CN101872844A - The material and the light-emitting component that are used for light-emitting component - Google Patents
The material and the light-emitting component that are used for light-emitting component Download PDFInfo
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Abstract
The invention provides the material that is used for light-emitting component of general formula (1) expression and driving voltage is low, the light-emitting component of excellent in te pins of durability.In the formula, R
1～R
6Identical or different respectively, from hydrogen atom, alkyl and aryl, select.A represents the aromatic hydrocarbyl of n valency.B represents alkyl or aryl.X represents carbon atom or nitrogen-atoms.N represents the natural number more than 2, below 6.In addition, having the substituting group of n phenanthroline skeleton or benzoquinoline skeleton can be identical or different respectively.
Description
The application is application number the dividing an application for the PCT application in the country's stage that enters of " material and the light-emitting component that are used for light-emitting component " that be 200480043850.4 (international filing date is on August 23rd, 2004), denomination of invention.
Technical field
The present invention relates to a kind of light-emitting component that is used for the material of light-emitting component and uses this material, relate to the light-emitting component in fields such as can being used for display element, flat-panel monitor, backlight, illumination, upholstery, directional beacon, billboard, Electrofax and optical signal generator.
Background technology
This year just active research from the negative electrode injected electrons and from the anode injected holes in by the organic fluorescent of the two poles of the earth clamping again in conjunction with the time luminous organic electroluminescent device.Focus concentrates under slim, the low driving voltage of this element high brightness luminescent and by selecting fluorescent material to carry out multicolor luminous feature.Since the C.W.Tang of Kodak etc. found that organic electroluminescent device is with high brightness luminescent, numerous research institutions were all studied at this point.
Further investigate for obtaining color monitor.For luminescent material, not only studied fluorescent material, also studied phosphor material etc.In addition, as electric charge transmitting material, primary study hole-transfer material has also carried out furtheing investigate (for example referring to patent documentation 1～5) to the electron transport material recently at present.
Patent documentation 1: the spy opens flat 5-331459 communique (claims)
Patent documentation 2: the spy opens 2000-119644 communique (17 pages)
Patent documentation 3: international No. 00/03565 brochure (claims) that disclose
Patent documentation 4: the spy opens 2003-115387 communique (claims)
Patent documentation 5: the spy opens 2003-123983 communique (claims)
Summary of the invention
But, the most poor durability of the present luminescent material that uses, hole-transfer material and electron transport material.This is that component life shortens because long-time energising causes element heating crystallization to occur.On the other hand, owing to give the sublimability of non-crystalline material low in order to suppress crystallization, so most of materials take place to decompose or sex change such as polymerization during vacuum evaporation.Even above-mentioned sex change does not influence element function in laboratory scale evaporation, also under carrying out the condition of long-time heating, a large amount of materials that drop into when producing in batches become the reason that reduces element function significantly, influence practicability.
In addition, be suitable for the most driving voltage height of light-emitting component of current material, must apply high voltage in order to obtain desirable brightness, therefore big to the load of light-emitting component, influence practicability.
The object of the present invention is to provide and to solve that above-mentioned prior art problems, driving voltage are low, the light-emitting component of excellent in te pins of durability.
The present invention relates to the material that is used for light-emitting component of general formula (1) expression.
(R herein,
1～R
6Identical or different respectively, from hydrogen atom, alkyl and aryl, select.A represents the aromatic hydrocarbyl of n valency.B represents alkyl or aryl.X represents carbon atom or nitrogen-atoms.N represents the natural number more than 2, below 6.Substituting group with n phenanthroline skeleton or benzoquinoline skeleton is identical or different respectively.)
The present invention relates to there is organic layer between anode and negative electrode, utilize the luminous element of electric energy, this organic layer contains the material that is used for light-emitting component of general formula (1) expression.
If use the material that is used for light-emitting component of the present invention, then can provide the light-emitting component of the low and excellent in te pins of durability of driving voltage.
Embodiment
At first, describe the material that is used for light-emitting component of general formula of the present invention (1) expression in detail.
Herein, R
1～R
6Identical or different respectively, among hydrogen atom, alkyl and aryl, select.A represents the aromatic hydrocarbyl of n valency.Herein, alkyl is meant for example representative examples of saturated aliphatic alkyl such as methyl, ethyl, propyl group, butyl, and aryl is meant for example aromatic hydrocarbyls such as phenyl, tolyl, xenyl, naphthyl, phenanthryl, anthryl, does not replace, and also can be substituted.The carbon number of alkyl is preferably more than 1, below 20.The carbon number of aryl is preferably more than 5, below 30.
X represents carbon atom or nitrogen-atoms.When X was carbon atom, the compound of general formula (1) was the compound with benzoquinoline skeleton.When X was nitrogen-atoms, the compound of general formula (1) was the compound with phenanthroline skeleton.In order further to reduce driving voltage of light-emitting, the carrier mobility height of preferred material.Therefore, the X of preferred formula (1) represents nitrogen-atoms.
N represents the natural number more than 2, below 6.Group with n phenanthroline skeleton or benzoquinoline skeleton can be identical or different respectively.Sublimability when considering vacuum evaporation and film form the balance of ability and can easily synthesize and make with extra care, and more preferably said n represents 2.
If the molecular weight of material is excessive, then sublimability reduces, and the probability of thermal decomposition becomes big during vacuum evaporation.On the other hand, if the molecular weight of material is too small, then to form the situation that performance that ability causes light-emitting component reduces more because of film.Consider that from the balance aspect of this sublimability and film formation ability the A of general formula (1) is preferably and replaces or unsubstituted phenylene or replacement or unsubstituted naphthylene.
In the general formula (1), it is one of feature of the present invention that the position of B is replaced by alkyl or aryl.Thus, the position of B is compared during with hydrogen atom, and becoming during vacuum evaporation is difficult to thermal decomposition.And crystallization is suppressed, thereby forms uniform film easily, even and luminous for a long time, also be difficult for the film deterioration that generation causes because of crystallization.The carbon number of alkyl is preferably more than 1, below 20.The carbon number of aryl is preferably more than 5, below 30.And B is preferably from methyl, the tert-butyl group, replacement or unsubstituted phenyl, reaches at least a kind that selects replacement or the unsubstituted naphthyl.
Wherein, particularly consider, more preferably use the material that is used for light-emitting component of general formula (2) expression from having excellent sublimability, film formation ability and synthetic easiness aspect.
(herein, A ' represents from 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, 1,5-naphthylene and 2, at least a kind of selecting in the 7-naphthylene.B ' represents from methyl, the tert-butyl group, replacement or unsubstituted phenyl, reaches at least a kind that selects replacement or the unsubstituted naphthyl.)
As the above-mentioned material that is used for light-emitting component, particularly can enumerate following structure, but be not particularly limited in this.
The material that is used for light-emitting component of general formula (1) expression can adopt following method synthetic, but is not particularly limited in this.
Method as the material that is used for light-emitting component that obtains general formula (1) expression, preferred following method: in the compound of the A that is equivalent to general formula (1), introduce reactive substituents, convert the phenanthroline skeleton or the benzoquinoline skeleton of general formula (1) then to, the B that obtains general formula (1) is the compound of hydrogen atom, next introduces B.
,, can enumerate acetyl group, iodo, bromo etc. herein, but be not particularly limited in this as reactive substituents.
