CN106715420A - Crosslinkable host materials - Google Patents

Crosslinkable host materials Download PDF

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Publication number
CN106715420A
CN106715420A CN201580051943.XA CN201580051943A CN106715420A CN 106715420 A CN106715420 A CN 106715420A CN 201580051943 A CN201580051943 A CN 201580051943A CN 106715420 A CN106715420 A CN 106715420A
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group
atoms
groups
substitution
benzo
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D·沃尔兹
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Samsung Display Co Ltd
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Signora Ltd By Share Ltd
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Priority to CN202211174439.7A priority Critical patent/CN115572284A/en
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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    • C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a crosslinkable organic molecule having a structure of the formula (1) and to the use thereof, wherein Ar is independently of one another, an unsaturated or aromatic carbo- or heterocyclic unit with 5 to 30 ring atoms, selected from the group consisting of naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, tetracene, pentacene, benzpyrene, furan, benzofuran, isobenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazol, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazine-imidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, isothiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzpyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,3,4- oxatriazole, 1,2,3,4-oxatriazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazin, purine, pteridine, indolizine, benzothiadiazole, indenocarbazole, indenofluorene, spirobifluorene, and indolocarbazole; D1 is a donor group having a structure of the formula (1a); and D2 is a donor group having a structure of the formula (1b).

Description

Cross-linking material of main part
Technical field
Make the present invention relates to the organic molecule of formula 1 and its in OLED (Organic Light Emitting Diode) and other light electric components For it is cross-linking, can liquid processing material of main part purposes.
Background technology
Organic electronic device is more and more frequently used in commercial product or will enter market circulation.Produced as existing business The example of product, refers to the organic or polymeric light-emitting diodes (OLED, PLED) in display device and display apparatus.It is organic too Positive electricity pond (O-SC), organic field effect tube (O-FET), OTFT (O-TFT), organic switching element (O- IC), organic optical amplifier or organic laser diode (O-Laser) enter the advanced studies stage and can be realized in future Huge meaning.The general structure of organic electroluminescent device is for example described in US 4539507 A, US 5151629 A, EP The 0676461 A and A of WO 98/27136.But there is Improvement requirement in such devices：
1. especially for blue emission or green emission, operation lifetime is still shorter, therefore at present commercially can only be real Existing simple application.
More 2. the compound for using is difficult to be dissolved in and common are machine solvent, purification during therefore, it is difficult to being synthesized, molten Material processing in liquid and the purification of device when preparing electronic equipment.
3. the material for being used according to prior art generally has low triplet energies.When with the material launched from triplet During combination, this causes transmitting to be quenched (extinguishing), and causes the efficiency to reduce.
Independently of each application purpose, many electronic equipments or optoelectronic device have and are adapted to the as follows of each application General Rotating fields：
(1) base material,
(2) electrode, the electrode is usually metal or inorganic, but can also be by organic or polymeric conductive material system Into when (3) need, for optional one or more electric charge injection layers or cushion of the unevenness of compensating electrode, its is usual Formed by the doped polymer of one or more conduction, (4) at least one organic semiconductor layers,
(5) when needing, optional one or more other charge transport layers or electric charge injection layer or electric charge barrier layer,
(6) to electrode, wherein the material referred in (2) is used, (7) encapsulation.
The present invention is related to especially but not exclusively Organic Light Emitting Diode (OLED=Organic Light Emitting Diode), polymeric light-emitting diodes (PLED=Polymer Light are generally also referred to as when using polymeric material Emitting Diode).Above-mentioned arrangement represents the general structure of optoelectronic device, wherein different layers can be assembled so that most The arrangement being made up of two electrodes (there is an organic layer between two electrodes) is formed in the case of simple.In this case, It is functional including luminous that organic semiconductor layer meets institute.Described based on poly- (to phenylene) for example in WO 9013148A1 This system.
The performance of OLED is not only determined by the emitter for using.Herein especially, the material that other are used, such as matrix material Material, hole barrier materials, electron transport material, hole mobile material and electron-blocking materials or exciton-blocking material also have weight Want meaning.Therefore the improvement of these materials can also cause significantly improving for OLED performances.For these materials, fluorescence OLED Improvement requirement is still present.In the prior art, especially using ketone (or phosphine oxide) as the matrix material for phosphorescent emitters Material.But as other host materials, Improvement requirement is still present when using these host materials, especially with regard to setting Standby efficiency and life-span.
The present invention provides a kind of compound, and the compound is suitable for fluorescence or phosphorescence or thermal activation delayed fluorescence (English Literary temperature activated delayed fluorescence) OLED (TADF-OLED), particularly phosphorescence or TADF-OLED, such as host material or as hole mobile material/electron-blocking materials or exciton-blocking material or conduct Electron transport material or hole barrier materials.
The content of the invention
The present invention relates to develop a kind of new crosslinking list as the basic structure in cross-linking organic semiconductor (formula 1a) First PG.This crosslink unit can be used in organic semiconductor, therefore organic semiconductor obtains crosslinking ability in itself.Therefore obtain The a large amount of novel organic semi-conductors collected in formula 1.Thus, the first aspect of the present invention is related to crosslink unit PG and its is having Purposes in the crosslinking of machine semiconductor.
Brief description of the drawings
Fig. 1：By introducing two by bridge (such as carbazole, phenoxazines, phenthazine and suitable cyclic heterocycle) conjugation Polymerizable groups, in principle for polymer chain provides two possible growth positions.
Fig. 2：Unsubstituted carbazole tends to degraded, wherein producing the polymer that 3,6- is connected.According to the present invention by introducing Substitution base avoids the situation.
Fig. 3：The symmetry that polymerizable unit PG reduces molecule is introduced by the side of the compound in specular, therefore Dissolubility is raised and the applicability to printing process and coating process is improved.Filming performance is also improved due to suppressing crystallization.
