CN100536194C - Electroluminescent element - Google Patents

Abstract

The invention discloses a preparing method of electroluminescent cell with buffer layer and luminous layer in the electroluminescent layer of electroluminescent cell, which comprises the following steps: forming imaging buffer layer through non-soluble photoproduced etching solvent, photoproduced anti-eroding stripping liquid and buffer layer of luminous layer solvent; forming imaging luminous layer on the buffer layer.

Description

The manufacture method of electroluminescent cell

The application is dividing an application of September 25 calendar year 2001 applying date, application number are 01142228.9, denomination of invention is electroluminescent cell manufacture method.

Technical field

The present invention relates to form the manufacture method of electroluminescence (the following EL that abbreviates as the sometimes) element of figure.

Background technology

EL element is combination in luminescent layer by comparative electrode injected holes and electronics, by the fluorescent material in its energy excitation luminescent layer, carries out luminous material according to the color of fluorescent material, behaves as self luminous screen display element and attractes attention.Wherein, use the organic film EL display of organic substance as luminescent material, even the not enough 10V of applied voltage, the luminous efficiency of realization high brightness luminescent etc. is also very high, can pass through the simple elements structure light-emitting, expectation can be applied to make in the simple display of the advertisement of the luminous demonstration of special pattern and other low price.

In the manufacturing of the display that uses this EL element, make electrode layer or organic EL layer form figure usually.As this method that makes EL element form figure, the method that method by shadow mask evaporation luminescent material is arranged, apply respectively by ink-jet, destroy the method, silk screen print method etc. of specific luminescent pigment by ultraviolet irradiation.But it is simple and form all attainable EL element of high accuracy figure to provide luminous efficiency and light to read efficient height, manufacturing process by these methods.

Summary of the invention

The present invention In view of the foregoing proposes, and its main purpose is, a kind of manufacture method that realizes luminous efficiency and read the efficient height, manufacturing process is simple and forms the EL element of high accuracy figure is provided.

In order to achieve the above object, the invention provides a kind of manufacture method of EL element, resilient coating and luminescent layer at least in constituting the organic electro luminescent layer of electroluminescent cell, utilize the photoetching technique method to form figure, has following operation: the photoresist that is insoluble to the solvent that is used to form resilient coating by utilization, make the resilient coating that is insoluble to photoresist solvent, photoresist stripper and is used to form the solvent of luminescent layer, form figure and form the operation of patterned resilient coating; Be insoluble to the photoresist of the solvent that is used to form luminescent layer by utilization, make the luminescent layer that is insoluble to photoresist solvent, development of photoresist liquid and photoresist stripper, form figure and on the resilient coating of former figuresization, form the operation of patterned luminescent layer.

Manufacture method according to EL element of the present invention, can make at least 1 layer of organic EL layer in the EL element form figure by photoetching technique method method, if therefore the method for passing through evaporation formation figure with present use compares, then owing to do not need to possess the vacuum equipment etc. of high-accuracy fine adjusting device, thereby can be than being easier to and making at an easy rate.On the other hand, compare with the pattern forming method that uses ink-jetting style, the auxiliary works that forms figure and matrix not being carried out aspect pretreated is preferred, and from discharging the relation of precision with ink gun, manufacture method of the present invention can be described as preferable methods for forming more high-precision figure.Therefore, according to the manufacture method of EL element of the present invention, can be than being easier to and obtaining at an easy rate high-accuracy fine EL element.

In the foregoing invention, the organic EL layer that above-mentioned use photoetching technique method method forms figure is preferably luminescent layer.This is because in EL element, luminescent layer is necessary layer, and can access necessary high-accuracy Micropicture when luminous.

In addition, in foregoing invention, preferred above-mentioned luminescent layer is insoluble to photoresist solvent, development of photoresist liquid and photoresist stripper, and photoresist is insoluble to the solvent that is used to form above-mentioned luminescent layer.For example, though with the method for utilizing dry corrosion or use the kind of photoetching technique method methods such as method of dry film relevant, when adopting general wet type photoetching technique method method, preferred luminescent layer and the photoresist that satisfies these conditions that use.

And, in foregoing invention, the luminescent layer that above-mentioned luminescent layer preferably constitutes through several photoetching technique method method formation variety classes luminescent layer.This is because by luminescent layer being made diverse a plurality of luminescent layer, if for example select red, green and blue etc., promptly can make it panchromaticization.

At this moment, the luminescent layer formation of the above-mentioned luminescent layer that forms later on for the 2nd time is Weak solvent for established luminescent layer preferably with solvent.This is because the luminescent layer that uses in the new luminescent layer that forms forms with solvent is Weak solvent for established luminescent layer, thereby when forming luminescent layer again on established luminescent layer, colour mixture can not occur.

At this moment, the luminescent layer that forms later on luminescent layer for the 2nd time form with solvent to the solubility of the luminescent layer that formed preferably under 25 ℃, 1 atmospheric pressure for below the 0.1g/g solvent.This is because so long as the solubility of this degree, even when forming luminescent layer again on the luminescent layer that has formed, established luminescent layer can or not colour mixture do not occurred by the solvent stripping yet yet.

In addition, the above-mentioned light wavelength that in proper order preferably obtains from above-mentioned luminescent layer through the formation of the luminescent layer of formation is for several times begun to form successively by the short wavelength.

Usually, in the occasion of the low 2 kinds of luminescent materials of long emission wavelength material of the high short-wave long light-emitting material of mixed tensor and energy, luminous based on the long emission wavelength material.This is because in the present invention, luminous optical wavelength begins to form successively from the short wavelength, the luminescent material of the luminescent layer that forms therefore becomes long wavelength's luminescent material, even when mixing the luminescent material of the luminescent layer that forms earlier afterwards in the luminescent layer of Xing Chenging, the short-wave long light-emitting material that forms earlier of sneaking into is luminous hardly, and it is extremely low that the possibility that problems such as colour mixture occur is reduced to.

Like this, through forming for several times the occasion of luminescent layer, preferred above-mentioned luminescent layer is 3 kinds of luminescent layers that send red, green and blue light.This is owing in order to make it luminous panchromaticly, preferably use red, green and blue 3 primary colors luminous usually.

In addition, in the present invention, the organic EL layer that above-mentioned use photoetching technique method method forms figure also can be a resilient coating.Among the present invention, when making luminescent layer form figure, preferably adopt the photoetching technique method as mentioned above, but this is not limited especially, also can adopt the photoetching technique method to make resilient coating form figure.The EL element that constitutes by organic polymer of luminescent layer particularly, preferred compositions resilient coating and luminescent layer aspect luminous efficiency, make both form figure by adopting photoetching technique method method this moment, can make cheap and high-quality EL element.

At this moment, preferred above-mentioned resilient coating is insoluble to photoresist solvent and photoresist stripper, and photoresist is insoluble to the solvent that is used to form above-mentioned resilient coating.Identical with the occasion of above-mentioned luminescent layer, though this is that the photoetching technique method method to whole employing wet types are carried out must satisfy above-mentioned condition because relevant with the kind of photoetching technique method method.

And, the preferred photoresist that is insoluble to the solvent that is used to form resilient coating that uses, after making the resilient coating formation figure of the solvent that is insoluble to photoresist solvent, photoresist stripper and is used to form luminescent layer, use is insoluble to the photoresist of the solvent that is used to form luminescent layer, makes the luminescent layer that is insoluble to photoresist solvent, development of photoresist liquid and photoresist stripper form figure.This is because as mentioned above in the EL element that luminescent layer is made of organic polymer, preferred compositions resilient coating and luminescent layer, preferably at first form the resilient coating that satisfies above-mentioned condition by photoetching technique method method this moment, then forms the method for the luminescent layer that satisfies above-mentioned condition.

Among the present invention, it also can be by applying on the organic EL layer that forms figure after photoresist, exposure, development make photoresist form figure that the figure of above-mentioned employing photoetching technique method method forms, utilize dry corrosion to remove the organic EL layer that photoresist is removed part, form figure.

This is owing to like this by adopting the method for dry corrosion organic EL layer, can form more high-precision figure.

At this moment, above-mentioned dry corrosion preferred reactive ion etching.This is because by using the reactive ion corrosion can remove organic EL layer effectively.

In addition, preferably in above-mentioned dry corrosion, use oxygen simple substance or oxygen-containing gas.This is owing to use oxygen simple substance or oxygen-containing gas, can glass or ITO effectively not removed organic EL layer with influencing by oxidation reaction.

And, preferably in above-mentioned dry corrosion, use atmospheric pressure plasma.This is because by using atmospheric pressure plasma can omit vacuum process, and can form figure in high production rate ground.

In addition, among the present invention, the figure of above-mentioned employing photoetching technique method method forms preferably by applying on the organic EL layer that forms figure after photoresist, exposure, development make photoresist form figure, in ultrasonic bath, remove the organic EL layer that photoresist has been removed part, form figure.

This is owing to by making in this way, form in the process of figure at the organic EL layer that uses photoresist, can not occur that each figure attenuates or inappropriate situation such as organic EL layer material outflow, can form figure accurately.

The invention provides a kind of at least 1 layer of EL element that forms the organic EL layer of figure that have, it is characterized in that, do not need dividing plate, auxiliary member and the auxiliary surface treatment that forms figure that forms figure.

EL element of the present invention is not owing to need dividing plate etc. as mentioned above, thereby has advantage cheaply.

In addition, the invention provides a kind of EL element with at least 1 layer of organic EL layer, it is characterized in that, above-mentioned organic EL layer is for forming the luminescent layer of figure, and the width in the even zone of non-uniform film thickness that forms in the luminescent layer end of above-mentioned formation figure is below the 15 μ m.

In the EL element of the present invention, the width in the even zone of non-uniform film thickness is below the 15 μ m, therefore the interval between the figure is diminished, thereby can form high-precision figure.Here, so-called " the even zone of non-uniform film thickness " expression begins the zone that film thickness reduces from the film thickness of flat, and the expression film thickness is the zone of flat average film thickness below 90%.

And, the invention provides a kind of EL element with at least 1 layer of organic EL layer, it is characterized in that, above-mentioned organic EL layer be can send multiple color of light formation a plurality of luminescent layers of figure, the distance between the adjacent luminescent layer that sends different colours light is below the 30 μ m.Like this, the distance between the pixel is diminished, therefore can carry out higher-quality image and show.

Wherein, preferred electrode layer and the insulating barrier that has substrate at least and on aforesaid substrate, form diagram shape, wherein, this insulating barrier has covered the marginal portion of above-mentioned electrode layer and the not luminous component of element.This is owing to do not need can prevent from the short circuit of luminous component, reduces the defective that causes because of element short circuit etc., and it is long and can obtain the element of stabilized illumination to make the life-span.

Description of drawings

Fig. 1 is an example of expression EL element manufacture method of the present invention, is that expression makes resilient coating form figure, makes the flow chart of the operation of monochromatic EL element.

Fig. 2 is other example of expression EL element manufacture method of the present invention, is that expression makes the luminescent layer of 3 kinds of colors form figure, makes the flow chart of the operation of panchromatic demonstration EL element.

Fig. 3 is for amplifying the amplification view of the section of luminescent layer marginal portion in the expression EL element of the present invention.

