CN101469265A - Organic electroluminescence material and element using the same - Google Patents
Organic electroluminescence material and element using the same Download PDFInfo
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- CN101469265A CN101469265A CNA2008101886315A CN200810188631A CN101469265A CN 101469265 A CN101469265 A CN 101469265A CN A2008101886315 A CNA2008101886315 A CN A2008101886315A CN 200810188631 A CN200810188631 A CN 200810188631A CN 101469265 A CN101469265 A CN 101469265A
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Abstract
An organic EL element having one or a plurality of organic layers including a light emitting layer between a pair of electrodes is arranged such that at least one layer of the above-mentioned organic layers contains a compound as expressed by the following general formula (1) independently or as a mixture. (where R1-R4 are selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, and an aryloxy group, and they may be the same groups or the groups different from one another, and A1-A4 are selected from the group consisting of a phenyl group which is either substituted or unsubstituted and a 5 or 6 member heterocyclic ring group which is either substituted or unsubstituted, and they may be the same groups or the groups different from one another.).
Description
Technical field
The present invention relates to be used to obtain the electroluminescent organic material that contains novel naphthalene derivatives of blue-light-emitting of purity of color excellence and the organic electroluminescent device (hereinafter referred to as organic EL) that uses this material.
Background technology
Organic EL owing to can be at full speed luminous, be suitable for the demonstration of live image for being the emissive type element of luminescent material with the organic compound, and component structure is simple in addition, has characteristics such as can making the display panel slimming.Because have the characteristic of this excellence, organic EL is universal day by day in daily life as portable phone, vehicle mounted indicating meter.
In addition, utilize different with LED, can to carry out face luminous, the characteristic of slim and light weight, developed as the technological development of illumination panel light source.
Above-mentioned organic EL by the luminescent pigment of the trace that mixes, is realized luminous high efficiency in matrix (ホ ス ト).Therefore, substrate material is important obtaining on the high efficiency organic EL.
In particular for obtaining the high white-light luminescent component of color developing, the substrate material that can be effectively obtains blue-light-emitting from the blue-light-emitting pigment is absolutely necessary.
As known blue-light-emitting substrate material in the past, naphthalene derivativeses shown in diphenylethyllene arylene derivatives shown in anthracene derivant shown in for example known following (changing 1), (the changing 2), following (the changing 3), following (the changing 4) etc. are (for example with reference to Japanese kokai publication hei 11-312588 communique, TOHKEMY 2005-222948 communique, Japanese kokai publication hei 2-247278 communique, J.Shi.et al., Applied Physics Letters, 80 (17) .p.3201).
[changing 1]
[changing 2]
[changing 3]
[changing 4]
But, above-mentioned Japanese kokai publication hei 11-312588 communique, TOHKEMY 2005-222948 communique, Japanese kokai publication hei 2-247278 communique, J.Shi.et al., Applied PhysicsLetters, the material of putting down in writing among 80 (17) .p.3201 turns blue green, nattier blue light, when using, be difficult to obtain the high blue-light-emitting of the desired purity of color of white-light luminescent component of high-color rendering as substrate material.
Summary of the invention
The present invention proposes in order to solve the problems of the technologies described above, and its purpose is, luminous novel organic EL Material of the blue emitting material that can make the purity of color excellence and the organic EL that uses this organic EL Material are provided.
Organic EL Material of the present invention is represented with following general formula (1).
[changing 5]
In the above-mentioned general formula (1), R
1～R
4Be selected from hydrogen, alkyl, cycloalkyl, alkoxyl group, cycloalkyloxy and the aryloxy, be identical or different separately group.A
1～A
4Be selected from replace or unsubstituted phenyl, 5 or 6 yuan replacement or unsubstituted heterocyclic in, be identical or different separately group.
By using such compound, can obtain as (development light territory, luminous territory as organic EL Material) useful, the blue-light-emitting of purity of color excellence.
In addition, organic EL of the present invention is characterized in that for to have 1 layer or the organic EL of multilayer organic layer that contains luminescent layer between pair of electrodes, and at least 1 layer of above-mentioned organic layer contains above-mentioned organic EL Material separately or with the form of mixture.
By using the organic EL Material of the invention described above, can constitute the element of the blue-light-emitting that presents the purity of color excellence.
In the above-mentioned organic EL, at least 1 layer of preferred above-mentioned organic layer for contain above-mentioned organic EL Material as substrate material, as the fluorescence of guest materials or the luminescent layer of phosphorescent material.
In addition, above-mentioned electrode is preferably on transparency carrier and forms that transparent conducting film forms.
As mentioned above, according to organic EL Material of the present invention,,, can provide the white-light luminescent component of high-color rendering by using this organic EL Material in order to obtain the blue-light-emitting of purity of color excellence.
Therefore, organic EL of the present invention, in recent years the OA computer that expectation is applied to require more excellent colorrendering quality with or the flat-panel monitor used of wall hanging TV set, and then the backlight of light source, liquid-crystal display or the measuring instrument class of illumination instrument, duplicating machine etc. utilizes in light source as the feature of planar luminous body, display panel, the sign lamp.
