CN104037336A - Organic electronic device and manufacturing thereof - Google Patents

Abstract

The present invention relates to an organic electronic device and a manufacturing thereof. The organic electronic device comprises a metal anode and a cavity injection layer. The organic electronic device further comprises a SAM located between the metal anode and the cavity injection layer, the SAM comprises a compound having a structure portion capable of absorbing on the surface of the metal anode and a hydrophilic structure portion. The present invention also relates to the manufacturing method of the organic electronic device. Preferably, the SAM is composed of sulpho-compound with a hydrophilic tail portion. A preferred embodiments comprise sulpho-alkane or sulpho-olefin derivatives having 6 to 24 carbon atoms, and a sulpho-aromatic derivatives having 5 to 14 carbon atoms in one or more aromatic ring. In any occasion the derivatives are replaced by hydrophilic groups selected from hydroxyl, carboxyl, carbonyl. Most preferably, the sulpho-compound having the hydrophilic tail portion is 11- sulfydryl-1 undecyl alcohol or 4-phenthiol.

Description

Organic electronic device and manufacture method thereof

Technical field

The present invention relates to the organic electronic device that comprises metal anode and hole injection layer, wherein said device further comprises the self-assembled monolayer that serves as wettable anticorrisive agent (SAM) between described metal anode and described hole injection layer, and relates to the method for manufacturing described device.

Background technology

Organic electronic device provides many potential advantages, comprises cheapness, low temperature, extensive manufacture in multiple substrate (comprising glass and plastics).The example of organic electronic device includes OLED, OTFT, organic photovoltaic devices, organic optical sensor and organic memory array device.

Compared with other Display Technique, organic light emitting diode display provide other advantage-especially they be become clear, bright-colored, switch and wide visual angle be provided fast.According to used material, can manufacture OLED device (this device comprises organic metal device here and comprises the device of one or more phosphors) with polymer or little molecule with a series of colors with in multicolor display.About general background information can reference example as WO90/13148, WO95/06400, WO99/48160 and US4,539,570, and " the Organic Light Emitting Materials and Devices " of Zhigang Li and Hong Meng writing, CRC Press (2007), ISBN10:1-57444-574X, it has described many materials and devices, and existing little molecule has again polymer.

In its most basic form, Organic Light Emitting Diode (OLED) comprises the luminescent layer between anode and negative electrode.Between anode and luminescent layer, include hole injection layer through being everlasting in.For example, energy difference between its work function for reducing anode [conventional tin indium oxide (ITO), because it is transparent] and the highest occupied molecular orbital (HOMO) of luminescent layer, thus the number that is introduced into the hole in luminescent layer increased.By anode and hole injection layer (if present), luminescent layer is injected in hole in operation and by negative electrode by electronic injection luminescent layer.Thereby the combination in luminescent layer of hole and electronics forms exciton, thereby then described exciton experience radiative decay provides light.

Some devices are also included thin polymer interlayer between hole injection layer and luminescent layer.This plays an important role improving aspect the life-span of device efficiency and RGB light emitting polymer (LEP) OLED.For example, have interlayer, can realize the blue LEP OLED with the external quantum efficiency that is greater than 5%, it is high by 35% when thering is no interlayer.It is believed that this may be due to the exciton quencher having prevented in hole injection layer/luminescent layer interface.

Another kind of important organic electronic device is OTFT.The various configurations of OTFT are known.A kind of such devices is isolated-gate field effect transistor (IGFET), it comprises source electrode and drain electrode, be arranged at the semi-conducting material in channel region therebetween, the grid of contiguous this semi-conducting material setting and be arranged at grid and channel region in semi-conducting material between insulation material layer.

The example of such OTFT is top-gate thin-film transistors, and it comprises source electrode and drain electrode, and it is spaced apart that this source electrode and drain electrode are positioned at channel region therebetween.Organic semiconductor is deposited in channel region and can above at least a portion of source electrode and drain electrode, extends.The insulating layer deposition of dielectric material is above organic semiconductor and can extend above at least a portion of source electrode and drain electrode.Finally, by gate deposition above insulating barrier.Grid is positioned at top, channel region and can above at least a portion of source electrode and drain electrode, extends.

Structure recited above is called as top grid OTFT, because grid is positioned at the top side of device.As an alternative, also the known grid that provides on the bottom side of device to be to form so-called bottom gate thin film transistor, and this bottom gate thin film transistor comprises and is deposited on suprabasil grid, and the insulating barrier of dielectric material deposited thereon.Source electrode and drain electrode are deposited on the insulating barrier top of dielectric material.It is spaced apart that source electrode and drain electrode are positioned at the channel region that is in grid top therebetween.Organic semiconductor is deposited in channel region and can above at least a portion of source electrode and drain electrode, extends.

Can change the conductivity of raceway groove by applying voltage at grid.By this way, can utilize transistor described in additional grid voltage opening and closing.Depend on the mobility of charge carrier in the organic semiconductor in the active region (raceway groove between source electrode and drain electrode) of device for the attainable drain current of given voltage.Therefore,, in order to realize high drain current with low operating voltage, OTFT must have the organic semiconductor that charge carrier animal migration is high in raceway groove.

As in OLED, hole injection layer can be included between source electrode and drain electrode and organic semiconductor layer.This plays following function: reduce the energy difference between the work function of electrode and the highest occupied molecular orbital of organic semiconductor layer (HOMO), thereby increase the number of introducing the hole in organic semiconductor layer.

Another important application of this technology be exploitation White OLED material and cheaply anode construction to make OLED illumination become feasible.This is very large potential market (according to estimates, reaching 6,300,000,000 dollars by 2018).For prior art, particularly fluorescent illumination, (its life-span can be shorter than the life-span of advertising in OLED illumination, can comprise that noxious substance comprises mercury and due to firmware loss and actual efficiency is low) and inorganic LED(its be good point-source of light, but matched well is not applied in large area light emitting even, diffusion) be direct and feasible competitor.OLED illumination is very suitable for requiring evenly, the application of the large area light emitting of diffusion.

Important immediate development is the development of OLED illumination tile, and wherein for example ITO of conventional anode material or gold (they be both difficult to process and expensive) are replaced (referring to for example WO-A-2004/068389) by precursor metal deposition technique that can Seterolithography.This method that forms conductive metal region in substrate is included in the solution of plated metal ion in substrate, and in substrate, deposit the solution of reducing agent, thereby make metal ion and reducing agent one react and in substrate, form conductive metal region in reaction solution.Use this technology, likely with the refined net of mode plated metal in substrate of simple, cheap solution processable.

For low cost metal for example aluminium and particularly copper, the ability that deposits the superfine grid of sub-10 micron dimension streaks in substrate has been opened and has been produced the gate of the possibility of highly flexible device (this forms and contrast with ITO, this ITO be fragility and during processing, may ftracture), wherein the fineness of grid gives anode high transparency.ITO also has the high resistivity throwing into question for large area lighting panel, for example, due to the large voltage drop meeting with towards device center, cause the remarkable decline of luminous intensity.The surface that the thin metal streak depositing by the method for WO-A-2004/068389 produces highly conductive, the voltage drop that this surface does not have ITO device to experience.

Use copper and for example WO-A-2004/068389 of other metal can optical design deposition technique in aluminium reduced cost, this is not still because replaced for example ITO(of expensive material and gold, in the time that transparency is inessential) and because disclosed electroless technology than typical case for the sputtering technology of ITO more simply, more cheap and more efficient.This exploitation at the low cost framework for OLED illumination and OTFT display is particular importance.In both, it is upper and then use remaining layer of other solution processable deposition techniques of this area previously known that metal streak (copper) is deposited on transparent substrates (glass) by the electroless technology by solution processable for example.

