: improve the structural element of the transition from so-called singlet state to triplet；

6th class: the form of resulting polymers or the structural element of luminescent color are influenced；

7th class: it is typically used as the structural element of skeleton.

Structural element herein can also have multiple functions, so that clearly sorting out not necessarily can be advantageous.For example, the The structural element of 1 class also is used as skeleton.

There is hole transport or hole injection property as organic functional material containing the structural element from the 1st class Polymer preferably contain the unit corresponding to above-mentioned hole transport or hole-injecting material.

The structural element of other preferred 1st classes be, for example, triarylamine, benzidine, four aryl-p-phenylenediamine, carbazole,, thiophene, pyrroles and furan derivatives and other heterocyclic compounds containing O, S or N with high HOMO.These arylamines Preferably there is the HOMO for higher than -5.8eV (relative to vacuum level), being particularly preferably higher than -5.5eV with heterocyclic compound.

The particularly preferably polymer with hole transport or hole injection property, contains at least one formula HTP- below 1 repetitive unit:

Wherein symbol has following meanings:

Ar¹It is in each case singly-bound or monocycle or polycyclic virtue identical or differently for different repetitive units Base group is optionally substituted；

Ar²It is in each case monocycle or polycyclic aryl group identical or differently for different repetitive units, It is optionally substituted；

Ar³It is in each case monocycle or polycyclic aryl group identical or differently for different repetitive units, It is optionally substituted；

M is 1,2 or 3.

Formula HTP-1 repetitive unit in unit particularly preferably selected from formula HTP-1A to HTP-1C:

Wherein symbol has following meanings:

R^aIt is H identical or differently at each occurrence, substituted or unsubstituted aromatics or heteroaromatic group, alkyl, ring Alkyl, alkoxy, aralkyl, aryloxy group, arylthio, alkoxy carbonyl, silicyl or carboxyl, halogen atom, cyano group, Nitryl group or hydroxyl group；

R is 0,1,2,3 or 4, and

S is 0,1,2,3,4 or 5.

The particularly preferably polymer with hole transport or hole injection property, contains at least one formula HTP- below 2 repetitive units:

-(T¹)_c-(Ar⁷)_d-(T²)_e-(Ar⁸)_f- HTP-2

Wherein symbol has following meanings:

T¹And T²Independently selected from thiophene, selenophen, thieno [2,3-b] thiophene, thieno [3,2-b] thiophene, dithieno Thiophene, pyrroles and aniline, wherein these groups can be by one or more group R^bReplace；

R^bAt each occurrence independently selected from halogen ,-CN ,-NC ,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) NR⁰R⁰⁰,-C (=O) X ,-C (=O) R⁰,-NH₂,-NR⁰R⁰⁰,-SH ,-SR⁰,-SO₃H ,-SO₂R⁰,-OH ,-NO₂,-CF₃,-SF₅, appoint Silicyl, carbyl or the hydrocarbyl group with 1 to 40 carbon atom in generation are chosen, the group is optionally substituted And optionally containing one or more hetero atoms；

R⁰And R⁰⁰It is H or the carbyl or hydrocarbyl group with 1 to 40 carbon atom optionally replaced each independently, The group is optionally substituted and optionally containing one or more hetero atom；

Ar⁷And Ar⁸Indicate monocycle or polycyclic aryl or heteroaryl group independently of one another, the group optionally by Replace and be optionally bonded to 2,3 of one or two adjacent thiophene or selenophen group；

C and e is 0,1,2,3 or 4 independently of one another, wherein 1 < c+e≤6；

D and f is 0,1,2,3 or 4 independently of one another.

The preferred embodiment of polymer with hole transport or hole injection property is especially described in WO 2007/131582 In 2008/009343 A1 of A1 and WO.

There is electron injection and/or electron-transport as organic functional material containing the structural element from the 2nd class The polymer of property preferably contains the unit corresponding to above-described electron injection and/or electron transport material.

Other preferred structure elements of the 2nd class with electron injection and/or electronic transport property derived from such as pyridine, Pyrimidine, pyridazine, pyrazine,Diazole, quinoline, quinoxaline and azophenlyene group and triarylborane group have low LUMO energy Other heterocyclic compounds containing O, S or N of grade.These structural elements of 2nd class preferably have less than -2.7eV (relative to vacuum Energy level), especially preferably less than -2.8eV LUMO.

The organic functional material may be preferred that the polymer containing the structural element from the 3rd class, wherein improving empty The structural element (structural element i.e. from the 1st class and the 2nd class) of cave and electron mobility is connected to each other directly.These are tied herein Some in structure element may be used as illuminator, and wherein such as green, red or yellow can be changed into luminescent color.Therefore, it Use for for example generating other luminescent colors by the polymer of initial blue light-emitting or broad-band illumination is advantageous.

The polymer with luminosity as organic functional material containing the structural element from the 4th class is preferable Contain the unit for corresponding to above-described luminiferous material.It is preferably the polymer containing phosphorescence groups herein, especially Above-described luminescent metal complexes contain the corresponding list for containing the 8th to 10 race's element (Ru, Os, Rh, Ir, Pd, Pt) Member.

It is used as the poly- of organic functional material containing the 5th class unit for improving the transition from so-called singlet state to triplet Closing object can be preferred in the carrier of phosphorescent compound, and the phosphorescent compound preferably contains above-mentioned 4th class formation element Polymer.Polymer triplet matrix can be used herein.