Specific embodiment
The present invention provides the organic molecule of formula 1,
Wherein
Ar=is independent of each other to have insatiable hunger and/or aromatic carbocyclic or the heterocyclic units of 5 to 30 annular atoms, selected from by naphthalene, Anthracene, phenanthrene, pyrene, dihydropyrene,Perylene, fluoranthene, benzanthracene, aphthacene, pentacene, BaP, furans, benzofuran, different benzo furan Mutter, thiophene, benzothiophene, isothiophene, dibenzothiophenes, pyrroles, indoles, iso-indoles, carbazole, pyridine, quinoline, isoquinoline Quinoline, acridine, phenanthridines, benzo -5,6- quinoline, benzo -6,7- quinoline, benzo -7,8- quinoline, phenthazine, phenoxazines, pyrazoles, Yin Azoles, imidazoles, benzimidazole, naphthalene imidazoles, luxuriant and rich with fragrance imidazoles, pyridine imidazoles, pyrazine imidazoles, quinoxaline imidazoles, oxazoles, benzoxazole, naphthalene Oxazole, En oxazole, Fei oxazole, isoxazoles, isothiazole, 1,3- thiazoles, benzothiazole, pyridazine, benzo pyridazine, pyrimidine, benzo are phonetic Pyridine, quinoxaline, pyrazine, azophenlyene, naphthyridines, azepine carbazole, benzo carboline, phenanthroline, 1,2,3- triazoles, 1,2,4- triazoles, benzene And triazole, 1,2,3- oxadiazoles, 1,2,4- oxadiazoles, 1,2,5- oxadiazoles, 1,3,4- oxadiazoles, 1,2,3- thiadiazoles, 1,2, 4- thiadiazoles, 1,2,5- thiadiazoles, 1,3,4- thiadiazoles, 1,3,5- triazines, 1,2,4- triazines, 1,2,3- triazines, tetrazolium, 1,2, 3,4- oxatriazoles, 1,2,3,4- oxatriazoles, 1,2,4,5- tetrazines, 1,2,3,4- tetrazines, 1,2,3,5- tetrazines, purine, pteridine, Yin Diindyl piperazine, diazosulfide, indeno carbazole, indenofluorene, spiro-bisfluorene and indolocarbazole composition group, its can each by one or Multiple group R1Substitution, two of which or multiple group R1 can be connected to each other and can form one or more rings；
D1=has the donor groups with electro transfer performance of the structure of formula 1a；
And
D2=has the donor groups with electro transfer performance of the structure of formula 1b；
And the symbol and index for being used meet：
N is the integer between 1 and 5；
O is the integer between 1 and 5；
P is the integer between 0 and 5；
PG is two identical or different polymerizable units, the polymerizable unit can by heat and/or acid catalysis or Base-catalyzed method, by the ultraviolet radiation under conditions of presence or absence of light trigger, or is gathered by microwave Close.In a preferred embodiment, it is functionalized on 3 of structure and 6.
X, Y represent covalent single bond or divalence organic bridge, described two independently of one another identical or differently when occurring every time Valency organic bridge be selected from by substitution and unsubstituted alkylidene (non-branching, branched or ring-type), alkenylene, alkynylene, arlydene and Heteroarylidene, O, NR3, C=CR3 2, C=NR3、SiR3 2S、S(O)、S(O)2、Se、Se(O)、Se(O)2、BR3、PR3、P(O)R3, with And the combination of these units is (such as by alkylidene (unbranched, branched or ring-type), alkenylene, alkynylene, the arlydene of O interruption And heteroarylidene) composition group；
Z is identical when occurring every time or differently represents CR2Or N；
R and R1It is identical or differently represent when occurring every time：
H, D, F, Cl, Br, I, B (OR3)2, CHO, C (=O) R3, CR3=C (R3)2, CN, C (=O) OR3, C (=O) N (R3)2, Si (R3)3, NO2, P (=O) (R3)2, OSO2R3, OR3, S (=O) R3, S (=O)2R3, or
With 1 to 20 alkyl of the straight chain of C atoms, alkoxy or alkylthio or branched with 3 to 20 C atoms Or the alkyl of ring-type, alkoxy or alkylthio or with 2 to 20 alkenyl or alkynyls of C atoms, wherein above-mentioned group is distinguished Can be by one or more groups R3Substitution, and one or more CH in wherein above-mentioned group2- group can be by-R3C= CR3-、-C≡C-、Si(R3)2, C=O, C=S, C=NR3,-C (=O) O- ,-C (=O) NR3-、NR3, P (=O) (R3)、-O-、- S-, SO or SO2Substitute, and one or more H atoms in wherein above-mentioned group can be by D, F, Cl, Br, I, CN or NO2Replace Generation, or
With 6 to 30 aromatic ring systems of aromatic ring atom, the aromatic ring system can respectively by one or more Group R3Substitution, or
With 6 to 30 aryloxy group of aromatic ring atom, the aryloxy group can be by one or more groups R3Substitution, its In two or more group R and R1Can be connected to each other and can form ring；
R2It is identical or differently represent when occurring every time：
H, D, F, Cl, Br, I, B (OR3)2, CHO, C (=O) R3, CR3=C (R3)2, CN, C (=O) OR3, C (=O) N (R3)2, Si (R3)3, N (R3)2, NO2, P (=O) (R3)2, OSO2R3, OR3, S (=O) R3, S (=O)2R3, or
With 1 to 20 alkyl of the straight chain of C atoms, alkoxy or alkylthio or branched with 3 to 20 C atoms Or the alkyl of ring-type, alkoxy or alkylthio or with 2 to 20 alkenyl or alkynyls of C atoms, wherein above-mentioned group is distinguished Can be by one or more groups R3Substitution, and one or more CH in wherein above-mentioned group2- group can be by-R3C= CR3-、-C≡C-、Si(R3)2, C=O, C=S, C=NR3,-C (=O) O- ,-C (=O) NR3-、NR3, P (=O) (R3)、-O-、- S-, SO or SO2Substitute, and one or more H atoms in wherein above-mentioned group can be by D, F, Cl, Br, I, CN or NO2Replace Generation, or
With 5 to 30 aromatics or heteroaromatic ring system of aromatic ring atom, the aromatics or heteroaromatic ring system can be with Respectively by one or more groups R3Substitution, or
With 5 to 60 aryloxy group or heteroaryloxy of aromatic ring atom, the aryloxy group or heteroaryloxy can be by one Individual or multiple group R3Substitution, two of which or multiple group R2Can be connected to each other and can form ring；
R3It is identical or differently represent when occurring every time：
H, D, F, Cl, Br, I, B (OR4)2, CHO, C (=O) R4, CR4=C (R4)2, CN, C (=O) OR4, C (=O) N (R4)2, Si (R4)3, N (R4)2, NO2, P (=O) (R4)2, OSO2R4, OR4, S (=O) R4, S (=O)2R4, or