In addition, in illuminating device in order to make maximizing efficiency, on the basal surface of substrate of glass, place coupling output film (outcoupling film), to improve for conventional I TO device to the transmitting in glass, this is the result reducing because of the guided mode due to the hole injection layer of glass-index-matched.In addition, utilize coupling output film to allow to use thicker hole injection layer to take out light from glass, thereby improve production efficiency.

Other appropriate technology for deposited copper and for example aluminium of other metal comprises vacuum moulding machine, printing and photoetching.

But, for the use existing problems of utilizing such as the metal streak of the deposition techniques of electroless technology, vacuum moulding machine or photoetching, for example copper of especially preferred metal (its not only cheap but also there is good conductivity) and aluminium.First, they are easily oxidized.If oxide layer develops on metal surface, this can improve the contact resistance between the hole injection layer depositing at metal with on it so.This causes the reduction of the hole supply of passing through metal/hole injection layer interface, and therefore reduces device efficiency.The second, hole injection layer comprises the compound such as PEDT, and this compound is the hydrophilic compounds by solution deposition.As a result, be not easy to deposit the aqueous solution of hole injection compound on metal surface.What need ideally, is some means that make the more hydrophilic combination with raising hole injection layer in surface.Obviously need to address these problems in the art.

Known many kinds of corrosion inhibitors in this area.Taking copper as example, can be by copper being immersed to lasting a few minutes of acetic acid aqueous solution so that cupric oxide be removed from the surface of copper.But oxide will start rapidly again to form in air.For copper, a widely used example of copper corrosion inhibitor is cuprotec3, and it comprises BTA.Also know in the art with BTA and suppress copper corrosion for some time with indazole especially, for example J.B.Cotton, I.R.Scholes, discloses and has studied the use of BTA and indazole in Br.Corros.J.2 (1967) 1.Ngoc Huu Huynh (thesis for the doctorate 2004, QUT) discloses and has used the heterocyclic compound of some quantity as the copper corrosion inhibitor in acid aqueous environments.In an example, disclose and realized copper corrosion in corrosive atmosphere with 4-carboxyl benzotriazole and 5-carboxyl benzotriazole and suppress.Select carboxyl according to following reason: think that they will strengthen corrosion and suppress in target aqueous corrosion environment.Do not have open or suggestion to prevent the copper corrosion causing because of atmospheric corrosion or because of electromigration effect with them.

J.M.Park and J.P.Bell, Epoxy Adhesion to Copper; Adhesive Aspects of Polymer Coatings.Symposium on Adhesion Aspects of Polymeric Coatings (1981:Minneapolis, 1983,205-224) improvement of the water-resistance by include copper-epoxy bond that benzotriazole derivatives (comprising 5-hydroxybenzotriazole) realizes between copper and epoxy layer disclosed.The focus of the disclosure document is joint that copper coin forms by for example the using epoxy resin improvement tolerance to water especially boiling water.For example US-A-2004/0217006, Vishnevs'kii, R.Fizika i Khimiya Tverdogo Tila (2006), 7 (4), in 748-750 and US-A-2009/0239380, disclose and used other benzotriazole and other aromatic derivative as the copper corrosion inhibitor in various devices (comprising electronic device).Many prior aries are concluded: can be by making the more hydrophobic copper corrosion increasing of realizing of benzotriazole derivatives.For example, referring to people such as X.R.Ye, Applied Surface Science135 (1998) 307.

But, in prior art, do not have open or suggestion in organic electronic device, to use following compound: thereby thereby this compound not only can prevent from the oxidation of metal anode but also can increase water contact angle increasing wettable ability by passivating metallic surfaces, thereby allow to deposit hydrophilic compounds, for example hole injection layer thereon from solution deposition.

Summary of the invention

The inventor has obtained the important breakthrough about organic electronic device and their preparation method, make it possible to solve utilize metal streak as the dual problem in anode (that is, first, thereby many be easy to oxidation because of increase contact resistance lower efficiency; Secondly and, the hole injection layer depositing on anode is included as for example PEDT of compound of hydrophilic compounds-be not easy to deposit hole on metal surface or on conventional corrosion inhibitor and injects the aqueous solution of compound).The inventor finds, by use the self-assembled monolayer of the molecule with property between metal surface and hole injection layer, likely not only prevented the oxidation of metal surface but also the water-wetted surface of expectation was provided, thereby guaranteed that the aqueous solution of the molecule for utilizing hole injection layer applied the environment that provides desirable.

Therefore, in the first embodiment of the present invention, a kind of organic electronic device is provided, described device comprises metal anode and hole injection layer, wherein said device further comprises self-assembled monolayer (SAM) between described metal anode and described hole injection layer, described SAM inclusion compound, this compound has lip-deep structure division (moiety) and the hydrophilic structure division that can be adsorbed onto described metal anode.

What below further discuss, there are the many examples that there are many examples of the suitable combination thing that can be adsorbed onto the lip-deep different structure part of metal anode or also have hydrophily suitable construction part as us.The key characteristic of organic electronic device of the present invention is the including in of SAM with these two kinds of structure divisions, and described two kinds of structure divisions have in fact two kinds of different functions.

The lip-deep structure division of metal anode that can be adsorbed onto of SAM is the passivation element that stops oxidation on metal surface, thereby minimize the contact resistance in device of the present invention, otherwise for example, because described oxidation on metal surface will occur the film (cupric oxide) that has from the teeth outwards metal oxide, thereby hinder the hole of passing through metal anode/hole injection layer interface to supply with.

Hydrophilic-structure part is following structure division: it is responsible for improving the contact angle of wettable ability, change and water on surface, with the respective compound of this hydrophilic radical not Comparatively speaking.This improvement of hydrophily/wettable ability provides water-wetted surface on metal, for the aqueous solution of the molecule with hole injection layer applies this metal carrying for desirable environment, thereby provides best hole injection layer.

In a second aspect of the present invention, a kind of method for the manufacture of organic electronic device is provided, the method includes the steps of:

(i) plated metal anode in substrate;

(ii) Energy Deposition forms the compound of SAM on described metal anode surface, and wherein said compound has can be adsorbed onto the lip-deep structure division of described metal anode and hydrophilic structure division; With

(iii) on this SAM, deposit hole injection layer.

In a third aspect of the present invention, a kind of compound is provided, thereby this compound can form the oxidation that stops described metal anode in order to the SAM of the metal anode in passivation organic electronic device, wherein said compound has hydrophilic radical to improve the surperficial wettable ability of described anode.

In a fourth aspect of the present invention, a kind of compound is provided, SAM in the organic electronic device that this compound can be formed for comprising metal anode and hole injection layer, wherein said SAM is between described metal anode and described hole injection layer, wherein compared with not there is not the other identity unit of described SAM, described SAM includes the contact resistance reducing between described metal anode and described hole injection layer in, and the described compound that can form described SAM further comprises hydrophilic structure division.

Embodiment

Include the SAM according to the present invention with above-mentioned performance in two problems in the key issue that organic electronic device of the present invention solved limiting device efficiency, comprise the device of the metal anode that is easy to oxidation, comprise the device of the streak of for example copper of metal refined net device or aluminium, the oxidation that is metal surface causes increasing (therefore hinder through the hole at metal/hole injection layer interface and supply with) with the contact resistance of hole injection layer and lacking water-wetted surface, this water-wetted surface applies the environment that provides desirable to produce the good coat of hydrophily hole injection layer in order to guarantee the aqueous solution of the molecule for utilizing hole injection layer.