It is suitable for the carbazole dimerization body unit of the especially carbazole and connection of the purpose, such as in such as 10304819 A1 of DE With described in 10328627 A1 of DE.Be equally applicable to this purpose be ketone, phosphine oxide, sulfoxide, sulfone and silane derivative and Similar compound, as described in such as 10349033 A1 of DE.Furthermore it is preferred that structural unit can be derived from above The compound described in conjunction with the host material being used together with phosphorescent compound.

Other organic functional materials are preferably to contain the form for the polymer that has an impact and/or the 6th class unit of luminescent color Polymer.Other than above-mentioned polymer, these polymer are that have at least one other aromatics or another conjugation Those of structure polymer, the polymer is not counting in above-mentioned classification.Therefore, these classifications to charge carrier mobility, Non-organic metal complex or singlet state-triplet transition only have minimum influence or do not influence.

Such structural unit can influence the form and/or luminescent color of resulting polymers.Depending on structure list Therefore member, these polymer are also used as illuminator.

In the case where fluorescence OLED, then therefore it is preferred to the aromatic structure elements with 6 to 40 C atoms, or Tolans, Stilbene or bisstyryl virtue ylidene derivatives unit, it is therein each to be replaced by one or more groups.Herein Particularly preferably using derived from the group of flowering structure: 1,4- benzene subunit, 1,4- naphthylene, 1,4- anthracene subunit or 9,10- Anthracene subunit, 1,6- pyrene subunit, 2,7- pyrene subunit or 4,9- pyrene subunit, 3,9- subunit or 3,10- subunit, 4,4'- phenylbenzene Fork, 4,4 "-terphenyl subunits, 4,4'- connection -1,1'- naphthylene, 4,4'- tolans subunit, 4,4'- Stilbene subunit or 4,4 "-are bis- Styryl virtue ylidene derivatives.

Polymer as organic functional material preferably comprises the unit of the 7th class, preferably comprises and is typically used as skeleton Aromatic structure with 6 to 40 C atoms.

These especially include 4,5- dihydro pyrene derivatives, 4,5,9,10- tetrahydro pyrene derivatives, fluorene derivative, such as public It opens in US 5962631,2006/118345 A1 of WO 2006/052457 A2 and WO, 9,9- spirobifluorene derivatives, such as It is disclosed in 2003/020790 A1 of WO, 9,10- phenanthrene derivatives, e.g., as disclosed in 2005/104264 A1 of WO, 9,10- Dihydro phenanthrene derivative, e.g., as disclosed in 2005/014689 A2 of WO, 5,7- dihydro-dibenzo oxepin derivatives And cis and trans indeno fluorene derivative, e.g., as disclosed in 2004/113412 A2 of WO 2004/041901 A1 and WO In and binaphthalene pitch derivative, e.g., as disclosed in 2006/063852 A1 of WO, and, for example, be disclosed in WO 2005/ 056633 A1、EP 1344788 A1、WO 2007/043495 A1、WO 2005/033174 A1、WO 2003/099901 A1 With other units in DE 102006003710.

The structural unit of 7th class particularly preferably selected from the following: fluorene derivative, e.g., as disclosed in US 5,962, 631, in 2006/118345 A1 of 2006/052457 A2 of WO and WO, spirobifluorene derivative, e.g., as disclosed in WO 2003/ In 020790 A1, benzfluorene, dibenzo fluorenes, benzothiophene and dibenzo fluorene group and its derivative, e.g., as disclosed in WO 2005/056633 A1, EP 1344788 is in A1 and 2007/043495 A1 of WO.

Especially preferred 7th class formation element is indicated by general formula PB-1:

Wherein symbol and label have following meanings:

A, B and B' is also identical or differently respectively bivalent group for different repeat units, the group is preferably selected from- CR^cR^d-、-NR^c-、-PR^c-、-O-、-S-、-SO-、-SO₂,-CO- ,-CS- ,-CSe- ,-P (=O) R^c,-P (=S) R^cAnd- SiR^cR^d-；

R^cAnd R^dAt each occurrence independently selected from H, halogen ,-CN ,-NC ,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) NR⁰R⁰⁰,-C (=O) X ,-C (=O) R⁰,-NH₂,-NR⁰R⁰⁰,-SH ,-SR⁰,-SO₃H ,-SO₂R⁰,-OH ,-NO₂,-CF₃,-SF₅, appoint Silicyl, carbyl or the hydrocarbyl group with 1 to 40 carbon atom in generation are chosen, the group can be optionally substituted simultaneously And it can be optionally containing one or more hetero atoms, wherein the group R^cAnd R^dThe fluorene group shape being optionally bonded with them At tap bolt group；

X is halogen；

R⁰And R⁰⁰It is H or the carbyl or hydrocarbyl group with 1 to 40 carbon atom optionally replaced each independently, The group can optionally be substituted and can be optionally containing one or more hetero atoms；

G is independently that 0 or 1 and h is independently 0 or 1 in each case in each case, wherein in subunit The summation of g and h is preferably 1；

M is >=1 integer；

Ar¹And Ar²Indicate that monocycle or polycyclic aryl or heteroaryl group, the group can optionally be taken independently of one another Generation and it can optionally be bonded to 7,8 or 8,9 of indeno fluorene group；And

A and b is 0 or 1 independently of one another.

If the group R^cAnd R^dThe fluorene group being bonded with these groups forms tap bolt group, then the group preferably indicates Two fluorenes of spiral shell.

The particularly preferably repetitive unit of formula PB-1 is selected from the unit of formula PB-1A to PB-1E:

Wherein R^cWith above in connection with meaning described in formula PB-1, r is 0,1,2,3 or 4, and R^eWith with group R^c Identical meaning.