Fig. 4 amplifies the amplification view of expression by the section of the luminescent layer marginal portion of existing ink-jet method formation.

Among the figure, 1,11---matrix; 3,13---resilient coating; 4,15---the positive photoresist layer; 7---luminescent layer; 14---the 1st luminescent layer; 18---the 2nd luminescent layer; 19---the 3rd luminescent layer.

Embodiment

The manufacture method of EL element of the present invention at first is described below, and secondly manufacture method manufacturing that explanation can be by this EL element has the EL element of the present invention of the new feature that did not in the past have.

The manufacture method of A, EL element

EL element manufacture method of the present invention is characterised in that, uses photoetching technique method method, makes at least 1 layer of organic EL layer that constitutes EL element form figure.

In the manufacture method of EL element of the present invention, form at least 1 layer of organic EL layer that constitutes EL element by photoetching technique method method like this, therefore with the vapour deposition method that was in the past undertaken by shadow mask relatively owing to do not need vacuum plant etc., can be easily and make organic EL layer form figure at an easy rate.On the other hand, form relatively, can carry out the preliminary treatment of matrix and anti-fluidity projection etc. is set between figure, form high-accuracy fine figure with the figure that adopts ink-jet method.Promptly, can obtain having the high-quality EL element of high accuracy figure at an easy rate according to the manufacture method of EL element of the present invention.

Below, specify the various piece in the EL element manufacture method of the present invention.

(organic EL layer)

EL element among the present invention is to have at least 1 layer of EL element that forms the organic EL layer of figure, particularly, at least by the 1st electrode layer, constitute, on above-mentioned EL layer, comprise at least 1 layer of organic EL layer that forms figure at EL layer that forms on above-mentioned the 1st electrode layer and the 2nd electrode layer that on above-mentioned EL layer, forms.

Wherein, on the EL layer, luminescent layer must be comprised at least, in addition, also resilient coating, hole transporting layer, hole injection layer, electron supplying layer, electron injecting layer etc. can be made up.

In addition, the organic EL layer of above-mentioned formation figure can be any one deck that constitutes above-mentioned EL layer, be preferably luminescent layer or resilient coating in the present invention, wherein can bring into play to greatest extent effect of the present invention aspect, preferably luminescent layer is formed figure as organic EL layer.And, from characteristics of luminescence aspect, we can say that be most preferred example with this luminescent layer and resilient coating as organic EL formation figure.

Particularly, on the 1st electrode layer, form resilient coating, and form figure by photoetching technique method method as organic EL layer, form luminescent layer more thereon, and form figure by photoetching technique method method as organic EL layer, the EL layer that further forms the 2nd electrode layer thereon is a preferred examples, and particularly above-mentioned luminescent layer is three kinds of luminescent layers, and forming the panchromatic EL element that figure obtains by 3 photoetching technique method methods is most preferred example.

Among the present invention, when making this organic EL layer form figure, have feature aspect the use photoetching technique method method formation figure, other layer can be made according to the method for using in the past.

(photoetching technique method)

In the manufacture method of EL element of the present invention, in that being formed, above-mentioned organic EL layer has feature aspect the figure.This photoetching technique method is to utilize the dissolubility of the rayed part of film to change by rayed, forms the method for arbitrary graphic according to the rayed figure.Below, this photoetching technique method is described.

(photoresist)

The photoresist that can use among the present invention can be a positivity, can be negativity also, is not particularly limited, but preferably is insoluble to the photoresist of the solvent that is used to form organic EL layers such as luminescent layer.

For example phenolic resins class, rubber+two-fold are nitride-based etc. as the photoresist that specifically can use.

(photoresist solvent)

Among the present invention, the photoresist solvent that uses during as the above-mentioned photoresist of coating, can prevent that above-mentioned organic EL layers such as luminescent layer from mixing with photo anti-corrosion agent material or dissolve when preventing the photoresist film forming, and keeping the original characteristics of luminescence, preferred use can not dissolved the material of organic EL Material such as luminescent layer material.If consider this point, as the photoresist solvent that can use among the present invention, preferred select luminescent layer formed with organic EL layers such as materials form with the solubility of material under 25 ℃, 1 atmospheric pressure being solvent below 0.001 (the g/g solvent), more preferably select the solvent below 0.0001 (the g/g solvent).

For example, form material dissolves in water solvent as resilient coating, the photoresist solvent that luminescent layer can use when being dissolved in nonpolarity organic solvent such as fragrant same clan, can exemplify with acetone, butanone is main ketone, with propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate is main cellosolve acetate esters, dihydroxypropane single-ether, propylene glycol monomethyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether is main cellosolve class, with methyl alcohol, ethanol, the 1-butanols, the 2-butanols, cyclohexanol is main alcohols, ethyl acetate, esters solvents such as butyl acetate, cyclohexane, decahydronaphthalene etc., so long as the solvent that satisfies condition also can use other solvent, also can be the mixed solvent more than 2 kinds.

(development of photoresist liquid)

In addition, as the development of photoresist liquid that can use among the present invention,, be not particularly limited as long as do not dissolve the material that forms above-mentioned organic EL layer.Particularly, can use organic bases developer solution of general use, in addition the aqueous solution that also can use inorganic base or resist etc. to develop.Preferably after developing, resist uses water rinse.

As the developer solution that can use among the present invention, preferred select luminescent layer formed with organic EL layers such as materials form with the solubility of material under 25 ℃, 1 atmospheric pressure being developer solution below 0.001 (the g/g developer solution), more preferably select the developer solution below 0.0001 (the g/g developer solution).

(stripper of photoresist)

And, as the stripper of the photoresist that can use among the present invention, must not dissolve above-mentioned organic EL layer, but dissolving photoresist layer can directly use aforesaid photoresist solvent.In addition, in the occasion of using positive corrosion-resisting agent, also can after having carried out the UV exposure, use the liquid that exemplifies as the resist developer solution to peel off.

And, also can use strong alkali aqueous solution, dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), N-N-methyl-2-2-pyrrolidone N-equal solvent and composition thereof, commercially available anticorrosive additive stripping liquid controlling.After resist is peeled off, also can use water rinse again with after the rinsings such as 2-propyl alcohol.

(forming the method for figure)

The figure of the photoetching technique method of passing through that adopts among the present invention forms, particularly, in the occasion of using positive photoresist, be after forming organic EL layer at first comprehensively, apply thereon comprehensively above-mentioned photo anti-corrosion agent material is dissolved in the photoresist agent solution that above-mentioned photoresist solvent obtains, make it dry, thereby at first form the photoresist layer.Then, this photoresist layer is carried out graph exposure, make the development of photoresist of exposed portion with above-mentioned resist developer solution.By this development, the photoresist of residual unexposed portion only.Thereby,, make organic EL layer form the method for figure by removing not by the organic EL layer of photoresist cover part.

In addition, method as above-mentioned comprehensive formation organic EL layer, same with the formation of common organic EL layer, be not particularly limited, except that vapour deposition method, spin coating method, casting, dip coating, coiling rod knife coating, knife coating, roll coating process, the intaglio process that can also exemplify fused solution, solution or the mixed liquor of electrodeposition process, materials used are brushed painting methods such as method, hectographic printing method, spraying process.

In the photoetching technique method of the present invention, also can apply photoresist on the organic EL layer that forms figure as mentioned above, exposure after the development, is removed the organic EL layer that photoresist is removed part with the dry corrosion method.

Usually, because the photoresist layer that forms is thick more a lot of than organic EL layer, so, can remove organic EL layer by all carrying out dry corrosion.

At this moment, the film thickness of photoresist layer is preferably in the scope of 0.1～10 μ m, more preferably in 0.5～5 mu m range.By making such film thickness, can keep the resist function of photoresist, carry out the dry corrosion of high manufacturing accuracy.

By combination dry corrosion method in part photoetching technique method, can make the end of corrosion more obvious like this, the width that therefore is present in the even zone of non-uniform film thickness of figure end can become narrower, and result's performance can form the more effect of high accuracy figure.

As the dry corrosion method that adopts among the present invention, preferred reactive ion etching.This is because by adopting the reactive ion corrosion, organic membrane sends chemical reaction, becomes the little compound of molecular weight, can gasify and evaporate, and by removing on the substrate, thus the processing that can corrode precision height, time weak point.

In addition, among the present invention, when carrying out above-mentioned dry corrosion, preferably use oxygen simple substance and oxygen-containing gas.Use oxygen simple substance or oxygen-containing gas, can decompose by the organic membrane oxidation reaction and remove, can remove unwanted organic substance, thereby can corrode precision height, short processing of time from substrate.In addition, owing under this condition, can not corrode oxidic transparent conducting films such as ITO commonly used, therefore can not damage electrode characteristic, aspect, purged electrode surface also is effective.

And, among the present invention, the preferred atmospheric pressure plasma that uses in the above-mentioned dry corrosion.By using atmospheric pressure plasma, the dry corrosion that vacuum plant must be arranged usually can under atmospheric pressure be carried out, thereby can shorten the processing time, and reduce cost.At this moment, corrosion can utilize organic substance by this fact of oxygen generation oxidation Decomposition in the atmosphere of plasma, but also can be by the replacement and any composition of adjusting reaction environment gas of circulation of gas.

The photoetching technique method of using among the present invention also can apply photoresist on the organic EL layer that forms figure, exposure after the development, is removed the organic EL layer that photoresist is removed part by solvent, thereby forms figure.The solvent that use this moment must not can be peeled off photoresist and can be dissolved or peel off luminescent layer, except that the coating solvent of luminescent layer, can select the solvent that satisfies condition.

In the photoetching technique method of the present invention, also can apply photoresist on the organic EL layer that forms figure, exposure after the development, is removed the organic EL layer that photoresist is removed part in ultrasonic bath, thereby forms figure.The solvent that uses must not can be peeled off photoresist and can be dissolved or peel off luminescent layer, except that the coating solvent of luminescent layer, can select the solvent that satisfies condition.

This is owing to use ultrasonic bath as mentioned above, in the figure forming process of the organic EL layer that uses photoresist, can not occur that each figure attenuates or inappropriate situation such as organic EL layer material outflow, can form high-accuracy fine figure, can the short time and high-accuracy formation imperceptibly aspect the figure be preferred.In addition, when making above-mentioned development of photoresist, also can use this ultrasonic bath to carry out.

Among the present invention, the ultrasonic waves condition optimization that is used for this ultrasonic bath with 20～100 kilo hertzs concussion frequency, carried out 0.1～60 second under 25 ℃, adopted this condition, can high-accuracyly at short notice form figure imperceptibly.

(resilient coating)

Among the present invention, being clipped in two EL layers between the electrode layer as mentioned above, must at least 1 layer be the organic EL layer that forms figure, preferably resilient coating or luminescent layer is formed figure as organic EL layer as mentioned above.Below, this resilient coating at first is described.

So-called resilient coating among the present invention is meant in order to be easy to be arranged between anode and the luminescent layer or between negative electrode and the luminescent layer to the luminescent layer iunjected charge, contains organic substance, particularly the layer of organic conductive equity.For example, have and improve the efficient that luminescent layer is injected in the hole, make the electroconductive polymer of function of the concavo-convex planarization of electrode etc.