As the method for introducing acetyl group, can enumerate the acyl groupization that Fred restrains Ford.As a reference; can enumerate the spy open the 27th page of flat 7-278537 communique " embodiment A. initial compounds (f) 2; 2 '-diacetyl-9; 9 '-spiral shell, two fluorenes " or Helvetica Chimica Acta; vol.52 (1969) the 1210th page " Experimenteller Tell2; 2 '-diacetyl-9,9 '-spirobifluorene (IV) " etc.Particularly, the compound that can make the A that is equivalent to general formula (1) in 50 ℃ of following and chloroacetic chloride and aluminium reactions, adopts common method to handle 1 in the 2-dichloroethanes, introduces acetyl group.Change the equivalent of chloroacetic chloride and aluminium chloride, can obtain 1～4 and replace body.
As additive method, also can adopt the method that trifluoro-methanesulfonyl oxy is converted into acyl group with palladium catalyst.As a reference, can enumerate the 1481st page of J.Org.Chem.vol.57 (1992) etc.Particularly; can be in dimethyl formamide and triethylamine, under the palladium catalyst, react with butyl vinyl ether down in 50～120 ℃ with the compound of the A that is equivalent to general formula (1) with trifluoro-methanesulfonyl oxy; adopt common method to handle, introduce acetyl group.This method also can use bromo, iodo to replace trifluoro-methanesulfonyl oxy to introduce acetyl group.
About the introducing of iodo, as a reference, can enumerate Tetrahedron Letters, the 1487th page of vol.38 (1997) etc.Particularly, the compound that can make the A that is equivalent to general formula (1) in carbon tetrachloride, 50 ℃～60 ℃ down with the reaction of iodine and two (trifluoroacetyl oxygen base) iodobenzene, adopt common method to handle, introducing iodine.
About the introducing of bromo, as a reference, can enumerate the 1098th page of Angew.Chem.Int.Ed.Engl.25 (1986) No.12 etc.Particularly, the compound that can make the A that is equivalent to general formula (1) at room temperature with bromine reaction, adopt common method to handle, introduce bromine.Can change the equivalent of bromine, obtain 1～4 and replace body.
Method about the phenanthroline skeleton or the benzoquinoline skeleton that above-mentioned reactive substituents are converted into general formula (1), as a reference, can enumerate Tetrahedron Letters, vol.40 (1999). the 7312nd page scheme or J.Org.Chem.1996,61. the 3020th page " 2-Phenyl-1; 10-phenanntoroline ", Tetrahedron Letters, vol.23 (1982). the 5291st page～the 5294th page etc.Particularly, can adopt following method to introduce phenanthroline skeleton or benzoquinoline skeleton, described method is to make the acetylate of the compound of the A that is equivalent to general formula (1) react the method that adopts common method to handle with 8-amino-7-quinoline aldehyde or 1-amino-2-naphthaldehyde under 50 ℃～reflux temperature in the presence of potassium hydroxide, in lower alcohol Huo dioxs such as ethanol, isopropyl alcohol; The iodide or the bromide of compound that will be equivalent to the A of general formula (1) carries out lithiumation in-100 ℃～50 ℃ with lithium alkylides such as lithium metal or tert-butyl lithium, n-BuLis in toluene, THF equal solvent, next react with phenanthroline class or benzo [h] quinolines in-20～60 ℃, after adopting common method to handle, the method that the compound that obtains is handled with manganese dioxide, nitrobenzene, quinhydrones, DDQ, air, oxygen, water etc. etc.
Introducing method as B, can enumerate following method: with B in the general formula (1) be the compound of hydrogen atom in toluene, THF equal solvent in-20～60 ℃ with as the lithium alkylide of the lithiumation thing of the alkyl or aryl of introducing herein or aryl lithium, as the alkyl magnesium halide or the halogenated aryl reactive magnesium of RMgBr, after adopting common method to handle, the compound that obtains at manganese dioxide, nitrobenzene, quinhydrones, is handled in DDQ, air, oxygen, the water etc.Abovementioned alkyl lithium, aryl lithium can obtain by making lithium alkylide reactions such as corresponding halogenated alkyl, halogenated aryl and lithium metal or n-BuLi.Alkyl magnesium halide, halogenated aryl magnesium can make corresponding halogenated alkyl, halogenated aryl and magnesium metal reaction and obtain.
The material that is used for light-emitting component of general formula (1) can be made with extra care by being used alone or in combination method for refining such as column chromatography, recrystallization, distillation.When adopting column chromatography, can use silica gel, aluminium oxide, florisil etc. to make with extra care as filler.When adopting recrystallization, can be separately or mixed toluene, hexane, oxolane, diox, dimethoxy-ethane, ethanol, methyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, positive butyrolactone, nitrobenzene, carrene, chloroform, dimethyl sulfoxide (DMSO), dimethyl formamide, 1-Methyl-2-Pyrrolidone, 1, normally used solvents such as 3-dimethyl-2-imidazolone, pyridine, triethylamine are made with extra care.
The present invention is the light-emitting component that contains the material that is used for light-emitting component of above-mentioned general formula (1) expression.
Light-emitting component of the present invention is made of anode and negative electrode and the organic layer that is present between above-mentioned anode and the negative electrode at least.
Mechanical strength in order to ensure light-emitting component preferably is formed on light-emitting component on the substrate.As substrate, preferably use glass substrates such as soda-lime glass or alkali-free glass.The thickness of glass substrate needs only to more than the 0.5mm so long as the thickness of sufficient to guarantee mechanical strength gets final product.About the material of glass, the preferred few material of the ion of stripping from glass, preferred alkali-free glass has been implemented SiO
2Soda-lime glass Deng barrier coat is also sold on market, therefore also can use this material.And, as long as anode can play consistently effect, just needn't use glass substrate, for example can on plastic base, form anode.
, be not particularly limited so long as can efficiently the hole be injected the material of organic layer and get final product as the material of anode, preferably use the bigger material of work function.For example can enumerate electric conductive polymers such as inorganic conductive material, polythiophene, polypyrrole and polyaniline such as tin oxide, indium oxide, indium tin oxide target conductive metal oxides such as (ITO) or metals such as gold, silver, chromium, cupric iodide, copper sulfide etc.Above-mentioned electrode material can use separately, also can the folded or mixing use with various material layers.
Be enough to the electric current that makes light-emitting component luminous as long as the resistance of electrode can be supplied with, consider, be preferably low resistance from the power consumption power aspect of light-emitting component.As long as for example be that the following ito substrate of 300 Ω/ just can be used as element electrode and plays a role, also can supply with the substrate about 10 Ω/ at present, therefore especially preferably use the following low resistance product of 100 Ω/.The thickness of ITO can be selected arbitrarily according to resistance value, usually between 100～300nn.ITO film formation method can be electron ray method, sputtering method and chemical reaction method etc., but is not particularly limited in this.