R^ePreferably-F ,-Cl ,-Br ,-I ,-CN ,-NO₂,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) NR⁰R⁰⁰,-C (= O) X ,-C (=O) R⁰,-NR⁰R⁰⁰, the silicyl with 4 to 40, preferably 6 to 20 C atoms that optionally replaces, aryl or Heteroaryl groups, or the straight chain with 1 to 20, preferably 1 to 12 C atom, branch or cricoid alkyl, alkoxy, alkyl Carbonyl, alkoxy carbonyl, alkyl carbonyl oxy or alkoxy carbonyloxy group group, wherein one or more hydrogen atoms can optionally by F or Cl replaces, and group R⁰、R⁰⁰Have with X above for meaning described in formula PB-1.

The particularly preferably repetitive unit of formula PB-1 is selected from the unit of formula PB-1F to PB-1I:

Wherein symbol has following meanings:

L is H, the alkyl or alkoxy base of halogen or the optionally fluorinated linear chain or branched chain with 1 to 12 C atom, It is preferred that representing H, F, methyl, isopropyl, tert-butyl, n-pentyloxy or trifluoromethyl；And

L' is the alkyl or alkoxy base of the optional fluorinated linear chain or branched chain with 1 to 12 C atom, is preferably represented N-octyl or n-octyloxy.

In order to implement the present invention, the preferably polymer of the structural element containing more than one above-mentioned 1st to 7 class. Furthermore it is proposed that, the polymer preferably comprises more than one structural element from said one classification, that is, includes The mixture of structural element selected from a classification.

Particularly preferred especially following polymer, the polymer is in addition at least one structure with luminosity Except element (the 4th class), preferably at least a kind of phosphorescence groups, also containing at least one other class of the above-mentioned 1st to 3,5 or 6 Structural element, wherein these structural elements are preferably selected from the 1st to 3 class.

If there is in polymer, then the ratio of the group of multiple classifications can in a wide range, and wherein these are It is well known by persons skilled in the art.If a kind of ratio of classification is rubbed preferably in each case >=5 present in polymer You are %, and mole %, then may be implemented astonishing advantage particularly preferably in each case >=10, wherein a kind of classification It is selected from the structural element of above-mentioned 1st to 7 class in each case.

The preparation of the copolymer to emit white light is especially described in detail in 10343606 A1 of DE.

In order to improve dissolubility, the polymer can contain corresponding group.It is preferred that can propose, the polymer Containing substituent group, so that there are an average of at least 2 non-aromatic carbon atoms for each repetitive unit, particularly preferably at least four is non- Aromatic carbon atom, especially preferably at least eight non-aromatic carbon atom, wherein average value is that index is equal.Single carbon atom can herein It is replaced by such as O or S.However, special ratios, optionally all repetitive units, which can not include, contains non-aromatic carbon atom Substituent group.It is preferably short chain substituent herein, because of the layer that long chain substituents may obtain usable organic functional material It has adverse effect.Substituent group preferably in straight chain contain at most 12 carbon atoms, preferably up to 8 carbon atoms, particularly preferably At most 6 carbon atoms.

The polymer as organic functional material can be random, alternating or regional rule copolymer according to the present invention, embedding The combination of section copolymer or these copolymer forms.

In another embodiment, the polymer as organic functional material can be the non-conjugated polymeric with side chain Object, wherein the embodiment is especially important for the phosphorescent OLED based on polymer.In general, phosphorescent polymer can be with By the free-radical polymerized acquisition of vinyl compound, wherein these vinyl compounds contain at least one and send out with phosphorescence The unit of body of light and/or at least one charge passing unit, as disclosed in especially in 7250226 B2 of US.Other phosphorus Photopolymer is especially described in 20,07/,211,243 20,07/,197,574 7250226 B2 and JP 2007/ of A2, US of A2, JP of JP In 059939 A.

In another preferred embodiment, non-conjugated polymeric object contains skeleton unit, is connected each other by spacer units It connects.The example of this triplet emitters based on non-conjugated polymeric object is e.g., as disclosed in DE 102009023154, wherein institute It states non-conjugated polymeric object and is based on skeleton unit.

In another preferred embodiment, non-conjugated polymeric object can be designed as fluorescent illuminant.Based on side chain Non-conjugated polymeric object the preferred fluorescent illuminant derivative containing anthracene or benzo anthryl group or these groups in the side chain, In these polymer be disclosed in such as JP 2005/108556, JP 2005/285661 and JP 2003/338375.

These polymer usually may be used as electron-transport or hole mobile material, and wherein these polymer are preferably designed for Non-conjugated polymeric object.

In addition, it is used as the functional compounds of organic functional material in the preparation, it is excellent in the case where polymer compound Choosing has >=10,000g/mol, particularly preferably >=20,000g/mol, especially preferably >=50,000g/mol molecular weight M_w。

The molecular weight M of polymer herein_wIt is preferred that 10,000g/mol to 2 is especially excellent in the range of 000,000g/mol 20,000g/mol to 1 is selected in, in the range of 000,000g/mol, very particularly preferably in 50,000g/mol to 300,000g/ In the range of mol.Molecular weight is determined by the GPC (=gel permeation chromatography) relative to inner polystyrene reference substance M_w。

The publication above quoted for representation function compound, is herein incorporated by reference for disclosure purposes In the application.