Description of drawings
Fig. 1 is the fluorescence spectrum figure of TMN1357.
Fig. 2 is the fluorescence spectrum figure of N20.
Fig. 3 is the schematic cross-section of layer structure of the organic EL of embodiment 2.
Fig. 4 is the luminescent spectrum figure of the organic EL of embodiment 2.
Fig. 5 is the luminescent spectrum figure of the organic EL of comparative example 2.
Fig. 6 is the luminescent spectrum figure of the organic EL of embodiment 3.
Fig. 7 is the luminescent spectrum figure of the organic EL of comparative example 3.
Embodiment
Below the present invention is carried out more specific description.
Organic EL Material of the present invention is the compound shown in the above-mentioned general formula (1).
This naphthalene derivatives is the novel cpd that obtains the blue-light-emitting of purity of color excellence, if use this compound that the white-light luminescent component of high-color rendering then can be provided.
In the above-mentioned general formula (1), R
1～R
4Be selected from hydrogen, alkyl, cycloalkyl, alkoxyl group, cycloalkyloxy and the aryloxy, be identical or different separately group.In addition, A
1～A
4Be selected from replace or unsubstituted phenyl, 5 or 6 yuan replacement or unsubstituted heterocyclic in, be identical or different separately group.
In the above-mentioned substituting group, alkyl is for example represented representative examples of saturated aliphatic alkyl such as methyl, ethyl, propyl group, butyl, can be the straight chain shape, also can be the side chain shape.
Cycloalkyl is saturated alicyclic hydrocarbon bases such as representative ring hexyl, norcamphyl (ノ Le ボ Le ニ Le base), adamantyl for example, can not replace, and also can be substituted.
Alkoxyl group is for example represented (the エ-テ Le by ehter bond such as methoxyl group
Close The Jie) the representative examples of saturated aliphatic alkyl, can be for the straight chain shape, also can be for the side chain shape.
Cycloalkyloxy for example representative ring hexyl etc. can not replace by the ring-type representative examples of saturated aliphatic alkyl of ehter bond, can be substituted yet.
Aryloxy is for example represented the aromatic hydrocarbyl by ehter bond such as phenoxy group, and aromatic hydrocarbyl can not replace, and can be substituted yet.
The phenyl that replaces is represented by the phenyl of alkyl, cycloalkyl, alkoxyl group, cycloalkyloxy, aryloxy replacement.
Heterocyclic radical represents also to contain any one group as ring formation element in nitrogen, sulphur or the oxygen except carbon.Can enumerate for example ， oxazole, oxadiazole, thiazole, thiadiazoles, furans, furazan, thiophene, pyrans, thiapyran, pyrroles, pyrazoles, tetrahydroglyoxaline, imidazoles, pyrazine, pyridine, pyridazine, pyrimidine, triazole, triazine etc., can not replace, also can be substituted.
Below, enumerate in the compound shown in the above-mentioned general formula (1), be bonded to A
1～A
4In any one substituent object lesson.In the replacement shown in following (change 6) or unsubstituted phenyl, 5 or 6 yuan replacement or unsubstituted heterocyclic, X represents with the bonding position of naphthalene nucleus, is A
1～A
4In bonding position.
[changing 6]
Further, below enumerate the structure of the particular compound in the compound shown in the above-mentioned general formula (1).
[changing 7]
[changing 8]
In the compound that above-mentioned (changing 7), (changing 8) are enumerated, enumerate 1,3,5 shown in following (changing 9) especially, 7-tetramethylphenyl naphthalene (being designated hereinafter simply as TMN1357) is as representative.
[changing 9]
Compound shown in the above-mentioned general formula (1) can synthesize by known building-up reactions in the past.
For example, replacing naphthalene with diamino is raw material, amino is replaced into the halogen of regulation by sandmeyer reaction.Di-substituted to the halogen that obtains, substituent position of bromination halogen in the presence of transition metal powders (being preferably iron powder) obtains bromine compounds (smelly plain body).
Then, by the linked reaction that this bromine compounds and the transition-metal catalysts such as use Ni, Pd of corresponding coupling agent carry out, the naphthalene derivatives shown in the synthetic above-mentioned general formula (1).
At this moment, the halogen during by suitable selection sandmeyer reaction can be in the linked reaction that transition-metal catalysts such as using Ni, Pd carries out, the compound shown in the synthetic asymmetrical above-mentioned general formula (1).
Raw material is not limited especially, except the diamino matrix (ジ ア ミ ノ body) of the above-mentioned naphthalene of enumerating, can also use dihalo-body (ジ Ha ロ ゲ Application body), dihydroxy matrix (ジ ヒ De ロ キ シ body), dialkoxy matrix (ジ ア Le コ キ シ body) etc.
In addition, use Diels-Alder reaction, also can synthesize the compound shown in the above-mentioned general formula (1).