Device of the present invention and manufacture method make possibility institute in the production of organic electronic device in steps (or nearly all, for example, depend on and use what material as the cathode material in OLED device) be solution processable and can be easy to be extended to the level of production (because the deposition technique based on solution does not need vacuum).The device that produces is relatively inexpensive and have the efficiency of improvement, comprises lower contact resistance, and this is the outstanding effect of corrosion inhibition providing due to the SAM using in device of the present invention.In addition,, owing to there is for example hydroxyl of hydrophilic-structure part or carboxyl on the lip-deep structure division that can be adsorbed onto metal anode, efficiency also improves.In the time making SAM be adsorbed onto on the surface of metal anode, by the aqueous solution to deposit on the water-wetted surface presenting by these groups hole injection layer greatly improved the wettable ability of metal surface and guarantee by outstanding, hole injection layer is deposited on metal surface uniformly.This further improves the injection of hole by hole injection layer by giving best metal-hole injection layer interface.

Although be not wishing to be bound by theory, we think that changing hydrophilic radical causes and the change of the contact angle of water can be adsorbed onto position on the lip-deep structure division of metal anode, and this causes the change of Surface binding energy.This causes the change of the wettable ability of the molecule of SAM in the time being adsorbed onto on metal surface.It is believed that the best that has realized surperficial energy in the time that the tie point of the hydrophilic-structure part in the compound of SAM on the lip-deep structure division that can be adsorbed onto described metal anode is following situation changes and therefore realized the improvement of the surperficial wettable ability of metal anode: when on the surface that can be adsorbed onto the lip-deep structure division of metal anode and be adsorbed to described metal anode, the distance on described hydrophilic-structure part and metal anode surface is maximized.

In a preferred embodiment of the invention, SAM is made up of the aromatic compounds with hydrophilic substituent.Preferably, the described aromatic compounds with hydrophilic substituent is benzotriazole derivatives, indazole derivative, benzimidizole derivatives, benzothiazole derivant or benzoxazole derivative, more preferably benzotriazole derivatives or indazole derivative, and be most preferably benzotriazole derivatives.Aromatic structure part is served as the lip-deep structure division that can be adsorbed onto metal anode.Especially, it is believed that aromatics ring nitrogen is the reason of absorption.

In the compound of the SAM existing in device of the present invention, hydrophilic substituent is preferably selected from hydroxyl, carboxyl, carbonyl and sulfo-substituting group, and its preferably hydroxyl or carboxyl substituent.When SAM is aromatic compounds for example when benzotriazole derivatives, hydrophilic substituent is the 4-position on this aromatic ring group or 5-position preferably, and more preferably in 5-position.Most preferred compound as the SAM in device of the present invention is 4-carboxyl benzotriazole, 5-carboxyl benzotriazole, 5-hydroxybenzotriazole and 4-hydroxybenzotriazole, and most preferably is 5-hydroxybenzotriazole or 5-carboxyl benzotriazole.

In another preferred embodiment of the present invention, SAM is made up of the thio-compounds with hydrophily afterbody.Preferred example comprises sulfo-alkane (thioalkane) and sulfo-alkene (thioalkene) derivative with 6-24 carbon atom and the sulfo-aromatic derivative in one or more aromatic rings with 5-14 carbon atom.The hydrophilic radical that is selected from hydroxyl, carboxyl and carbonyl at derivative described in every kind of situation replaces.Most preferably, the described thio-compounds that has a hydrophily afterbody is 11-sulfydryl-1-undecyl alcohol or 4-thiophenol.

The organic electronic device of the present invention that comprises SAM discussed above comprises metal anode.The metal of oxidation that the metal anode in device of the present invention at room temperature (is typically 25 to 37 DEG C) typically in air.This has contained the most of metal except inert metal gold, platinum and palladium to a certain extent.In prior art, in device, often manufacture the anode in the unessential device of transparency with gold.But it suffers various problems.First, apparently, it is very expensive.Secondly, it is difficult to processing because it can only deposit by heat deposition technology.Therefore the device of the present invention that, comprises SAM discussed above preferably wherein metal anode in air under room temperature (typically 25 to 37 DEG C) oxidable those devices.More preferably, they are the metals that are selected from copper, aluminium, nickel and silver, more preferably copper.Preferably, anode is the form of the metal streak of patterning.Further discuss more below, this can for example, deposit by electroless technology (disclosed technology in WO-A-2004/068389).As an alternative, it can deposit by vacuum moulding machine or photoetching.These technology can plated metal streaks and can be produced the accurate patterning streak (for example superfine grid) with sub-10 micron dimension streaks.

Hole injection layer preferably comprises electric conducting material.It helps to be injected to the hole in luminescent layer by anode.The preferred embodiment of the material that can be used for forming hole injection layer is the material of high conductivity, particularly there are those materials of high transverse conduction, to make current spread from device anode (this is particular importance in the time that anode is the form of copper metal streak of for example patterning of metal streak of patterning).The representative example of the material that can be used for forming hole injection layer comprises poly-(3,4-ethene dioxythiophene) (PEDT), with poly-(3,4-rthylene dioxythiophene)-poly-(styrene sulfonate) (PEDT:PSS) (as disclosed together with other doping PEDT with in EP0947123 in EP0901176), as US5723873 and US5798170 in disclosed polyaniline; Polypyrrole; Polyacrylic acid; And fluorinated sulfonic, for example the optional polythiophene replacing or poly-(thienothiophene) for example PH510, commercially available a kind of PEDT:PSS from Heraeus and PEDT:PSS ratio are 1:2.5.By 5%DMSO(by weight) be added into PH510 to conductance is increased to >300Scm ^-1.Preferably, hole injection layer comprises poly-(3,4-ethene dioxythiophene) (PEDT), poly-(3,4-rthylene dioxythiophene)-poly-(styrene sulfonate) (PEDT:PSS), polyaniline or polypyrrole, and most preferably be PEDT or PEDT:PSS.

Organic electronic device according to the present invention is any device that comprises metal anode and hole injection layer, the result of wherein improving as the wettable ability of metal surface is included in the corrosion resistance that increases metal anode, reduces contact resistance, is improved the deposition of hole injection layer according to SAM's of the present invention, and result has improved device efficiency.Typical example includes OLED (comprising OLED illuminating device), OTFT, organic photovoltaic devices, organic optical sensor and organic memory array device.

Preferably, this device (for example OLED) comprises:

(i) metal anode;

(ii) the SAM of inclusion compound, described compound has can be adsorbed onto the lip-deep structure division of described metal anode and hydrophilic structure division;

(iii) hole injection layer;

(iv) organic luminous layer; With

(v) negative electrode.

More preferably, this device (for example OLED) comprises:

(i) substrate;

(ii) described suprabasil metal anode;

(iii) the SAM being formed by compound, this compound has can be adsorbed onto the lip-deep structure division of described metal anode and hydrophilic structure division;

(iv) the hole injection layer on described metal anode;

(v) organic luminous layer; With

(vi) the negative electrode on described organic luminous layer.

Particularly preferred device (for example OLED) comprises interlayer (interlayer) and electron injecting layer in addition.Preferably, interlayer is between hole injection layer and luminescent layer and/or is between anode and hole injection layer.If existed, electron injecting layer is between negative electrode and organic luminous layer.Preferred OLED of the present invention comprises the interlayer being between hole injection layer and luminescent layer.