Preparation according to the present invention may include all organic functions necessary to produce the corresponding function layer of electronic device Material.For example, if hole transport, hole injection, electron-transport or electron injecting layer are exactly from a kind of functional compounds structure It builds, then the preparation just includes this compound as organic functional material.If luminescent layer including, for example, illuminator with The composition of matrix or material of main part, then the preparation just includes that illuminator has with the conduct of the mixture of matrix or material of main part Machine functional material, as elsewhere in this application in greater detail.

Other than the component, preparation according to the present invention may include other additives and processing aid.These are especially Addition including surface reactive material (surfactant), lubricant and grease, the additive of change viscosity, increase conductivity Agent, dispersing agent, hydrophobing agent, adhesion promotor, flow improving agent, defoaming agent, degasser, reactivity or non-reacted dilution Agent, filler, auxiliary agent, processing aid, dyestuff, pigment, stabilizer, sensitizer, nano particle and inhibitor.

The invention further relates to the methods for being used to prepare preparation according to the present invention, wherein will at least the first organic solvent 1,1- At least one organic functional material mixing of diphenylethlene derivative and the functional layer that can be used for producing electronic device.

Preparation according to the present invention can be used for producing layer or multilayered structure, and wherein organic functional material is such as used to produce excellent The electronics or photoelectric subassembly of choosing are present in layer as needed for OLED.

Preparation of the invention can be preferably used for forming functional layer in substrate or on one of layer for being applied to substrate. Substrate can be with or without bank structure.

The invention further relates to a kind of methods for producing electronic device, wherein preparation according to the present invention is applied to base It is on bottom and dry.

Such as applied by overflowing, dip-coating, spraying, spin coating, silk screen printing, relief printing plate printing, intaglio plate printing, rotating print, roller coating, Flexographic plate printing, hectograph printing or nozzle print, preferably inkjet printing, can be in the upper preparation of one of substrate or the layer for being applied to substrate The functional layer.

After the functional layer that preparation according to the present invention is applied to substrate or has been applied, step can be dried To remove solvent from above-mentioned continuous phase.Drying preferably can be carried out and be carried out the relatively long time at relatively low temperatures, To avoid bubble formation and obtain even spread.Drying is more preferable 150 DEG C to 250 DEG C, optimal preferably at 80 DEG C to 300 DEG C It is carried out at a temperature of selecting 160 DEG C to 200 DEG C.It dries herein preferably 10^-6Millibar within the scope of 2 bars, more preferably 10^-2 Millibar within the scope of 1 bar, most preferably 10^-1It is carried out under millibar to the pressure within the scope of 100 millibars.In the drying process, base The temperature at bottom can change between -15 DEG C to 250 DEG C.The dry duration depends on degree of drying to be achieved, wherein It can optionally be combined at relatively high temperature with sintering and remove a small amount of water, wherein it is preferred that be sintered.

Furthermore it is proposed that, which is repeated as many times, wherein forming similar and different functional layer.It can send out herein The raw crosslinking for being formed by functional layer is to prevent its dissolution, as disclosed in such as 0 637 899 A1 of EP.

The invention further relates to one kind can pass through the method electronic device obtained for producing electronic device.

The invention further relates to a kind of electronic device, it includes at least one organic functions that the electronic device, which has at least one, The functional layer of material, the electronic device can be obtained by the above-mentioned method for producing electronic device.

Electronic device refers to the device including anode, cathode and at least one functional layer between them, wherein the function Layer includes at least one organic compound or organo-metallic compound.

The organic electronic device is preferably organic electroluminescence device (OLED), polymer electroluminescent device (PLED), organic integrated circuits (O-IC), organic field effect tube (O-FET), Organic Thin Film Transistors (O-TFT), organic It is lighting transistor (O-LET), organic solar batteries (O-SC), organic photovoltaic (OPV) battery, organic optical detector, organic Photoreceptor, organic field quenching device (O-FQD), two pole of organic electric transducer, light-emitting electrochemical cell (LEC) or organic laser It manages (O-laser), more preferable organic electroluminescence device (OLED) or polymer electroluminescent device (PLED).

Active component is usually the organic or inorganic material introduced between the anode and the cathode, and wherein these active components are real Property that is existing, maintaining and/or improve electronic device, such as its performance and/or its service life, active component be, for example, charge injection, Charge transmission or charge blocking material, but especially luminescent material and host material.Therefore it can be used for producing the function of electronic device The organic functional material of ergosphere preferably comprises the active component of electronic device.

Organic electroluminescence device is a preferred embodiment of the present invention.The organic electroluminescence device includes yin Pole, anode and at least one luminescent layer.

It is also preferable that using the mixture of two or more triplet emitters and matrix.With luminous compared with shortwave The triplet emitters of spectrum are used as the co-substrate with the triplet emitters compared with long wave luminescent spectrum herein.

The ratio of host material in luminescent layer in the case is preferably 50 volume % to 99.9 for fluorescent light-emitting layer Volume %, more preferably 80 volume % are to 99.5 volume %, most preferably 92 volume % to 99.5 volume %, and for phosphorescence Luminescent layer is 85 volume % to 97 volume %.

Correspondingly, the ratio of dopant is preferably 0.1 volume % to 50 volume % for fluorescent light-emitting layer, more preferably 0.5 volume % to 20 volume %, most preferably 0.5 volume % to 8 volume %, and for phosphorescence luminescent layer be 3 volume % extremely 15 volume %.

The luminescent layer of organic electroluminescence device can also cover following system, and the system includes that a variety of host materials are (mixed Close matrix system) and/or a variety of dopants.Equally, in this case, the dopant be usually in system ratio it is lesser Material and the host material are the materials of large percentage in system.However, on rare occasion, individual matrix material in system The ratio of material is likely less than the ratio of respective dopant agent.