Organic EL of the present invention with layer of the organic EL Material that contains the above-mentioned blue-light-emitting that obtains the purity of color excellence, structure for stacked 1 layer or multilayer organic layer between electrode, specifically, can enumerate the 1st electrode/luminescent layer/the 2nd electrode, the 1st electrode/hole transporting layer/luminescent layer/electron supplying layer/the 2nd electrode, the 1st electrode/hole transporting layer/luminescent layer/the 2nd electrode, the 1st electrode/luminescent layer/electron supplying layer/structures such as the 2nd electrode.
Further, can form the known rhythmo structure that also contains hole injection layer, cavity conveying luminescent layer, electron injecting layer, electron transport luminescent layer etc.
The electrode of organic EL of the present invention is preferably and forms the electrode that transparent conducting film forms on transparency carrier.
Aforesaid substrate forms the supporter of organic EL, when substrate one side is light-emitting area, and the preferred transparency carrier that has light transmission for visible light that uses.Transmittance is preferably more than 80%, more preferably more than 85%.More preferably more than 90%.
As above-mentioned transparency carrier, usually use glass substrates such as opticglass, silica glass, non-alkali glass, pyrex, silicoaluminate glass such as BK7, BaK1, F2, acrylic resins such as PMMA, polycarbonate, the polyether sulphur acid esters (polymeric substrates of polyester such as Port リ エ-テ Le ス Le ホ ネ-ト), polystyrene, polyolefine, Resins, epoxy, polyethylene terephthalate etc.
The thickness of aforesaid substrate is generally about 0.1～10mm, but considers physical strength, weight etc., is preferably 0.3～5mm, more preferably 0.5～2mm.
In addition, among the present invention, the 1st electrode is set on aforesaid substrate preferably.The 1st electrode is generally anode, formations such as the metal by work function big (more than the 4eV), alloy, conductive compound, and preferably the form with transparency electrode forms on above-mentioned transparency carrier.
This transparency electrode is used metal oxides such as tin indium oxide (ITO), indium zinc oxide, zinc oxide usually, particularly considers from aspects such as the transparency or electroconductibility, preferably uses ITO.
The thickness of this transparency electrode in order to ensure the transparency and electroconductibility, is preferably 80～400nm, more preferably 100～200nm.
Anodic forms usually and is undertaken by sputtering method, vacuum vapour deposition etc., and preferably the form with transparent conducting film forms.
On the other hand, when above-mentioned anode was the 1st electrode, the negative electrode of 2nd electrode opposed with it constituted by metal, alloy, the conductive compound of work function little (4eV is following).For example can enumerate aluminium, aluminium-lithium alloy, magnesium-silver alloys etc.
The thickness of above-mentioned negative electrode is preferably 10～500nm, more preferably 50～200nm.
Above-mentioned anode and negative electrode can form by normally used method film forming such as sputtering method, ion plating method or vapour deposition methods.
The material that uses in above-mentioned hole injection layer, hole transporting layer, the cavity conveying luminescent layer is not limited especially, can from material known, suitably select to use.
Specifically, can enumerate two (two (p-methylphenyl) aminophenyls)-1, the 1-hexanaphthene (common name: TAPc), Spiro-TPD (change 10), N, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (common name: TPD), N, N '-phenylbenzene-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (common name: α-NPD), TPTE (changing 11), star-like amine (ス -バ-ス ト ア ミ Application
) (changing 12), styryl amine arylamines derivatives such as (changing 13).
[changing 10]
[changing 11]
[changing 12]
[changing 13]
In addition, also can use two (N-aryl carbazoles) (changing 14), two (N-thiazolinyl carbazoles), two (N-alkyl carbazole) carbazole derivative of etc.ing, pyrazoline derivative, compound of styryl such as (changing 15), (changing 16), (change 17) with and derivative.
[changing 14]
[changing 15]
[changing 16]
[changing 17]
In addition, can also use anthracene, benzophenanthrene (triphenylene), perylene, naphthalene, pyrene, coronene,
, condensed polycyclc aromatic hydrocarbon compound and their derivatives such as tetracene, naphthacene, phenanthrene, polynuclear compound and their derivatives such as p-terphenyl, quaterphenyl, metaphenylene (m-Off ェ ニ レ Application) (changing 18), (changing 19).
[changing 18]
[changing 19]
Further, as hole injection layer, hole transporting layer, cavity conveying luminescent layer, can use above-mentioned organic compound is dispersed in the material that obtains in polymkeric substance, oligopolymer or the dendritic macromole, or the material that obtains of polymerization materialization, oligomeric materialization or dendritic macromoleization.
In addition, also can use so-called pi-conjugated polymkeric substance such as p-phenylene vinylene's (Port リ パ ラ Off ェ ニ レ Application PVC ニ レ Application), poly-fluorenes or derivatives thereof, with poly-(N-vinylcarbazole) is the cavity conveying non-conjugated polymeric thing of representative, is the σ conjugated polymers etc. of representative with the polysilanes.Further, can also use so-called conjugate class oligopolymer such as fluorenes oligopolymer or derivatives thereof etc.