Also preferred device of the present invention is sealed to avoid the intrusion of moisture and oxygen.Can use conventional wrapper technology.

Substrate can be for example glass of any material or the plastics that in this area, tradition is used.Substrate is preferably transparent.Preferably, substrate also has good barrier property to stop moisture or oxygen to be invaded in device.

Metal anode can comprise and has any metal that is suitable for hole and injects the work function in luminescent layer.If do not require that anode is transparent (if for example negative electrode is transparent), can use so opaque electric conducting material for example opaque metal as anode.Preferably, described metal is to be for example adapted to pass through electroless deposition techniques, so that the metal of low cost, thin grid streak, copper or aluminium to be provided.

Preferably for example, by electroless deposition techniques anode, disclosed technology in WO-A-2004/068389.These technology can make to become possibility by spin coating or ink-jet printer plated metal streak, make it possible to produce with the streak of 10 micron dimensions the streak (for example superfine grid) of accurate patterning.As an alternative, can pass through blanket formula ion sputtering (for example, referring to US-A-5,556,520) deposition anode.

After deposition anode, processed to remove all oxides and other material from metallic surface.First, used ultraviolet ray-ozone treatment to clean approximately 2 minutes to remove any organic contamination.Then, immediately substrate is immersed to the acetic acid aqueous solution that temperature is 50-70 DEG C (preferably 60 DEG C) (typically 1 to 5M, preferably 2M acetic acid) or the glacial acetic acid that immerses under room temperature continues 1 minute with the surface removal oxide from anode.It is shifted out and uses nitrogen gun rapid draing immediately from acetic acid solution.Then immediately will be deposited on suprabasil dry oxide-free anode shift to apply (we have found that before beginning passivating process and have the window of maximum 2 minutes) with lower one deck of technique.

Preferably provide the example above by the processing method deposition SAM(based on solution).Can use any traditional processing method based on solution.The representative example of the processing method based on solution comprises spin coating, intaglio printing, flexographic printing, dip-coating, the coating of slit die formula, scraper for coating and ink jet printing.In the preferred method of one, deposit by spin coating.SAM(is self-assembled monolayer) during soak time from the liquid deposition of Metal Contact on this metal.The use of spinner allows excessive SAM solution removal and effective backwashing manner.Condition (RPM etc.) does not affect the thickness of SAM.Therefore, be transferred to after spinner in substrate, can by target SAM for example in isopropyl alcohol solution by its submergence.Then typically stopped for 30 seconds to 5 minute preferably 1 minute to 3 minutes and most preferably 2 minutes.After excessive SAM solution is rinsed out, with solvent by substrate submergence and start to rotate step (typically from 500 to 2000rpm, preferably 1000rpm, typical case is with 200 to 400rpm/s acceleration, preferably 300rpm/s).Typically implement rotation and continue the period of 15 seconds to 1 minute, preferably continue 30 seconds.In the time that this period finishes, make the gained substrate of the SAM layer with deposition in nitrogen glove box, stand dehydration baking (for example continuing 15 minutes at 70 DEG C).

Preferably on SAM layer, deposit hole injection layer (providing the example above) by the processing method based on solution.Can use any traditional processing method based on solution.The representative example of the processing method based on solution comprises spin coating, intaglio printing, flexographic printing, dip-coating, the coating of slit die formula, scraper for coating and ink jet printing.In a kind of method for optimizing, deposit by spin coating.Target thickness based on this layer is selected for example spin coating speed of parameter, acceleration and the time for spin coating hole injection layer.After deposition, preferably by heating, hole injection layer is annealed, for example in air, at 150 to 200 DEG C, continue 5-30 minute.

In device of the present invention, can use and be suitable as any compound of hole injection layer or the combination of compound.For example, can use PH510 as above.Other representative instance of the lamellar compound of knowing is discussed above, has been there is but can use any compound that makes its character that is suitable as hole injection layer.

The thickness of hole injection layer preferably 15 to 200nm and 150nm more preferably.

In device of the present invention, the optional interlayer existing can comprise conventional any interlayer for this purposes.The representative instance of lamellar compound comprises poly-(2,7-(9,9-di-n-octyl fluorenes)-alternately-(Isosorbide-5-Nitrae-phenylene-((4-secondary butyl phenenyl) imino group)-Isosorbide-5-Nitrae-phenylene)) (TFB).

TFB-EP2?228?847

TFB

Another example is copolymer 1.This is the copolymer of the crosslinking agent TFBBCB that comprises 50% monomer 1,42.5%FDA and 7.5%.

Monomer 1 (WO01/96454)-

WO2005/049546(Dow)

WO2005-052027TFB-BCB。

Preferably deposit this interlayer by the processing method based on solution.Can use the processing method based on solution of any routine.The representative example of the processing method based on solution comprises spin coating, intaglio printing, flexographic printing, dip-coating, the coating of slit die formula, scraper for coating and ink jet printing, for example spin coating.Target thickness based on this interlayer is selected for example spin coating speed of parameter, acceleration and the time for this interlayer of spin coating.After deposition, preferably make interlayer crosslinked by heating, for example in nitrogen glove box, at 150 to 200 DEG C, continue 30 to 120 minutes.

The thickness of interlayer is preferably 5 to 50nm, and more preferably 10 to 40nm, and most preferably 20 to 30nm.

The organic luminous layer existing in device of the present invention can comprise organic light emission compound and/or the organic luminescence polymer of any routine.Preferably organic luminous layer comprises light emitting polymer.An example of such luminous organic material is blend 1, and it is the blend of copolymer 2 and monomer 2.Monomer 2 is phosphorescence green dopant-be called face formula three (2-phenylpyridine) iridium or Ir (ppy) ₃.Can use similar phosphorescence all to join or assorted iridium complex of joining.For Ir (ppy) ₃material of main part can be phenanthrene or propellane polymer or non-polymeric main body or poly-fluorenes.Suitable organophosphor optical compounds is recorded in following books: " the Organic Light Emitting Materials and Devices " that Zhigang Li and Hong Meng write, the 369th to 375 pages of CRC Press (2007) ISBN1-57444-574-X.These books have been described multiple light emitting polymer in the 2nd chapter, comprise that fit for service gathers fluorenes, PPV and polythiophene.Copolymer 2 is by 25% monomer 1/ monomer 3(1:1) and the copolymer that forms of 75% monomer 1/ monomer 4.

Monomer 2

Monomer 1 (WO01/96454 is usually)-

Monomer 3

WO2002/083760

Monomer 4

Preferably prepare organic luminous layer by the solution that deposits organic luminescence polymer on hole injection layer or interlayer.Can use the processing method based on solution of any routine.The representative instance of the processing method based on solution comprises spin coating, intaglio printing, flexographic printing, dip-coating, the coating of slit die formula, scraper for coating and ink jet printing.In a kind of method for optimizing, deposit by spin coating.Target thickness based on luminescent layer is selected for example spin coating speed of parameter, acceleration and the time for spin coating luminescent layer.After deposition, preferably that organic luminous layer is dry, for example in nitrogen glove box at 100-150 DEG C.

The thickness of luminescent layer is preferably 50 to 350nm and more preferably 75 to 150nm.

Preferably prepare the electron injecting layer of optional existence by deposit solution on luminescent layer.The method is with similar for the method for interlayer.In device of the present invention, the optional electron injecting layer existing can comprise the electron injecting layer of any routine, typical example can comprise the thin layer of metal halide, for example LiF or NaF, or preferably organic compound or the salt with the organic compound of metal ion mixing, it can deposit from organic solution, for example phenol lithium salts and 4,7-diphenyl-1,10-phenanthroline.