, be not particularly limited so long as electronics can be injected efficiently the material of organic layer and get final product as the material of negative electrode, generally speaking can enumerate platinum, gold, silver, copper, iron, tin, zinc, aluminium, indium, chromium, lithium, sodium, potassium, cerium, calcium and magnesium etc.In order to improve electron injection efficiency and element characteristic, preferred lithium, sodium, potassium, cerium, calcium, magnesium or contain the alloy of above-mentioned low workfunction metal.Generally speaking, above-mentioned low workfunction metal majority is unstable in atmosphere, therefore as preference, for example can enumerate use is doped with the stable high electrode of micro-lithium, cerium or magnesium (film thickness gauge of vacuum evaporation is shown as below the 1nm) in organic layer method, can use lithium fluoride, cerium fluoride, lithia and cerium oxide and so on inorganic salts, but be not particularly limited in this.And; for guard electrode; as preference, can enumerate metals such as stacked platinum, gold, silver, copper, iron, tin, aluminium and indium or use the alloy of above-mentioned metal and inorganic matters such as silicon dioxide, titanium oxide and silicon nitride, polyvinyl alcohol, vinyl chloride, hydro carbons macromolecular compound etc.
The manufacture method of above-mentioned electrode is not particularly limited as long as be the method that resistance heating, electron ray, sputter, ion plating and coating etc. can obtain conducting.
The organic layer that constitutes light-emitting component of the present invention is made of the material that one or two or more kinds is used for light-emitting component.The material that is used for light-emitting component herein is meant self luminous compound and helps any compound of the luminous compound of above-claimed cpd, promptly participates in luminous compound.Particularly, be equivalent to hole-transfer material, luminescent material and electron transport material etc., the material that is used for light-emitting component of the present invention is also included within wherein.The material that is used for light-emitting component of the present invention also can be used as luminescent material at above-mentioned material, considers from the high aspect of electron transport ability, is preferably used as the electron transport material.
As the configuration example of organic layer, except the structure of only forming by luminescent layer, can enumerate 1) hole transport layer/luminescent layer/electron transfer layer and, 2) stepped construction such as luminescent layer/electron transfer layer.In addition, above-mentioned each layer can be made of individual layer respectively, also can be made of multilayer.When hole transport layer and electron transfer layer were made of multilayer, the layer of contact electrode one side was called hole injection layer and electron injecting layer, and in the following description, hole injection layer is included in the hole transport layer, and electron injecting layer is included in the electron transfer layer.
Hole transport layer is stacked or mix one or two or more kinds hole-transfer material or formed by the mixture of hole-transfer material and high polymer binder.In addition, also can in the hole-transfer material, add iron chloride (III) and so on inorganic salts cambium layer.Preference as the hole-transfer material, for example can enumerate 4,4 '-two (N-(3-aminomethyl phenyl)-N-phenyl amino) biphenyl, 4,4 '-two (N-(1-naphthyl)-N-phenyl amino) biphenyl, 4,4 ', 4 " triphenylamine derivative such as (3-aminomethyl phenyl (phenyl) amino) triphenylamine-three; two (N-pi-allyl carbazoles) or two two carbazole derivates such as (N-alkyl carbazoles); indole derivatives; pyrazoline derivative; stilbene compounds; hydrazone compounds, benzofuran derivatives or thiophene derivant oxadiazole derivative, phthalocyanine derivates, heterocyclic compounds such as derivatives of porphyrin, side chain has the Merlon or the styrene derivative of above-mentioned monomer in the polymer class, Polyvinyl carbazole and polysilane etc.Make the necessary film of light-emitting component, hole and can inject and the compound that can transmit the hole gets final product so long as can form, be not particularly limited from anode.
Among the present invention, luminescent layer can be made of individual layer, also can be made of multilayer, can be any, is formed by luminescent material respectively, can be the mixture of material of main part and dopant material, and also the main consuming body material separately can use any.That is, only material of main part or dopant material are luminous in each luminescent layer for light-emitting component of the present invention, also can material of main part and dopant material all luminous.Material of main part and dopant material can be respectively same kind, also can be the combination of multiple material, can be any.Dopant material can be included in whole material of main parts, also can be included in the part material of main part, can be any.Dopant material can be stacked, also can disperse, and can be any.If the amount of dopant material is too much, the concentration frosting phenomenon then appears, and therefore preferably use below the 20 weight %, more preferably use below the 10 weight % with respect to material of main part.As the doping method of dopant material, can adopt and the material of main part method of evaporation altogether, also can with the material of main part premixed after carry out evaporation.
Luminescent material of the present invention can be fluorescence, also can be phosphorescent, can be any.Need to prove that the fluorescence radiation among the present invention is meant luminous because of due to the migration between the identical state of spin multiplicity, phosphorescence is luminous to be meant luminous because of due to moving between the different state of spin multiplicity.For example following from singlet excited is fluorescence radiation to the luminous of ground state (generally speaking the ground state of organic compound is singlet state) migration, and following from triplet excited state is that phosphorescence is luminous to the luminous of ground state migration.
The dopant material that uses among the present invention is not particularly limited, can uses compound known, can from various materials, select according to desirable illuminant colour.
Particularly, as indigo plant～blue-green dopant material, can enumerate naphthalene, anthracene, luxuriant and rich with fragrance, pyrene, benzo [9,10] luxuriant and rich with fragrance perylene, fluorenes, aromatic compound or derivatives thereofs such as indenes, furans, the pyrroles, thiophene, thiophene is coughed up (silole), the 9-silicon heterofluorene, 9, the two silicon heterofluorenes of 9 '-volution, benzothiophene, benzofuran, indoles, dibenzothiophenes, dibenzofurans, imidazopyridine, phenanthroline, pyrazine, 1, the 5-benzodiazine, quinoxaline, pyrrolopyridine, thioxanthene, aromatic heterocyclic compounds or derivatives thereofs such as imidazopyridine, the distyrene benzene derivative, the tetraphenylbutadiene derivative, stilbene derivative, the aldazine derivative, coumarin derivative, imidazoles, thiazole, thiadiazoles, carbazole oxazole oxadiazole, Zole derivatives and metal complex and N such as triazole, N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-4,4 '-diphenyl-1, the aryl amine derivatives of 1 '-diamines representative etc., but be not limited thereto.
As green～yellow dopant material, can enumerate coumarin derivative, the phthalimide derivative, Naphthalamide derivatives, the Perynone derivative, Pyrrolopyrrole derivatives, cyclopentadiene derivant, acridone derivatives, quinacridone derivative, Pyrrolopyrrole derivatives, aphthacene derivatives such as Pyrromethene derivative and rubrene etc., and, can also enumerate in and introduce aryl as the compound that above-mentioned indigo plant～the blue-green dopant material is enumerated as preference, heteroaryl, aryl vinyl, amino, but the substituent compound of long wavelengthizations such as cyano group.
And; as orange～red dopant material, can enumerate two (Naphthalamide derivatives such as diisopropyl phenyl) perylene tetracarboxylic acid acid imide; the Perynone derivative; pentanedione or with the terres rares complexes such as Eu complex as dentate such as benzoyl acetone and phenanthroline; 4-(dicyano methylene)-2-methyl-6-(to the dimethylamino styryl)-4H-pyrans or its analog; the magnesium phthalocyanine; metal phthalocyanine derivatives such as aluminium chlorine phthalocyanine; the rhodamine compound; denitrification flavine (deazaflavin) derivative of mixing; coumarin derivative; quinacridone derivative phenoxazine derivative oxazine derivative; quinazoline derivant; the Pyrromethene derivative; Pyrrolopyridine derivatives; the spiny dogfish derivative; the violanthrone derivative; azophenlyene derivative phenoxazine derivative and thiadiazoles and pyrene derivatives etc.And, as preference, can also enumerate and introduce the substituent compound that aryl, heteroaryl, aryl vinyl, amino, cyano group etc. can the long wavelengthizations as above-mentioned indigo plant～blue-green and in as green～compound that yellow dopant material is enumerated.And, as preference, can also enumerate with three (2-phenylpyridine) iridium (III) be representative be the phosphorescent metal complex of central metal with iridium or platinum.