In addition, as hole injection layer, except above-mentioned materials, can also use electric conductive polymers such as metal phthalocyanine class and metal-free phthalocyanine class, carbon film, fluorohydrocarbon film (Off ロ ロ カ-ボ Application film), polystyrolsulfon acid (PEDOT-PSS), polyaniline.
Further, can make four cyano to organic class oxidisability doping agents such as secondary methylbenzoquinone (テ ト ラ シ ア ノ キ ノ ジ メ Application), trinitro-fluorenone, mineral-type oxidisability doping agents such as vanadium oxide, molybdenum oxide, Tungsten oxide 99.999, aluminum oxide act on above-mentioned organic compound, form radical cation, inject transfer layer as the hole.The oxidisability concentration of dopant of this hole being injected transfer layer does not limit especially, but is preferably about 0.1～99 weight %.
In addition, the material that uses in electron injecting layer, electron supplying layer, the electron transport luminescent layer is not limited especially, can from material known, suitably select to use.
Specifically, can enumerate polynuclear compound and their derivatives such as p-terphenyl, quaterphenyl, metaphenylene (changing 18), (changing 19), compound of styryl and their derivatives such as (changing 15), (changing 16), (changing 17).
In addition, can also use anthracene, benzophenanthrene, perylene, naphthalene, pyrene, coronene,
, condensed polycyclc aromatic hydrocarbon compound and their derivatives such as tetracene, naphthacene, phenanthrene, condensed heterocyclic compouds and their derivatives such as phenanthroline, bathophenanthroline, bathocuproine, phenanthridines, acridine, quinoline, quinoxaline, pyridine (changing 20), pyrimidine, pyrroles, pyrazoles, pyridazine, pyrazine, phthalazines, naphthyridines, quinazoline, cinnolines, thiazole, oxadiazole, oxazole, triazine, azophenlyene, imidazoles, benzoxazole, benzothiazole, benzoglyoxaline, triazole, porphyrin.
[changing 20]
In addition, for example can also use central metals such as hydroxyquinoline aluminium complex (ア Le ミ キ ノ リ ノ-Le Wrong body), benzoxazole zinc complex, benzothiazole zinc complex, azomethine zinc complex, europium complex, iridium complex, platinum complex to have the metallo-chelate material that Al, Zn, Be, Ir, Pt, Tb, Eu etc., part tool have oxadiazole, thiadiazoles, phenylpyridine, quinoline structure.
Can also use silicon to cough up silicoorganic compound and their derivatives such as (silole), siloxanes, organoboron compound and their derivatives such as triaryl boron, pentavalent phosphorous compound such as triaryl phosphine oxide and their derivative etc.
Further, as electron injecting layer, electron supplying layer, electron transport luminescent layer, can use above-mentioned organic compound is dispersed in the material that obtains in polymkeric substance, oligopolymer or the dendritic macromole, or the material that obtains of polymerization materialization, oligomeric materialization or dendritic macromoleization.
In addition, also can use so-called pi-conjugated polymkeric substance such as p-phenylene vinylene, poly-fluorenes or derivatives thereof, be the electron transport non-conjugated polymeric thing etc. of representative with Ju Yi Xi oxadiazole.Further, can also use so-called conjugate class oligopolymer such as fluorenes oligopolymer or derivatives thereof etc.
Constituent material as electron injecting layer, except above-mentioned organic compound, can also use metal simple-substances such as Ba, Ca, Li, Cs, Mg, Sr, W, metal fluorides such as magnesium fluoride, Calcium Fluoride (Fluorspan), strontium fluoride, barium fluoride, lithium fluoride, cesium fluoride, Al-Li alloy metal alloys such as (ア Le ミ リ チ ウ system alloys), metal oxides such as magnesium oxide, strontium oxide, aluminum oxide, the organic complex of metals such as polymethylmethacrylate sodium polystyrene sulfonate.
Further, can make organic class reductibility doping agents such as oxine class Cs, Li organometallic complex act on above-mentioned organic compound, form free radical anion, inject transfer layer as electronics.
In addition, can also be with metal simple-substances such as Ba, Ca, Li, Cs, Mg, Sr, W, metal oxides such as magnesium oxide, strontium oxide, aluminum oxide, metal-salts such as magnesium fluoride, Calcium Fluoride (Fluorspan), strontium fluoride, barium fluoride, lithium fluoride, cesium fluoride, cesium chloride, strontium chloride, mineral-type reductibility doping agent mixes or disperses, form free radical anion, inject transfer layer as electronics.
The reductibility concentration of dopant of above-mentioned electronics being injected transfer layer does not limit especially, but is preferably about 0.1～99 weight %.
In addition, the organic layer of organic EL of the present invention can use bipolar material (バ イ Port-ラ material) to constitute.Bipolar material refers to can carry in hole and the electronics any one, material that itself can be luminous.
The material that uses in bipolar transfer layer, the bipolarity luminescent layer is not limited especially.