The resilient coating that uses among the present invention, prevents to crosstalk for the diode characteristic of holding element in the high occasion of its conductivity, is preferably formed figure.Therefore, preferably form figure according to the present invention.In addition,, also can not form figure sometimes, and, also resilient coating can be set sometimes in the occasion of the element that saves resilient coating in high occasion of the resistance of resilient coating etc.

Among the present invention, when resilient coating and luminescent layer are formed figure as above-mentioned organic EL layer by the photoetching technique method, the material that forms resilient coating is preferably selected to be insoluble to the photoresist solvent and the material that is used to form the solvent of luminescent layer, and the material that more preferably forms resilient coating sometimes selects to be insoluble to the material of photoresist stripper.

On the other hand, form luminescent layer, and when only be resilient coating as the layer that organic EL layer forms figure by the photoetching technique method, the material of formation resilient coating preferably selects to be insoluble to the material of photoresist solvent and photoresist stripper by vacuum film formation etc.

Material as the formation resilient coating that uses among the present invention, specifically can exemplify polymer, the inorganic oxide of cavity conveying materials such as poly-alkylthrophene derivative, polyaniline derivative, triphenylamine organic polymeric membrane such as sol-gel film, fluoroform, contain lewis acidic organic compound film etc., as long as satisfy above-mentioned relevant deliquescent condition, be not particularly limited, also can after film forming, satisfy above-mentioned condition by reaction, polymerization or fire etc.In addition, when making luminescent layer, can use padded coaming, hole-injecting material, the hole transporting material of general use by vacuum film formation etc.

In addition, the solvent that uses when forming resilient coating among the present invention, as long as can disperse or dissolve padded coaming, not special the qualification, in panchromatic figure formation etc., in the time of must repeatedly carrying out the film forming of resilient coating, be necessary to use the resilient coating solvent that does not dissolve photo anti-corrosion agent material, further preferably do not dissolve the resilient coating solvent of luminescent layer.As the resilient coating solvent that can use among the present invention, the solubility of preferably selecting anticorrosive additive material more preferably is chosen as the following solvent of 0.0001 (g/g solvent) under 25 ℃, 1 atmospheric pressure being solvent below 0.001 (the g/g solvent).In addition, as the resilient coating solvent, the solubility of more preferably selecting luminescent material is especially preferably selected the following solvent of 0.0001 (g/g solvent) under 25 ℃, 1 atmospheric pressure being solvent below 0.001 (the g/g solvent).Can exemplify water, based on the alcohols of methyl alcohol, ethanol, dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), N-N-methyl-2-2-pyrrolidone N-equal solvent are so long as the solvent that satisfies condition also can use other solvent.In addition, also solvent more than 2 kinds can be used.

Specify the example that adopts the photoetching technique method to make sort buffer layer formation figure with Fig. 1.

Fig. 1 is that expression adopts method of the present invention to make resilient coating and luminescent layer form figure, makes the flow chart of monochromatic EL element.At first shown in Fig. 1 (a), form resilient coating 3 all sidedly having formed on the matrix 1 on the 1st electrode layer 2 of figure.Then shown in Fig. 1 (b), on resilient coating 3, form positive type resist layer 4, carry out preceding baking.Then shown in Fig. 1 (c),, carry out ultraviolet graph exposure 6 with partly shading of mask 5.Then shown in Fig. 1 (d), by the resist developing liquid developing, water carries out rinsing, removes the photoresist and the resilient coating of exposed portion.Then shown in Fig. 1 (e), peel off resist, can form the figure of the resilient coating 3 that has covered the 1st electrode layer 2 by anticorrosive additive stripping liquid controlling.Then shown in Fig. 1 (f), form luminescent layer 7 at the 1st electrode layer 2 that has formed figure on the matrix 1 with on the resilient coating 3 that is provided with on the 1st electrode layer 2 comprehensively.Then shown in Fig. 1 (g), on luminescent layer 7, form positive photoresist layer 4, carry out preceding baking.Then shown in Fig. 1 (h),, carry out ultraviolet graph exposure 6 with partly shading of mask 5.Then shown in Fig. 1 (i), by the resist developing liquid developing, water carries out rinsing, removes the photoresist of exposed portion.Then as Fig. 1 (j) shown in, carry out rinsing with the solvent of luminescent layer, remove the luminescent layer 7 that the formation figure exposes.Then shown in Fig. 1 (k), peel off resist by anticorrosive additive stripping liquid controlling.Shown in Fig. 1 (l), form the 2nd electrode layer 8 at last, can make EL element from EL light 9 to the below of figure that send.

(luminescent layer)

Then, illustrate by the present invention to form figure, as the luminescent layer of organic EL layer.

As the material that forms this luminescent layer,, be not particularly limited so long as contain the material that sends fluorescence and luminous material gets final product.As the material that forms luminescent layer, can have both lighting function and cavity conveying function or electron transport function, the material that is preferably formed luminescent layer is the material that is insoluble to above-mentioned photoresist solvent, above-mentioned development of photoresist liquid and above-mentioned photoresist stripper.In addition, this occasion, the photoresist that uses when preferably adopting the photoetching technique method to make luminescent layer form figure uses the material that is insoluble to the solvent that is used to form luminescent layer.

Material as the formation luminescent layer that can use among the present invention can exemplify following material.

1, pigment material

As the pigment material, can exemplify cyclopentamine derivative, tetraphenylbutadiene derivative, triphenylamine derivative, oxadiazole derivative, pyrazolo quinoline, distyrene base benzene derivative, distyrene base virtue ene derivative, silanol derivative, thiphene ring derivative, pyridine ring derivative, perilla ketone derivative, perillene derivative, Oligopoly thiophene derivative, triphenylamine derivative, oxadiazole dimer, pyrazoline dimer etc.

2, metal complex composition material

As the metal complex composition material can exemplify aluminium oxyquinoline complex compound, benzo oxyquinoline beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azo methyl zinc complex, porphyrin zinc complex, europium complex etc., central metal comprises Al, Zn, Be etc. or rare earth metals such as Tb, Eu, Dy, the dentate bag is drawn together the metal complex of oxadiazole, thiadiazoles, phenylpyridine, phenyl benzimidazole, quinoline structure etc. etc.

3, high score subclass material

As high score subclass material, can exemplify poly (phenylenevinylene) derivative, polythiofuran derivative, poly radical derivative, polysilane derivative, polyacetylene derivative etc., make the material of poly-fluorene derivative, Polyvinyl carbazole derivative, above-mentioned chromatoplast, metal complex class luminescent material producing high-molecular etc.

In the present invention, can use luminescent layer to form the viewpoint of this advantage of luminescent layer accurately by the photoetching technique method, more preferably use above-mentioned high score subclass material as luminescent material with coating liquid from effective utilization.

4, dopant material

In order in luminescent layer, to improve luminous efficiency, emission wavelength is changed, can mix.As this dopant material, can exemplify perillene derivative, coumalin derivative, rubrene derivative, quinacridone derivative, squalene derivative, derivatives of porphyrin, phenylethylene pigment, aphthacene derivative, pyrazoline derivative, decacyclene, thiophene evil hexazinone etc.

5, luminescent layer applies and uses solvent

Luminescent layer applies with solvent in the occasion of using with resilient coating, resilient coating and luminescent layer material mixing or dissolving in order to prevent to make the luminescent layer film forming, and keep the original characteristics of luminescence of luminescent material, preferred luminescent layer coating is not dissolved resilient coating with solvent.

From this viewpoint, luminescent layer applies with solvent and preferably selects the solubility of cushioning layer material more preferably to select the solvent below 0.0001 (the g/g solvent) under 25 ℃, 1 atmospheric pressure being solvent 0.001 (g/g solvent) below.

And; in the occasion of coated with multiple layer luminescent layer, when forming the 2nd kind of luminescent layer that color is later, in order to prevent photoresist layer and luminescent layer material mixing or dissolving; and the luminescent layer of protecting all to form figure, preferred luminescent layer applies and does not dissolve photoresist with solvent.

From this viewpoint, luminescent layer applies with solvent and preferably selects the solubility of photoresist more preferably to select the solvent below 0.0001 (the g/g solvent) under 25 ℃, 1 atmospheric pressure being solvent 0.001 (g/g solvent) below.For example, be dissolved in water system or DMF at resilient coating, DMSO, alcohol isopolarity solvent, and when photoresist is general phenolic positive corrosion-resisting agent, can exemplify with benzene, toluene, various isomers of dimethylbenzene and composition thereof, trimethylbenzene, naphthane, cymene, cumene, ethylo benzene, diethylbenzene, butyl benzene, chlorobenzene, various isomers of dichloro-benzenes and composition thereof etc. are main aromatic series kind solvent, with methyl phenyl ethers anisole, phenetole, butyl phenylate, oxolane, the 2-butanone, 1, the 4-dioxane, Anaesthetie Ether, Di Iso Propyl Ether, diphenyl ether, dibenzyl ether, diethylene glycol dimethyl ethers etc. are main ether solvent, carrene, 1, the 1-dichloroethanes, 1, the 2-dichloroethanes, trichloroethylene, tetrachloro-ethylene, chloroform, carbon tetrachloride, chloride kind solvents such as 1-chloronaphthalene, cyclohexanone etc., other solvents that satisfy condition also can use, and also can be the mixed solvents more than 2 kinds.

(forming the occasion of multiple luminescent layer)

Among the present invention, the preferred luminescent layer that adopts the photoetching technique method to form the variety classes luminescent layer for several times of above-mentioned luminescent layer.This is because luminescent layer is made diverse a plurality of luminescent layer, if select for example red, green and blue, can carry out panchromaticization.

At this moment, based on following reason, the 2nd the luminescent layer formation of the above-mentioned luminescent layer of formation later on is Weak solvent to the luminescent layer that has formed preferably with solvent.In addition, so-called " Weak solvent " is meant the little solvent of dissolving solute ability among the present invention.

That is to say, applying luminescent layer on the luminescent layer that has formed (below be sometimes referred to as existing luminescent layer) again forms when forming luminescent layer with coating, owing on existing luminescent layer, formed resist layer usually, thereby luminescent layer formation can not contact all with coating with existing luminescent layer.But owing to the end of common existing luminescent layer is not covered by resist layer, thereby luminescent layer formation contacts with existing luminescent layer with coating in this section.When contacting like this, form with the solvent that contains in the coating for luminescent layer, the occasion that existing luminescent layer is easy to dissolve, the luminescent material of existing luminescent layer is dissolved to luminescent layer and forms with in the coating, thereby colour mixture occurs.The present invention because luminescent layer forms with the Weak solvent of solvent use to existing luminescent layer, has solved the problems referred to above in order to address this problem.

Fig. 2 represents an example of the manufacture method of EL element of the present invention.In this example, shown in Fig. 2 (a), at first on matrix 11, formed the 1st electrode layer 12 and the resilient coating 13 of figure.Be elaborated later on about this resilient coating.