Negative electrode is selected to have allows the material of electronic injection to the work function in luminescent layer.Other factors affects the selection of negative electrode, for example the harmful interactional possibility between negative electrode and luminescent material.Negative electrode can be made up of for example aluminium lamination of homogenous material.As an alternative, it can comprise various metals, and the bilayer of for example low-work-function material and high work function material, as disclosed calcium and aluminium in WO98/10621.Negative electrode can contain containing simple substance barium layer, as for example at WO98/57381, Appl.Phys.Lett.2002,81 (4), 634 and WO02/84759 in disclosed.The thin layer (for example 1-5nm is thick) that negative electrode can for example, comprise metallic compound between one or more conductive layers of the luminescent layer of OLED and negative electrode (one or more metal levels).Exemplary metallic compound comprises that the oxide of alkali metal or alkaline-earth metal or fluoride inject with auxiliary electron, for example disclosed lithium fluoride in WO00/48258; As at Appl.Phys.Lett.2001, disclosed barium fluoride in 79 (5), 2001; And barium monoxide.In order to provide electronics to the efficient injection in device, negative electrode preferably has and is less than 3.5eV, is more preferably less than 3.2eV, is most preferably less than the work function of 3eV.The work function of metal can be referring to for example Michaelson, J.Appl.Phys.48 (11), 4729,1977.

Negative electrode can be opaque or transparent.Transparent cathode is particularly advantageous for active-matrix device, because the drive circuit being positioned at least in part below light emitting pixel through the utilizing emitted light of the transparent anode in such devices stops.The layer that transparent cathode comprises electron injection material, this layer is enough thin so that be transparent.Conventionally, the transverse conduction of this layer will be low due to its thinness (thinness).In this case, being combined with compared with thick-layer of electron injection material layer and for example indium tin oxide of transparent conductive material.

Will be appreciated that transparent cathode device does not need to have transparent anode (certainly, unless needed transparent device completely), and therefore can replace or supplement the transparent anode for bottom-emission device with for example aluminium lamination of layer of reflective material.The example of transparent cathode device is disclosed in GB2348316 for example.

Preferably, not having electron injecting layer and negative electrode is the sodium fluoride lamination of standard, for example NaF (2nm)/Al (100nm)/Ag (100nm).

Suitable encapsulating material comprises sheet glass, there is the film of suitable barrier property, as silicon dioxide, silicon monoxide, silicon nitride or be disclosed in polymer in WO01/81649 for example and the alternative stacked of dielectric material, or be disclosed in the airtight container in WO01/19142 for example.In the situation of transparent cathode device, can deposit transparent encapsulated layer reach micron-sized thickness as silicon monoxide or silicon dioxide, but in a preferred embodiment, the thickness of this layer is within the scope of 20-300nm.

According in the method for second aspect present invention, preferably use the metal pretreated anode of reagent so that from all metal oxides of the surface removal of described metal anode and organic material.First, utilize ultraviolet ray-ozone treatment to be cleaned approximately 2 minutes to remove any organic contamination.Then, immediately substrate is immersed anhydrous acetic acid or acetic acid aqueous solution (be 1 to 5M acetic acid aqueous solution, the preferably acetic acid aqueous solution of 2M, temperature is 30-90 DEG C, preferably 60 DEG C, or be the glacial acetic acid under room temperature) continue 1 minute so that from the surface removal oxide of anode.It is shifted out and uses nitrogen gun rapid draing immediately from acetic acid solution.Then immediately will be placed in suprabasil dry oxide-free anode shift so that with lower one deck coating of technique.

In a preferred embodiment of second aspect present invention, will utilize agent treatment to be incorporated in a solution procedure of processing with the deposition that can form on the surface of metal anode the compound of SAM to remove all metal oxides from metal surface.

We think that in method aspect second of the present invention,, compared with there is no the equalization compound of described hydrophilic radical, the hydrophilic-structure part of the compound of SAM is improved the wettable ability of this SAM.In addition,, compared with not there is not the other identity unit of described SAM, described SAM includes the contact resistance reducing between metal anode and hole injection layer in.

In the preferred embodiment of second aspect present invention, a kind of method is provided, wherein metal anode is the form of the metal streak of patterning, for example, by (being selected from vapour deposition, sputter code-pattern sputter, as at for example US-A-5, described in 556,520) and the method for electroless be deposited in substrate, preferably deposit by electroless.Electroless technology is particularly preferably as disclosed electroless technology in WO-A-2004/068389.This comprises in its most basic form: the solution of the ion of described metal is in suprabasil deposition, and the solution of reducing agent is in described suprabasil deposition, thereby thereby make metal ion and the reducing agent metallic region that forms conduction in described substrate that reacts in reaction solution in substrate, form the metallic region of conducting electricity.Typically for example, by the reaction between activator (being different from the second conducting metal of the first conducting metal) activator metal ion and reducing agent.If used, thereby first activator is typically deposited on the structure that produces patterning in substrate.Then the first metal ion and reducing agent are deposited in substrate successively, thereby generation has the expectation anode of the metal streak form of desired pattern.

Comprise the following steps according to the preferred method of the present invention:

(i) in substrate of glass, pass through the metal streak of electroless deposit patterned, be preferably the metal streak of copper, preferably by deposit the solution of ion of described metal in substrate of glass, and in described substrate of glass, deposit the solution of reducing agent, thereby make metal ion and reducing agent one react and form the metal streak of described patterning to form the metallic region of conduction in described substrate in reaction solution;

(ii) processing the metal streak of described patterning with 1 to 5M acetic acid solution is then dried immediately to remove all oxides from metallic surface;

From liquid deposition can step (ii) the surface of metal streak of described patterning of preparation form the compound of SAM, the described compound that wherein can form SAM has the lip-deep structure division of the metal streak that can be adsorbed onto described patterning and further has hydrophilic structure division, implements described deposition by the method that is selected from spin coating, dip-coating, the coating of slit die formula, scraper for coating and ink jet printing;

Method by being preferably selected from spin coating, dip-coating, the coating of slit die formula, scraper for coating and ink jet printing step (iii) on the SAM of preparation from liquid deposition hole injection layer;

Optionally the method by being selected from spin coating, dip-coating, the coating of slit die formula, scraper for coating and ink jet printing step (iv) on the described hole injection layer of preparation from liquid deposition interlayer;

Method by being selected from spin coating, dip-coating, the coating of slit die formula, scraper for coating and ink jet printing step (iii) in the described hole injection layer of preparation or step (v) on the interlayer of preparation from liquid deposition organic luminous layer; With

Step (vi) in deposition cathode on the described organic luminous layer of preparation, preferably, by hot evaporation metal, metal oxide or metal halide on described organic luminous layer, be preferably NaF/Al/Ag negative electrode.

Brief description of the drawings

Fig. 1 a and 1b are the schematic diagrames of typical OLED;

Fig. 2 is according to the schematic diagram of typical bottom emission body OLED of the present invention;

Fig. 3 be the square root yield of the device according to the present invention with respect to the coordinate diagram of energy (eV), compare to show relative work function with control device;

Fig. 4 a, 4b, 4c, 4d, 4e, 4f and 4g be according to the present invention the root mean square yield at different time measured of device compared with control device with respect to the coordinate diagram of energy (eV), in order to exhibit stabilization;

Fig. 5 a is the current density (mA/cm of device compared with control device according to the present invention with 5b ²) with respect to the coordinate diagram of voltage (V) and the feature of part thereof;

Fig. 6 a and 6b be according to the present invention the efficiency (EQE) of device compared with control device with respect to coordinate diagram and the local feature thereof of voltage (V);

Fig. 7 is the current density (mA/cm of best device ²) with respect to the coordinate diagram of voltage (V);

Fig. 8 is that the efficiency (EQE) of best device is with respect to the coordinate diagram of voltage (V); And

Fig. 9 is that efficiency (Lm/W) is with respect to brightness (Cd/m ²) coordinate diagram.