Mixed-matrix system preferably comprises two or three of different host material, more preferably two different matrix materials Material.It is with electron-transporting that one of two kinds of materials, which are preferably the material with hole transporting property and another material, herein The material of matter.However, the required electron-transport and hole transporting property of mixed-matrix component can also be combined mainly or entirely In single mixed-matrix component, wherein another or a variety of mixed-matrix components meet other functions.Described two differences Host material herein can be with 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, most preferably 1:4 is extremely The ratio of 1:1 exists.Mixed-matrix system is preferred in phosphorescent organic electroluminescent device.About its of mixed-matrix system Its details is found in such as WO 2010/108579.

In addition to these layers, organic electroluminescence device may also include other layer, such as one in each case Or multiple hole injection layers, hole transmission layer, hole blocking layer, electron transfer layer, electron injecting layer, exciton barrier-layer, electronics Barrier layer, charge generation layer (IDMC 2003, Taiwan；Session 21OLED(5),T.Matsumoto,T.Nakada, J.Endo,K.Mori,N.Kawamura,A.Yokoi,J.Kido,Multiphoton Organic EL Device Having Charge Generation Layer (the multi-photon OLED device with charge generation layer)) and/or organic or inorganic p/n Knot.One or more hole transmission layers can be for example with metal oxide such as MoO herein₃Or WO₃Or with (complete) fluorinated short of electricity Sub- aromatic compounds carries out p-type doping, and/or one or more electron transfer layers can be by n-type doping.It equally can will be in electroluminescent hair Have the function of that such as exciton blocking and/or the middle layer of control charge balance introduce between two luminescent layers in optical device.However, It is noted that each of these layers not there must be.These layers equally can be using as defined above according to this hair Exist when bright preparation.

In yet another embodiment of the present invention, the device includes multiple layers.Preparation according to the present invention herein may be used It is preferred for producing hole transport, hole injection, electron-transport, electron injection and/or luminescent layer.

Therefore, the invention further relates to a kind of electronic device, the electronic device includes at least three layers, but preferably at one In embodiment, the electronic device includes from hole injection, hole transport, shines, electron-transport, electron injection, charge Whole layers in blocking and/or charge generation layer, and wherein at least one layer by make according to the present invention Preparation obtains.The thickness of the layer such as hole transport and/or hole injection layer can be preferably in the model of 1nm to 500nm In enclosing, more preferably in the range of 2nm to 200nm.

In addition, the device may include the layer being made of other low molecular weight compounds or polymer, the layer is not yet logical It crosses using preparation according to the present invention and applies.These can also be by evaporating low molecular weight compound next life in high vacuum It produces.

In addition, preferably use such compound, do not used with pure material, with any required type Mixture (blend) the form use of other polymer, oligomer, dendritic macromole or low molecular weight substance.These can example Such as improve electronic property or their own shines.

In a preferred embodiment of the present invention, preparation according to the present invention includes organic functional material, is used as Material of main part or host material in luminescent layer.Other than material of main part or host material, preparation also may include above-mentioned herein Illuminator.Organic electroluminescence device may include one or more luminescent layers herein.If there is multiple luminescent layers, then these are sent out Photosphere preferably has multiple luminescence peaks between 380nm and 750nm, causes generally white luminous, that is, can fluoresce Or phosphorescent a variety of luminophors are in the luminescent layer.Very particularly preferably be Three-tider architecture, wherein described three A layer is displayed in blue, green and orange or red shine (for basic structure, see, for example, WO 2005/011013).It emits white light Device be suitable as the backlight of such as LCD display or for general illumination application.

In addition, multiple OLED can be arranged with being stacked on one another, so that the efficiency about light output to be achieved further increases.

In order to improve the coupling output of light, the final organic layer in light emission side in OLED is for example also possible to nanometer foam Form, cause total reflection ratio reduce.

It is also preferable that following organic electroluminescence device, wherein one or more layers are applied by sublimation method, Wherein by being lower than 10 in vacuum sublimation unit^-5Millibar, preferably shorter than 10^-6Millibar, more preferably less than 10^-7The pressure of millibar Vapor deposition under power applies the material.

Furthermore it is proposed that, one or more layers of electronic device according to the present invention are by OVPD (organic vapors Deposition) technique or applied by means of carrier gas distillation, wherein 10^-5Apply the material under millibar to 1 bar of pressure.

Furthermore it is proposed that, for example by spin coating from solution, or by means of any desired Method of printing such as silk Net printing, flexographic plate printing or hectograph printing, but particularly preferably LITI (light-initiated thermal imaging, thermal transfer) or inkjet printing, To generate one or more layers of electronic device according to the present invention.

These layers can also by wherein do not use formula (I), (II), (IIa), (III) or (IIIa) compound method To apply.Herein can be it is preferable to use orthogonal solvents, the orthogonal solvents are although dissolve the functional material of layer to be applied, no Dissolution applies the layer of the functional material to it.

The device generally comprises cathode and anode (electrode).For purposes of the present invention, the electrode (cathode, anode) It is selected in the following manner, so that their energy band energy and the energy band energy of adjacent organic are corresponding as closely as possible, To ensure efficient electronics or hole injection.