And, adopt spin coating method that the 1st luminescent layer is formed and apply thereon all sidedly with coating.It is by the luminescent material and the solvent that send the 1st kind of color of light at least that the 1st luminescent layer forms with coating, and the material of composition such as the dopant that adds in case of necessity.Use coating by dry, as to solidify coating comprehensively the 1st luminescent layer formation, form the 1st luminescent layer 14[Fig. 2 (a)].

Then, on the 1st luminescent layer 14, apply positive corrosion-resisting agent comprehensively, form positive type resist layer 15[Fig. 2 (b)], do not expose for making the part that forms the 1st luminescent layer 14, use shadow mask 16 figure irradiation ultraviolet radiation 17[Fig. 2 (c)].Then, the exposed portion of positive type resist layer 15 is developed, use water rinse, shown in Fig. 2 (d), remove the positive type resist layer 15 of exposed portion with the resist developer solution.Then,, only remove part the 1st luminescent layer 14 that is not covered by positive type resist layer 15 by using the luminescent layer developing liquid developing, residual positive type resist layer 15 and by the 1st luminescent layer 14[Fig. 2 (e) of its covering].In addition, the development of luminescent layer can adopt dry corrosion to carry out as described later at this moment.

Then, by spin coating method etc. the 2nd luminescent layer is formed with coating and apply [Fig. 2 (f)] thereon comprehensively.The 2nd luminescent layer forms and to form with coating identically with coating and above-mentioned the 1st luminescent layer, is by luminescent material and solvent, and the material of composition such as the dopant that adds in case of necessity.Wherein, the luminescent layer that is used for the 2nd luminescent layer forms with solvent and selects Weak solvent to above-mentioned the 1st luminescent layer.

At this moment, by Fig. 2 (f) as can be seen, the 2nd luminescent layer that above-mentioned comprehensive coating occurred forms the part that contacts with the 1st luminescent layer 14 with coating.That is to say that the 1st residual luminescent layer 14 is covered its surface by positive type resist layer 15 on matrix 11 as mentioned above, but is exposed state with the end a of luminescent layer developing liquid developing.Therefore, use coating if apply above-mentioned the 2nd luminescent layer formation thereon, at this end a, the 1st luminescent layer 14 forms with the 2nd luminescent layer and contacts with coating.At this moment, use the luminescent layer formation solvent of above-mentioned the 1st luminescent layer as Weak solvent because the 2nd luminescent layer forms with coating, therefore the 1st luminescent layer, particularly luminescent material stripping form with the amount in the solvent very small to above-mentioned the 2nd luminescent layer.

Then, form and use coating by dry, above-mentioned the 2nd luminescent layer of curing, form the 2nd luminescent layer 18, the composition of the 1st luminescent layer 14 in the 2nd luminescent layer 18, particularly the stripping quantity of the luminescent material of the 1st luminescent layer 14 is considerably less, therefore, can make the possibility that problems such as colour mixture in the 2nd luminescent layer 18, occur become very little.

Then, shown in Fig. 2 (g), form positive type resist layer 15 comprehensively, shown in Fig. 2 (h),, shadow mask 16 is set, with ultraviolet ray 17 exposures in order to block the part that forms the 1st and the 2nd luminescent layer.Use the resist developing liquid developing then, by water rinse, the positive type resist layer of residual formation the 1st and the 2nd luminescent layer part is removed other parts.Then, remove the 2nd luminescent layer that exposes with the 2nd luminescent layer developer solution.At this moment, the 2nd luminescent layer developer solution selects to use the Weak solvent to the 1st luminescent layer.This is because when the 2nd luminescent layer is developed, the 2nd luminescent layer developer solution contacts with the part of the 1st luminescent layer at above-mentioned the 1st luminescent layer end a, therefore by using Weak solvent to the 1st luminescent layer, can avoid problems such as colour mixture as above-mentioned the 2nd luminescent layer developer solution.

Shown in Fig. 2 (i), by with this 2nd luminescent layer developing liquid developing, only remove part the 2nd luminescent layer 18 that does not have residual positive type resist layer 15, the only remaining part that is covered by positive type resist layer 15.In addition, the developing procedure of the 2nd luminescent layer 18 also can adopt dry corrosion method described later.

And, same with the formation of the 1st and the 2nd luminescent layer, adopt comprehensive the 3rd luminescent layer formation coating that apply such as spin coating method.The 3rd luminescent layer of this moment forms with coating also identical with coating with the formation of the above-mentioned the 1st and the 2nd luminescent layer, has luminescent material and solvent, and the dopant that adds in case of necessity.In addition, the 3rd luminescent layer that uses this moment forms with solvent and selects above-mentioned the 1st luminescent layer 14 and the 2nd luminescent layer 18 solvents as Weak solvent.

Shown in Fig. 2 (j), applying the 3rd luminescent layer like this forms when using coating, at initial the 1st luminescent layer 14 end a that form, the 1st luminescent layer forms with the 3rd luminescent layer of coating and contacts with coating, and at the end b and the end c of the 2nd luminescent layer 18, the 2nd luminescent layer forms with the 3rd luminescent layer of coating and contacts with coating.At this moment, same because the formation of the 3rd luminescent layer is Weak solvent with solvent to the 1st luminescent layer 14 and the 2nd luminescent layer 18, therefore above-mentioned the 1st luminescent layer 14 and the 2nd luminescent layer 18 strippings to the 3 luminescent layers form with the amount in the coating considerably less.Therefore, dry afterwards, curing the 3rd luminescent layer forms the occasion that forms the 3rd luminescent layer 19 with coating, also can not occur problems such as colour mixture in the 3rd luminescent layer 19.

Then, on the 3rd luminescent layer 19, form positive type resist layer 15 (Fig. 2 (j)) comprehensively.Shown in Fig. 2 (k),, shadow mask 16 is set then, with ultraviolet ray 17 exposures in order to block the part that forms the 1st, the 2nd and the 3rd luminescent layer.Make its development with the resist developer solution, use water rinse.Then, use the 3rd luminescent layer to develop with developer solution, this moment, same the 3rd luminescent layer was the solvent of Weak solvent with developer solution selection use to above-mentioned the 1st luminescent layer 14 and the 2nd luminescent layer 18, particularly luminescent material separately.Therefore, in the developing procedure of the 3rd luminescent layer, the 1st luminescent layer 14 and/or the 2nd luminescent layer 18, particularly their luminescent material can be not molten in developer solution and problem such as colour mixture takes place.

Shown in Fig. 2 (l), develop by make the 3rd luminescent layer 19 with this 3rd luminescent layer developer solution, only remove part the 3rd luminescent layer 19 that is not covered, remaining other part that is covered by positive type resist layer 15 by positive type resist layer 15.

Carry out lift-off processing with anticorrosive additive stripping liquid controlling then, peel off top one deck by the part that forms resist, shown in Fig. 2 (m), peel off the luminescent layer of 3 kinds of colors that form so-called the 1st luminescent layer 14 (being generally blue), the 2nd luminescent layer (being generally green), the 3rd luminescent layer (being generally red).Last shown in Fig. 2 (n), on these luminescent layers, form the 2nd electrode layer 20, thereby can make EL element from EL light 21 to the below of figure that send.

Among the present invention, so-called Weak solvent is illustrated under 25 ℃, 1 atmospheric pressure, it is below the 0.1g/g solvent to the solubility of the luminescent layer constituent material of the luminescent layer that formed that the luminescent layer of the luminescent layer that forms later on for the 2nd time forms with solvent, among the present invention below the preferred especially 0.05g/g solvent of above-mentioned solubility.

This is because so long as the solubility of this degree, even the luminescent layer constituent material that has formed is dissolved into the luminescent layer of the luminescent layer of new formation and forms with in the solvent, the luminescent layer constituent material that has formed is sneaked into the interior occasion of luminescent layer of new formation, its amount is also considerably less, thereby problems such as colour mixture can not take place.

In addition, among the present invention, by the occasion of photoetching technique method formation luminescent layer, preferably these a plurality of luminescent layers are begun to form successively from short wavelength side by the light wavelength that each luminescent layer obtains for several times.It is the reasons are as follows.

That is to say that the fluorescence luminescent material causes that in the occasion of blend of colors more than 2 kinds energy is moved to low-level exciton by the high-caliber exciton of excitation energy, observes the fluorescence that is sent by the lowest excited state usually.Just, when the low long emission wavelength composition of short-wave long light-emitting composition that energy is high and energy mixed, long emission wavelength composition luminous was main luminous.The present invention utilizes the character of this luminescent material, begins to form successively by the luminescent layer from the light that sends the short wavelength, formerly forms the 2nd luminescent layer that is formed by long emission wavelength material more on the 1st luminescent layer that is formed by the short-wave long light-emitting material.Therefore, when on the matrix of above-mentioned the 1st luminescent layer formation figure, making the 2nd luminescent layer film forming, even form the end stripping part luminescent material of figure by the 1st luminescent layer, mix with the 2nd luminescent layer, the excitation energy generation energy of luminescent material moves in the 1st luminescent layer, also can only observe the light that sends by the 2nd luminescent layer, thereby can make the reduction of the characteristics of luminescence be reduced to bottom line.

About this point, further use above-mentioned Fig. 2 to describe.Fig. 2 (a) to (e) is identical with above-mentioned explanation, therefore in this description will be omitted.Among Fig. 2 (f), apply the 2nd luminescent layer all sidedly with spin coating method etc. and form and use coating.The 2nd luminescent layer of this moment forms and forms with coating identical with coating with above-mentioned the 1st luminescent layer, by luminescent material and solvent, and the compositions such as dopant that add in case of necessity, the light wavelength that luminescent material sent that the light ratio of selecting luminescent material allow to be used for the 2nd luminescent layer that luminescent material sent is used for the 1st luminescent layer is long.

At this moment, by Fig. 2 (f) as can be seen, the 2nd luminescent layer that above-mentioned comprehensive coating occurs forms the part that contacts with the 1st luminescent layer 14 with coating.That is to say that the 1st residual on the above-mentioned matrix 11 luminescent layer 14 is covered its surface by positive type resist layer, be exposed state with the end a of luminescent layer developing liquid developing.Therefore, if apply above-mentioned the 2nd luminescent layer formation coating thereon, contact with coating with the formation of the 2nd luminescent layer at this end a the 1st luminescent layer 14.At this moment, because forming, the 2nd luminescent layer contains solvent as mentioned above with coating, though therefore depend on the dissolubility of the luminescent material that contains in this solvent and the 1st luminescent layer, the part of the luminescent material of the 1st luminescent layer may form with in the coating by stripping to the 2 luminescent layers.If form with the state in the coating with luminescent material stripping to the 2 luminescent layers of the 1st luminescent layer like this, dry, solidify to form the 2nd luminescent layer 18, then the 2nd luminescent layer 18 contains the luminescent material in the 1st luminescent layer.But, in this example, according to above-mentioned standard, the i.e. light wave length that luminescent material sent in the light ratio that luminescent material sent the 2nd luminescent layer in the 1st luminescent layer, select luminescent material in the 1st luminescent layer and the luminescent material in the 2nd luminescent layer, even therefore sneak into the occasion of the luminescent material of the 1st luminescent layer in the 2nd luminescent layer, because above-mentioned reason can make the luminous possibility of luminescent material of the 1st luminescent layer in the 2nd luminescent layer reduce.