With 1 to 20 alkyl of the straight chain of C atoms, alkoxy or alkylthio or branched with 3 to 20 C atoms Or the alkyl of ring-type, alkoxy or alkylthio or with 2 to 20 alkenyl or alkynyls of C atoms, wherein above-mentioned group is distinguished Can be by one or more groups R4Substitution, and one or more CH in wherein above-mentioned group2- group can be by-R4C= CR4-、-C≡C-、Si(R4)2, C=O, C=S, C=Se, C=NR4,-C (=O) O- ,-C (=O) NR4-、NR4, P (=O) (R4) ,-O- ,-S-, SO or SO2Substitute, and one or more H atoms in wherein above-mentioned group can by D, F, Cl, Br, I, CN or NO2Substitute, or
With 5 to 60 aromatics or heteroaromatic ring system of aromatic ring atom, the aromatics or heteroaromatic ring system can be with Respectively by one or more groups R4Substitution, or
With 5 to 60 aryloxy group or heteroaryloxy of aromatic ring atom, the aryloxy group or heteroaryloxy can be by one Individual or multiple group R4Substitution, two of which or multiple group R3Can be connected to each other and can form ring；
R4It is identical or differently represent H, D, F or aliphatic series, aromatics or miscellaneous with 1 to 20 C atom when occurring every time Aromatic organic radicals, wherein one or more H atoms can also be substituted by D or F；Two of which or multiple substituent Rs4Can be with that This connects and forms ring；
And wherein it is attached with Ar in singly-bound form on the position represented with # respectively.
In one embodiment, polymerizable groups PG is independently selected from following compound
Wherein wave represents the link position on the matrix of D1.
In one embodiment, the group Ar of organic molecule has following structure
Wherein W is identical when occurring every time or differently represents CR1Or N (as defined above), and especially at least one W It is not CR1。
In another embodiment, compound of the invention is PYD2 type compounds,
For example
PYD2 types
In another preferred embodiment, compound of the invention is mCPy type compounds, for example
MCPy types
In another preferred embodiment, compound of the invention is DIHAPY type compounds, for example
DIHAPY types
Additionally, the compound being shown below equally is the preferred embodiment of the compound of formula 1
Have been surprisingly found that the obvious advantage compared to prior art.Needed using the known crosslinking concept of oxetanes Want additional agents and be unfavorable for component's life.When two (4- ethenyl aromatic yls) amine is crosslinked using ultraviolet radiation, this hand The high temperature of Duan Suoxu and reaction time long are unfavorable.The crosslinking of the compound of divinyl substitution is it is known that, wherein by second Alkenyl is placed on different carbazole groups.But do not have to find positive interaction between polymerizable groups.
At present surprisingly it has been found that introducing crosslinkable groups by conjugation spacer group (according to the matrix of formula 1a) Generate unexpected advantage：By introducing two polymerizable groups, these polymerizable groups pass through bridge construction (such as click Azoles , phenoxazines, phenthazine and suitable cyclic heterocycle) conjugation is formed, for polymer chain provides two possible growth positions.From By base by complete separating group delocalization, you can carry out chain growth with two molecular positions.Can be in the following way The possible synthesis of N- aryl-divinyl carbazole is carried out, is reacted by Kumada and vinyl is formed by corresponding dibromide (Tetrahedron.54 (1998), 12707-12714).By combining crosslinkable units and feature point in single functional group Son, the synthesis cost for preparing material reaches minimum, because need to only introduce two in functional material instead of multiple groups Bromine carbazole group (referring to embodiment 3).Dibromo carbazole group easily and can be selected by means of the coupled reaction of palladium chtalyst Property ground be transformed into desired divinyl carbazole group.Other synthesis for example in order to adjust electrical property and/or solubility are adjusted Then substantially can more simply carry out.Being capable of easily activated material, therefore phase by the electronics coupled between two vinyl System than replacing in the divinyl of the decoupled conjunction of electronics can be crosslinked under the ultraviolet dosage of lower temperature or lower, this It is substantially more economical for functional material.
Its advantage for causing is：Generally prevent organic, amorphous thin film crosslinking.The process is subject to diffusion to control, Because speed depend primarily on activatable free radical after solid is diffused through can it is more than enough promptly run into can attack monomer.By In the free radical for generating the flank offense that from two spaces can separate, another being crosslinked in the unit interval is walked substantially Rapid possibility is doubled.Therefore, it is possible to realize reaction conversion ratio and shorter crosslinking time higher.
Further, since increased delocalization, the activation barrier of addition is reduced, therefore is more quickly carried out in time.
The 3rd optional advantage is realized when carbazole (Y=singly-bounds) is optionally employed：When using carbazole group, the structure The known degradation mechanism of unit is oligomeric/new keys connection (Fig. 2).The performance of component changes, its energy water due to the process Put down change and mid-term causes component damage.By making the reactive position saturation of hole transporting unit (such as by tertiary fourth Base), described problem can be avoided.But it is producing the disadvantage is that, on the one hand making parameter (such as charge carrier mobility) negative Change, is likely to result in morphological problems, is particularly separated, i.e. such as material of main part and/or the emitter molecule for wherein including Crystallization.On the other hand the blocking group described in the long period of operation of component is also possible to separate, and causes above mentioned problem.In the present invention An embodiment in, unstable tertiary alkyl is substituted by the secondary alkyl of stabilization.