The cathode preferably comprises metal complex, the metal with low work function, metal alloy or multilayered structure, described Metal alloy or multilayered structure include various metals for example alkaline-earth metal, alkali metal, main group metal or lanthanide series (such as Ca, Ba, Mg, Al, In, Mg, Yb, Sm etc.).In the case of the multi-layer structure, in addition to the metal, it is possible to use have relatively high Other metals of work function such as Ag and Ag nano wire (Ag NW), in this case, usually using the combination of metal, such as Ca/Ag or Ba/Ag.The thin of the material with high dielectric constant can also be introduced preferably between metallic cathode and organic semiconductor Middle layer.Be suitable for this purpose is, for example, alkali metal fluoride or alkali earth metal fluoride, is also possible to aoxidize accordingly Object (such as LiF, Li₂O、BaF₂, MgO, NaF etc.).The thickness degree of this layer is preferably between 0.1nm and 10nm, more preferably Between 0.2nm and 8nm, most preferably between 0.5nm and 5nm.

The anode preferably comprises the material with high work function.The anode preferably has to be greater than relative to vacuum The current potential of 4.5eV.It on the one hand, suitable for this purpose is that there is the metal of high redox potential, such as Ag, Pt or Au.Separately It on the one hand, can also preferably metal/metal oxide electrode (such as Al/Ni/NiO_x、Al/PtO_x).For some applications, electrode At least one of must be it is transparent, in favor of organic material (O-SC) irradiation or light coupling output (OLED/PLED, O-laser).Preferred structure uses transparent anode.Preferred anode material is electric conductivity mixed-metal oxides herein.Especially Preferably tin indium oxide (ITO) or indium zinc oxide (IZO).It is also preferable that electric conductivity adulterates organic material, especially lead Electrical doped polymer, such as the derivative of poly- (ethylene dioxythiophene) (PEDOT) and polyaniline (PANI) or these polymer Object.It is also preferable that the hole mobile material of p-type doping is applied to anode as hole injection layer, wherein suitable p-type is mixed Miscellaneous dose is metal oxide, such as MoO₃Or WO₃, or (complete) fluorinated electron deficient aromatic compounds.Other suitable p-type dopings Agent is HAT-CN (six cyano, six azepine terphenyl fork) or the compound N PD9 from Novaled.Such layer simplifies Hole injection in the material with low HOMO, i.e. big HOMO value.

In general, may be used in other layers for all material in layer according to prior art, and ability Field technique personnel will without creative efforts in electronic device by these materials each with Material according to the invention combines.

Depending on application, the device is by correspondingly structuring, setting contact and last quilt in a way known It is tightly sealed, because the service life of the device sharply shortens in the presence of water and/or air.

Preparation according to the present invention and the electronic device, particularly organic electroluminescence device that can be obtained by preparation, are compared Astonishing one or more of advantage below is distinguished by the prior art:

1. the electronic device that preparation according to the present invention can be used to obtain is compared to the electronics device for using conventional method to obtain Part shows very high stability and very long service life.

2. conventional method processing can be used in preparation according to the present invention, to also therefore can be realized cost advantage.

3. the organic functional material used in preparation according to the present invention is not by any specific limitation, so that of the invention Method can be used comprehensively.

4. the coating that preparation of the invention can be used to obtain shows excellent quality, especially in the homogeneity side of coating Face situation is such.

These above-mentioned advantages are not along with the damage of other electronic properties.

It should be pointed out that the variant of embodiment described in the present invention is fallen within the scope of the present invention.Unless expressly excluded, Otherwise each feature disclosed in the present invention can be provided identical, equivalent or similar purpose alternative features replacement.Therefore, it removes Non- to be otherwise noted, otherwise each feature disclosed in the present invention is considered as that the example of universal serial is either equivalent or similar Feature.

All features of the invention can be combined with each other in any way, unless certain features and/or step are mutually to arrange Reprimand.This is particularly suitable for preferred feature of the invention.Equally, the feature of optional combination can be used alone (rather than group It closes and uses).

It should also be noted that many features, especially those of the preferred embodiment of the present invention feature, be to have wound in itself The property made, a part without being regarded as merely embodiments of the present invention.For these features, except presently claimed Except each invention or as the presently claimed substitution respectively invented, independent protection can be sought.

Introduction about technical movements disclosed by the invention can be carried out refining and combining with other embodiments.

The present invention is explained in greater detail below with reference to embodiment, but is not limited except as.

Those skilled in the art, which will enable with the specification, produces other electronic devices according to the present invention, without It makes the creative labor, therefore the present invention can be implemented in entire scope claimed.

Embodiment

Example given below is prepared using device architecture shown in Fig. 1.The hole injection layer of all embodiments (HIL) and hole transmission layer (HTL) is prepared by InkJet printing processes, to obtain desired thickness.It is real for luminescent layer Each solvent used in example 1 and 2 is applied to be listed in the table below in 2:

Table 2: solvent list used in Examples 1 and 2

Using 40mm parallel-plate geometry and using TA instrument ARG2 rheometer in 10s-1 to 1000s^-1Shear rate The viscosity of measurement preparation and solvent in range.In 200s^-1To 800s^-1Between measurement is averaged, in 200s^-1To 800s^-1It Between temperature and shear rate accurately control.The viscosity provided in table 3 is temperature and 500s of the every kind of preparation at 25 DEG C^-1's The viscosity measured under shear rate.Every kind of solvent measurement is three times.Shown viscosity number is averaged to the measured value.

Preferably, the surface tension of the mixture of the organic solvent can be in the range of 15mN/m to 80mN/m, more It is preferred that in the range of 20mN/m to 60mN/m, most preferably in the range of 25mN/m to 40mN/m.Surface tension can be used FTA (First Ten Angstrom) 1000 contact angle angular instruments measure at 20 DEG C.The details of this method can be from First Ten Angstrom is obtained, " using drop shape method surface tension " as published by Roger doctor P.Woodward.Preferably, hanging drop Method can be used for determining surface tension.At room temperature progress of all measurements within the scope of 20 DEG C to 25 DEG C.For every kind of preparation, survey Measure three drops.The measurement is averaged to obtain end value.For the plurality of liquid with known surface tension to the work Tool is periodically mutually verified.