The cross section of the basic structure by typical OLED1 shown in Fig. 1 a.Glass or plastic-substrates 2 are carried transparent anode layer 4, described transparent anode layer 4 for example comprises metal (for example copper or the aluminium) anode as the metal streak form of patterning, it has the grid of sub-10 micron dimensions, deposits hole injection layer 6, interlayer 8, organic luminous layer 10 and negative electrode 12 on described grid.The transparent polymer that helps the hole injection layer 6 of the hole energy level of coupling anode layer 4 and luminescent layer 10 to comprise conduction.Negative electrode 12 comprises for example triple layer of sodium fluoride, aluminium and silver.Provide respectively and being connected of power supply 18 with the contact wire 14 and 16 of anode and negative electrode.

In so-called " bottom emission body " device, deposit multilayer laminated construction on the front surface of flat glass substrate, it is with the reflection electrode layer (normally negative electrode) away from substrate, thus in luminescent layer the inner light producing through substrate by device coupling output.The example of bottom emission body 1a is shown in Fig. 1 a, wherein passes transparent anode 4 and substrate 2 utilizing emitted lights 20 and negative electrode 12 and reflects.

On the contrary, in so-called " top emitters ", deposit multilayer laminated construction on the rear surface of substrate 2, and in luminescent layer 10, the inner light producing does not pass through substrate 2 through transparent electrode layer 12 coupled outside.The example of top emitters 1b is shown in Fig. 1 b.Normally transparent electrode layer 12 is negative electrodes, but also can build the device through anode transmitting.For example can make cathode layer 12 substantial transparent by keeping cathode layer thickness to be less than about 50-100nm.

In Fig. 2, illustrate and passed according to the cross section of bottom emission body device of the present invention.Glass or plastic-substrates 2 are carried transparent anode layer 4, metal (for example copper) anode of the metal streak form as patterning that described transparent anode layer 4 comprises about 100nm thickness.Can be for example disclosed in WO-A-2004/068389 or (for example cover ion sputtering by blanket by electroless technology for example code-pattern sputter) deposit this anode.The SAM22 that deposition is made up of compound on metal streak 4, described compound has can be adsorbed onto the lip-deep structure division of described metal anode and hydrophilic structure division, for example for example 5-hydroxybenzotriazole of hydrophilic benzotriazole derivatives or 5-carboxyl benzotriazole.On SAM, deposit hole injection layer 6.Then one after the other deposit interlayer 8, organic luminous layer 10 and negative electrode 12.The transparent polymer that helps the hole injection layer 6 of the hole energy level of coupling anode layer 4 and luminescent layer 10 to comprise conduction.Negative electrode 12 comprises for example triple layer of sodium fluoride, aluminium and silver.Provide respectively and being connected of power supply 18 with the contact wire 14 and 16 of anode and negative electrode.

Can further understand the present invention by consideration following examples.

The preparation of substrate and the measurement of the final water contact angle of processing substrate that the different SAM of embodiment 1 use process

(a) pass through the substrate of 2 inches of (5.08cm) 100nm copper is prepared in code-pattern sputter.Then the gained substrate that preparation deposits copper anode is thereon for the selected molecule of liquid deposition from as SAM.Process is as follows:

(b) prepare the black preparation of SAM.For this reason, clean 10ml bottle and dry up by nitrogen gun with oxolane.The institute's testing SA M material that takes desired amount in the glove box with inert nitrogen environment is put into 10ml bottle.In this glove box under the same conditions, to the expectation solvent (being isopropyl alcohol in this test) that adds appropriate amount in this 10ml bottle.Then by mixture vortex 1 to 2 minute, be placed into subsequently upper 1 hour of heat block or until be dissolved in completely in solution.

(c) also prepare the bath of acetic acid solution.This relates to the PVDF(polyvinylidene fluoride that uses 0.45 μ m) filter is filled into the 2M acetic acid of 200ml nearly in beaker.Then beaker is heated to 60 DEG C.Make before use the stable at least 20-30 minute of solution temperature.

(d) 2 inches of panel preliminary treatment

Use UV treatment that 2 inches of (5.08cm) substrates of preparation in above-mentioned steps (a) are cleaned to 120 seconds to remove any organic contamination.Then 60 DEG C of 2M acetic acid beakers substrate being put into above-mentioned steps (c) preparation continue 1 or 3 minute to remove all oxides from metal surface.Then substrate taken out and be dried (not having water to rinse) with nitrogen spray gun immediately.

(e) SAM of 2 inches of preliminary treatment panels processes

2 inches of (5.08cm) pretreated substrates are transferred to Karl-Suss spinner immediately to carry out SAM processing.Use 0.45 μ m PTFE(polytetrafluoroethylene with the SAM[of preparation in step (b) above) filter filtered] this pretreated substrate of submergence and then make it shelve 2 minutes.Then use the isopropyl alcohol (having used 0.45 μ m PTFE to be filtered) of 10ml to rinse substrate.For this reason, use the isopropyl alcohol of 2ml by first submergence of substrate.Then make substrate rotate with 1000rpm/300rpms/60s, and during rotation drip the solvent that is coated with other 8ml.In the time that this time finishes, make the gained substrate that deposits SAM on it in 70 DEG C of nitrogen gun, stand dehydration baking 15 minutes.

Carry out series of experiments to measure the water contact angle of undressed copper (being with or without ozone treatment), and this and the water contact angle when with following various compound treatment copper surface are contrasted.

The results are summarized in table 1.

Table 1

Material	Water contact angle (degree)
		120 seconds ultraviolet and ozones	31.5
Without ultraviolet and ozone	31
		BTA (BTA)	65
4-hydroxybenzotriazole	54
		5-carboxyl benzotriazole	30
F4TCNQ	71
		MBI	71
MBT	67
		HBT	31
HUT	32

This shows that water contact angle exists changes, and this depends on the substituent hydrophily on character and the particularly aryl of the surperficial compound for processing copper.The change of water contact angle can change metallic surface energy.This causes the improvement combination of the structure division that can be adsorbed to metal surface with improvement in hydrophilicity and the wettable ability increasing.In the time contrasting with the control sample (31 °) without ultraviolet and ozone, CBTA (30 °), HBT (31 °) and HUT (32 °) provide acceptable water contact angle.These SAM have hydrophily afterbody.Good wettable ability (the control sample here) on the copper that non-SAM processes has the fact (it is disadvantageous for Electronic Performance) of copper oxide owing to them, but non-oxide copper only provides not good enough wettable ability.Untreated copper soaks well but has oxide layer thereon, and this provides not good enough device performance.Once oxide is removed, copper does not just show good soaking until oxide forms again, therefore needs to protect copper with the SAM that gives good water contact angle.

Also think that the variation of position of hydrophilic radical will change surperficial energy.This will cause the change of the wettable ability of compound in the time being attached to copper pattern substrate, therefore provide making the maximized possibility of wettable ability.Our result of calculation shows and can on SAM molecule, make that it is in from metal surface maximum distance apart while being adsorbed onto metal surface by actual when the surperficial structure division of being adsorbed to of SAM molecule by hydrophilic radical is connected to, obtains the maximization of wettable ability.5-hydroxybenzotriazole and 5-carboxyl triazole are two examples.If the surface that compound also can be adsorbed to metal anode to form SAM, this thought can be applied to when be connected on phenyl ring any position time the group of hydrophilic any kind can be provided.