Molecule of the invention has the donor groups D2 with planar structure of formula 1b, therefore charge carrier mobility Significantly improved compared to the molecule with unbridged arylamine.Unbridged arylamine exists compared to donor monomer of the invention It is substantially more unstable in OLED, because not connected aryl can be separated relatively simply.Additionally, unbridged arylamine is triple State energy is considerably higher.Due to unmatched triplet energies, the compound is not suitable as thermal activation delayed fluorescence (TADF) material of main part of transmitter and phosphorescent emitter, is particularly not suitable for especially important blueness from the point of view of industrial point of view.
Additionally, optionally using polymerizable groups PG in the symmetrical compound of minute surface.By respectively in a carbazyl list Introduce the symmetry (Fig. 3) that two crosslinkable units PG reduce molecule in unit, thus dissolubility raise and to printing process and The applicability of coating process is improved.Filming performance is also improved due to suppressing crystallization.
In one embodiment, in compound of the invention two polymerizable groups PG conjugation and spatially It is closer to each other.Need the presence of at least two PG in order to be crosslinked, in molecule.It is preferred that precisely the presence of two polymerizable units, because It is that from the point of view of statistics, with the increase of the number of the polymerizable groups PG in molecule, the uncrosslinked unit of radical form exists The possibility being retained in after polymerization in polymer film increases.The free radical serves as so-called electric charge carrier in light electric components Trap and make its degradation in efficiency.
In a preferred embodiment in accordance with this invention, using carbazole as donor groups.Known unsubstituted carbazole The shortcoming of unit is low HOMO energy.HOMO energy is according to being substituted by -6.0 to -5.6eV.Therefore, it is difficult to adapt to generally make Generally hole injection layer (such as PEDOT of the HOMO energy with -5.1eV:PSS).In order in realizing OLED components Low connection voltage, it is advantageous that the energy difference between carbazole derivates and the HOMO of hole injection layer is as small as possible.Due to substitution Base causes that HOMO energy raises 50 to 200meV, therefore the energy difference is smaller relative to unsubstituted carbazole derivates.
One aspect of the present invention changes photoelectric properties in known organic semiconductor using crosslink unit, so that root Requirement (HOMO and LUMO, T1, S1, hole transport, electric transmission, hole are realized as well as possible in component according to application purpose Stop, electronic blocking, solubility, orthogonal solubility and bridging property such that it is able to realize Mnltilayered structures after removing solution).In order to Further set up luminous efficiency and the life-span of component, component in itself in appeal to more high-purity organic layers, wherein each list Layer has the function (electric charge injection, electric charge transmission, electrostatic barrier layer, emission layer, electrode etc.) of difference.Generally successively in high vacuum In by distillation these layers are applied on corresponding base material.With the product number of the suitable general marketplace in organic electronic field Increase, especially for the Organic Light Emitting Diode (OLED) of monitor market and illumination market, urgent may need to realize Substituting and low cost the approach of preparation for the manufacturing technology set up based on vacuum.
The advance film as obtained in solution can be made to change into insoluble network using polymerizable groups.Therefore can apply Apply other layer via solution on the base material of cloth, without causing the mixing on interface, also do not result in the layer being previously deposited Dissolving.
By the innovation, the pure of small molecule of the invention is realized using the preparation method based on solvent of low cost Degree.This allows to prepare the most modern Mnltilayered structures with the loss of less material, in contrast to this, existing in OLED components The number of the functional layer of deposition is reduced.
Surprisingly it has been found that by the compound that formula 1 is determined cause organic electroluminescent device especially with regard to the life-span, Efficiency and driving voltage are significantly improved.When using compound of the invention as host material, it is also especially suitable for The situation of green and blue phosphorescent electroluminescence device.Therefore the material and the organic electroluminescent comprising the compound Equipment is subject of the present invention.
Compound of the invention can also not used using the cross-linking method by photochemical crosslinking or heat cross-linking Cannot be prepared in the case of the compound it is effective, long-lived and can liquid processing OLED.
Therefore one aspect of the present invention provides new bipolar material of main part, and the material of main part is given by functionality Two crosslinkable groups PG of conjugation are introduced on body unit (such as carbazole, phenoxazine or phenthazine) so as to make in light electric components Used time has the improvement performance on efficiency, life-span and driving voltage.
Another aspect of the present invention is related to the organic molecule of the type described herein to make in emission layer in light electric components It is to inject material for the host material (material of main part) of luminescent radiation sources and/or as electron transport material and/or as hole Expect and/or as the purposes of hole barrier materials.
In one embodiment of the invention, the organic molecule of the type described herein is preferably with other with least one The form of the mixture of compound is used in the emission layer of light electric components.It is preferred here that, the organic molecule in mixture is Host material.
In a preferred embodiment in accordance with this invention, the organic molecule of the type described herein is correspondingly used as photoelectricity structure The host material for luminescent radiation sources in part.
Smooth electric components of the invention are preferably selected from group consisting of：
- organic light emission component (OLED),
- light-emitting electrochemical cell,
- OLED sensors, particularly in the gas sensor and vapor sensor of external non-tight shielding,
- organic photovoltaic cell,
- organic field effect tube,
- organic laser, and
- frequency reducing conversion element.
Another aspect of the present invention is related to the organic molecule comprising at least one type described herein and at least one hair The mixture of light emitter.
Another aspect of the present invention is related to the organic molecule comprising at least one type described herein or described herein The preparation of mixture and at least one solvent.
In one embodiment, the organic material as host material in optics illuminated component (particularly OLED) Number is between 50% and 99%.