For example can enumerate, compound of styryl and their derivatives such as (changing 15), (changing 16), (changing 17), polycyclc aromatic compound and their derivatives such as p-terphenyl, quaterphenyl, metaphenylene (changing 18), (changing 19), anthracene, benzophenanthrene, perylene, naphthalene, pyrene, coronene,
, condensed polycyclc aromatic hydrocarbon compound and their derivatives such as tetracene, naphthacene, phenanthrene, two (N-aryl carbazoles), two (N-thiazolinyl carbazoles), two carbazole derivative such as (N-alkyl carbazoles) (changing 14), condensed heterocyclic compouds such as thiophene.
In addition, as object lessons in addition such as these derivatives, can enumerate 4,4-two (2,2-phenylbenzene-ethene-1-yl) biphenyl (DPVBi) (changing 21), spiro6 (changing 22), 2,2 ', 7,7 '-four (carbazoles-9-yl)-9,9 '-spiral shell-two fluorenes (changing 23), 4,4 '-two (N-carbazyls)-2 ', 3 ', 5 ', 6 '-tetraphenyl-p-terphenyl (changing 24), 1, two (the carbazole)-9-yls of 3-)-and benzene (changing 25), the 3-tertiary butyl-9, (the common name: TBADN) (change 26) of 10-two (naphthalene-2-yl) anthracene.
[changing 21]
[changing 22]
[changing 23]
[changing 24]
[changing 25]
[changing 26]
As bipolar material, use above-mentioned organic compound is dispersed in the material that obtains in polymkeric substance, oligopolymer or the dendritic macromole, or the material that obtains of polymerization materialization, oligomeric materialization or dendritic macromoleization.
In addition, also can use so-called pi-conjugated polymkeric substance such as p-phenylene vinylene, poly-fluorenes or derivatives thereof, be the non-conjugated polymeric thing etc. of representative with the Polyvinyl carbazole.Further, can also use so-called conjugate class oligopolymer such as fluorenes oligopolymer or derivatives thereof etc.
In addition, can also use have the cavity conveying sexual function, the monomer of electron transport sexual function exists in a part poly-multipolymer, dendritic macromoles such as (vinyl triarylamine second alkene oxadiazoles).
Further, can use above-mentioned oxidisability doping agent or reductibility doping agent to act on the material that above-mentioned bipolar material obtains, form hole injection layer or electron injecting layer.The oxidisability doping agent is preferably molybdenum oxide, vanadium oxide especially.
Organic EL Material shown in the above-mentioned general formula (1) can be used for luminescent layer separately, but also can disperse or mix with in addition hole transporting material, luminescent material, electron transport materials etc., is used in combination with above-mentioned any one organic layer.
In the organic EL of the present invention, the above-mentioned blue emitting material of preferred especially use forms the luminescent layer of the substrate material that contains other simultaneously as guest materials.The concentration of the organic EL Material shown in the above-mentioned general formula (1) of this moment is preferably 0.1～99 weight %.In addition, can with other more than 2 kinds substrate material be used in combination.
When using the organic EL Material shown in the above-mentioned general formula (1) as the substrate material of luminescent layer, the guest materials of this luminescent layer can be fluorescence or phosphorescent luminescent material.
For example can enumerate, polynuclear compound such as p-terphenyl, quaterphenyl and their derivative, compound of styryl and their derivatives such as (changing 15), (changing 16), (changing 17), the tetraphenylbutadiene derivative, pyrazoline derivative ， oxadiazole derivative, coumarin derivatives, styryl sulfonamide derivatives (change 13), anthracene (changing 27), benzophenanthrene, perylene, naphthalene (changing 28), pyrene, coronene,
, condensed polycyclc aromatic hydrocarbon compound and their derivative such as tetracene, naphthacene, phenanthrene.
In addition, for example can also use central metals such as hydroxyquinoline aluminium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethine zinc complex, europium complex, terbium complex, iridium complex, platinum complex to have the metallo-chelate material that Al, Zn, Be, Ir, Pt, Tb, Eu etc., part tool have oxadiazole, thiadiazoles, phenylpyridine, quinoline structure.Specifically, can enumerate with FIrpic (change 29) be representative metallo-chelate with and derivative.
[changing 27]
[changing 28]
[changing 29]
Luminescent layer can constitute by above-mentioned bipolar material.Independent or contain the organic EL Material shown in the above-mentioned general formula (1) in the layer that forms by bipolar material with the form of mixture, can obtain blue-light-emitting thus.
The bipolar material that uses in this luminescent layer can fluoresce for itself or the material of phosphorescence.Bipolar material can contain any one of hole injection transfer layer, luminescent layer and electronics injection transfer layer.
In addition, can be guest materials with the material shown in the above-mentioned general formula (1), substrate material uses fluorescence or the luminiferous material of phosphorescence.
Substrate material as this moment, can enumerate metaphenylene derivative (changing 18), (changing 19), ketone compounds such as diaryl ketone with and derivative, two (N-aryl carbazoles) (change 14), two (N-thiazolinyl carbazoles), two carbazole derivative such as (N-alkyl carbazoles) are with Ir (ppz)
3(changing 30) is the iridium complex of representative.