Then, for Fig. 2 (g) and Fig. 2 (i), carry out the operation same with above-mentioned explanation.Then, same with the formation of the 1st and the 2nd luminescent layer, with comprehensive the 3rd luminescent layer formation coating that applies such as spin coating methods.The 3rd luminescent layer of this moment forms and also forms same with coating with the above-mentioned the 1st and the 2nd luminescent layer with coating, have luminescent material and solvent, and the dopant that adds in case of necessity, select employed luminescent material this moment, make the fluorescence that luminescent material sent that is used for the 3rd luminescent layer longer than the wavelength of the fluorescence that luminescent material sent that is used for above-mentioned the 1st luminescent layer and above-mentioned the 2nd luminescent layer.

Like this when coating is used in the formation of coating the 3rd luminescent layer, for example shown in Fig. 2 (j), end a at initial the 1st luminescent layer 14 that forms, the 1st luminescent layer forms with the 3rd luminescent layer of coating and contacts with coating, and at the end b and the end c of the 2nd luminescent layer 18, the 2nd luminescent layer forms with the 3rd luminescent layer of coating and contacts with coating.At this moment, luminescent material in same the 1st luminescent layer and the luminescent material in the 2nd luminescent layer may be dissolved into the 3rd luminescent layer and form with in the solvent in the coating, and stripping to the 3 luminescent layers form with in the coating.This occasion also is the luminescent material of selecting in above-mentioned the 3rd luminescent layer, make its wavelength long than the fluorescence that luminescent material sent in luminescent material in the 1st luminescent layer and the 2nd luminescent layer, therefore because above-mentioned reason, luminescent material in luminescent material in the 1st luminescent layer and the 2nd luminescent layer luminous possibility in the 3rd luminescent layer diminishes, and can reduce the worry that colour mixture occurs.

Among the present invention, preferably apply according to the short order of the light wavelength that luminescent material sent that forms luminescent layer like this.Particularly, be generally and obtained full-colour image, the luminescent material of red fluorescence, the luminescent material that sends the luminescent material of green fluorescence and send blue-fluorescence are sent in use as luminescent material, when using this luminescent material, preferred this luminescent material is according to short wavelength's order, promptly blue, green, red order applies and forms the luminescent layer that contains these luminescent materials.

Wherein, can exemplify distyrene base benzene derivative, oxadiazole derivative and their polymer, Polyvinyl carbazole derivative, poly radical derivative, poly-fluorene derivative etc. as the luminescent material that sends blue-fluorescence that can use among the present invention, the Polyvinyl carbazole derivative of wherein preferred macromolecular material, poly radical derivative, poly-fluorene derivative, but this is not particularly limited.

In addition, as the luminescent material that sends green fluorescence, can exemplify quinacridone derivative, coumarin derivative and their polymer, poly (phenylenevinylene) derivative, poly-fluorene derivative etc., the poly (phenylenevinylene) derivative of wherein preferred macromolecular material, poly-fluorene derivative, but this is not particularly limited.

And, as the luminescent material that sends red fluorescence, coumarin derivative, thiphene ring compound and their polymer, poly (phenylenevinylene) derivative, polythiofuran derivative, poly-fluorene derivative etc. are arranged, the poly (phenylenevinylene) derivative of wherein preferred macromolecular material, polythiofuran derivative, poly-fluorene derivative, but this is not particularly limited.

(other organic EL layer)

1, charge transport layer

Also can exemplify electric charge injection layer as organic EL layer of the present invention.Comprise hole injection layer and/or electron injecting layer in this electric charge injection layer.This as the spy open put down in writing in the flat 11-4011 communique, so long as generally be used for getting final product of EL element, be not particularly limited.

In addition, luminescent material, hole transporting material or the electron transport materials of the above-mentioned layer of formation both can be used alone, but also also mix together respectively.The layer that contains same material can be 1 layer, also can be multilayer.

2, electrode layer

Among the present invention, electrode layer is not particularly limited so long as be usually used in getting final product of EL element, and the electrode layer that is provided with on matrix earlier is called the 1st electrode layer, is called the 2nd electrode layer forming the electrode layer that is provided with behind the organic EL layer.These electrode layers are made up of anode and negative electrode, and any one in anode and the negative electrode is transparent or semitransparent, as anode in order to be easy to injected hole, the preferred big electric conducting material of work function.In addition, also can mix multiple material.The all preferred as far as possible little material of resistance of any electrode layer generally uses metal material, also can use organic substance or inorganic compound.

As preferred anode material, can exemplify ITO, yttrium oxide, gold etc.Can exemplify magnesium alloy (MgAg and other), aluminium alloy (AlLi, AlCa, AlMg and other), calcium metal and the little metal of work function as preferred cathode material.

3, insulating barrier

In the EL element of the present invention, form the marginal portion of figure and the not luminous component of element in order to cover the 1st electrode layer that forms on the matrix, and, also can set in advance insulating barrier and making luminous component become opening in order do not need to prevent from the luminous component short circuit.Like this, can reduce defectives such as element short circuit, obtain the element of life-span length and stabilized illumination.

As usually known, for example can use UV curable resin material etc., film thickness with 1 μ m forms figure, make organic EL layer form the occasion of figure with dry corrosion among the present invention, preferred insulating barrier has the dry corrosion tolerance, the occasion that tolerance is little, form more than the 1 μ m, the film thickness of 1.5～10 μ m for example preferably can not cause damagedly by dry corrosion, more preferably forms the film thickness of 2～5 μ m.

B, EL element

The following describes EL element of the present invention.EL element of the present invention has three kinds of execution modes that the following describes, and any one can be made by the manufacture method of above-mentioned EL element.Below each execution mode is described.

(the 1st kind of execution mode)

The 1st kind of execution mode of EL element of the present invention is to have at least 1 layer of EL element that has formed the organic EL layer of figure, it is characterized in that, do not need dividing plate, auxiliary member and the auxiliary surface treatment that forms figure that forms figure.

Though the EL element of present embodiment has the organic EL layer that has formed figure, dividing plate, auxiliary member and the auxiliary surface treatment that forms figure that forms figure all do not need.Therefore has the favourable advantage in cost aspect.

In the present embodiment, above-mentioned organic EL layer is preferably with not forming with the macromolecular material that vapour deposition method forms.In addition, above-mentioned organic EL layer especially preferably must form the luminescent layer of figure.

For other structure, with illustrate in the manufacture method of above-mentioned EL element same, therefore omit explanation herein.

(the 2nd kind of execution mode)

The 2nd kind of execution mode of EL element of the present invention is the EL element with at least 1 layer of organic EL layer, it is characterized in that, above-mentioned organic EL layer is the luminescent layer that has formed figure, the width in the even zone of non-uniform film thickness that forms in the above-mentioned luminescent layer end that has formed figure is below 15 μ m, preferably below 10 μ m, below 7 μ m.Wherein, so-called " the even zone of non-uniform film thickness " is to be present in the marginal portion, and film thickness reaches the zone of flat average film thickness below 90%.

Adopt in the EL element that the manufacture method of above-mentioned EL element obtains, it is different with this luminescent layer that obtains by ink-jet method etc. to make luminescent layer form luminescent layer that figure obtains by the photoetching technique method, and its film thickness is even and can freely control the edge shape of luminescent layer peripheral part according to etching condition.Therefore, can adjust fringe region, i.e. the width in the even zone of so-called non-uniform film thickness among the present invention, can access the edge is upright shape, be the material of the narrow width in the even zone of non-uniform film thickness, perhaps the edge is taper, i.e. the big material of width in the even zone of non-uniform film thickness.

On the other hand, the existing even zone of non-uniform film thickness that forms the luminescent layer of figure by ink-jet method has the width that surpasses 15 μ m usually.Therefore, be difficult to make the formation pixel of all kinds that forms by this formation graphical method to be provided with densely.

Wherein, Fig. 3 represents the even zone of the non-uniform film thickness in the EL element luminescent layer of the present invention, i.e. marginal portion, and Fig. 4 represents the existing even zone of non-uniform film thickness that forms the luminescent layer of figure by ink-jet method.By these figure as can be seen, the even regional broad of non-uniform film thickness of the marginal portion of the existing luminescent layer that forms figure by ink-jet method, but the width in the even zone of the non-uniform film thickness in the EL element luminescent layer of the present invention is very narrow.

The EL element of present embodiment is because the non-uniform film thickness of luminescent layer end is spared the width in zone below above-mentioned numerical value, has following advantage: therefore the distance between each pixel is diminished, like this each pixel can be set densely, can access the EL element that can obtain high quality image.

In the present embodiment, the material that the forms luminescent layer high-molecular organic material that also preferably can not form with vapour deposition method.Preferred in addition luminescent layer is at least 3 layers, can access full-colour image like this.In addition, identical about other structure, material etc. with the manufacture method of above-mentioned EL element, therefore omit explanation herein.

(the 3rd kind of execution mode)

The 3rd kind of execution mode of the present invention is that EL element is the EL element with at least 1 layer of organic EL layer, it is characterized in that, above-mentioned organic EL layer for can send multiple color of light formation a plurality of luminescent layers of figure, distance between the adjacent luminescent layer that sends different colours light is below 30 μ m, below the preferred 20 μ m, below the preferred especially 15 μ m.

In addition, the gap between the pixel that constitutes by each luminescent layer that has formed figure of the distance expression between the wherein so-called luminescent layer.

The ink-jet method of knowing most during the wet type figure of luminescent layer forms, because the uniformity of film edge part is low, ink hit location instability, in order to stipulate the scope of the moistening expansion of ink, be necessary to be provided with anti-ink dike or form anti-ink figure etc., the distance that has therefore formed between the luminescent layer of figure is at least more than the 40 μ m usually.Therefore, can not make pixel pitch little, for example the following element of 42 μ m spacings forms figure.

On the other hand, the EL element of present embodiment belongs to the EL element that can make macromolecule or low mulecular luminescence layer by the wet type film forming, luminescent layer forms the precision height of figure, in addition, different with the marginal portion of the luminescent layer that is formed with figure by drying, owing to adopted by dissolving or corrosion and removed the method that does not need part, thereby the film uniformity height of luminescent layer, and begin to have only for example tilting zone of 5 μ m from the end that forms figure.Therefore, the occasion making full-color display can make the distance between each pixel of luminous component diminish, and can make aperture opening ratio become big like this.In addition, because the distance between the pixel is diminished, thereby each pixel can be set densely.

The high-molecular organic material identical with the 2nd kind of execution mode, that the material that forms luminescent layer in the present embodiment also preferably can not form with vapour deposition method.Preferred in addition luminescent layer is at least 3 layers, can access full-colour image like this.In addition, identical about other structure, material etc. with the manufacture method of above-mentioned EL element, therefore omit explanation herein.

(other)

EL element described in above-mentioned the 1st kind of execution mode, the 2nd kind of execution mode and the 3rd kind of execution mode preferably has following structure at least: substrate, on aforesaid substrate, form the electrode layer of diagram shape, and cover the not insulating barrier of luminous component of the marginal portion of above-mentioned electrode layer and element.