Another aspect of the present invention is related to the light electric components of the organic molecule comprising the type described herein.Here, according to Smooth electric components of the invention include at least one layer being located between anode and negative electrode, the layer having comprising the type described herein Machine molecule is for example as the host material (material of main part) for luminescent radiation sources and/or as electron transport material and/or work For hole-injecting material and/or as hole barrier materials.Here, light electric components can be selected from by organic light emission component, organic Diode, organic photovoltaic cell, organic transistor, Organic Light Emitting Diode, light-emitting electrochemical cell, organic field effect tube The group constituted with organic laser.
Another aspect of the present invention is related to the method for preparing light electric components, wherein having using the type described herein Machine molecule.
The a part of of methods described can be that organic molecule of the invention is coated on carrier.Can optionally by true Sky evaporation or wet-chemical mode are coated.
For this common method is well known by persons skilled in the art and can be readily applied to comprising being described herein The light electric components of the organic molecule of type.
When light electric components, organic molecule of the invention especially has the following advantages that relative to prior art：
A. the charge carrier mobility in component is improved compared to the system according to prior art.
B. the efficiency of component is higher compared to system according to prior art.
C. the stability of component is higher compared to system according to prior art.
D. the life-span of component is higher compared to system according to prior art.
The present invention is explained in greater detail without the limitation present invention by following examples.
Embodiment
Embodiment 1：Molecule of the invention
As shown all molecules with crosslinkable groups ethylidene in following table.It is known to those skilled in the art how Substituting crosslinkable groups PG is introduced in the molecule, so as to obtain other molecules of the invention.
Embodiment 2：For synthesizing molecule of the invention such as 2-N- (carbazyl) 6-N- (3,6- divinyl carbazoles Base)-pyridine (molecule 1) synthesis sequentially
First step of replacing：
Carbazole (10mmol, 1.00 equivalents) and sodium hydride (60% has paraffin, 500mg, 13mmol, 1.3 equivalents) mixing And dissolved portionwise with 110mL dioxs altogether under a nitrogen.The formation of velocity adaptive hydrogen is added so as to avoid overfoaming.Completely Reaction 15 minutes is stirred at room temperature after addition, heating 15 minutes is then refluxed for.Form the yellow solution of clarification, the solution Send intense fluorescence under ultraviolet light (366nm is excited).Be added dropwise in the reactive mixture 2,6- difluoro pyridines (1.15g, 10mmol, 1.00 equivalents).Fluorescence substantially weakens under ultraviolet light.Reactant mixture is heated at reflux until reactant reacts completely (control to react by HPLC, GC-MS or DC；Usual 4h).It is cooled to after room temperature and is quenched under a nitrogen by the way that 10mL water is added dropwise Excessive alkali.Reactant mixture is added into 200mL saturated nacl aqueous solutions and crude product is separated by suction filtration and water is used (300mL) and methyl alcohol (60mL) are cleaned.The solid of acquisition is impregnated with 200mL hot toluenes and abandon insoluble residue.Decompression is removed Remove solvent and with pentane (300mL) and diethyl ether (200mL) wash products and be vacuum dried.In the form of buff white solid Separation product and typically without being further purified by further react.By the vacuum sublimation under 250 DEG C, 0.002mbar Or the product with purity assay can be obtained by MPLC purifying (eluent gradient hexamethylene-dichloromethane).
Second step of replacing：
Similarly synthesized with first step, but wherein replace carbazole using dibromo carbazole and use the first substitution The product of step replaces 2,6- difluoro pyridines, and replaces the yellow solution of clarification to be deposited before 2,6- difluoro pyridines are added In suspension.
2-N- (carbazyl) -6-N- (3,6- dibromos carbazyl)-pyridine (h6-2).
White powder (95%)-due to analyzable NMR spectra can not be recorded insoluble in conventional NMR solvents.–IR(ATR) 1650(vw),1571(m),1466(vs),1447(vs),1429(m),1375(m),1331(m),1308(m),1277(m), 1222(m),1183(w),1159(w),1058(w),1020(w),867(w),825(w),809(m),794(m),741(s), 720(s),660(w),634(vw),616(vw),563(w),526(w),491(w),436(w),418(m)cm-1。–HRMS (FAB-MS,3-NBA):C29H17N3 79Br2Calculated value 564.9784, measured value 564.9733.
Coupled reaction for introducing polymerizable unit PG：
Pd (PPh are used under argon gas3)4(5 moles of %, in terms of Br) and boron derivative KF3BCH=CH2(2 equivalents, in terms of Br) Dissolving 2-N- carbazyls -6-N- (3,6- dibromo carbazyl)-pyridine (h6-2) (10mmol, 1 equivalent) (50mL toluene/ethanols/ KOHaq=3/3/1) and it is heated at reflux 24.By alumina filter reactant mixture (Brockman 1) and pure by MPLC Change (eluent gradient hexamethylene-dichloromethane).
2-N- (carbazyl) -6-N- (3,6- divinyl carbazyl)-pyridine (molecule 1).
Buff white solid (36%).–1H NMR (500MHz, chloroform-d) δ=8.20-7.98 (m, 7H), 7.72-7.61 (m, 2H), 7.61-7.50 (m, 2H), 7.50-7.31 (m, 4H), 6.94 (dd, J=17.5,10.9Hz, 2H), 5.91-5.79 (m,2H),5.39–5.25(m,2H)。–13C NMR (126MHz, chloroform-d) δ=151.5,140.7,140.4,139.6, 139.5,137.0,131.3,126.4,124.9,124.6,121.3,120.2,118.0,114.9,114.6,112.3, 112.2,112.0,100.0。
Embodiment 3：Molecule 2
2-N- (carbazyl) -6-N- (3,6-di- (4- ethenylphenyls)-carbazyl)-pyridine (molecule 2).