[changing 30]
As above-mentioned substrate material, can use the material that above-mentioned organic compound polymerization materialization, oligomeric materialization or dendritic macromoleization are obtained.
In addition, also can use so-called pi-conjugated polymkeric substance such as poly-fluorenes, be the non-conjugated polymeric thing etc. of representative with the Polyvinyl carbazole.Further, can also use so-called conjugate class oligopolymer such as fluorenes oligopolymer or derivatives thereof etc.
The formation of above-mentioned each organic layer can be passed through drying processes such as vacuum vapour deposition, sputtering method, and ink jet method, casting method, dip coating, rod are coated with damp process such as method, scraper plate coating method, rolling method, grooved roll coating method (グ ラ PVC ア コ-ト method), offset printing method, spraying method to carry out.Preferably form film by vacuum vapour deposition.
In addition, the thickness of above-mentioned each layer is considered the adaptability between each layer or the whole bed thickness of requirement etc., according to suitable situation decision, but is preferably 5nm～5 μ m usually.
Have separately or containing with the form of mixture in the organic EL of layer of the organic EL Material shown in the above-mentioned general formula (1), the blue-light-emitting of the high color purity that will obtain by the organic EL Material shown in the above-mentioned general formula (1) makes up with green and emitting red light, can obtain high white luminous of color developing thus.
Specifically, as the white luminous method that obtains high-color rendering, have in the blue-light-emitting that is undertaken by the organic EL Material shown in the above-mentioned general formula (1) add green emitting and from the yellow to the orange luminescence as the method for complementary color, or make the luminous independently method of each blueness, green, the red illuminating material that contain the material shown in the above-mentioned general formula (1) etc.
Above-mentioned green luminescent material or red illuminating material can be fluorescence or phosphorescent luminescent material.
For example can enumerate, novel arylamine compound and their derivatives such as quinacridone derivative, the sour cyanines derivative in side, derivatives of porphyrin, coumarin derivatives, dicyano pyran derivate, anthradiamine, condensed polycyclc aromatic hydrocarbon compound and their derivative ， thiophene evil hexazinone, quinoxaline derivatives, carbazole derivative, fluorene derivativess such as perylene, rubrene, tetracene, decacyclene.
In addition, for example can use central metals such as hydroxyquinoline aluminium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethine zinc complex, europium complex, terbium complex, iridium complex, platinum complex to have the metallo-chelate material that Al, Zn, Be, Ir, Pt, Tb, Eu etc., part tool have oxadiazole, thiadiazoles, phenylpyridine, quinoline structure.Specifically, can enumerate with Ir (ppy)
3(changing 31), Irpiq
3(change 32) for the metallo-chelate of representative with and derivative.
[changing 31]
[changing 32]
[embodiment]
Below based on embodiment the present invention is carried out more specific description, but the present invention is not limited by following embodiment.
[embodiment 1]
(TMN1357's is synthetic)
According under show that synthetic schemes synthesizes TMN1357.
[changing 33]
At first, make 1,5-diaminonaphthalene 2.0g (12.6mmol) is suspended in the aqueous sulfuric acid, after the ice-cooled Sodium Nitrite 2.0g (29.0mmol) of the adding down aqueous solution carries out diazotization (tetrazotization), adds the urea aqueous solution, with excessive Sodium Nitrite reaction.This solution is joined in the hydrobromic acid aqueous solution of CuBr 5.0g (34.9mmol) in ice-cooled being divided into down for several times, carry out bromination by sandmeyer reaction.
Further,, filter the solid of separating out, after water, the alcohol washing, carry out vacuum and heating drying room temperature reaction 2～3 hours.
Serves as to launch solvent silicagel column purifying with the black solid that obtains with normal hexane/chloroform mixed solvent.
The product that obtains by MS,
1H-NMR analyzes, and the result is accredited as object 1, the 5-dibromine naphthalene.The receipts amount is 1.32g (yield is 36.6%).
With above-mentioned obtain 1, after 5-dibromine naphthalene 1.32g (4.62mmol) and iron powder 0.30g (5.37mmol), tetracol phenixin join in the reaction vessel, (0.60ml, carbon tetrachloride solution 11.6mmol) also stirred, 55 ℃ of reactions 2 hours to add bromine 1.85g.
In this reaction solution, drop into sodium thiosulfate solution and remove unreacted bromine, use chloroform extraction.After the extraction, carry out separatory, chloroform layer washes with water 2 times, reclaims chloroform, and the crystallization of separating out is washed with alcohol.
The crystallization that obtains is passed through
1H and
13C-NMR analyzes, and the result is accredited as the object bromide.The receipts amount is 1.30g (yield is 63.4%).