In second experiment subsequently, measure the contact angle with SCA126-2 (PEDT).The results are shown in table 2.

Table 2

Material	SCA126-2 contact angle (degree)
		120 seconds ultraviolet and ozones	47
There is no ultraviolet and ozone	40
		4-hydroxybenzotriazole	58
5-carboxyl benzotriazole	38
		F4TCNQ	29
MBI	78
		MBT	67
HBT	35
		HUT	32

Again, in the time contrasting with the control sample (40 °) that there is no ultraviolet and ozone, CBTA (38 °), HBT (35 °) and HUT (32 °) provide acceptable contact angle.

The work function of substrate and the comparison of stability that embodiment 2SAM processes

(a) substrate that checks preparation in embodiment 1 with AC-2 is to determine their photoelectron spectrum, and the square root of photoelectric yield (it is proportional with the photoelectron number of counting) is with respect to the coordinate diagram of incident photon energy.This provides the work function of SAM copper after treatment with respect to the measurement of the work function of native copper.Within 1 minute after SAM finishes dealing with, measure.As seen from Figure 3, compared with the work function of native copper, the AC-2 response of the copper substrate of processing from F4TCNQ, HOTBA, CBTA, HBT and HUT shows higher work function.By contrast, all show work function lower compared with the work function of native copper from the AC-2 response of MBI and MBT.

(b) same program in (a) according to above subsequently, but repeatedly get measurement result to determine the stability of substrate after the preparation of the copper of processing at SAM specifically.Particularly, after 1 minute, 10 minutes and 3 hours, get measurement result.Can find out that from Fig. 4 a, 4b, 4c, 4d, 4e, 4f and 4g the copper substrate that HOTBA, CBTA, HBT and HUT process demonstrates outstanding stability within the whole 3 hour period of test, but F4TCNQ, MBI and MBT all show not good enough stability, and their work function moves towards the work function of native copper within the test period of 3 hours.Processing with CBTA in the situation on copper surface, for example coordinate diagram with respect to energy from square root yield, there is the skew with respect to native copper in (more than about 5.2eV) under higher-energy.This has confirmed as the result in conjunction with CBTA, and the surface of copper exists significantly difference, has confirmed that the stable of CBTA adheres to.

The preparation of the OLED that embodiment 3 comprises CBTA SAM

Preparation comprises following OLED device:

Substrate is the glass available from Corning.

Anode is the copper anode that is deposited on suprabasil 100nm thickness by the code-pattern sputtering technology described in embodiment 1.By photo-patterning technology, copper pattern is changed into metal grill.

Use UV treatment that the substrate of preparation is cleaned to 120s to remove any organic contamination.Then substrate is placed in 60 DEG C of 2M acetic acid beakers of preparation to 1 minute to remove all oxides from metal surface.Then substrate taken out and be dried (not having water to rinse) with nitrogen spray gun immediately.

If existed, SAM is 5-carboxyl benzotriazole (also referred to as BTA-5-carboxylic acid) and is deposited on copper anode, to provide the layer of SAM as described in example 1 above by spin coating.In " short SAM " device, substrate stands 1 minute SAM to be processed, but in " long SAM " device, substrate stands 3 minutes SAM and processes.Sample in contrast, prepares other device (" IPA flushing " device), wherein only in circulator, adds isopropyl alcohol and there is no 5-carboxyl benzotriazole.By this control sample add to determine whether any benefit of seeing be attributable simply to SAM or whether any benefit result from solvent washing (but as in " IPA flushing " device, carry out solvent washing do not have SAM molecule).

Hole-injecting material is PH510, and commercially available a kind of PEDT:PSS from Heraeus and PEDT:PSS ratio are 1:2.5.By 5%DMSO(by weight) be added into PH510 to conductance is increased to >300Scm ^-1.

Sandwich material is copolymer 1 (comprises 50% monomer 1,42.5%FDA monomer and 7.5% crosslinking agent TFBBCB copolymer-referring to above).Electroluminescence layer is blend, i.e. the blend of copolymer 2 and monomer 2 (referring to above).Negative electrode is NaF (2nm)/Al (100nm)/Ag (100nm).

Use Karl-Suss spinner by spin coating from liquid deposition hole injection layer (air, speed of rotation 1500rpm continues 60 seconds).Then in air, it is dried to 15 minutes at 130 DEG C.Gained hole injection layer is that 150nm is thick.

Then (glove box, speed of rotation 150rpm continues 6 seconds from xylene solution deposition copolymer 1 interlayer (referring to above) on the hole injection layer depositing in back on each test component, to use Karl-Suss spinner; Then at N ₂in glove box, at 180 DEG C, be cross-linked (X-link) 60 minutes).Gained copolymer 1 interlayer is that 22nm is thick.

Deposit each interlayer on each test component after, then on the interlayer depositing in back on each test component, use Karl-Suss spinner to deposit electroluminescence layer from xylene solution, (in glove box, speed of rotation 1500rpm continues 7 seconds to the blend (referring to above) that described electroluminescence layer is made up of copolymer 2 and monomer 2; Then it is toasted 10 minutes in glove box at 130 DEG C).Gained copolymer 2: monomer 2 blend electroluminescence layers are that 100nm is thick.

Finally, after depositing electroluminescence layer on each interlayer in each test component, in a vacuum by Continuous Heat evaporation to the pantostrat of each test component blanket-deposited sodium fluoride (2nm), aluminium (100nm) and silver (100nm) to provide triple layer NaF/Al/Ag negative electrode.

The details of the test component of preparing according to said procedure is as shown in table 3:

Table 3

Fig. 5 a and 5b illustrate the current density (mA/cm of the device of preparation above ²) with respect to the coordinate diagram of voltage (V) and local feature wherein, below having shown:

● isopropyl alcohol flushing gives the processing of the current density identical with control device-isopropyl alcohol does not affect device performance, therefore shows that isopropyl alcohol rinses the reduction that does not cause leakage current.

● including in of SAM layer makes the current density of the device that comprises copper anode be promoted to the more approaching current density level realizing about gold anode.

● process between long SAM processing and seem almost not have difference at short SAM.

Below having confirmed about the measurement result (referring to Fig. 7 to 9) of best device:

● confirm that SAM subitem (split) rises to the current density of copper anode more to approach the level that control sample gold anode is realized.

● in addition, confirm to process between long SAM processing and seem almost not have difference at short SAM.

● isopropyl alcohol rinses subitem and provides and the copper control sample identical current density of itemizing, thereby confirms for having the being seen current density increase of copper that SAM processes in fact owing to SAM, instead of is attributable simply to the other processing of substrate.

In these experiments, the device of preparation is at 1000Cd/m ²under device data be shown in following table 4:

Table 4

Median is at 1000Cd/m ²

Subitem title	Voltage	Electric current	Efficiency Lm/W
				1) golden control sample	5.60	1.8	30.95
2) copper control sample	6.10	1.9	26.40
				3) short SAM	5.62	1.8	31.29
4) long SAM	5.74	1.9	29.49
				5) IPA_ rinses	6.16	2.0	25.42

■ SAM subitem makes the improved efficiency of copper anode to more approaching the level that gold anode is realized.

■ processes between long SAM processing and seems almost not have difference at short SAM.