Synthesis with molecule 1 is similarly synthesized, but wherein uses (HO)2BPhCH=CH2As boron derivative.Rice Yellow solid (50%).–1H NMR (500MHz, chloroform-d) δ=8.47-8.41 (m, 2H), 8.25-8.04 (m, 7H), 7.80- 7.62 (m, 8H), 7.61-7.52 (m, 4H), 7.47 (ddd, J=8.5,7.2,1.3Hz, 2H), 7.38 (td, J=7.5, 1.0Hz, 2H), 6.82 (dd, J=17.6,10.9Hz, 2H), 5.84 (dd, J=17.5,0.9Hz, 2H), 5.31 (dd, J= 10.9,0.9Hz,2H)ppm。–13C NMR (126MHz, chloroform-d) δ=151.6,151.41,140.96,139.49,139.37, 136.51,136.17,134.37,127.33,127.0,126.7,126.7,126.4,125.8,125.3,124.6,121.4, 120.2,118.4,114.6,113.7,112.5,111.9ppm。–IR(ATR)2922(vw),1730(vw),1625(vw), 1570(m),1477(m),1439(vs),1375(m),1324(m),1220(m),1186(m),1029(w),987(vw),902 (w),841(w),794(m),747(s),721(s),668(vw),640(vw),597(vw),560(vw),499(vw),420 (w)cm-1。–.HRMS(FAB-MS,3-NBA,C45H32N3) calculated value 614.2591, measured value 614.2593.

Claims (18)

1. a kind of organic molecule of the structure with formula 1,
Wherein
Ar=is independent of each other to have insatiable hunger and/or aromatic carbocyclic or the heterocyclic units of 5 to 30 annular atoms, selected from by naphthalene, anthracene, Phenanthrene, pyrene, dihydropyrene,Perylene, fluoranthene, benzanthracene, aphthacene, pentacene, BaP, furans, benzofuran, different benzo furan Mutter, thiophene, benzothiophene, isothiophene, dibenzothiophenes, pyrroles, indoles, iso-indoles, carbazole, pyridine, quinoline, isoquinoline Quinoline, acridine, phenanthridines, benzo -5,6- quinoline, benzo -6,7- quinoline, benzo -7,8- quinoline, phenthazine, phenoxazines, pyrazoles, Yin Azoles, imidazoles, benzimidazole, naphthalene imidazoles, luxuriant and rich with fragrance imidazoles, pyridine imidazoles, pyrazine imidazoles, quinoxaline imidazoles, oxazoles, benzoxazole, naphthalene Oxazole, En oxazole, Fei oxazole, isoxazoles, isothiazole, 1,3- thiazoles, benzothiazole, pyridazine, benzo pyridazine, pyrimidine, benzo are phonetic Pyridine, quinoxaline, pyrazine, azophenlyene, naphthyridines, azepine carbazole, benzo carboline, phenanthroline, 1,2,3- triazoles, 1,2,4- triazoles, benzene And triazole, 1,2,3- oxadiazoles, 1,2,4- oxadiazoles, 1,2,5- oxadiazoles, 1,3,4- oxadiazoles, 1,2,3- thiadiazoles, 1,2, 4- thiadiazoles, 1,2,5- thiadiazoles, 1,3,4- thiadiazoles, 1,3,5- triazines, 1,2,4- triazines, 1,2,3- triazines, tetrazolium, 1,2, 3,4- oxatriazoles, 1,2,3,4- oxatriazoles, 1,2,4,5- tetrazines, 1,2,3,4- tetrazines, 1,2,3,5- tetrazines, purine, pteridine, Yin Diindyl piperazine, diazosulfide, indeno carbazole, indenofluorene, spiro-bisfluorene and indolocarbazole composition group, its optionally each by one or Multiple group R1 substitution, wherein optionally two or more group R1 are connected to each other and form one or more rings；
D1=has the donor groups of the structure of formula 1a；
And
D2=has the donor groups of the structure of formula 1b；
Wherein it is attached with Ar in singly-bound form on the position represented with # respectively；
And the symbol and index used in it meet：
N is the integer between 1 and 5；
O is the integer between 1 and 5；
P is the integer between 0 and 5；
PG：One or more identical or different polymerizable units, the polymerizable unit can be urged by thermocatalytic and/or acid Change or base-catalyzed method, by the ultraviolet radiation under conditions of presence or absence of light trigger, or by microwave And be polymerized；
X, Y every time occur when it is identical or differently represent covalent single bond or divalence organic bridge, the divalence organic bridge be selected from by Substitution and unsubstituted alkylidene (non-branching, branched or ring-type), alkenylene, alkynylene, arlydene and heteroarylidene, O, NR3、 C=CR3 2, C=NR3、SiR3 2S、S(O)、S(O)2、Se、Se(O)、Se(O)2、BR3、PR3、P(O)R3The group of composition, wherein also may be used Being the combination of these units；
Z is identical when occurring every time or differently represents CR2Or N；
R and R1It is identical or differently represent when occurring every time：
H, D, F, Cl, Br, I, B (OR3)2, CHO, C (=O) R3, CR3=C (R3)2, CN, C (=O) OR3, C (=O) N (R3)2, Si (R3)3, NO2, P (=O) (R3)2, OSO2R3, OR3, S (=O) R3, S (=O)2R3, or
With 1 to 20 alkyl of the straight chain of C atoms, alkoxy or alkylthio or with 3 to 20 branched or rings of C atoms The alkyl of shape, alkoxy or alkylthio or with 2 to 20 alkenyl or alkynyls of C atoms, wherein above-mentioned group respectively can be with By one or more groups R3Substitution, and one or more CH in wherein above-mentioned group2- group can be by-R3C= CR3-、-C≡C-、Si(R3)2, C=O, C=S, C=NR3,-C (=O) O- ,-C (=O) NR3-、NR3, P (=O) (R3)、-O-、- S-, SO or SO2Substitute, and one or more H atoms in wherein above-mentioned group can be by D, F, Cl, Br, I, CN or NO2Replace Generation, or
With 6 to 30 aromatic ring systems of aromatic ring atom, the aromatic ring system can respectively by one or more groups R3 Substitution, or
With 6 to 30 aryloxy group of aromatic ring atom, the aryloxy group can be by one or more groups R3Substitution, wherein two Individual or multiple group R and R1Can be connected to each other and can form ring；
R2It is identical or differently represent when occurring every time：
H, D, F, Cl, Br, I, B (OR3)2, CHO, C (=O) R3, CR3=C (R3)2, CN, C (=O) OR3, C (=O) N (R3)2, Si (R3)3, NO2, P (=O) (R3)2, OSO2R3, OR3, S (=O) R3, S (=O)2R3, or