The material of main part that uses among the present invention is not particularly limited preferred the use at present as fused-ring derivatives such as known anthracene of luminous element or pyrenes, with three (oxine) aluminium (III) is the metal chelating mould assembly oxynoide compound of representative, distyrene derivatives such as distyrene anthracene derivant or distyrene benzene derivative, the tetraphenylbutadiene derivative, coumarin derivative oxadiazole derivative, Pyrrolopyridine derivatives, the Perynone derivative, cyclopentadiene derivant oxadiazole derivative, thiadiazoles and pyridine derivate, Pyrrolopyrrole derivatives, the polyphenylacetylene derivative of polymer class, polyparaphenylene's derivative, polythiofuran derivative.
The material of main part that shows the luminescent layer that phosphorescence is luminous is not particularly limited, can enumerate 4,4 '-two (carbazole-N-yl) biphenyl or N, N '-diphenyl-3, carbazole derivates such as 3 '-two carbazoles, N, N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-4,4 '-diphenyl-1,1 '-diamines, N, N '-dinaphthyl-N, N '-diphenyl-4,4 '-diphenyl-1, triphenylamine derivatives such as 1 '-diamines, indole derivatives, triazole oxadiazole, Zole derivatives such as imidazoles, phenanthroline derivative, quinoline, quinoxaline derivant, 1, the 5-naphthyridine derivative, oligomeric pyridine derivate such as bipyridine and terpyridyl etc.
Among the present invention, electron transfer layer is meant to be responsible for injecting electronics and transmitting the layer of electronics from negative electrode, wishes its electron injection efficiency height, transmits the electronics that is injected into efficiently.Therefore, require it to be that electron affinity is big and electron mobility big and also when excellent in stability, manufacturing and when use be difficult to produce the material of the impurity that becomes trap.But, under the situation of the transmission balance of consideration hole and electronics, main performance combine again with hole from anode and can stop efficiently to cathode side mobile do the time spent, even the material that the electron transport ability is so not high, the effect that also can improve luminous efficiency and electron transport ability are high is identical.At this moment, electron transfer layer has the effect that can stop the hole trapping layer that the hole moves efficiently.
Electron transfer layer of the present invention is stacked or mix one or two or more kinds or formed by the mixture of electron transport material and high polymer binder.In addition, also can in the electron transport material, mix inorganic salts cambium layer such as metal, lithium fluoride or cerium fluoride such as lithium or cerium.
As the electron transport material, the material that is used for light-emitting component more preferably of the present invention also can use with the 8-hydroxyquinoline derivative metal complex of oxine aluminium as representative, the tropolone metal complex, flavonols metal complex perylene derivative, the Perynone derivative, naphthalene derivatives, coumarin derivative, pyridine derivate, quinoline, quinoxaline derivant, the benzoquinoline derivative, phenanthroline derivative, thiophene derivant oxazole derivative, thiazole oxadiazole derivative, triazole derivative, benzothiazole derivant benzoxazole derivative, benzimidizole derivatives, the diphenyl phosphine oxide derivative, thiophene is coughed up derivative, the tri-phenyl-silane derivative, the aldazine derivative, the distyrene derivative, pyrazines derivatives etc.
Be used for above-mentioned hole transport layer, luminescent layer, the material of electron transfer layer can be stacked, the material that mixes one or two or more kinds forms each layer, also can be dispersed in the polyvinyl chloride as high polymer binder, Merlon, polystyrene, poly-(N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfones, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polysulfones, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane resin equal solvent soluble resin, or phenol resin, xylene resin, Petropols, urea resin, melmac, unsaturated polyester resin, alkyd resins, epoxy resin, use in the curable resins such as silicones etc.Above-mentioned high polymer binder is used to form heat-staple film, preferably adopts rubbing method or ink-jet method this moment.
The formation method of the organic layer in the light-emitting component of the present invention is not particularly limited in resistance heating evaporation, electron beam evaporation plating, sputter, molecule layered manner, rubbing method etc.Usually consider preferred resistance heating evaporation or electron beam evaporation plating from the characteristic aspect.The thickness of layer also depends on the resistance value of organic layer, can't limit, preferably between 1～1000nm.
Electric energy mainly is meant direct current among the present invention, also can adopt pulse current or alternating current.Current value and magnitude of voltage are not particularly limited, consider consumption electric power, the life-span of element, be set at the current value and the magnitude of voltage that can obtain high-high brightness with alap energy.
Light-emitting component of the present invention preferably uses the matrix type light-emitting component.Herein, matrix type is meant that the pixel arrangement that is used to show becomes cancellate light-emitting component, with the set display text or the image of pixel.The shape and the size of pixel depend on purposes.For example, usually using on one side is image and the literal demonstration that the following quadrilateral pixels of 300 μ m is carried out personal computer, monitor, TV etc., under the situation of display floater and so on giant display, Yi Bian use pixel as the mm grade.When carrying out the monochrome demonstration,, when carrying out the colour demonstration, arrange the red, green, blue pixel and show as long as arrange homochromy pixel.At this moment, typical arrangement mode has triangular form and stripe shape.As the driving method of this matrix, can drive in method or the active matrix any successively for line.Line drives successively has advantage of simple structure, considers operating characteristic, adopts active matrix more favourable sometimes, preferably uses according to purposes.
Light-emitting component of the present invention also is preferably used as the segment type light-emitting component.Herein, segment type is meant in order to show predetermined information and forms pattern, makes definite regional luminous light-emitting component.For example, can enumerate the demonstration, the panel demonstration of automobile etc. of operating state of demonstration, audio equipment or the electromagnetic cooker etc. of moment in digital dock or the thermometer or temperature.Above-mentioned matrix shows that demonstration also can co-exist among the identical panel with section.
Light-emitting component of the present invention also is preferably used as backlight.Herein, backlight mainly uses in order to improve the visuognosis of not carrying out self light-emitting display device, is used for liquid crystal indicator, clock, audio equipment, car panel, display panel, directional beacon etc.Particularly as be used for liquid crystal indicator, wherein with the slim backlight that turns to the personal computer of problem because existing backlight is made of fluorescent lamp or light guide plate, therefore be difficult to slimming, and backlight of the present invention is characterised in that slim, light weight.
Embodiment
Below, enumerate embodiment and comparative example explanation the present invention, but the present invention is not limited to following example.
Embodiment 1 (E-20's is synthetic)
Make 8-amino-7-quinoline aldehyde 101g 1, the reaction down 10 hours that refluxes among 3-diacetyl benzene 45g, 85% potassium hydroxide 100g and the ethanol 1800ml adopts common method to handle, and obtains 1,3-two (1,10-phenanthroline-2-yl) benzene 100g.With above-mentioned 1,3-two (1,10-phenanthroline-2-yl) benzene 40.8g in toluene 750ml with phenyl lithium (0.94M cyclohexane/ethereal solution) 400ml ice-cooled reaction down 2.5 hours, adopt common method to handle.The product and the nitrobenzene 118g that obtain were reacted 3 hours down at 110 ℃, adopt common method to handle, obtain 22.8gE-20.