Like this, the marginal portion owing to cover the electrode layer that forms diagram shape with insulating barrier can reduce defectives such as aforesaid element short circuit.

Wherein,, so long as getting final product, the common substrates such as glass that use in EL element are not particularly limited as the substrate that uses.

In addition, what illustrate in the manufacture method about electrode layer and insulating barrier and above-mentioned EL element is same, therefore omits explanation herein.

(concrete material is formed)

The above-mentioned suitable combination of materials that can utilize the dissolubility to specific solvent to make EL element of the present invention form figure is exemplified below.

Resilient coating: poly-alkylthrophene derivative, polyaniline derivative

Luminescent layer: poly (phenylenevinylene) derivative, poly-fluorene derivative, Polyvinyl carbazole derivative

Photoresist: positive corrosion-resisting agent (phenolic resins class)

Photoresist solvent: cellosolve, cellosolve acetic acid esters

Development of photoresist liquid: organic base developer solution

Photoresist stripper: cellosolve, cellosolve acetic acid esters, acetone

Form the luminescent layer solvent: dimethylbenzene, toluene

On the other hand, even commonly used EL element material and photo anti-corrosion agent material, for example Xia Mian combination, also improper in the present invention when making up (but various material and other material type can become suitable material).

Resilient coating: poly-alkylthrophene derivative, polyaniline derivative

Luminescent layer: TPD/Alq3, Polyvinyl carbazole+oxadiazole derivative+fluorchromes with following structure

[changing 1]

[changing 2]

Photoresist: positive corrosion-resisting agent (phenolic resins class)

Photoresist solvent: cellosolve, cellosolve acetic acid esters

Development of photoresist liquid: organic base developer solution

Photoresist stripper: cellosolve, cellosolve acetic acid esters, acetone

Form the luminescent layer solvent: dichloroethanes (the occasion vacuum film formation of TPD/Alq3)

Among the present invention, if use Polyvinyl carbazole+oxadiazole derivative+fluorchromes to be luminescent layer, because in resist film forming, Bao Li Shi oxadiazole derivative and fluorchrome stripping, thereby improper.In addition, use TPD/Alq3 to be luminescent layer, because in resist film forming, TPD and Alq3 stripping when peeling off, the heating steps in the photoetching makes reasons such as TPD crystallization, and is also improper.

In addition, the present invention has more than and is limited to above-mentioned execution mode.Above-mentioned execution mode is an example, all have with claim scope of the present invention in the identical in fact structure of the technological thought recorded and narrated and bring into play the material of same purpose effect, include in technical scope of the present invention.

Embodiment

Further specify the present invention below by embodiment.

[embodiment 1: luminescent layer is the occasion of individual layer]

The formation of 3 * 3 square inches of rinsings, thickness of slab 1.1mm the ito substrate of figure, as matrix that uses in the present embodiment and the 1st electrode layer.

Measure following chemical formula (1) expression the resilient coating coating liquid (poly-(3,4) ethylidene dioxy thiophene/polystyrolsulfon acid ester (PEDT/PSS): Beyer corporate system (BaytronP)) 0.5ml, drip central part to matrix, be rotated coating.

[changing 3]

Keep forming for 20 seconds resilient coating under 2500rpm, 150 ℃ following dry 5 minutes.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, kept for 20 seconds then, form resist layer.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, simultaneously on the fine setting exposure machine, the exposure shadow mask is set, the part of desiring to remove resilient coating is carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist and the resilient coating of exposed portion.The back baking was removed whole photoresists with acetone after 30 minutes under 120 ℃, made the resilient coating that is insoluble to acetone form figure arbitrarily.

(formation of luminescent layer figure)

The 1wt% xylene solution 2ml of the poly (phenylenevinylene) derivative luminous high polymer MEH-PPV of chemical formula (2) expression drips the central part to matrix below measuring on resilient coating has formed the matrix of figure, is rotated coating.

[changing 4]

Keep forming for 10 seconds luminescent layer under 2000rpm, 80 ℃ following dry 1 hour.Film thickness is 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, kept for 20 seconds then, form resist layer.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, simultaneously on the fine setting exposure machine, the exposure shadow mask is set, the part of desiring to remove luminescent layer is carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.The back baking was removed the luminescent layer that photoresist is removed part with toluene after 30 minutes under 90 ℃.Remove whole photoresists with acetone, make the luminescent layer that is insoluble to acetone form figure arbitrarily.

90 ℃ down after dry 1 hour, then on the matrix that obtains with the thickness evaporation Ca of 500 dusts as the 2nd electrode layer (upper electrode), again with the thickness evaporation Ag of 2500 dusts as protective layer, make EL element.

The resolution of the figure that obtains depends on the resolving power of positive corrosion-resisting agent, is existing evaporation shadow mask method, the irrealizable resolution of ink-jet method in the present embodiment.Can form the high accuracy circuit of 10 μ m.

(evaluation of the EL element characteristics of luminescence)

With ITO electrode (the 1st electrode layer) is anode, and Ag electrode (the 2nd electrode layer) is a negative electrode, connects, by power supply meter external dc power supply.Luminous when confirming to add 10V, can be evaluated as and use the photoetching technique method to form the deterioration that figure does not cause luminous starting voltage.In addition, do not see that luminous efficiency reduces yet.And, form figure by making resilient coating, can improve the insulating properties between the anode line, and reduce the incidence of crosstalking.

[embodiment 2: luminescent layer is 3 layers a occasion]

Similarly to Example 1, make resilient coating form figure.

As the 1st luminescent layer, formed the 1wt% xylene solution 2ml of measuring poly (phenylenevinylene) derivative luminous high polymer MEH-PPV on the matrix of figure at resilient coating, drip central part to matrix, be rotated coating.Under 2000rpm, keep forming for 10 seconds luminescent layer.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, kept for 20 seconds then, form resist layer.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, on the fine setting exposure machine, the exposure shadow mask is set simultaneously, desiring beyond the illuminating part of the 1st kind of color is removed the part of luminescent layer and carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.The back baking was removed the luminescent layer that photoresist is removed part with toluene after 30 minutes under 90 ℃, obtained the matrix that the 1st illuminating part is protected by photoresist and the resilient coating of the 2nd, the 3rd illuminating part exposes.

As the 2nd luminescent layer, measure the 1wt% xylene solution 2ml of poly (phenylenevinylene) derivative luminous high polymer MEH-PPV, drip central part to matrix, be rotated coating.Under 2000rpm, keep forming for 10 seconds luminescent layer.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, kept for 20 seconds then, form resist layer.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, on the fine setting exposure machine, the exposure shadow mask is set simultaneously, desiring beyond the 1st, the 2nd illuminating part is removed the part of luminescent layer and carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.The back baking was removed the luminescent layer that photoresist is removed part with toluene after 30 minutes under 90 ℃, obtained the matrix that the 1st and the 2nd luminous component is protected by photoresist and the resilient coating of the 3rd luminous component exposes.

As the 3rd luminescent layer, measure the 1wt% xylene solution 2ml of poly (phenylenevinylene) derivative luminous high polymer MEH-PPV, drip central part to matrix, be rotated coating.Under 2000rpm, keep forming for 10 seconds luminescent layer.Film thickness reaches 800 dusts as a result.

Measure positive resist agent solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, kept for 20 seconds then, form resist layer.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, on the fine setting exposure machine, the exposure shadow mask is set simultaneously, desiring beyond the 1st to the 3rd luminous component is removed the part of luminescent layer and carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.The back baking was removed the luminescent layer that photoresist is removed part with toluene after 30 minutes under 90 ℃, obtained the matrix that the 1st to the 3rd luminous component is protected by photoresist.Remove whole photoresists with acetone then.

90 ℃ down after dry 1 hour, then on the matrix that obtains with the thickness evaporation Ca of 500 dusts as the 2nd electrode layer (upper electrode), again with the thickness evaporation Ag of 2500 dusts as protective layer, make EL element.

The resolution of the figure that obtains depends on the resolving power of positive corrosion-resisting agent, is existing evaporation shadow mask method, the irrealizable resolution of ink-jet method in the present embodiment.Can form the high accuracy circuit of 10 μ m.

(evaluation of the EL element characteristics of luminescence)

With ITO electrode (the 1st electrode layer) is anode, and Ag electrode (the 2nd electrode layer) is a negative electrode, connects, by power supply meter external dc power supply.The the 1st to the 3rd illuminating part can be luminous respectively when confirming to add 10V, can be evaluated as to use the photoetching technique method to form the deterioration that figure does not cause luminous starting voltage.In addition, do not see that luminous efficiency reduces yet.And, form figure by making resilient coating, can improve the insulating properties between the anode line, and reduce the incidence of crosstalking.

[embodiment 3: the change of solvent]

Except that the Polyvinyl carbazole of using following chemical formula (3) expression as luminescent layer, toluene as the luminescent layer solvent, make EL element similarly to Example 1.

[changing 5]

The resolution of the figure that obtains depends on the resolving power of positive corrosion-resisting agent, is existing evaporation shadow mask method, the irrealizable resolution of ink-jet method in the present embodiment.Can form the high accuracy circuit of 10 μ m.

(evaluation of the EL element characteristics of luminescence)

With ITO electrode (the 1st electrode layer) is anode, and Ag electrode (the 2nd electrode layer) is a negative electrode, connects, by power supply meter external dc power supply.Luminous when confirming to add 15V, can be evaluated as and use the photoetching technique method to form the deterioration that figure does not cause luminous starting voltage.In addition, do not see that luminous efficiency reduces yet.And, form figure by making resilient coating, can improve the insulating properties between the anode line, and reduce the incidence of crosstalking.

[embodiment 4: adopt the figure of dry corrosion to form]

(film forming of resilient coating)

The formation of 3 * 3 square inches of rinsings, thickness of slab 1.1mm the ito substrate of figure, as matrix that uses in the present embodiment and the 1st electrode layer.Measure resilient coating coating liquid [Beyer corporate system; BaytronP is (shown in the above-mentioned chemical formula (1).)] 0.5ml, drip central part to matrix, be rotated coating.Maintenance cambium layer in 20 second under 2500rpm.Film thickness reaches 800 dusts as a result.

(figure of luminescent layer forms)

Formed the 1wt% xylene solution 2ml of measuring poly (phenylenevinylene) derivative luminous high polymer MEH-PPV on the matrix of figure at resilient coating, dripped central part, be rotated coating to matrix.Maintenance cambium layer in 10 second under 2000rpm.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, simultaneously on the fine setting exposure machine, the exposure shadow mask is set, the part of desiring to remove luminescent layer is carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.

120 ℃ of down back bakings after 30 minutes were carried out oxygen plasma treatment 20 minutes under the power of the pressure of 150 millitorrs, 150W.Because photoresist is than resilient coating and luminous bed thickness more than 5 times, thereby only do not peel off with the luminescent layer and the resilient coating of photoresist protection part, the ITO electrode is exposed.Obtain the matrix that the 1st illuminating part is protected by photoresist.

