CN103811676A - Organic light emitting device with electron-transporting layer - Google Patents

Organic light emitting device with electron-transporting layer Download PDF

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CN103811676A
CN103811676A CN201310547238.1A CN201310547238A CN103811676A CN 103811676 A CN103811676 A CN 103811676A CN 201310547238 A CN201310547238 A CN 201310547238A CN 103811676 A CN103811676 A CN 103811676A
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alkyl
aryl
hydrogen
halogen
heteroaryl
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张翠
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LIYANG JIANGDA TECHNOLOGY TRANSFER CENTER Co Ltd
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LIYANG JIANGDA TECHNOLOGY TRANSFER CENTER Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE

Abstract

The invention discloses an organic light emitting device with an electron-transporting layer. The organic light emitting device with the electron-transporting layer sequentially comprises a substrate, an anode, an organic light emitting layer, the electron-transporting layer and a cathode, wherein the organic light emitting layer is made of benzothiophene polymers with general formula (I) structures, and the electron-transporting layer is made of acrylic acid polymers. Efficient light emitting polymers are used as the organic light emitting layer in the light emitting diode of the organic light emitting device with the electron-transporting layer, and meanwhile, polymers which can match excellently with the organic light emitting layer are used as the electron-transporting layer, so that the light-emitting performance of the light emitting diode can be remarkably improved.