■ isopropyl alcohol rinses subitem and provides and the copper control sample similar efficiency of itemizing--for the efficiency increase of seeing with the copper that SAM processes in fact owing to SAM--not only owing to the another processing of substrate.

Can see according to the performance of the device of the 5-of comprising carboxyl triazole of the present invention (no matter short or long process) and significantly be better than copper control device (and isopropyl alcohol control device) from above table thus.In addition, can see that performance (especially for weakness reason) is quite approaching with the performance of golden control device.This provides strong evidence: SAM layer include the double effect really with expectation in: the wettable ability of the contact resistance of minimizing and increase.

Claims (23)

1. an organic electronic device, described device comprises metal anode and hole injection layer, wherein said device further comprises the self-assembled monolayer (SAM) between described metal anode and described hole injection layer, described SAM inclusion compound, this compound has lip-deep structure division and the hydrophilic-structure part that can be adsorbed onto described metal anode.

2. according to the organic electronic device of claim 1, wherein in hydrophilic-structure part described in the compound of SAM, the tie point on the described lip-deep structure division that can be adsorbed onto described metal anode makes: when on the surface that can be adsorbed onto the lip-deep structure division of described metal anode and be adsorbed onto described metal anode, the distance on described hydrophilic-structure part and metal anode surface is maximized.

3. according to the organic electronic device of claim 1 or claim 2, wherein, compared with there is no the equalization compound of described hydrophilic radical, the described hydrophilic-structure part of the compound of SAM is improved the wettable ability of SAM.

4. according to the organic electronic device of claims 1 to 3 any one, wherein, compared with the non-existent other identity unit of wherein said SAM, described SAM comprises the contact resistance reducing between described metal and described hole injection layer.

5. according to the organic electronic device of claim 1 to 4 any one, wherein said SAM is made up of the aromatic compounds with hydrophilic substituent.

6. according to the organic electronic device of claim 5, the wherein said aromatic compounds with hydrophilic substituent is benzotriazole derivatives or indazole derivative.

7. according to the organic electronic device of claim 1 to 6 any one, wherein said hydrophilic substituent is selected from hydroxyl, carboxyl, carbonyl and sulfo-substituting group.

8. according to the organic electronic device of claim 5 to 7 any one, 4-position or the 5-position of wherein said hydrophilic substituent on aromatic ring group.

9. according to the organic electronic device of claim 5 to 8 any one, wherein said SAM is made up of benzotriazole derivatives, and this benzotriazole derivatives is selected from the group being made up of 4-hydroxyl-1-BTA, 5-hydroxyl-1-BTA, 4-carboxyl-1-BTA and 5-carboxyl-1-BTA.

10. according to the organic electronic device of claim 1 to 4 any one, wherein said SAM is made up of the sulfo-aromatic derivative that has sulfo-alkane or the sulfo-alkene derivatives of 6-24 carbon atom or have a 5-14 carbon atom in one or more aromatic rings, wherein said sulfo-alkane, sulfo-alkene and sulfo-aromatic derivative are replaced by hydrophilic radical, and this hydrophilic radical is selected from hydroxyl, carboxyl and carbonyl.

11. according to the organic electronic device of claim 1 to 10 any one, and the metal of wherein said metal anode is copper, aluminium, nickel or silver.

12. according to the organic electronic device of claim 1 to 11 any one, and wherein this metal anode is the form of the metal streak of patterning.

13. according to the organic electronic device of claim 1 to 12 any one, wherein said hole injection layer comprises and is selected from least one following compound: poly-(3,4-ethene dioxythiophene) (PEDT), poly-(3,4-ethene dioxythiophene)-poly-(styrene sulfonate) (PEDT:PSS), polyaniline, PEDT:PSS ratio be 1:2.5 PEDT:PSS or polypyrrole, preferably PEDT or PEDT:PSS.

Manufacture the method for organic electronic device for 14. 1 kinds, the method includes the steps of:

(i) plated metal anode in substrate;

(ii) Energy Deposition forms the compound of self-assembled monolayer (SAM) on described metal anode surface, and wherein said compound has can be adsorbed onto the lip-deep structure division of described metal anode and hydrophilic structure division; With

(iii) on SAM, deposit hole injection layer.

15. according to the method for claim 14, wherein uses described in reagent preliminary treatment metal anode so that from all metal oxides of the surface removal of described metal anode.

16. according to the method for claim 15, wherein with metal anode described in anhydrous acetic acid or acetic acid aqueous solution preliminary treatment.

17. according to the method for claim 14, and wherein, compared with the non-existent other identity unit of wherein said SAM, described SAM comprises the contact resistance reducing between described metal anode and described hole injection layer.

18. according to the method for claim 14, and wherein said SAM is made up of benzotriazole derivatives or indazole derivative.

19. according to the method for claim 18, and wherein said SAM has the substituent hydrophilic substituent of the hydroxyl of being selected from, carboxyl, carbonyl and sulfo-.

20. according to the method for claim 19,4-position or the 5-position of wherein said substituting group on aromatic ring group.

21. according to the method for claim 14, wherein said SAM is made up of the sulfo-aromatic derivative that has sulfo-alkane or the sulfo-alkene derivatives of 6-24 carbon atom or have a 5-14 carbon atom in one or more aromatic rings, and the hydrophilic radical that wherein said sulfo-alkane, sulfo-alkene and sulfo-aromatic derivative are selected from hydroxyl, carboxyl and carbonyl replaces.

22. methods according to claim 14 to 21 any one, wherein said hole injection layer comprises poly-(3,4-ethene dioxythiophene) (PEDT), poly-(3,4-ethene dioxythiophene)-poly-(styrene sulfonate) (PEDT:PSS), polyaniline or polypyrrole, preferably PEDT or PEDT:PSS.

23. 1 kinds of methods for the preparation of Organic Light Emitting Diode, the method includes the steps of:

(i) in substrate of glass, pass through the metal streak of electroless deposit patterned, be preferably the metal streak of copper, preferably by deposit the solution of ion of described metal in substrate of glass, and in described substrate of glass, deposit the solution of reducing agent, thereby make metal ion and reducing agent one react and form the metal streak of described patterning to form the metallic region of conduction in described substrate in reaction solution;

(ii) processing the metal streak of described patterning with 1 to 5M acetic acid solution is then dried immediately to remove all oxides from metallic surface;

From liquid deposition can step (ii) the surface of metal streak of described patterning of preparation form the compound of self-assembled monolayer (SAM), the described compound that wherein can form SAM has the lip-deep structure division of the metal streak that can be adsorbed onto described patterning and further has hydrophilic structure division, implements described deposition by the technique that is selected from spin coating, dip-coating, the coating of slit die formula, scraper for coating and ink jet printing;

Method by being selected from spin coating, dip-coating, the coating of slit die formula, scraper for coating and ink jet printing step (iii) on the SAM of preparation from liquid deposition hole injection layer;

Optionally the method by being selected from spin coating, dip-coating, the coating of slit die formula, scraper for coating and ink jet printing step (iv) on the described hole injection layer of preparation from liquid deposition interlayer;

Method by being selected from spin coating, dip-coating, the coating of slit die formula, scraper for coating and ink jet printing step (iii) in the described hole injection layer of preparation or step (v) on the interlayer of preparation from liquid deposition organic luminous layer; With

Step (vi) in deposition cathode on the described organic luminous layer of preparation, preferably, by hot evaporation metal, metal oxide or metal halide on described organic luminous layer, be preferably NaF/Al/Ag negative electrode.