On the matrix that obtains, rotate the coated with buffer layer coating liquid, obtain the resilient coating of 800 dusts.Then measure the 1wt% xylene solution 2ml of poly (phenylenevinylene) derivative luminous high polymer MEH-PPV, drip central part, be rotated coating, as the 2nd luminescent layer to matrix.Maintenance cambium layer in 10 second under 2000rpm.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, on the fine setting exposure machine, the exposure shadow mask is set simultaneously, desiring beyond the illuminating part of the 1st kind of color and the 2nd kind of color is removed the part of luminescent layer and carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.

120 ℃ of down back bakings after 30 minutes were carried out oxygen plasma treatment 20 minutes under the power of the pressure of 150 millitorrs, 150W.Because photoresist is than resilient coating and luminous bed thickness more than 5 times, thereby only do not peel off with the luminescent layer and the resilient coating of photoresist protection part, the ITO electrode is exposed.Obtain the matrix that the 1st and the 2nd luminous component is protected by photoresist.

On the matrix that obtains, rotate the coated with buffer layer coating liquid, obtain the resilient coating of 800 dusts.Then measure the 1wt% xylene solution 2ml of poly (phenylenevinylene) derivative luminous high polymer MEH-PPV, drip central part, be rotated coating, as the 3rd luminescent layer to matrix.Maintenance cambium layer in 10 second under 2000rpm.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, on the fine setting exposure machine, the exposure shadow mask is set simultaneously, desiring beyond the illuminating part of 3 kinds of colors of the 1st kind of color to the is removed the part of luminescent layer and carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.

120 ℃ of down back bakings after 30 minutes were carried out oxygen plasma treatment 20 minutes under the power of the pressure of 150 millitorrs, 150W.Because photoresist is than resilient coating and luminous bed thickness more than 5 times, thereby only do not peel off luminescent layer and resilient coating with photoresist protection part.Obtain the matrix that the 1st to the 3rd luminous component is protected by photoresist.Remove whole photoresists with acetone then.

100 ℃ down after dry 1 hour, then on the matrix that obtains with the thickness evaporation Ca of 500 dusts as the 2nd electrode layer (upper electrode), again with the thickness evaporation Ag of 2500 dusts as protective layer, make EL element.

(evaluation of the EL element characteristics of luminescence)

With the ITO electrode is positive pole, and the Ag electrode is a negative pole, connects, by power supply meter external dc power supply.The the 1st to the 3rd illuminating part respectively can be luminous when confirming to add 10V.

[embodiment 5: the use of atmosphere plasma]

Except that using atmospheric pressure plasma replacement oxygen plasma, make element similarly to Example 4.Similarly to Example 4, can form figure, confirm that the 1st to the 3rd illuminating part respectively can be luminous.

[embodiment 6: the use of ultrasonic bath]

(film forming of resilient coating)

The formation of 6 * 6 square inches of rinsings, thickness of slab 1.1mm the ito substrate of figure, as matrix and the 1st electrode layer.Measure resilient coating coating liquid (Beyer corporate system; Shown in the above-mentioned chemical formula of BaytronP[(1).]) 0.5ml, drip central part to matrix, be rotated coating.Maintenance cambium layer in 20 second under 2500rpm.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, simultaneously on the fine setting exposure machine, the exposure shadow mask is set, the part of desiring to remove resilient coating is carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist and the resilient coating of exposed portion.The back baking was removed whole photoresists with acetone after 30 minutes under 120 ℃, made the resilient coating that is insoluble to acetone form figure arbitrarily.

(film forming of luminescent layer)

Formed the 1wt% xylene solution 2ml of measuring poly (phenylenevinylene) derivative luminous high polymer MEH-PPV on the matrix of figure at resilient coating, dripped central part, be rotated coating, as the 1st luminescent layer to matrix.Maintenance cambium layer in 10 second under 2000rpm.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, on the fine setting exposure machine, the exposure shadow mask is set simultaneously, desiring beyond the illuminating part of the 1st kind of color is removed the part of luminescent layer and carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.The back baking was removed the luminescent layer that photoresist is removed part with toluene after 30 minutes under 120 ℃ in ultrasonic bath, obtained the matrix that the 1st illuminating part is protected by photoresist.

Measure the 1wt% xylene solution 2ml of poly (phenylenevinylene) derivative luminous high polymer MEH-PPV, drip central part, be rotated coating, as the 2nd luminescent layer to matrix.Maintenance cambium layer in 10 second under 2000rpm.Film thickness reaches 800 dusts as a result.By peeling off photoresist with acetone, peel off the photoresist that forms on the 1st luminescent layer top that has formed figure, peel off the 2nd luminescent layer simultaneously, the 1st luminescent layer that has formed figure is exposed.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, on the fine setting exposure machine, the exposure shadow mask is set simultaneously, the desire beyond the illuminating part of the 1st kind of color and the 2nd kind of color is removed the part of removing luminescent layer carry out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.The back baking was removed the luminescent layer that photoresist is removed part with toluene after 30 minutes under 120 ℃ in ultrasonic bath, obtained the matrix that the 1st and the 2nd luminous component is protected by photoresist.

Measure the 1wt% xylene solution 2ml of poly (phenylenevinylene) derivative luminous high polymer MEH-PPV, drip central part, be rotated coating, as the 3rd luminescent layer to matrix.Maintenance cambium layer in 10 second under 2000rpm.Film thickness reaches 800 dusts as a result.By peeling off photoresist with acetone, peel off the photoresist that forms on the 1st and the 2nd luminescent layer top that has formed figure, peel off the 3rd luminescent layer simultaneously, the 1st and the 2nd luminescent layer that has formed figure is exposed.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, on the fine setting exposure machine, the exposure shadow mask is set simultaneously, desiring beyond the 1st to the 3rd illuminating part is removed the part of luminescent layer and carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.The back baking was removed the luminescent layer that photoresist is removed part with toluene after 30 minutes under 120 ℃ in ultrasonic bath, obtained the matrix that the 1st to the 3rd luminous component is protected by photoresist.Remove whole photoresists with acetone then, the luminescent layer that has formed figure is exposed.

100 ℃ down after dry 1 hour, then on the matrix that obtains with the thickness evaporation Ca of 500 dusts as the 2nd electrode layer (upper electrode), again with the thickness evaporation Ag of 2500 dusts as protective layer, make EL element.

(evaluation of the EL element characteristics of luminescence)

With the ITO electrode is positive pole, and the Ag electrode is a negative pole, connects, by power supply meter external dc power supply.The the 1st to the 3rd illuminating part respectively can be luminous when confirming to add 10V.

[embodiment 7: the formation of insulating barrier]

The formation of 3 * 3 square inches of rinsings, thickness of slab 1.1mm the ito substrate of figure, as matrix and the 1st electrode layer.This moment ITO figure, circuit is 84 μ m, the gap is 16 μ m.The negative resist that is made of insulating properties UV gel-type resin with the width of 26 μ m in the end of above-mentioned gap portion and ITO (per 5 μ m) forms the insulating barrier that film thickness is 5 μ m.Other forms EL element similarly to Example 4.

Even after the figure that is used to form the 1st, the 2nd and the 3rd illuminating part forms, insulating barrier can be not damaged yet, can be used as insulating barrier performance function, confirms that the 1st～the 3rd illuminating part can be luminous respectively.Therefore, even can find out the formation insulating barrier, also can form figure equally with the occasion of embodiment 4.

[embodiment 8: the solvent of luminescent layer]

(film forming of resilient coating)

The formation of 6 * 6 square inches of rinsings, thickness of slab 1.1mm the ito substrate of figure, as matrix and the 1st electrode layer.[Beyer corporate system BaytronP is shown in the above-mentioned chemical formula (1) to measure the resilient coating coating liquid.] 0.5ml, drip central part to matrix, be rotated coating.Maintenance cambium layer in 20 second under 2500rpm.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to above-mentioned matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, simultaneously on the fine setting exposure machine, the exposure shadow mask is set, the part of desiring to remove resilient coating is carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist and the resilient coating of exposed portion.The back baking was removed whole photoresists with acetone after 30 minutes under 120 ℃, made the resilient coating that is insoluble to acetone form figure arbitrarily.

(film forming of luminescent layer)

Formed at resilient coating on the matrix of figure and measured Polyvinyl carbazole [shown in the above-mentioned chemical formula (3).] 2wt% toluene solution 2ml, drip central part to matrix, be rotated coating, as the 1st luminescent layer.Maintenance cambium layer in 10 second under 2000rpm.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, on the fine setting exposure machine, the exposure shadow mask is set simultaneously, the desire beyond the luminous component of the 1st luminescent layer is removed the part of removing luminescent layer carry out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.The back baking was removed the luminescent layer that photoresist is removed part with toluene (the 1st luminescent layer developer solution) after 30 minutes under 120 ℃ in ultrasonic bath, obtained the matrix that the 1st luminous component is protected by photoresist.

Measure shown in the above-mentioned chemical formula of poly (phenylenevinylene) derivative luminous high polymer MEH-PPV[(2)] 1wt% xylene solution 2ml, drip central part to matrix, be rotated coating, as the 2nd luminescent layer.Maintenance cambium layer in 10 second under 2000rpm.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, on the fine setting exposure machine, the exposure shadow mask is set simultaneously, desiring beyond the luminous component of the 1st luminescent layer and the 2nd luminescent layer is removed the part of luminescent layer and carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.The back baking was removed the luminescent layer that photoresist is removed part with dimethylbenzene (the 2nd luminescent layer developer solution) after 30 minutes under 120 ℃ in ultrasonic bath, obtained the matrix that the 1st and the 2nd luminescent layer is protected by photoresist.

Remove whole photoresists with acetone then, the luminescent layer that has formed figure is exposed.

100 ℃ down after dry 1 hour, then on the matrix that obtains with the thickness evaporation Ca of 500 dusts as the 2nd electrode layer (upper electrode), again with the thickness evaporation Ag of 2500 dusts as protective layer, make EL element.

Wherein, the luminescent layer of the 2nd luminescent layer forms with solvent and luminescent layer developer solution---dimethylbenzene is the 0.01g/g solvent with respect to the solubility of the 1st luminescent layer under 25 ℃, 1 atmospheric pressure, is the 0.1g/g solvent with respect to the solubility of the 2nd luminescent layer under 25 ℃, 1 atmospheric pressure in addition.

(evaluation of the EL element characteristics of luminescence)

With the ITO electrode is positive pole, and the Ag electrode is a negative pole, connects, by power supply meter external dc power supply.When confirming to add 10V can colour mixture not appear by the 1st light from light source when adding 20V by the 2nd light from light source.

[comparative example 1]

Be the 1st luminescent layer except that making MEH-PPV, to make Polyvinyl carbazole be the 2nd luminescent layer, identical with embodiment, carries out the element manufacturing.The result is when applying the 2nd luminescent layer and when the 2nd luminescent layer is developed, and the 1st luminescent layer flows out, and causes colour mixture, can not obtain good figure.

The luminescent layer of the 2nd luminescent layer of this moment forms with solvent and luminescent layer developer solution---toluene is the 0.1g/g solvent with respect to the solubility of the 1st luminescent layer under 25 ℃, 1 atmospheric pressure, is the 0.1g/g solvent with respect to the solubility of the 2nd luminescent layer under 25 ℃, 1 atmospheric pressure in addition.