Description

A kind of organic luminescent device with electron transfer layer
Technical field
The present invention relates to a kind of luminescent device, relate in particular to a kind of light-emitting diode.
Background technology
Organic luminescent device, especially Organic Light Emitting Diode has lower cost for material, driving voltage is low, active illuminating, the feature such as visual angle is wide, and energy consumption is low, more be easy to large area moulding, emission wavelength can be by advantages such as Molecular Design regulate, can be widely used in the panchromatic flat-panel screens of high-resolution, also can be applied to polymer solar battery.
When adding forward bias at Organic Light Emitting Diode two ends, hole is injected into the valence band of organic luminous layer and is moved to negative pole by positive pole, and electronics is injected into the conduction band of organic luminous layer and is moved to positive pole by negative pole.Hole and electronics are captured mutually in transition process, are combined into exciton, the electronics generation radiation transistion of exciton state, and energy discharges with photon form, realizes electroluminescence.But, in prior art still there are some defects in light-emitting diode, the material usefulness deficiency of for example hole injection layer and electron transfer layer, the complicated process of preparation of flexible light-emitting diode, cost is high, the luminescent properties of the light-emitting diode of preparation can not be satisfied the demand, and therefore wishes that a kind of luminous efficiency of research and development is higher, the better Organic Light Emitting Diode of performance.
Summary of the invention
Organic luminescent device of the present invention comprises substrate, anode, organic luminous layer, electron transfer layer and negative electrode successively, wherein,
The material of organic luminous layer is the benzothiophene base polymer with general formula (I) structure,
Figure BDA0000409107270000021
Wherein, R 1be selected from C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C6-C14 aryl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 2be selected from hydrogen, C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 3be selected from hydrogen, halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l;
R 4be selected from hydrogen, halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l;
R 5be selected from hydrogen, halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l;
R 6be selected from hydrogen, halogen, C1-C12 alkyl, C2-C12 thiazolinyl, C6-C14 aryl, C5-C14 heteroaryl, C6-C14 aryl alkyl, C5-C14 heteroaryl alkyl, C3-C12 heterocycle, C3-C7 cycloalkyl or C3-C7 cycloalkenyl group;
Be selected from-NR of A jsO 2r k,-OR n,-NR osO 2nR pr q; Be selected from-CO-of B ,-SO 2-;
R 1, R 6when non-hydrogen, can optionally be replaced by one or more following group: halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l; R 2when non-hydrogen, can optionally be replaced by one or more following group: halogen or-OR m;
In above-mentioned, R a, R b, R c, R d, R e, R f, R g, R h, R i, R j, R k, R l, R n, R o, R p, R qindependently selected from hydrogen or C1-C6 alkyl or C6-C14 aryl; R mindependently selected from hydrogen or C1-C6 alkyl.
Preferably, described R 1be selected from C6-C14 aryl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 2be selected from C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 6be selected from C6-C14 aryl, C5-C14 heteroaryl, C6-C14 aryl alkyl, C5-C14 heteroaryl alkyl, C3-C12 heterocycle, C3-C7 cycloalkyl or C3-C7 cycloalkenyl group;
R 1, R 6can optionally be replaced by one or more following group: halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l; R 2when non-hydrogen, can optionally be replaced by one or more following group: halogen or-OR m;
In above-mentioned, R a, R b, R c, R d, R e, R f, R g, R h, R i, R j, R k, R lindependently selected from hydrogen or C1-C6 alkyl or C6-C14 aryl; R mindependently selected from hydrogen or C1-C6 alkyl.
Preferably, described R 1be selected from C6-C14 aryl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 2be selected from C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 6be selected from C6-C14 aryl, C5-C14 heteroaryl, C6-C14 aryl alkyl, C5-C14 heteroaryl alkyl, C3-C12 heterocycle, C3-C7 cycloalkyl or C3-C7 cycloalkenyl group;
R 1, R 6can optionally be replaced by one or more following group: halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l; R 2when non-hydrogen, can optionally be replaced by one or more following group: halogen or-OR m;
A is hydroxyl;
In above-mentioned, R a, R b, R c, R d, R e, R f, R g, R h, R i, R j, R k, R lindependently selected from hydrogen or C1-C6 alkyl or C6-C14 aryl; R mindependently selected from hydrogen or C1-C6 alkyl.
The material of electron transfer layer is acrylic acid series polymeric compounds, comprising produce the general formula (VI) of carboxyl and the polymer that general formula (VII) forms under sour effect,
Figure BDA0000409107270000041
In formula, R 7represent alkyl or cycloalkyl, R 8represent hydrogen atom or methyl; R 9represent tertiary alkyl or 2-THP trtrahydropyranyl, R 10represent hydrogen atom or methyl.
Substrate can be hard substrate or flexible substrate, wherein hard substrate preferred glass, pottery, metal etc.; The preferred polyethylene terephthalate of flexible substrate, polymethyl methacrylate etc.
Anode is preferably tin indium oxide.
Negative electrode is preferably Ag conducting resinl, can be also Ag film or Ba/Al film.
On the basis of the above-mentioned light emitting layer material that the present invention significantly improves in luminous efficiency, pass through again great many of experiments, adopt above-mentioned organic polymer as electric transmission layer material, it is pleasantly surprised that result is made us, above-mentioned electron transfer layer coordinates excellent with light emitting layer material, the luminous efficiency of light-emitting diode is significantly improved, on average reaches more than 13%.
Term in the present invention has following general significance:
Term " alkyl " refer to straight or branched saturated, the aliphatic hydrocarbon group that contains 1-8 carbon atom (preferably 1-6 carbon atom); C1-n alkyl represents the saturated aliphatic group of 1-n carbon atom, comprise straight chain and branched group (for example " C1-20 alkyl ", refer to that this group is alkyl, and the carbochain amount of carbon atom of alkyl is between 1～20, containing 1 carbon atom, 2 carbon atoms, 3 carbon atoms etc., until comprise the alkyl of 20 carbon atoms.And the restriction of this 1-20 does not comprise the carbon number of the replacement on alkyl, as replace " alkyl " in alkylamino, in the time being not particularly limited its carbon number, the carbon number that only refers to the moieties wherein indicating is 1-20, and does not comprise other the substituent carbon numbers on substituent carbon number and the amino on alkyl.Adopt the statement of " C1-8 alkyl " to represent the alkyl that contains 1～8 carbon atom in this alkyl.) " thiazolinyl " comprise the straight chain and the branched hydrocarbyl that contain at least one carbon-carbon double bond and 2-8 carbon atom (preferably 2-6 carbon atom); " alkynyl " comprises the straight chain and the branched hydrocarbyl that contain at least one carbon carbon triple bond and 2-8 carbon atom (preferably 2-6 carbon atom).Haloalkyl, represents the alkyl that halogen atom replaces, and this replacement comprises monosubstituted and polysubstituted, and wherein the concept of alkyl is described above.C1～8 haloalkyl, the carbon number that refers to the alkyl in haloalkyl is 1～8.Haloalkyl refers to the group that on alkyl, H atom is replaced by halogen atom; As perfluoroalkyl refers to the group that the H on alkyl is all replaced by F.
Term " aryl " herein refers to aromatic systems, can be monocycle or many aromatic rings that condense or that link together originally, thereby at least a portion is condensed or the ring that connects forms the virtue system of conjugation.Aromatic yl group includes, but are not limited to: phenyl, naphthyl, tetralyl.Aryl can be optionally substituted, as being selected from the aryl that group replaced or the heterocycle of lower group by 1-4: halogen, CN, OH, NO 2, amino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxyl, aryloxy group, replacement alkoxyl, alkyl-carbonyl, alkyl carboxyl, alkyl amino or arylthio.Preferably, substituting group is halogen, C1-C4 alkyl.
Heterocyclic radical, refers to the heteroatomic cyclic groups by 3 to 8 annular atomses such as containing N, O, S, and in this group, hetero-atom can only contain N atom, also can contain O or S atom.Wherein heteroatomic number can be one, can be also multiple.This heterocycle can be saturated class cycloalkanes structure, can be also undersaturated aromatic ring class formation.More specifically, this term nitrogen heterocycle includes but not limited to pyrrole radicals, nafoxidine base, piperidyl, piperazinyl, morpholinyl, piperazinyl, pyrimidine radicals, imidazole radicals etc.Heterocycle also can comprise any many rings, and wherein arbitrary above-mentioned heterocycle can condense in aromatic ring.
Halogen refers to F, Cl, Br or I.
The salt of formula (I) polymer can be the acid-addition salts of formula (I) polymer, can include but not limited to the salt forming with following inorganic acid: example hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the salt forming with organic acid, organic acid refers to acetic acid, oxalic acid, succinic acid, tartaric acid, methanesulfonic acid and maleic acid; Can be the salt of formula (I) polymer with enough acidity, as alkali metal salt or alkali salt (calcium salt, magnesium salts or ammonium salt etc.).
Accompanying drawing explanation
Fig. 1 is organic light-emitting device structural representation of the present invention.
Embodiment
In order to make the clearer understanding of those skilled in the art technical scheme of the present invention, below in conjunction with accompanying drawing, its embodiment is described.
As shown in Figure 1, light-emitting diode of the present invention comprises substrate 1, anode 2, organic luminous layer 3, electron transfer layer 6 and negative electrode 4 successively.Wherein,
Substrate 1 can be hard substrate or flexible substrate.Hard substrate preferred glass, pottery, metal etc.; The preferred macromolecular material of flexible substrate is as polyethylene terephthalate, polymethyl methacrylate etc.
Anode 2 preferably adopts tin indium oxide (ITO), utilizes vacuum sputtering to cover above substrate.Negative electrode 4 is preferably Ag conducting resinl, can be also Ag film or Ba/Al film.
The material of electron transfer layer is acrylic acid series polymeric compounds, comprising produce the general formula (VI) of carboxyl and the polymer that general formula (VII) forms under sour effect,
Figure BDA0000409107270000071
In formula, R 7represent alkyl or cycloalkyl, R 8represent hydrogen atom or methyl; R 9represent tertiary alkyl or 2-THP trtrahydropyranyl, R 10represent hydrogen atom or methyl.
Organic luminous layer 3 adopts the method preparations such as spin coating, printing conventionally.
The material of organic luminous layer 3 is the benzothiophene base polymers with general formula (I) structure:
Wherein, R 1be selected from C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C6-C14 aryl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 2be selected from hydrogen, C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 3be selected from hydrogen, halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l;
R 4be selected from hydrogen, halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l;
R 5be selected from hydrogen, halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l;
R 6be selected from hydrogen, halogen, C1-C12 alkyl, C2-C12 thiazolinyl, C6-C14 aryl, C5-C14 heteroaryl, C6-C14 aryl alkyl, C5-C14 heteroaryl alkyl, C3-C12 heterocycle, C3-C7 cycloalkyl or C3-C7 cycloalkenyl group;
Be selected from-NR of A jsO 2r k,-OR n,-NR osO 2nR pr q; Be selected from-CO-of B ,-SO 2-;
R 1, R 6when non-hydrogen, can optionally be replaced by one or more following group: halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l; R 2when non-hydrogen, can optionally be replaced by one or more following group: halogen or-OR m;
In above-mentioned, R a, R b, R c, R d, R e, R f, R g, R h, R i, R j, R k, R l, R n, R o, R p, R qindependently selected from hydrogen or C1-C6 alkyl or C6-C14 aryl; R mindependently selected from hydrogen or C1-C6 alkyl.
Preferably, described R 1be selected from C6-C14 aryl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 2be selected from C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 6be selected from C6-C14 aryl, C5-C14 heteroaryl, C6-C14 aryl alkyl, C5-C14 heteroaryl alkyl, C3-C12 heterocycle, C3-C7 cycloalkyl or C3-C7 cycloalkenyl group;
R 1, R 6can optionally be replaced by one or more following group: halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l; R 2when non-hydrogen, can optionally be replaced by one or more following group: halogen or-OR m;
In above-mentioned, R a, R b, R c, R d, R e, R f, R g, R h, R i, R j, R k, R lindependently selected from hydrogen or C1-C6 alkyl or C6-C14 aryl; R mindependently selected from hydrogen or C1-C6 alkyl.