The compound that obtains is dissolved in CDCl
3In, use
1H-NMR measures, and observes following peak.
1H-NMR(ppm)：9.75(s，
1H)、8.72(d·d，2H)、8.57-8.17(m，12H)、7.90-7.82(m，5H)、7.61-7.48(m，6H)。
Need to prove that this E-20 uses oil diffusion pump 1.0 * 10
-3Carry out being used for light-emitting component behind the sublimation purifying under the pressure of Pa, under about 320 ℃.The purity of E-20 behind the sublimation purifying is used HPLC (C8 post, eluent: 0.1% phosphate aqueous solution/acetonitrile) measure.As a result, HPLC purity (measuring the area % at wavelength 254nm place) is 99.9%.Among the following embodiment, HPLC purity makes to use the same method and measures.
Embodiment 2 (E-9's is synthetic)
1-bromonaphthalene 11.9g and lithium 1.6g were reacted 3 hours under the room temperature in ether 58ml, the deep purple solution that generates at room temperature is added drop-wise to 1, in the toluene suspension-turbid liquid (100ml) of 4-two (1,10-phenanthroline-2-yl) benzene 5.0g.Reaction adopted common method to handle after 3 days under the room temperature.The product that obtains was reacted 3 hours under room temperature with manganese dioxide 100g in carrene 400ml, adopt common method to handle, obtain 1.14g E-9.
1H-NMR(CDCl
3，ppm)：8.55-7.16(m，30H)。
Need to prove that this E-9 carries out being used for light-emitting component behind the sublimation purifying similarly to Example 1.HPLC purity behind the sublimation purifying (measuring the area % at wavelength 254nm place) is 99.8%.
Embodiment 3 (E-57's is synthetic)
With 2,7-dihydroxy naphthlene 54.0g is dissolved among the carrene 680ml pyridine 136ml, and 0 ℃ drips trifluoromethanesulfanhydride anhydride (Tokyo changes into industry (strain) system) 228g down.5 ℃ of down reactions 2 hours, then at room temperature react 1 day after, adopt common method to handle, obtain 2,7-two (trifluoro-methanesulfonyl oxy) naphthalene 143g.With this 2,7-two (trifluoro-methanesulfonyl oxy) naphthalene 143g and n-butyl vinyl ether 216ml, triethylamine 113ml, 1,3-two (diphenylphosphino) propane 2.78g, acid chloride 0.76g, dimethyl formamide 680m mix, 70～85 ℃ of reactions 2 days down.Adopt common method to handle, obtain 2,7-diacetyl naphthalene 40g.With this 2,7-diacetyl naphthalene 4.62g in ethanol 220ml 60 ℃ down with 8-amino-7-quinoline aldehyde 7.87g, potassium hydroxide 7.9g reaction, the employing common method is handled, and obtains 2,7-two (1,10-phenanthroline-2-yl) naphthalene 4.44g.With this 2,7-two (1,10-phenanthroline-2-yl) naphthalene 5.48g at room temperature reacted 2 days with phenyl lithium (2.0M cyclohexane/ethereal solution) 22.6ml in toluene 200ml, adopted common method to handle.The product that obtains was reacted 2.5 hours under room temperature with manganese dioxide 100g in carrene 400ml, adopt common method to handle, obtain 0.93g E-57.
1H-NMR(CDCl
3，ppm)：8.96(s，2H)、8.86(d·d，2H)、8.61-8.51(m，4H)、8.42-8.34(m，6H)、8.18(d·d，4H)、7.84(m，4H)、7.65-7.48(m，6H)。
Need to prove, this E-57 is carried out being used for light-emitting component behind the sublimation purifying similarly to Example 1.HPLC purity behind the sublimation purifying (measuring the area % at wavelength 254nm place) is 99.8%.
Embodiment 4 (E-25's is synthetic)
1-bromo-4-tert-butyl benzene 5.88g and lithium 0.76g were reacted 5 hours under refluxing in Anaesthetie Ether 50ml, the grey solution that generates is added drop-wise to 1 under ice-cooled, in the toluene suspension-turbid liquid (150ml) of 3-two (1,10-phenanthroline-2-yl) benzene 4.0g.After 1 hour, adopt common method to handle in ice-cooled reaction down.The product that obtains was at room temperature reacted 30 minutes with manganese dioxide 66g in carrene 150ml, adopt common method to handle, obtain 3.65g E-25.
1H-NMR(CDCl
3，ppm)：9.81(s，1H)、8.71(d·d，2H)、8.51-8.38(m，8H)、8.31(d，2H)、8.14(d，2H)、7.88-7.81(m，5H)、7.58(d，4H)、1.43(s，18H)。
Need to prove, this E-25 is carried out being used for light-emitting component behind the sublimation purifying similarly to Example 1.HPLC purity behind the sublimation purifying (measuring the area % at wavelength 254nm place) is 99.9%.
Embodiment 5 (E-23's is synthetic)
Make 5-bromo-meta-xylene 6.18g and lithium 0.92g in Anaesthetie Ether 50ml, reflux under reaction 5 hours, ice-cooledly down the grey drips of solution that generates is added to 1, in the toluene suspension-turbid liquid (100ml) of 3-two (1,10-phenanthroline-2-yl) benzene 3.63g.Reaction adopted common method to handle after 2 hours under the room temperature.The product that obtains was at room temperature reacted 2 hours with manganese dioxide 63g in carrene 200ml, adopt common method to handle, obtain 1.4g E-23.
1H-NMR(CDCl
3，ppm)：9.53(s，1H)、8.72(d·d，2H)、8.46-8.14(m，12H)、7.85-7.79(m，5H)、7.13(s，2H)、2.47(s，12H)。
Need to prove, this E-23 is carried out being used for light-emitting component behind the sublimation purifying similarly to Example 1.HPLC purity behind the sublimation purifying (measuring the area % at wavelength 254nm place) is 99.8%.
Embodiment 6 (E-21's is synthetic)
Make 4-toluene bromide 6.84g and lithium 1.1g in Anaesthetie Ether 60m, reflux under reaction 5 hours, ice-cooledly down the grey drips of solution that generates is added to 1, in the toluene suspension-turbid liquid (100ml) of 3-two (1,10-phenanthroline-2-yl) benzene 4.34g.Ice-cooled reaction down adopted common method to handle after 2 hours.The product that obtains was at room temperature reacted 2 hours with manganese dioxide 75g in carrene 200ml, adopt common method to handle, obtain 2.1g E-21.
1H-NMR(CDCl
3，ppm)：9.72(s，1H)、8.72(d·d，2H)、8.53-7.36(m，19H)、2.48(s，6H)。
Need to prove, this E-21 is carried out being used for light-emitting component behind the sublimation purifying similarly to Example 1.HPLC purity behind the sublimation purifying (measuring the area % at wavelength 254nm place) is 99.8%.
Embodiment 7 (E-33's is synthetic)
1-bromonaphthalene 3.57g and lithium 0.48g were reacted 3 hours under the room temperature in Anaesthetie Ether 50ml, and ice-cooled following deep purple solution with generation is added drop-wise to 1, in the toluene suspension-turbid liquid (100ml) of 3-two (1,10-phenanthroline-2-yl) benzene 2.5g.Reaction adopted common method to handle after 2 hours under the room temperature.The product that obtains was at room temperature reacted 15 minutes with manganese dioxide 50g in carrene 500ml, adopt common method to handle, obtain 0.4g E-33.