Embodiment 1 is made by using identical framework, wherein inkjet printing HIL and HTL is to realize identical thickness. Solvent used in EML is different, and details are listed in Table 3 below.

Table 3: the details of preparation used in embodiment 1

The description of manufacturing process

The substrate of glass that will be covered with preparatory structuring ITO and bank material uses ultrasonic cleaning in isopropanol, then uses Deionized water cleaning, it is then dry with air gun, then anneal 2 hours in 230 DEG C of heating plate.

Hole injection layer (HIL) inkjet printing of PEDOT-PSS (Clevios Al4083, Heraeus) will be used to base On bottom and it is dried in vacuo.Then HIL is annealed 30 minutes at 185 DEG C in air.

On HIL, inkjet printing hole transmission layer (HTL) is dried in vacuo and anneals at 210 DEG C in nitrogen atmosphere 30 minutes.As the material of hole transmission layer, polymer HTM-1 is used.The structure of polymer HTM-1 is as follows:

Also it inkjet printing green light emitting layer (G-EML) inkjet printing, vacuum drying and anneals at 160 DEG C in nitrogen atmosphere 10 minutes.In all embodiments for the ink of green light emitting layer containing there are two types of material of main part (i.e. HM-1 and HM-2) and one Kind triplet emitters (EM-1).The material: HM-1:HM-2:EM-1=40:40:20 is used according to following ratio.Such as from table 3 it can be seen, only solvent is different between embodiment and embodiment.The structure of these materials is as follows:

All ink jet printing processes are completed under yellow light and environmental condition.

Then device is transferred in vacuum deposition chamber, wherein completing hole blocking layer (HBL) using thermal evaporation, electronics passes The deposition of defeated layer (ETL) and cathode (Al).Then device is characterized in glove box.

As the hole barrier materials of hole blocking layer, ETM-1 is used.The material has a structure that

In electron transfer layer (ETL), the 50:50 mixture of ETM-1 and LiQ is used.LiQ is 8-hydroxyquinoline lithium.

In order to measure the OLED performance in terms of current density-luminous density (luminance)-voltage performance, by by The scanning voltage for-the 5V to 25V that Keithley 2400 source measuring unit provides drives the device.Pass through Keithley 2400SMU records the voltage in OLED device and the electric current by OLED device.With the photodiode detector part of calibration Brightness (brightness).Photoelectric current is measured with Keithley 6485/E pico-ampere table.For spectrum, luminance sensor It is connected to the glass fibre replacement of Ocean Optics USB2000+ spectrometer.

Results and discussion

Embodiment 1

Utilize the OLED device for using 1,1- diphenylethlene to prepare as the printable layer of the solvent of luminescent layer inkjet printing. The structure of pixelation OLED device is glass/ITO/HIL (40nm)/HTM (20nm)/EML (60nm)/HBL (10nm)/ETL (40nm)/Al, wherein making bank in advance in substrate to form pixelation device.In this case, green luminescent material with 14mg/ml concentration is dissolved in 1,1- diphenylethlene.

In 1000cd/m²Under luminous efficiency be 39.25cd/A.The efficiency of the OLED device is very good, in 1000cd/m² Under voltage be 7.05V.

Such as Fig. 2 as can be seen that gained film shows fabulous homogeneous film formation property.

Comparative example 1

Utilize the OLED device for using 3- phenoxy group-toluene to prepare as the printable layer of the solvent of luminescent layer inkjet printing. The structure of pixelation OLED device is glass/ITO/HIL (40nm)/HTM (20nm)/EML (60nm)/HBL (10nm)/ETL (40nm)/Al, wherein making bank in advance in substrate to form pixelation device.In this case, green luminescent material with 14mg/ml concentration is dissolved in 1,1- diphenylethlene.

In 1000cd/m²Under luminous efficiency be 47.51cd/A.The efficiency of the OLED device is very good, but in 1000cd/ m²Under voltage be 9.79V.

Such as Fig. 3 as can be seen that with 1,1- diphenylethlene is compared, and gained film shows poor film-forming quality.

Claims

1. a kind of preparation, the preparation contains at least one organic functional material and 1, the 1- diphenylethlene as the first solvent Derivative.

2. preparation according to claim 1, wherein first organic solvent is according to 1, the 1- diphenyl second for leading to formula (I) Ene derivative

Wherein

R¹And R²It is identical or different at each occurrence, and be F, Cl, Br, I, NO₂, CN is straight with 1 to 20 carbon atom The alkyl or alkoxy base of chain or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, wherein one A or multiple non-adjacent CH₂Group can be by-O- ,-S- ,-NR⁵-、-CONR⁵,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replacement, and wherein one or more hydrogen atoms can be replaced by F, or have 4 to 14 carbon atoms and can be by one or more A non-aromatic R⁵The aryl or heteroaryl group that group replaces, and multiple substitutions on same ring or on two different rings Base R⁵Can be formed together again can be by multiple substituent Rs⁵Substituted monocycle or polycyclic aliphatic series, aromatics or heteroaromatic ring system；