Preferably, described R 1be selected from C6-C14 aryl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 2be selected from C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 6be selected from C6-C14 aryl, C5-C14 heteroaryl, C6-C14 aryl alkyl, C5-C14 heteroaryl alkyl, C3-C12 heterocycle, C3-C7 cycloalkyl or C3-C7 cycloalkenyl group;
R 1, R 6can optionally be replaced by one or more following group: halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l; R 2when non-hydrogen, can optionally be replaced by one or more following group: halogen or-OR m;
A is hydroxyl;
In above-mentioned, R a, R b, R c, R d, R e, R f, R g, R h, R i, R j, R k, R lindependently selected from hydrogen or C1-C6 alkyl or C6-C14 aryl; R mindependently selected from hydrogen or C1-C6 alkyl.
Described polymer comprises: 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-phenyl benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-6-phenyl benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-ethyl-4-methylcyclohexyl formamido)-6-phenyl benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-benzyl-4-methylcyclohexyl formamido)-6-phenyl benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-4-methylcyclohexyl formamido)-7-phenyl benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-4-Methyl benzenesulfonyl amido)-7-phenyl benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(naphthyl-1-position) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(xenyl-4-position) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(1 hydrogen-indoles-5-position) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(pyridine-3-position) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(benzofuran-2-position) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(4-Trifluoromethoxyphen-l) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(furyl-2-position) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(3,5-bis trifluoromethyl phenyl) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(benzothiophene-2-position) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(4-chlorphenyl) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(4-tert-butyl-phenyl) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(4-fluorophenyl) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(thienyl-2-position) benzo [b] thiophene-2-carboxylic acid, 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-(2-chlorphenyl) benzo [b] thiophene-2-carboxylic acid, also [b] thiophene-2-carboxylic acid of 3-(nitrogen-isopropyl-4-methyl cyclohexyl formamido)-7-bromobenzene.
The present invention is on the basis of above-mentioned light emitting layer material, through great many of experiments, final selected above-mentioned organic polymer thing is as electric transmission layer material, it is pleasantly surprised that result is made us, above-mentioned electric transmission layer material coordinates excellent with light emitting layer material, the luminous efficiency of light-emitting diode is significantly improved, on average reaches more than 13%.
The manufacture method of light-emitting diode of the present invention comprises the steps:
Preparing substrate 1, for the ease of the device performance parameter relatively making, substrate dimension is identical, it is 15 millimeters × 15 millimeters, square resistance is about 20 ohm/, use successively acetone, micron order semiconductor special purpose detergent, deionized water, the ultrasonic processing of isopropyl alcohol 10 minutes, clean anode substrate surface, puts into subsequently and at 80 ℃ of constant temperature ovens, leaves standstill 4 hours and dry.
Prepare anode 2, the anode of light-emitting diode adopts tin indium oxide, utilizes vacuum sputtering to cover above substrate.Anode substrate after oven dry is removed the organic deposit film of anode substrate surface attachment for 10 minutes with plasma bombardment with oxygen plasma etch instrument, and improve the work function of anode surface.
Prepare organic luminous layer 3, conventionally adopt the method such as spin coating, printing to be formed on anode surface the organic luminous layer that adopts said method of the present invention to prepare.Organic luminous layer adopts above-mentioned polymeric material of the present invention.Macromolecular LED polymer is placed in clean bottle, proceeds to nitrogen film forming special gloves case, is mixed with solution by dissolution with solvents, is placed on mixing platform and stirs, and obtains clear filtrate with 0.45 micron of membrane filtration.In the nitrogen protection film forming special gloves case of anhydrous and oxygen-free, deposit organic luminous layer, be adsorbed on high-speed rotary painting on sol evenning machine make by anode substrate, thickness is controlled by the rotating speed that regulates sol evenning machine.The optimum thickness of organic luminous layer is 70～90 nanometers, by surface profiler actual measurement monitoring.
Prepare electron transfer layer 6, use the material of acrylic acid series polymeric compounds mentioned above as electron transfer layer, thickness is about 1 nanometer.
Prepare negative electrode 4, negative electrode be generally utilize vacuum evaporation by metal evaporation on the surface of electron transfer layer 6.Above-mentioned device is put into respective metal electrode on the method evaporation that vacuum coating equipment utilizes conventional vacuum evaporation, and plating chamber vacuum degree is 3 × 10 -4below pa, plated film speed and each layer of metal electrode film thickness are monitored in real time by quartz vibrator film thickness monitor.Adopt the method evaporation Ag metallic film of vacuum evaporation to make negative electrode.Also can make negative electrode by evaporation Ba/Al metallic film.
Another method of making negative electrode is on the film of organic luminous layer, evenly to apply one deck conducting resinl, and 2 hours accelerated solidification of 60 ℃ of heating, preferably apply Ag conducting resinl as negative electrode.
Light-emitting diode of the present invention compared with prior art has following beneficial effect: the organic luminous layer of employing is as efficient light emitting polymer, and the luminescent properties of light-emitting diode is significantly improved.Adopt the organic polymer material of novel electron transfer layer, itself and organic luminous layer fiting effect make us pleasantly surprised, and luminous efficiency significantly improves.
Certainly; the present invention also can have other various embodiments; in the situation that not deviating from spirit of the present invention and essence thereof; those of ordinary skill in the art are when making according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection range of the appended claim of the present invention.