With 1 to 20 alkyl of the straight chain of C atoms, alkoxy or alkylthio or with 3 to 20 branched or rings of C atoms The alkyl of shape, alkoxy or alkylthio or with 2 to 20 alkenyl or alkynyls of C atoms, wherein above-mentioned group respectively can be with By one or more groups R3Substitution, and one or more CH in wherein above-mentioned group2- group can be by-R3C= CR3-、-C≡C-、Si(R3)2, C=O, C=S, C=NR3,-C (=O) O- ,-C (=O) NR3-、NR3, P (=O) (R3)、-O-、- S-, SO or SO2Substitute, and one or more H atoms in wherein above-mentioned group can be by D, F, Cl, Br, I, CN or NO2Replace Generation, or
With 5 to 30 aromatics or heteroaromatic ring system of aromatic ring atom, the aromatics or heteroaromatic ring system can be respectively By one or more groups R3Substitution, or
With 5 to 60 aryloxy group or heteroaryloxy of aromatic ring atom, the aryloxy group or heteroaryloxy can by one or Multiple group R3Substitution, two of which or multiple group R2Can be connected to each other and can form ring；
R3It is identical or differently represent when occurring every time：
H, D, F, Cl, Br, I, B (OR4)2, CHO, C (=O) R4, CR4=C (R4)2, CN, C (=O) OR4, C (=O) N (R4)2, Si (R4)3, N (R4)2, NO2, P (=O) (R4)2, OSO2R4, OR4, S (=O) R4, S (=O)2R4, or
With 1 to 20 alkyl of the straight chain of C atoms, alkoxy or alkylthio or with 3 to 20 branched or rings of C atoms The alkyl of shape, alkoxy or alkylthio or with 2 to 20 alkenyl or alkynyls of C atoms, wherein above-mentioned group respectively can be with By one or more groups R4Substitution, and one or more CH in wherein above-mentioned group2- group can be by-R4C= CR4-、-C≡C-、Si(R4)2, C=O, C=S, C=Se, C=NR4,-C (=O) O- ,-C (=O) NR4-、NR4, P (=O) (R4) ,-O- ,-S-, SO or SO2Substitute, and one or more H atoms in wherein above-mentioned group can by D, F, Cl, Br, I, CN or NO2Substitute, or
With 5 to 60 aromatics or heteroaromatic ring system of aromatic ring atom, the aromatics or heteroaromatic ring system can be respectively By one or more groups R4Substitution, or
With 5 to 60 aryloxy group or heteroaryloxy of aromatic ring atom, the aryloxy group or heteroaryloxy can by one or Multiple group R4Substitution, two of which or multiple group R3Can be connected to each other and can form ring；
R4It is identical or differently represent H, D, F or the aliphatic series with 1 to 20 C atom, aromatics or heteroaromatic have when occurring every time Machine group, wherein one or more H atoms can also be substituted by D or F；Two of which or multiple substituent Rs4Can be connected to each other And form ring；
And wherein it is attached with Ar in singly-bound form on the position represented with # respectively.
2. organic molecule according to claim 1, wherein Ar has following structure
Wherein W is identical when occurring every time or differently represents CR1Or N, and wherein at least one W is not CR1
Wherein
R1Identical or differently represent H, D, F, Cl, Br, I, the B (OR when occurring every time3)2, CHO, C (=O) R3, CR3=C (R3)2, CN, C (=O) OR3, C (=O) N (R3)2, Si (R3)3, NO2, P (=O) (R3)2, OSO2R3, OR3, S (=O) R3, S (= O)2R3, or
With 1 to 20 alkyl of the straight chain of C atoms, alkoxy or alkylthio or with 3 to 20 branched or rings of C atoms The alkyl of shape, alkoxy or alkylthio or with 2 to 20 alkenyl or alkynyls of C atoms, wherein above-mentioned group respectively can be with By one or more groups R3Substitution, and one or more CH in wherein above-mentioned group2- group can be by-R3C= CR3-、-C≡C-、Si(R3)2, C=O, C=S, C=NR3,-C (=O) O- ,-C (=O) NR3-、NR3, P (=O) (R3)、-O-、- S-, SO or SO2Substitute, and one or more H atoms in wherein above-mentioned group can be by D, F, Cl, Br, I, CN or NO2Replace Generation, or
With 6 to 30 aromatic ring systems of aromatic ring atom, the aromatic ring system can respectively by one or more groups R3 Substitution, or
With 6 to 30 aryloxy group of aromatic ring atom, the aryloxy group can be by one or more groups R3Substitution, wherein two Individual or multiple group R and R1Can be connected to each other and can form ring；
R3It is identical or differently represent when occurring every time：
H, D, F, Cl, Br, I, B (OR4)2, CHO, C (=O) R4, CR4=C (R4)2, CN, C (=O) OR4, C (=O) N (R4)2, Si (R4)3, N (R4)2, NO2, P (=O) (R4)2, OSO2R4, OR4, S (=O) R4, S (=O)2R4, or
With 1 to 20 alkyl of the straight chain of C atoms, alkoxy or alkylthio or with 3 to 20 branched or rings of C atoms The alkyl of shape, alkoxy or alkylthio or with 2 to 20 alkenyl or alkynyls of C atoms, wherein above-mentioned group respectively can be with By one or more groups R4Substitution, and one or more CH in wherein above-mentioned group2- group can be by-R4C= CR4-、-C≡C-、Si(R4)2, C=O, C=S, C=Se, C=NR4,-C (=O) O- ,-C (=O) NR4-、NR4, P (=O) (R4) ,-O- ,-S-, SO or SO2Substitute, and one or more H atoms in wherein above-mentioned group can by D, F, Cl, Br, I, CN or NO2Substitute, or
With 5 to 60 aromatics or heteroaromatic ring system of aromatic ring atom, the aromatics or heteroaromatic ring system can be respectively By one or more groups R4Substitution, or
With 5 to 60 aryloxy group or heteroaryloxy of aromatic ring atom, the aryloxy group or heteroaryloxy can by one or Multiple group R4Substitution, two of which or multiple group R3Can be connected to each other and can form ring；
R4It is identical or differently represent H, D, F or the aliphatic series with 1 to 20 C atom, aromatics or heteroaromatic have when occurring every time Machine group, wherein one or more H atoms can also be substituted by D or F；Two of which or multiple substituent Rs4Can be connected to each other And form ring.