1H-NMR(CDCl
3，ppm)：9.43(s，1H)、9.02(d，2H)、8.53(d，2H)、8.40(d，2H)、8.29-7.43(m，23H)。
Need to prove, this E-33 is carried out being used for light-emitting component behind the sublimation purifying similarly to Example 1.HPLC purity behind the sublimation purifying (measuring the area % at wavelength 254nm place) is 99.8%.
Embodiment 8 (E-4's is synthetic)
Make 1,4-two (1,10-phenanthroline-2-yl) benzene 2.5g in toluene 100ml with phenyl lithium (2.0M cyclohexane/ethereal solution) 11.5ml in ice-cooled down reaction 1 hour, at room temperature reacted 4 hours then, adopt common method to handle.The product that obtains was at room temperature reacted 5 minutes with manganese dioxide 50g in carrene 400ml, adopt common method to handle, obtain 0.80gE-4.
1H-NMR(CDCl
3，ppm)：8.75(s，4H)、8.53(d，4H)、8.39-8.18(m，8H)、7.84(s，4H)、7.65-7.50(m，6H)。
Need to prove, this E-4 is carried out being used for light-emitting component behind the sublimation purifying similarly to Example 1.HPLC purity behind the sublimation purifying (measuring the area % at wavelength 254nm place) is 99.9%.
Embodiment 9 (E-8's is synthetic)
Make 1-bromo-4-tert-butyl benzene 3.68g and lithium 0.48g in Anaesthetie Ether 50ml, reflux under reaction 5 hours, ice-cooledly down the grey drips of solution that generates is added to 1, in the toluene suspension-turbid liquid (150ml) of 4-two (1,10-phenanthroline-2-yl) benzene 2.5g.After 3 hours, adopt common method to handle in ice-cooled reaction down, obtain 1.66g E-8.
1H-NMR(CDCl
3，ppm)：8.73(s，4H)、8.45-8.15(m，12H)、7.82(s，4H)、7.62-7.12(m，4H)、1.40(s，18H)。
Need to prove, this E-8 is carried out being used for light-emitting component behind the sublimation purifying similarly to Example 1.HPLC purity behind the sublimation purifying (measuring the area % at wavelength 254nm place) is 99.9%.
Embodiment 10 (E-17's is synthetic)
Make 1 under ice-cooled, 3-two (1,10-phenanthroline-2-yl) benzene 5.0g reacted 5 hours with lithium methide (2.2M ethereal solution) 17.3ml in toluene 120ml, adopted common method to handle.The product that obtains was at room temperature reacted 2 hours with manganese dioxide 70g in carrene 500ml, adopt common method to handle, obtain 4.25g E-17.
1H-NMR(CDCl
3，ppm)：9.28(s，1H)、8.64(d·d，2H)、8.38(d，4H)、8.17(d，2H)、7.82-7.75(m，5H)、7.54(d，2H)、3.01(s，6H)。
Need to prove, this E-17 is carried out being used for light-emitting component behind the sublimation purifying similarly to Example 1.HPLC purity behind the sublimation purifying (measuring the area % at wavelength 254nm place) is 99.8%.
Embodiment 11
Preparation is that to adopt the sputter vapour deposition method to form thickness be the ito substrate of the ITO film of 130nm as anode for the alkali-free glass surface of 1.1mm at thickness.After using photoetching process that this ITO film is formed pattern, be cut into the size of 46mm * 38mm, being produced on substrate center portion, to have width be the substrate of the ITO film of 12mm.
This substrate is cleaned with " Semicoclean 56 " (FURUUCHI chemistry (strain) system), be placed in the vacuum deposition apparatus after handling with UV ozone, being vented to vacuum degree is 5 * 10
-5Pa.Disposing under the organic layer usefulness state of shadow mask with the foursquare peristome of 15mm, utilize electrical resistance heating, at first, as hole-injecting material, evaporation thickness is the copper phthalocyanine of 20nm, as the hole-transfer material, evaporation thickness is 4,4 '-two (N-(1-naphthyl)-N-phenyl amino) biphenyl of 100nm.Then, as luminescent material, evaporation thickness is the trihydroxy quinoline aluminum complex (Alq3) of 50nm.Then, as the electron transport material, evaporation thickness is the above-mentioned E-20 of 100nm.Then, with lithium doping in the organic layer of 0.5nm.Then, change organic layer the negative electrode shadow mask of the peristome with 45 * 12nm into shadow mask, evaporation thickness is the aluminium of 200nm, makes negative electrode.So-called herein thickness is meant quartzy starting of oscillation formula thickness monitor show value.Make the light-emitting component of the light-emitting zone that has 45 * 5mm on the substrate thus.When in this light-emitting component, flowing through the direct current of 1mA, obtain brightness and be 200 banks/square metre green emitting.Need to prove that it is to measure under 0.2 degree, the condition of response time as 1ms at angle of visibility that luminance meter (topological Kang She system, BM-8) is used in brightness.The driving voltage of this moment is 5.5V.The durability of this light-emitting component is very excellent, 1mA decide under the current drives condition kept 85% brightness through 1000 hours.
When in the vacuum pond, this light-emitting component being implemented 1mA pulsed drive (Duty than be 1/60, current value during pulse is 60mA), confirm good luminous.
Residue behind the recovery E-20 evaporation is measured HPLC purity.HPLC purity (measuring the area % at wavelength 254nm place) is 99.9% as a result, and compares before the evaporation, and purity does not reduce.Hence one can see that, and the sublimability of E-20 is good, do not take place to decompose during evaporation or sex change such as polymerization.
Embodiment 12～20
Use the material of putting down in writing in the table 1 as the electron transport material, in addition, fully similarly make light-emitting component with embodiment 11.The evaluation result of the light-emitting component that obtains and the HPLC purity of the residue behind the evaporation are shown in table 1.
Table 1
| The electron transport material | Illuminant colour | Brightness (cd/m 2) | Driving voltage (V) | Through the brightness conservation rate (%) after 1000 hours | The HPLC purity (%) of residue behind the evaporation | |
| Embodiment 11 | ??E-20 | Green | ??200 | ??5.5 | ??85 | ??99.9 |
| Embodiment 12 | ??E-9 | Green | ??195 | ??5.4 | ??78 | ??99.8 |
| Embodiment 13 | ??E-57 | Green | ??195 | ??5.6 | ??80 | ??99.8 |
| Embodiment 14 | ??E-25 | Green | ??203 | ??5.5 | ??85 | ??99.9 |
| Embodiment 15 | ??E-23 | Green | ??198 | ??5.6 | ??85 | ??99.8 |
| Embodiment 16 | ??E-21 | Green | ??197 | ??5.5 | ??85 | ??99.8 |
| Embodiment 17 | ??E-33 | Green | ??202 | ??5.4 | ??85 | ??99.8 |
| Embodiment 18 | ??E-4 | Green | ??205 | ??5.4 | ??86 | ??99.9 |
| Embodiment 19 | ??E-8 | Green | ??206 | ??5.4 | ??87 | ??99.9 |
| Embodiment 20 | ??E-17 | Green | ??208 | ??5.6 | ??80 | ??99.8 |
Comparative example 1
In addition P-1 as the electron transport material uses following formula to represent, fully similarly makes light-emitting component with embodiment 11.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 200 banks/square metre green emitting.The driving voltage of this moment is 7.0V.This light-emitting component 1mA decide reduce by half through brightness in 900 hours under the current drives condition.