Claims (6)

1. there is an organic luminescent device for electron transfer layer, comprise the substrate, anode, organic luminous layer, electron transfer layer and the negative electrode that stack gradually, it is characterized in that,
The material of described electron transfer layer is acrylic acid series polymeric compounds, comprising produce the general formula (VI) of carboxyl and the polymer that general formula (VII) forms under sour effect,
Figure FDA0000409107260000011
In formula, R 7represent alkyl or cycloalkyl, R 8represent hydrogen atom or methyl; R 9represent tertiary alkyl or 2-THP trtrahydropyranyl, R 10represent hydrogen atom or methyl;
The material of described organic luminous layer is the benzothiophene base polymer with general formula (I) structure,
Wherein, R 1be selected from C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C6-C14 aryl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 2be selected from hydrogen, C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 3be selected from hydrogen, halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l;
R 4be selected from hydrogen, halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l;
R 5be selected from hydrogen, halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l;
R 6be selected from hydrogen, halogen, C1-C12 alkyl, C2-C12 thiazolinyl, C6-C14 aryl, C5-C14 heteroaryl, C6-C14 aryl alkyl, C5-C14 heteroaryl alkyl, C3-C12 heterocycle, C3-C7 cycloalkyl or C3-C7 cycloalkenyl group;
Be selected from-NR of A jsO 2r k,-OR n,-NR osO 2nR pr q; Be selected from-CO-of B ,-SO 2-;
R 1, R 6when non-hydrogen, can optionally be replaced by one or more following group: halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l; R 2when non-hydrogen, can optionally be replaced by one or more following group: halogen or-OR m;
In above-mentioned, R a, R b, R c, R d, R e, R f, R g, R h, R i, R j, R k, R l, R n, R o, R p, R qindependently selected from hydrogen or C1-C6 alkyl or C6-C14 aryl; R mindependently selected from hydrogen or C1-C6 alkyl.
2. Organic Light Emitting Diode as claimed in claim 1, is characterized in that, described R 1be selected from C6-C14 aryl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 2be selected from C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 6be selected from C6-C14 aryl, C5-C14 heteroaryl, C6-C14 aryl alkyl, C5-C14 heteroaryl alkyl, C3-C12 heterocycle, C3-C7 cycloalkyl or C3-C7 cycloalkenyl group;
R 1, R 6can optionally be replaced by one or more following group: halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l; R 2when non-hydrogen, can optionally be replaced by one or more following group: halogen or-OR m;
In above-mentioned, R a, R b, R c, R d, R e, R f, R g, R h, R i, R j, R k, R lindependently selected from hydrogen or C1-C6 alkyl or C6-C14 aryl; R mindependently selected from hydrogen or C1-C6 alkyl.
3. Organic Light Emitting Diode as claimed in claim 1, is characterized in that, described R 1be selected from C6-C14 aryl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 2be selected from C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C3-C12 heterocycle, C3-C18 heteroaryl alkyl, C6-C18 aryl alkyl or C3-C7 cycloalkyl;
R 6be selected from C6-C14 aryl, C5-C14 heteroaryl, C6-C14 aryl alkyl, C5-C14 heteroaryl alkyl, C3-C12 heterocycle, C3-C7 cycloalkyl or C3-C7 cycloalkenyl group;
R 1, R 6can optionally be replaced by one or more following group: halogen, nitro ,-NR ar b,-SO 2r c,-SO 2nR dr e,-CONR fr g,-NR hcOR i,-NR jsO 2r k, azido, cyano group, trifluoromethyl, trifluoromethoxy, C1-C6 alkyl or-OR l; R 2when non-hydrogen, can optionally be replaced by one or more following group: halogen or-OR m;
A is hydroxyl;
In above-mentioned, Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Rl is independently selected from hydrogen or C1-C6 alkyl or C6-C14 aryl; Rm is independently selected from hydrogen or C1-C6 alkyl.
4. Organic Light Emitting Diode as claimed in claim 1, is characterized in that, described substrate can be hard substrate or flexible substrate, wherein hard substrate preferred glass, pottery, metal etc.; The preferred polyethylene terephthalate of flexible substrate, polymethyl methacrylate etc.
5. Organic Light Emitting Diode as claimed in claim 1, is characterized in that, described anode is preferably tin indium oxide.
6. Organic Light Emitting Diode as claimed in claim 1, is characterized in that, described negative electrode is preferably Ag conducting resinl, can be also Ag film or Ba/Al film.
CN201310547238.1A 2013-11-06 2013-11-06 Organic light emitting device with electron-transporting layer Pending CN103811676A (en)