R³And R⁴It is identical or different at each occurrence, and be H, F, Cl, Br, I, NO₂, CN, with 1 to 20 carbon atom The alkyl or alkoxy base of straight chain or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, wherein One or more non-adjacent CH₂Group can be by-O- ,-S- ,-NR⁵-、-CONR⁵,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replacement, and wherein one or more hydrogen atoms can be replaced by F, or have 4 to 14 carbon atoms and can by one or Multiple non-aromatic R⁵The aryl or heteroaryl group that group replaces, and multiple on same ring or on two different rings take For base R⁵Can be formed together again can be by multiple substituent Rs⁵Substituted monocycle or polycyclic aliphatic series, aromatics or heteroaromatic ring system；

R⁵It is identical or different in each case, and be with 1 to 20 carbon atom straight chain alkyl or alkoxy base or Branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, wherein one or more non-adjacent CH₂Group It can be replaced by-O- ,-S- ,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C-, and wherein one or more hydrogen atoms can be by F Replacement, or there are 4 to 14 carbon atoms and can be by one or more non-aromatic R³The aryl or heteroaryl group that group replaces, And

3. preparation according to claim 2, wherein first organic solvent is according to 1, the 1- diphenyl second for leading to formula (I) Ene derivative, wherein

R¹And R²It is identical or different at each occurrence, and be the alkyl or alkoxy base of the straight chain with 1 to 20 carbon atom Group or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, wherein one or more non-adjacent CH₂ Group can be by-O- ,-S- ,-NR⁵-、-CONR⁵,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replacement；

R³And R⁴It is identical or different at each occurrence, and be H, the alkyl or alkoxy of the straight chain with 1 to 20 carbon atom Group or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, wherein one or more are non-adjacent CH₂Group can be by-O- ,-S- ,-NR⁵-、-CONR⁵,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replacement；

R⁵It is identical or different in each case, and be with 1 to 20 carbon atom straight chain alkyl or alkoxy base or Branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, wherein one or more non-adjacent CH₂Group It can be replaced by-O- ,-S- ,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C-；And

M and n is 0 or 1, preferably 0 identical or differently at each occurrence.

4. preparation according to claim 2 or 3, wherein first organic solvent is according to 1, the 1- hexichol for leading to formula (I) Base ethene derivatives, wherein

R¹And R²It is identical or different at each occurrence, and be linear alkyl groups with 1 to 20 carbon atom or have 3 To the branch or cricoid alkyl group of 20 carbon atoms；

R³And R⁴It is H；And

M and n is 0 or 1, preferably 0 identical or differently at each occurrence.

5. according to one or more preparations in claim 2 to 4, wherein first organic solvent is according to general formula (II) 1,1- diphenylethlene

6. according to claim 1 to one or more preparations in 5, wherein the surface tension of first organic solvent ≥25mN/m。

7. according to claim 1 to one or more preparations in 6, wherein based on the total of the solvent in the preparation Amount, the content of first solvent is in the range of 50 volume % to 100 volume %.

8. according to claim 1 to one or more preparations in 7, wherein the boiling point of first solvent is at 100 DEG C To in the range of 400 DEG C.

9. according to claim 1 to one or more preparations in 8, wherein the preparation is different from comprising at least one Second solvent of first solvent.

10. according to claim 1 to one or more preparations in 9, wherein the boiling point of second solvent is at 100 DEG C To in the range of 400 DEG C.

11. according to claim 1 to one or more preparations in 10, wherein at least one organic functional material In first solvent and solubility in second solvent in the range of 1g/l to 250g/l.

12. according to claim 1 to one or more preparations in 11, wherein the surface tension of the preparation is in 1mN/ In the range of m to 70mN/m.

13. according to claim 1 to one or more preparations in 12, wherein the viscosity of the preparation 1mPa.s extremely In the range of 50mPa.s.

14. according to claim 1 to one or more preparations in 13, wherein the total weight based on the preparation, institute Content of at least one organic functional material in the preparation is stated in the range of 0.001 weight % to 20 weight %.

15. according to claim 1 to one or more preparations in 14, wherein at least one organic functional material Selected from organic conductor, organic semiconductor, organic fluorescent compounds, Phosphorescent compound, organic light-absorbing compound, You Jiguang Quick compound, organic photosensitive agent and other organic light-activated compounds, for example, transition metal, rare earth metal, lanthanide series and The metal-organic complex of actinides.

16. preparation according to claim 15, wherein at least one organic functional material is selected from fluorescent illuminant, phosphorus Light illuminator, material of main part, host material, exciton-blocking material, electron transport material, electron injection material, hole conductor material Material, hole-injecting material, n-type dopant, p-type dopant, wide bandgap material, electron-blocking materials and hole barrier materials.

17. preparation according to claim 15, wherein at least one organic functional material is selected from hole injection, sky Cave transmission shines, the organic semiconductor of electron-transport and electron injection material.

18. preparation according to claim 17, wherein at least one organic semiconductor is selected from hole injection, hole passes Defeated and luminescent material.

19. preparation according to claim 18, wherein hole injection and hole mobile material be polymerizable compound or The blend of person's polymerizable compound and non-polymeric compound.

20. a kind of be used to prepare according to claim 1 to the method for one or more preparations in 19, wherein will be described At least one organic functional material is mixed at least described first solvent.

21. a kind of method for being used to prepare electroluminescent device, wherein at least one layer of the electroluminescent device is with such as Under type preparation: by according to claim 1 in 19 one or more preparations depositions, be preferably printed upon surface On, and be subsequently dried.

22. a kind of electroluminescent device, wherein at least one layer is prepared as follows: will be according to claim 1 to 19 In one or more preparations depositions, preferably print on the surface, and be subsequently dried.