Comparative example 2
In addition P-2 as the electron transport material uses following formula to represent, fully similarly makes light-emitting component with embodiment 11.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 190 banks/square metre green emitting.The driving voltage of this moment is 6.8V.This light-emitting component 1mA decide reduce by half through brightness in 1000 hours under the current drives condition.
Comparative example 3
In addition P-3 as the electron transport material uses following formula to represent, fully similarly makes light-emitting component with embodiment 11.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 195 banks/square metre green emitting.The driving voltage of this moment is 7.1V.This light-emitting component 1mA decide reduce by half through brightness in 500 hours under the current drives condition.
Comparative example 4
In addition P-4 as the electron transport material uses following formula to represent, fully similarly makes light-emitting component with embodiment 11.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 200 banks/square metre green emitting.The driving voltage of this moment is 7.2V.This light-emitting component 1mA decide reduce by half through brightness in 450 hours under the current drives condition.
Comparative example 5
In addition P-5 as the electron transport material uses following formula to represent, fully similarly makes light-emitting component with embodiment 11.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 180 banks/square metre green emitting.The driving voltage of this moment is 7.0V.This light-emitting component 1mA decide reduce by half through brightness in 300 hours under the current drives condition.
Comparative example 6
In addition P-6 as the electron transport material uses following formula to represent, fully similarly makes light-emitting component with embodiment 11.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 190 banks/square metre green emitting.The driving voltage of this moment is 6.8V.This light-emitting component 1mA decide reduce by half through brightness in 700 hours under the current drives condition.
Comparative example 7
In addition P-7 as the electron transport material uses following formula to represent, fully similarly makes light-emitting component with embodiment 11.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 195 banks/square metre green emitting.The driving voltage of this moment is 5.6V.This light-emitting component 1mA decide under the current drives condition kept 80% brightness through 1000 hours.
The residue that reclaims behind this P-7 evaporation is measured HPLC purity.HPLC purity (measuring the area % at wavelength 254nm place) is 98.0% as a result, compares purity with (99.9%) before the evaporation and reduces.Hence one can see that, and P-7 decomposes when evaporation.
Comparative example 8
In addition P-8 as the electron transport material uses following formula to represent, fully similarly makes light-emitting component with embodiment 11.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 200 banks/square metre green emitting.The driving voltage of this moment is 5.5V.This light-emitting component 1mA decide under the current drives condition kept 80% brightness through 1000 hours.
The residue that reclaims behind this P-8 evaporation is measured HPLC purity.HPLC purity (measuring the area % at wavelength 254nm place) is 98.2% as a result, compares purity with (99.8%) before the evaporation and reduces.Hence one can see that, and P-8 decomposes when evaporation.
Embodiment 21
As luminescent material, use trihydroxy quinoline aluminum complex (Alq3) as material of main part, use 4-(dicyano the methylene)-2-tert-butyl group-6-(1,1,7,7-tetramethyl julolidine groups-9-Ene alkynyl base)-4H-pyrans (DCJTB) is as guest materials, and making doping content is 2%, in addition, fully similarly make light-emitting component with embodiment 11.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 200 banks/square metre orange red luminous.The driving voltage of this moment is 5.5V.The durability of this light-emitting component is very excellent, 1mA decide under the current drives condition kept 80% brightness through 1000 hours.
Embodiment 22～30
Use the material of putting down in writing in the table 2 as the electron transport material, in addition, make light-emitting component identically with embodiment 21.The evaluation result of the light-emitting component that obtains is shown in table 2.
Table 2
| The electron transport material | Illuminant colour | Brightness (cd/m 2) | Driving voltage (V) | Through the brightness conservation rate (%) after 1000 hours | |
| Embodiment 21 | ??E-20 | Orange red | ??200 | ??5.5 | ??80 |
| Embodiment 22 | ??E-9 | Orange red | ??200 | ??5.4 | ??80 |
| Embodiment 23 | ??E-57 | Orange red | ??200 | ??5.5 | ??80 |
| Embodiment 24 | ??E-25 | Orange red | ??205 | ??5.5 | ??82 |
| The electron transport material | Illuminant colour | Brightness (cd/m 2) | Driving voltage (V) | Through the brightness conservation rate (%) after 1000 hours | |
| Embodiment 25 | ??E-23 | Orange red | ??200 | ??5.5 | ??80 |
| Embodiment 26 | ??E-21 | Orange red | ??206 | ??5.4 | ??81 |
| Embodiment 27 | ??E-33 | Orange red | ??200 | ??5.6 | ??79 |
| Embodiment 28 | ??E-4 | Orange red | ??205 | ??5.4 | ??82 |
| Embodiment 29 | ??E-8 | Orange red | ??208 | ??5.4 | ??82 |
| Embodiment 30 | ??E-17 | Orange red | ??208 | ??5.6 | ??80 |
Comparative example 9
Use aforesaid P-1 as the electron transport material, in addition, make light-emitting component identically with embodiment 21.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 180 banks/square metre orange red luminous.The driving voltage of this moment is 7.5V.This light-emitting component 1mA decide reduce by half through brightness in 1000 hours under the current drives condition.
Comparative example 10
Use aforesaid P-2 as the electron transport material, in addition, make light-emitting component identically with embodiment 21.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 180 banks/square metre orange red luminous.The driving voltage of this moment is 7.3V.This light-emitting component 1mA decide reduce by half through brightness in 1000 hours under the current drives condition.
Comparative example 11
Use aforesaid P-3 as the electron transport material, in addition, make light-emitting component identically with embodiment 21.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 190 banks/square metre orange red luminous.The driving voltage of this moment is 7.4V.This light-emitting component 1mA decide reduce by half through brightness in 800 hours under the current drives condition.
Comparative example 12
Use aforesaid P-4 as the electron transport material, in addition, make light-emitting component identically with embodiment 21.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 200 banks/square metre orange red luminous.The driving voltage of this moment is 7.5V.This light-emitting component 1mA decide reduce by half through brightness in 800 hours under the current drives condition.
Comparative example 13
Use aforesaid P-5 as the electron transport material, in addition, make light-emitting component identically with embodiment 21.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 190 banks/square metre orange red luminous.The driving voltage of this moment is 7.5V.This light-emitting component 1mA decide reduce by half through brightness in 600 hours under the current drives condition.
Comparative example 14
Use aforesaid P-6 as the electron transport material, in addition, make light-emitting component identically with embodiment 21.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 200 banks/square metre orange red luminous.The driving voltage of this moment is 6.5V.This light-emitting component 1mA decide reduce by half through brightness in 1000 hours under the current drives condition.
Embodiment 31
As luminescent material, use 4,4 '-two (diphenylacetylene) biphenyl (DPVBi) as material of main part, use two (carbazyl vinyl) biphenyl (BCZVBi) as guest materials, making doping content is 5%, in addition, fully similarly makes light-emitting component with embodiment 11.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 190 banks/square metre blue-light-emitting.The driving voltage of this moment is 4.8V.Thus, the material that is used for light-emitting component of the present invention also can play a role at blue light emitting device.This light-emitting component 1mA decide reduce by half through brightness in 100 hours under the current drives condition, this be since be not electron transport material but material of main part through the time crystallization.