3. organic molecule according to claim 1 and 2, wherein (Ar)nSelected from group consisting of：
Wherein * represents the link position on D1 or D2, and the unit specified and is limited in group such as claim 1 or 2.
4. the organic molecule according to any one of claims 1 to 3, wherein crosslinkable groups PG is selected from group consisting of：
5. the method for being used to prepare the organic molecule according to any one of Claims 1-4, methods described has following step Suddenly：
The reaction and then the reaction with double bromination donor groups D1 of donor groups D2 and double fluorination Ar are carried out, PG- is then introduced mono- Unit,
Wherein
Ar=has the aromatics or heteroaromatic ring system of 5 to 30 annular atoms, selected from by naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene,Perylene, Fluoranthene, benzanthracene, aphthacene, pentacene, BaP, furans, benzofuran, isobenzofuran, thiophene, benzothiophene, different benzene Bithiophene, dibenzothiophenes, pyrroles, indoles, iso-indoles, carbazole, pyridine, quinoline, isoquinolin, acridine, phenanthridines, benzo -5,6- Quinoline, benzo -6,7- quinoline, benzo -7,8- quinoline, phenthazine, phenoxazines, pyrazoles, indazole, imidazoles, benzimidazole, naphthalene miaow It is azoles, luxuriant and rich with fragrance imidazoles, pyridine imidazoles, pyrazine imidazoles, quinoxaline imidazoles, oxazoles, benzoxazole, naphthoxazole, En oxazole, Fei oxazoles, different Oxazole, isothiazole, 1,3- thiazoles, benzothiazole, pyridazine, benzo pyridazine, pyrimidine, benzo pyrimidine, quinoxaline, pyrazine, azophenlyene, naphthalene Pyridine, azepine carbazole, benzo carboline, phenanthroline, 1,2,3- triazoles, 1,2,4- triazoles, BTA, 1,2,3- oxadiazoles, 1, 2,4- oxadiazoles, 1,2,5- oxadiazoles, 1,3,4- oxadiazoles, 1,2,3- thiadiazoles, 1,2,4- thiadiazoles, 1,2,5- thiadiazoles, 1,3,4- thiadiazoles, 1,3,5- triazines, 1,2,4- triazines, 1,2,3- triazines, tetrazolium, 1,2,3,4- oxatriazoles, 1,2,3,4- Evil Triazole, 1,2,4,5- tetrazines, 1,2,3,4- tetrazines, 1,2,3,5- tetrazines, purine, pteridine, indolizine, diazosulfide, indeno The group of carbazole, indenofluorene, spiro-bisfluorene and indolocarbazole composition, it is optionally each replaced by one or more groups R1, wherein Optional two or more group R1 are connected to each other and form one or more rings；
D1=has the donor groups of the structure of formula 1a；
D2=has the group with donor performance of the structure of formula 1b；
Wherein it is attached with Ar in singly-bound form on the position represented with # respectively；
And wherein other symbols have the implication specified in claims 1 to 3.
6. method according to claim 5, wherein being reacted by adding highly basic.
7. the method according to claim 5 or 6, methods described further includes the step of adding oxidant and optionally enters One step includes adding other steps of selenium or sulphur or Lloyd's's reagent, and the oxidant is independently from each other hydrogen peroxide, peroxide Change hydrogen-urea-addition product, oxygen or ozone.
8. purposes of a kind of organic molecule according to any one of Claims 1-4 in light electric components.
9. purposes according to claim 8, the preferably organic molecule wherein in emission layer, the conduct in light electric components Be particularly well-suited to luminescent radiation sources host material and/or as electron transport material and/or as hole injecting material and/or As hole barrier materials.
10. purposes according to claim 8 or claim 9, wherein light electric components are selected from group consisting of：
- organic light emission component (OLED),
- light-emitting electrochemical cell,
- OLED sensors, particularly in the gas sensor and vapor sensor of external non-tight shielding,
- organic photovoltaic cell,
- organic field effect tube,
- organic laser, and
- frequency reducing conversion element.
A kind of 11. smooth electric components, including the organic molecule according to any one of Claims 1-4.
12. smooth electric components according to claim 11, it is characterised in that the organic molecule is used in emission layer, preferably As the host material for being particularly well-suited to luminescent radiation sources and/or as electron transport material and/or as hole injecting material And/or as hole barrier materials.
13. a kind of mixtures, comprising the organic molecule according to any one of Claims 1-4 and at least one luminescence emissions Body.
A kind of 14. preparations, want comprising at least one organic molecule according to any one of Claims 1-4 or according to right Seek the mixture and at least one solvent described in 13.
15. is a kind of for preparing the method for light electric components, wherein using organic point according to any one of Claims 1-4 Son.
16. methods according to claim 15, it is characterised in that coated on carrier according to any one of Claims 1-4 Described organic molecule.
17. methods according to claim 16, it is characterised in that be coated by wet-chemical mode.
18. methods according to claim 16, it is characterised in that be coated by being evaporated in vacuo.
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