Add above-mentioned obtain 1,3,5,7-tetrabromo naphthalene 1.2g (2.70mmol) and 3-aminomethyl phenyl boric acid 2.21g (16.2mmol), Pd (PPh
3)
40.78g (0.675mmol), THF/ toluene (1/1) mixed solvent, further add 2M Na
2CO
32.86g (27.0mmol) aqueous solution, reflux is 48 hours under nitrogen atmosphere gas, carries out linked reaction.
This reaction soln is injected in the water, extracts with toluene.Toluene layer washes with water 2 times, reclaims solvent, serves as to launch solvent silicagel column purifying with chloroform/normal hexane mixed solvent.
The crystallization that obtains is passed through
1H-NMR analyzes, and the result is accredited as object TMN1357.The receipts amount is 0.91g (yield is 69.0%).
Below use it further at 210 ℃, 3.0 * 10
-4The TMN1357 that the Pa sublimation purification obtains.
Will by above-mentioned synthetic TMN1357 with thickness 300nm evaporation on quartz glass substrate, carry out fluorometric analysis.
This fluorescence spectrum as shown in Figure 1.
[comparative example 1]
Short wavelength's blue emitting material (N20) shown in above-mentioned (changing 13) is dissolved in fluorometric analysis with in the chloroform, with concentration 10
-5The solution of mol/l carries out fluorometric analysis.
This fluorescence spectrum as shown in Figure 2.
The result of above-mentioned fluorometric analysis, by Fig. 1,2 as can be known, the TMN1357 of solid state compares with the dilute solution of N20, shows the very big wavelength of fluorescence in short wavelength's one side.
Therefore think that the matrix that TMN1357 uses as the high color purity blue emitting material that with N20 is representative is useful.
[embodiment 2]
As substrate material, have the luminescent layer that is doped with N20 with TMN1357, use the organic EL of the compound (DTVPF) shown in above-mentioned (changing 17) as containing of organic EL Material layer shown in Figure 3 structure by following method manufacturing.
(the 1st electrode)
At first, to forming the glass substrate of the nesa coating (ITO) behind the formation pattern that thickness is 150nm, with the ultrasonic washing that utilizes pure water and tensio-active agent to carry out, utilize flowing water washing that pure water carries out, ultrasonic washing that the 1:1 mixing solutions that utilizes pure water and Virahol carries out, utilize the order of the boiling washing that Virahol carries out to carry out carrying out washing treatment.With slowly pull-up in the Virahol of this substrate from boiling, dry in methanol vapor, carry out the ultraviolet and ozone washing at last.
With this substrate is anode 1, is configured in the vacuum chamber vacuum exhaust to 1 * 10
-6Torr sets in advance each molybdenum system boat of being filled with deposition material respectively and is used for the film forming evaporation mask of predetermined pattern in this vacuum chamber, to the heating of switching on of above-mentioned boat, deposition material is evaporated, and carries out the film forming of each organic layer thus successively.
(hole injection transfer layer)
As the cavity conveying material, use the compound (DTVPF) shown in above-mentioned (changing 19), with molybdic oxide (MoO
3) together simultaneously to the heating of switching on of each boat, carry out common evaporation.Form DTVPF:MoO
3The hole injection layer 2 of=67:33, thickness are 10nm.
Then form the hole transporting layer 3 that only contains DTVPF, thickness is 56nm.
(luminescent layer)
Form the luminescent layer 4 of TMN1357:N20=94:6, thickness is 15nm.
(electronics injection transfer layer)
Formation contains the electron supplying layer 5 of DTVPF, and thickness is 38nm.
Form the electron injecting layer 6 as the DTVPF:Liq=50:50 of electron transport material thereon, thickness is 10nm.
(the 2nd electrode)
Vacuum chamber is being kept under the state of vacuum, changing mask, negative electrode evaporation mask is set, forming aluminium (Al) layer, thickness is 100nm, as negative electrode 7.
Make vacuum chamber return to normal atmosphere, take out the substrate that above-mentioned evaporation has each layer, transfer in the glove box of nitrogen replacement, use of the sheet glass sealing of UV cured resin, obtain organic EL by other.
If the layer structure of this element of schematic illustration then is ITO (150nm)/DTVPF:MoO
3(10nm, 67:33)/DTVPF (56nm)/TMN1357:N20 (15nm, 94:6)/DTVPF (38nm)/DTVPF:Liq (10nm, 50:50)/Al (100nm).
This organic EL is applied 100A/m
2Galvanic current the time luminescent spectrum as shown in Figure 4.
As shown in Figure 4, it is luminous to obtain deriving from the pure blue of N20.
In addition, the colourity of this glow color is at CIE coordinate (1000A/m
2) in, (x y)=(0.157,0.043), is the high blue-light-emitting of purity of color.
[comparative example 2]
With the compound (TBADN) shown in above-mentioned (changing 26) is substrate material, makes the organic EL with the luminescent layer that is doped with N20 similarly to Example 2.
If the layer structure of this element of schematic illustration then is ITO (150nm)/NS21:MoO
3(59nm, 90:10)/NS21 (10nm)/TBADN:N20 (30nm, 97:3)/BAlq (5nm)/DPB (16nm)/DPB:Liq (5nm, 74:26)/Al (100nm).
