CN100551186C - Electroluminescent cell and manufacture method thereof - Google Patents
Electroluminescent cell and manufacture method thereof Download PDFInfo
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- CN100551186C CN100551186C CNB2005101140255A CN200510114025A CN100551186C CN 100551186 C CN100551186 C CN 100551186C CN B2005101140255 A CNB2005101140255 A CN B2005101140255A CN 200510114025 A CN200510114025 A CN 200510114025A CN 100551186 C CN100551186 C CN 100551186C
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Abstract
The invention provides a kind of EL element and manufacture method thereof that can easy manufacturing, EL element be at least by the 1st electrode, in EL layer that forms on the 1st electrode and the formed EL element of the 2nd electrode that on this EL layer, forms, form 1 layer at least and produce wetability by rayed and be varied to layering.
Description
The application is application number the dividing an application for China's application of " electroluminescent cell and manufacture method thereof " that be CN01117383.1 (applying date is February 23 calendar year 2001), denomination of invention.
Technical field
The invention relates to electroluminescent cell (being also referred to as EL element in this specification), particularly organic film EL element, and manufacture method about can in display unit, using.
Background technology
EL element is subjected to extensive attention as the application of self luminous planar display element, wherein, organic film EL as luminescent material shows with organic substance, even apply the following voltage of 10V, can realize that also high briliancy is luminous, luminous efficiency is very high, also can be luminous with simple component structure, and expectation is applied to high-accuracy panchromatic demonstration or makes the advertisement of the luminous demonstration of specific pattern and the demonstration of the low modest simple and easy demonstration usefulness of other prices.
Therefore, when the display unit of EL element is used in actual manufacturing, need electrode and organic EL layer to form pattern, the typical case says to be needed photoetching process and utilizes the complicated patterns film formation device to form the operation of pattern, thereby brings the complicated and expense of operation to rise.Utilizing the mask evaporation that organic EL Material is formed in the method for patterning, need high vacuum plant, and exist qualification rate low, the problem that expense raises.On the other hand, utilize ink-jet method to form method of patterning.Though operation is fairly simple, there is the problem that qualification rate is low and film thickness uniformity worsens.When requiring advertisement with multiple shape such as EL element and large tracts of land, the problem of existence is that productivity ratio is obviously low.
Like this, in EL element, during particularly organic EL display was made, aspects such as for electrode, organic EL layer and insulating barrier etc. are formed pattern, process number is many, qualification rate, productivity ratio, cost still had a lot of problems.In order to improve display performance, the most important thing is to improve the pattern precision of luminescent layer, thus require on electrode, accurately to dispose luminescent layer, and require evenly configuration film thickness.
Summary of the invention
The purpose of this invention is to provide EL element and the manufacture method thereof that to make more easily, particularly provide luminescent layer, next door layer etc. to constitute layer and obtain accurate pattern precision, the good EL element of uniformity of luminance, and manufacture method simultaneously.
Present inventors find, on by rayed generation wetability variation stratification, carry out pattern exposure, form the pattern that produces by wetability difference, utilize this pattern to form EL layer, next door layer, insulating barrier, the 1st electrode or the 2nd electrode etc., thereby can solve above-mentioned problem, and finish the present invention.
Therefore, the feature of EL element of the present invention is, this EL element is at least by the 1st electrode, the EL layer that forms on above-mentioned the 1st electrode, EL element with the 2nd electrode formation that on above-mentioned EL layer, forms, at least form 1 layer and produce wetability by rayed and be varied to layering, promptly rayed causes wetability and is varied to layering.
Description of drawings
Fig. 1 is a routine structural representation sectional drawing of EL element of the present invention.
Fig. 2 is a routine structural representation sectional drawing of EL element of the present invention.
Fig. 3 is a routine structural representation sectional drawing of EL element of the present invention.
Fig. 4 is a routine structural representation sectional drawing of EL element of the present invention.
Fig. 5 is a routine structural representation sectional drawing of EL element of the present invention.
Fig. 6 is a routine structural representation sectional drawing of EL element of the present invention.
Fig. 7 is a routine structural representation sectional drawing of EL element of the present invention.