Comparative example 15
Use aforesaid P-2 as the electron transport material, in addition, make light-emitting component identically with embodiment 31.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 150 banks/square metre blue-light-emitting.The driving voltage of this moment is 6.5V.This light-emitting component 1mA decide reduce by half through brightness in 10 hours under the current drives condition.
Embodiment 32
Use 1 as material of main part, 4-diketo-2,5-two (3, the 5-dimethyl benzyl)-3,6-two (4-aminomethyl phenyl) pyrrolo-[3,4-c] pyrroles, as guest materials, use 4,4-two fluoro-1,3,5,7-tetraphenyl-4-borine-3a, 4a-diaza-indacene, making doping content is 1%, in addition, makes light-emitting component with embodiment 21 identically.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 210 banks/square metre emitting red light.The driving voltage of this moment is 5.2V.The durability of this light-emitting component is very excellent, 1mA decide under the current drives condition kept 80% brightness through 1000 hours.
Embodiment 33～41
Use the material of putting down in writing in the table 3 as the electron transport material, in addition, make light-emitting component identically with embodiment 32.The evaluation result of the light-emitting component that obtains is shown in table 3.
Table 3
| The electron transport material | Illuminant colour | Brightness (cd/m 2) | Driving voltage (V) | Through the brightness conservation rate (%) after 1000 hours | |
| Embodiment 32 | ??E-20 | Red | ??210 | ??5.2 | ??80 |
| Embodiment 33 | ??E-9 | Red | ??200 | ??5.3 | ??81 |
| Embodiment 34 | ??E-57 | Red | ??203 | ??5.4 | ??81 |
| Embodiment 35 | ??E-25 | Red | ??210 | ??5.2 | ??81 |
| Embodiment 36 | ??E-23 | Red | ??200 | ??5.2 | ??79 |
| Embodiment 37 | ??E-21 | Red | ??212 | ??5.2 | ??81 |
| Embodiment 38 | ??E-33 | Red | ??210 | ??5.0 | ??80 |
| Embodiment 39 | ??E-4 | Red | ??216 | ??5.1 | ??82 |
| The electron transport material | Illuminant colour | Brightness (cd/m 2) | Driving voltage (V) | Through the brightness conservation rate (%) after 1000 hours | |
| Embodiment 40 | ??E-8 | Red | ??215 | ??5.1 | ??82 |
| Embodiment 41 | ??E-17 | Red | ??210 | ??5.5 | ??80 |
Comparative example 16
Use aforesaid P-1 as the electron transport material, in addition, make light-emitting component identically with embodiment 32.When in this light-emitting component, flowing through the 1mA direct current, obtain brightness and be 200 banks/square metre emitting red light.The driving voltage of this moment is 6.5V.This light-emitting component 1mA decide reduce by half through brightness in 1000 hours under the current drives condition.
Embodiment 42
To be that to adopt the sputter vapour deposition method to form thickness on the alkali-free glass surface of 1.1mm be the size that the ito substrate of the ITO film of 130nm is cut into 46mm * 38mm at thickness.Use photoetching process to be processed into the strip pattern of 300 μ m spacings (residual width 270 μ m) * 32 this ITO film.Be connected with external electric easily for the long side direction that makes the ITO bar is one-sided, spreading to spacing is 1.27mm (the peristome width is 800 μ m).This substrate is cleaned with " Semicoclean56 " (FURUUCHI chemistry (strain) system), be placed in the vacuum deposition apparatus after handling with UV ozone, the vacuum degree that is vented in the device is 5 * 10
-4Below the Pa.Utilize electrical resistance heating, at first, as the hole-transfer material, evaporation thickness is 4,4 '-two (N-(tolyl)-N-phenyl amino) biphenyl of 150nm, and as luminescent material, evaporation thickness is the trihydroxy quinoline aluminum complex of 50nm.Then, as the electron transport material, evaporation thickness is the E-20 of 100nm.So-called herein thickness is meant the show value of quartzy starting of oscillation formula thickness monitor.Then, the mask that will utilize Wet-type etching to be provided with the peristome (residual width be 50 μ m, be equivalent to spacing be 300 μ m) of 16 250 μ m on thickness is the kovar alloy plate of 50 μ m carries out the mask exchange in a vacuum, itself and ITO bar are intersected vertically, fix with magnet from the negative, make mask and ito substrate driving fit.With after lithium doping is in the 0.5nm organic layer, evaporation 200nm aluminium is made 32 * 16 dot matrix elements then.This element is applied matrix driving, can not have and carry out the literal demonstration with crosstalking.
Industrial applicability
Of the present invention for light-emitting component material and use the light-emitting component of this material to be applicable to show the fields such as element, flat-panel monitor, backlight, illumination, upholstery, directional beacon, billboard, Electrofax and optical signal generator.
Claims (4)
1. light-emitting component, its between anode and negative electrode, have organic layer, by the luminous element of electric energy, wherein, this organic layer contains hole transport layer, luminescent layer and electron transfer layer, this electron transfer layer contains the material that is used for light-emitting component of general formula (1) expression,
Herein, R
1～R
6Identical or different respectively, among hydrogen atom, alkyl and aryl, select, A represents the phenylene or the naphthylene of n valency, and B represents alkyl or aryl, and X represents nitrogen-atoms, and n represents 2, the substituting group with n phenanthroline skeleton is identical or different respectively.
2. light-emitting component as claimed in claim 1, wherein, the B of above-mentioned general formula (1) be selected from methyl, the tert-butyl group, phenyl, and naphthyl at least a kind.
3. the described light-emitting component of claim 1 of general formula (2) expression,
Herein, A ' expression is selected from 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, 1,5-naphthylene and 2, in the 7-naphthylene at least a kind, B ' expression be selected from methyl, the tert-butyl group, phenyl, and naphthyl at least a kind.
4. light-emitting component as claimed in claim 1, wherein, described organic layer is hole injection layer, hole transport layer, luminescent layer and electron transfer layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101987559A CN101872844B (en) | 2004-08-23 | 2004-08-23 | Material for luminous element and luminous element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106057863A (en) * | 2016-08-15 | 2016-10-26 | 深圳市华星光电技术有限公司 | Multi-primary-color OLED display device |
| CN109728204A (en) * | 2018-12-29 | 2019-05-07 | 上海天马微电子有限公司 | A method of preparing OLED organic function layer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5393614A (en) * | 1992-04-03 | 1995-02-28 | Pioneer Electronic Corporation | Organic electroluminescence device |
| WO2002043449A1 (en) * | 2000-11-24 | 2002-05-30 | Toray Industries, Inc. | Luminescent element material and luminescent element comprising the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106057863A (en) * | 2016-08-15 | 2016-10-26 | 深圳市华星光电技术有限公司 | Multi-primary-color OLED display device |
| CN106057863B (en) * | 2016-08-15 | 2019-05-31 | 深圳市华星光电技术有限公司 | More primary colors OLED displays |
| CN109728204A (en) * | 2018-12-29 | 2019-05-07 | 上海天马微电子有限公司 | A method of preparing OLED organic function layer |
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| CN101872844B (en) | 2012-08-08 |
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