This organic EL is applied 100A/m
2Galvanic current the time luminescent spectrum as shown in Figure 5.And, in order to compare, the luminescent spectrum of (only TBADN) when not mixing N20 is shown in the lump also.
As shown in Figure 5, when using TBADN, can not get deriving from the blue-light-emitting of N20 as substrate material.
In addition, the colourity of this glow color is at CIE coordinate (100A/m
2) in, (x y)=(0.151,0.080), is the low blue-light-emitting of purity of color.
[embodiment 3]
With TMN1357 is substrate material, makes the organic EL with the luminescent layer that is doped with the short wavelength's blue emitting material (TPA) shown in above-mentioned (changing 27) similarly to Example 2.
If the layer structure of this element of schematic illustration then is ITO (150nm)/DTVPF:MoO
3(10nm, 67:33)/DTVPF (56nm)/TMN1357:TPA (20nm, 98:2)/DTVPF (15nm)/DTVPF:Liq (10nm, 50:50)/Al (100nm).
This organic EL is applied 1000A/m
2Galvanic current the time luminescent spectrum as shown in Figure 6.
As shown in Figure 6, it is luminous to obtain deriving from the pure blue of TPA.
In addition, the colourity of this glow color is at CIE coordinate (1000A/m
2) in, (x y)=(0.165,0.083), is the high blue-light-emitting of purity of color.
[comparative example 3]
With TBADN is substrate material, makes the organic EL with the luminescent layer that is doped with TPA similarly to Example 2.
If the layer structure of this element of schematic illustration then is ITO (150nm)/DTVPF:MoO
3(10nm, 67:33)/DTVPF (56nm)/TBADN:TPA (20nm, 98:2)/DTVPF (15nm)/DTVPF:Liq (10nm, 50:50)/Al (100nm).
This organic EL is applied 1000A/m
2Galvanic current the time luminescent spectrum as shown in Figure 7.
As shown in Figure 7, it is luminous not obtain deriving from the pure blue of TPA.
Find that by the foregoing description 3, comparative example 3 TMN1357 compares with TBADN, as the matrix excellence of the high blue emitting material of purity of color.
As from the foregoing, the organic EL Material according to shown in the general formula of the present invention (1) obtains the high blue-light-emitting of purity of color, the practicality height, and expectation is applied to require in the light source or display unit of high color purity.
Claims (4)
1. the electroluminescent organic material that the general formula shown in the following Chemical formula 1 is represented,
[changing 1]
Wherein, R
1～R
4Be selected from hydrogen, alkyl, cycloalkyl, alkoxyl group, cycloalkyloxy and the aryloxy, be identical or different separately group, A
1～A
4Be selected from replace or unsubstituted phenyl, 5 or 6 yuan replacement or unsubstituted heterocyclic in, be identical or different separately group.
2. organic electroluminescent device, it is for having 1 layer or the organic electroluminescent device of multilayer organic layer that contains luminescent layer between pair of electrodes, it is characterized in that at least 1 layer of described organic layer contains the described electroluminescent organic material of claim 1 separately or with the form of mixture.
3. organic electroluminescent device as claimed in claim 2 is characterized in that at least 1 layer of described organic layer for to contain as the described electroluminescent organic material of the claim 1 of substrate material with as the fluorescence of guest materials or the luminescent layer of phosphorescent material.
4. as claim 2 or 3 described organic electroluminescent devices, it is characterized in that described electrode forms for formation transparent conducting film on transparency carrier.
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| JP2007332578 | 2007-12-25 | ||
| JP2007332578 | 2007-12-25 | ||
| JP2008287552 | 2008-11-10 |
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|---|---|
| JP (1) | JP4646157B2 (en) |
| CN (1) | CN101469265A (en) |
| TW (1) | TW200930787A (en) |
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|---|---|---|---|---|
| JP4628435B2 (en) * | 2008-02-14 | 2011-02-09 | 財団法人山形県産業技術振興機構 | Organic electroluminescence device |
| JP2012087187A (en) * | 2010-10-18 | 2012-05-10 | Kaneka Corp | Light-emitting material and organic el element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6137886A (en) * | 1984-07-31 | 1986-02-22 | Canon Inc | El element |
| AU4964290A (en) * | 1989-01-18 | 1990-08-13 | President And Fellows Of Harvard College | Compositions and methods for treating or preventing aids, arc and hiv infection |
| US5989737A (en) * | 1997-02-27 | 1999-11-23 | Xerox Corporation | Organic electroluminescent devices |
| JP4003824B2 (en) * | 2001-07-11 | 2007-11-07 | 富士フイルム株式会社 | Light emitting element |
| JP2007084485A (en) * | 2005-09-22 | 2007-04-05 | Kyoto Univ | Naphthalene derivative, organic semiconductor material, and light-emitting transistor element and organic electroluminescent element using the semiconductor material |
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2008
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| JP2009173873A (en) | 2009-08-06 |
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