[embodiment 9: the emission wavelength of luminescent layer]

(film forming of resilient coating)

The formation of 6 * 6 square inches of rinsings, thickness of slab 1.1mm the ito substrate of figure, as matrix and the 1st electrode layer.[Beyer corporate system BaytronP is shown in the above-mentioned chemical formula (1) to measure the resilient coating coating liquid.] 0.5ml, drip central part to matrix, be rotated coating.Maintenance cambium layer in 20 second under 2500rpm.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to above-mentioned matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, simultaneously on the fine setting exposure machine, the exposure shadow mask is set, the part of desiring to remove resilient coating is carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist and the resilient coating of exposed portion.The back baking was removed whole photoresists with acetone after 30 minutes under 120 ℃, made the resilient coating that is insoluble to acetone form figure arbitrarily.

(film forming of luminescent layer)

Having formed at resilient coating on the matrix of figure and measured blue emitting material---Polyvinyl carbazole is [shown in the above-mentioned chemical formula (3).] 2wt% toluene solution 2ml, drip central part to matrix, be rotated coating, as the 1st luminescent layer.Maintenance cambium layer in 10 second under 2000rpm.Film thickness reaches 800 dusts as a result.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, on the fine setting exposure machine, the exposure shadow mask is set simultaneously, desiring beyond the luminous component of the 1st luminescent layer is removed the part of luminescent layer and carried out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.The back baking was removed the luminescent layer that photoresist is removed part with toluene after 30 minutes under 120 ℃ in ultrasonic bath, obtained the matrix that the 1st luminescent layer is protected by photoresist.

Measure the orange luminescence material---shown in the above-mentioned chemical formula of poly (phenylenevinylene) derivative luminous high polymer MEH-PPV[(2)] 1wt% toluene solution 2ml, drip central part to matrix, be rotated coating, as the 2nd luminescent layer.Maintenance cambium layer in 10 second under 2000rpm.Film thickness reaches 800 dusts as a result.By peeling off photoresist with acetone, peel off the photoresist that forms on the 1st luminescent layer top that has formed figure, peel off the 2nd luminescent layer simultaneously, the 1st luminescent layer that has formed figure is exposed.

Measure positive photoresist solution (Tokyo Ying Huashe system; OFPR-800) 2ml drips the central part to matrix, is rotated coating.Under 500rpm, kept for 10 seconds, under 2000rpm, keep 20 seconds, cambium layer then.Film thickness reaches about 1 μ m as a result.80 ℃ of preceding down bakings 30 minutes.Then, on the fine setting exposure machine, the exposure shadow mask is set simultaneously, desiring beyond the luminous component of the 1st luminescent layer and the 2nd luminescent layer is removed the luminescent layer zone carry out ultraviolet exposure.With resist developer solution (Tokyo Ying Huashe system; NMD-3) develop after 20 seconds, use water rinse, remove the photoresist of exposed portion.The back baking was removed the luminescent layer that photoresist is removed part with toluene after 30 minutes under 120 ℃ in ultrasonic bath, obtained the matrix that the 1st and the 2nd luminescent layer is protected by photoresist.

Remove whole photoresists with acetone then, the luminescent layer that has formed figure is exposed.

100 ℃ down after dry 1 hour, then on the matrix that obtains with the thickness evaporation Ca of 500 dusts as the 2nd electrode layer (upper electrode), again with the thickness evaporation Ag of 2500 dusts as protective layer, make EL element.

(evaluation of the EL element characteristics of luminescence)

With the ITO electrode is positive pole, and the Ag electrode is a negative pole, connects, by power supply meter external dc power supply.Can send near the light of maximum wavelength 430nm that comes from Polyvinyl carbazole by the 1st luminescent layer when confirming to add 20V, can send near the light of maximum wavelength 590nm that comes from MEH-PPV by the 2nd luminescent layer when adding 10V.

Infer that this moment, a part of Polyvinyl carbazole flowed out to the 2nd luminescent layer by the end of the 1st luminescent layer, mix with MEH-PPV at the illuminating part of the 2nd luminescent layer, but affirmation does not derive from the light of Polyvinyl carbazole.

[comparative example 2]

Except that making MET-PPV is that the 1st luminescent layer, Polyvinyl carbazole are the 2nd luminescent layer, carries out the element manufacturing equally with embodiment.

With the ITO electrode is positive pole, and the Ag electrode is a negative pole, connects, by power supply meter external dc power supply.Can send near the light of maximum wavelength 590nm that comes from MEH-PPV by the 1st luminescent layer when confirming to add 10V, when adding 10V can by the 2nd luminescent layer send come from Polyvinyl carbazole and MEH-PPV have near the luminous of 2 peaks 430nm and the 590nm.

Its reason is, when applying the 2nd luminescent layer, flows out MEH-PPV by the end of the 1st luminescent layer that has formed figure, causes colour mixture in the luminous component and the Polyvinyl carbazole of the 2nd luminescent layer.

According to the present invention, owing to be to make at least 1 layer of organic EL layer in the EL element form the EL element that figure obtains by the photoetching technique method, therefore with the method comparison that formed figure by evaporation in the past, owing to do not need to have the vacuum equipment of governor motion etc., thereby can be than being easier to and making at an easy rate.On the other hand, compare with the method that forms figure by ink-jet, do not needing the auxiliary member that forms figure and carrying out aspect the preliminary treatment preferred matrix, and because the relation of ink gun and accuracy of spray we can say that manufacture method of the present invention is a preferable methods for forming more high-precision figure.Therefore, according to the manufacture method of EL element of the present invention, can be than being easier to and obtaining at an easy rate high-precision EL element.

In addition, according to the present invention, can provide and not sneak into impurity in the luminescent layer, luminous efficiency and light are read the efficient height, realization simplified manufacturing process, a large amount of manufacture method and EL element of producing, forming the EL element of the figure of high definition and energy uniformly light-emitting, the minimizing of crosstalking.

More specifically, for example, can reduce crosstalking in the simple matrix element drives process by making resilient coating form figure.In addition, apply resilient coating and the luminescent layer make and form figure, can carry out simultaneously that laser is for example removed or the removing of the insoluble part of being undertaken by wiping usually, thereby can make work simplification by making.And dividing plate, auxiliary member with anti-performance of ink and the auxiliary surface treatment with anti-performance of ink that forms figure that forms figure all do not need, and can make work simplification on the one hand at this yet.In addition, the present invention is for in luminous EL element of arbitrary graphic or the panchromatic luminous EL element any one, and the EL element of using flexible substrate, also is good controlling aspect glow color and the formation figure.

[changing 1]

[changing 2]

[changing 3]

[changing 4]

[changing 5]

Claims (20)

1. the manufacture method of an electroluminescent cell, resilient coating and luminescent layer at least in the organic electro luminescent layer that constitutes electroluminescent cell utilize the photoetching technique method to form figure, have following operation:

Be insoluble to the photoresist of the solvent that is used to form resilient coating by utilization, make the resilient coating that is insoluble to photoresist solvent, photoresist stripper and is used to form the solvent of luminescent layer, form figure and form the operation of patterned resilient coating,

Be insoluble to the photoresist of the solvent that is used to form luminescent layer by utilization, make the luminescent layer that is insoluble to photoresist solvent, development of photoresist liquid and photoresist stripper, form figure and on the resilient coating of former figuresization, form the operation of patterned luminescent layer.

2. the manufacture method of electroluminescent cell according to claim 1 in the operation that forms described patterned resilient coating, is included in the operation of peeling off described photoresist after utilizing photoresist to carry out graphically to resilient coating.

3. the manufacture method of electroluminescent cell according to claim 1 and 2, the aforementioned solvent that is used to form luminescent layer is a Weak solvent with respect to the resilient coating that has formed.

4. the manufacture method of electroluminescent cell according to claim 3, the described solvent that is used to form luminescent layer, its with respect to solubility of the resilient coating that has formed under 25 ℃, 1 atmospheric pressure for below the 0.001g/g solvent.

5. the manufacture method of electroluminescent cell according to claim 1 and 2, described luminescent layer is the luminescent layer that diverse luminescent layer is formed through several photoetching technique method.

6. the manufacture method of electroluminescent cell according to claim 5, the luminescent layer of the described luminescent layer that forms later on for the 2nd time forms uses solvent, is Weak solvent to the luminescent layer that has formed.

7. the manufacture method of electroluminescent cell according to claim 6, the luminescent layer of the luminescent layer that forms later on for the 2nd time forms use solvent, and its solubility with respect to the luminescent layer that has formed is below the 0.1g/g solvent under 25 ℃, 1 atmospheric pressure.

8. the manufacture method of electroluminescent cell according to claim 5, the formation of described luminescent layer through forming for several times is to be begun to form successively from the short wavelength by the light wavelength that described luminescent layer obtains in proper order.

9. the manufacture method of electroluminescent cell according to claim 5, described luminescent layer is 3 kinds of luminescent layers that send red, green and blue light.

10. the manufacture method of an electroluminescent cell, resilient coating and luminescent layer at least in the organic electro luminescent layer that constitutes electroluminescent cell utilize the photoetching technique method to form figure, have following operation:

The resilient coating that formation is insoluble to photoresist solvent, photoresist stripper and is used to form the solvent of luminescent layer, on described resilient coating, form the luminescent layer that is insoluble to photoresist solvent, development of photoresist liquid and photoresist stripper then, the photoresist that utilization is insoluble to the solvent that is used to form resilient coating and is used to form the solvent of luminescent layer makes described resilient coating and luminescent layer form figure simultaneously.

11. manufacture method according to claim 1 or 10 described electroluminescent cells, the figure of described use photoetching technique method forms, be by on resilient coating that forms figure and/or luminescent layer, applying photoresist, exposure, after development makes photoresist form figure, use dry corrosion to remove resilient coating and/or luminescent layer that photoresist is removed part, form figure.

12. the manufacture method of electroluminescent cell according to claim 11, described dry corrosion are the reactive ion corrosion.

13. the manufacture method of electroluminescent cell according to claim 11 is used oxygen simple substance or oxygen-containing gas in the described dry corrosion.

14. the manufacture method of electroluminescent cell according to claim 11 is used atmospheric pressure plasma in the described dry corrosion.

15. the manufacture method of electroluminescent cell according to claim 11, the gas that uses in the described dry corrosion are a kind of gas.

16. manufacture method according to claim 1 or 10 described electroluminescent cells, the figure of described use photoetching technique method forms, be by on resilient coating that forms figure and/or luminescent layer, applying photoresist, exposure, after development makes photoresist form figure, in ultrasonic bath, remove resilient coating and/or luminescent layer that photoresist is removed part, form figure.

17., after making described luminescent layer or described resilient coating and described luminescent layer form figure, form the 2nd electrode layer according to the manufacture method of claim 1 or 10 described electroluminescent cells.

18. the manufacture method of electroluminescent cell according to claim 17 forms the 2nd electrode layer at the resilient coating of described formation figure and above the luminescent layer and side.

19. the manufacture method of electroluminescent cell according to claim 5 after forming described diverse luminescent layer, forms the 2nd electrode layer.

20. the manufacture method of electroluminescent cell according to claim 17, the figure of the luminescent layer of described formation figure is the figure different with the figure of the 2nd electrode layer.

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