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Publication number Priority date Publication date Assignee Title
JPH10289785A (en) * 1997-02-17 1998-10-27 Nippon Steel Corp Organic electroluminescent element and manufacture therefor
US20010041270A1 (en) * 2000-05-12 2001-11-15 Junya Maruyama Light-emitting device
CN1554726A (en) * 2003-12-27 2004-12-15 复旦大学 Polymer material for electroluminescent device and its preparing method
CN102725693A (en) * 2010-01-19 2012-10-10 富士胶片株式会社 Photosensitive resin composition, cured film, method for forming cured film, organic EL display device, and liquid crystal display device
CN103035854A (en) * 2012-11-30 2013-04-10 江苏威纳德照明科技有限公司 Manufacturing method for polymer light-emitting diode including electron transfer layer
CN103094489A (en) * 2012-11-30 2013-05-08 江苏威纳德照明科技有限公司 Macromolecule light-emitting diode provided with electronic transport layer

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10289785A (en) * 1997-02-17 1998-10-27 Nippon Steel Corp Organic electroluminescent element and manufacture therefor
US20010041270A1 (en) * 2000-05-12 2001-11-15 Junya Maruyama Light-emitting device
CN1554726A (en) * 2003-12-27 2004-12-15 复旦大学 Polymer material for electroluminescent device and its preparing method
CN102725693A (en) * 2010-01-19 2012-10-10 富士胶片株式会社 Photosensitive resin composition, cured film, method for forming cured film, organic EL display device, and liquid crystal display device
CN103035854A (en) * 2012-11-30 2013-04-10 江苏威纳德照明科技有限公司 Manufacturing method for polymer light-emitting diode including electron transfer layer
CN103094489A (en) * 2012-11-30 2013-05-08 江苏威纳德照明科技有限公司 Macromolecule light-emitting diode provided with electronic transport layer

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