Fig. 8 is a routine manufacture method key diagram of EL element of the present invention.
Fig. 9 is a routine manufacture method key diagram of EL element of the present invention.
Figure 10 is a routine manufacture method key diagram of EL element of the present invention.
Figure 11 is the characteristics of luminescence presentation graphs of EL element among the routine D-1.
Embodiment
EL element
As mentioned above, EL element feature of the present invention be at least by the 1st electrode, in EL layer that forms on above-mentioned the 1st electrode and the formed EL element of the 2nd electrode that on above-mentioned EL layer, forms, form 1 layer at least and produce wetability by rayed and be varied to layering by containing photocatalyst layer etc.EL element of the present invention can contain some random layer that is useful on EL element usually.When EL element is when trickle pixel is formed the demonstration of panchromatic demonstration of pattern, efficient of the present invention not only greatly but also good.
1 kind of scheme of-Di-
Fig. 1 is a routine sectional drawing of EL element of the present invention, and structure is on base material 1, successively lamination the 1st electrode 2, contain photocatalyst layer 3, EL layer 5 and the 2nd electrode 6, the wetability changing unit 3 in containing photocatalyst layer 3 ' and EL layer 5 between, form another EL layer 4.
2 kinds of schemes of-Di-
Fig. 2 is the sectional drawing that is used for illustrating the 1st kind of EL element of the present invention's the 2nd scheme.21 is pattern-like the 1st electrodes, the 24th among the figure, pattern-like the 2nd electrode, the 22nd, and wetability is varied to layering, the 23rd, luminescent layer, the 26th, base material, the 29th, insulating barrier.
As shown in Figure 2, the 1st kind of EL element structure of the present invention is and the corresponding luminescent layer 23 of this pattern in 21,24 clampings of 2 pattern-like electrodes, and, the component layer 22 of the wetting variation of formation between pattern electrode 21 and luminescent layer 23.
Wetability is varied to layering 22 laminations after on the base material 26 that is provided with the 1st electrode 21 and insulating barrier 29, its surface is used with the 1st electrode 21 identical patterned mask or exposed portions and is used the mask broader than electrode pattern, form pattern by rayed, be positioned at the surface that wetability on pattern-like the 1st electrode 21 is varied to layering 22, rayed position as the surface wettability that improves relative laminated material by rayed, perhaps, not by light-struck position, form pattern as the surface that is varied to layering 22 in the wetability that pattern-like the 1st electrode 21 positions are not set.Equally, utilize at the rayed position and do not carry out in the rayed position, with respect to the surface wettability difference of the formation luminescent layer material of laminated material, luminescent layer 23 formation patterns.At this moment to prevent that short circuit from being purpose, preferably will form between electrode 21 marginal portions and electrode 21 of pattern, live with insulating barrier 29 is topped.
Followingly the 2nd kind of EL element in the present invention's the 2nd scheme is described according to Fig. 3.EL element shown in Figure 3 is luminescent layer 33 boundary members in the 1EL element, and next door layer 37 is set, and more can prevent conducting between electrode by the next door layer.Form the material of next door layer, can use to have 10
7The high-molecular organic material of the above resistance of Ω cm preferably uses ultraviolet curing resin.By the next door layer is coloured to dead colors such as black, can obtain distincter demonstration.The thickness of next door layer 37 is 0.1-10 μ m, is preferably 1-2 μ m.
EL element shown in Figure 3 after with electrode 31 and insulating barrier 39 formation patterns, forms wetability and is varied to layering 32.Then, the position pattern exposure that will not form electrode pattern forms the rayed position, when forming next door layer material etc. by coatings such as even coatings, can be on the rayed position only lamination form the material of next door layer.Afterwards,, when using ultraviolet curing resin, carry out uniform exposure, make the material cured that forms the next door layer, simultaneously, the wetability on the electrode pattern is varied to layered transformation becomes the rayed position as the material that forms the next door layer.Then, by utilizing ink-jetting style etc., the same luminescent layer that is coated with Fig. 2 forms luminescent layer, makes the EL element the same with Fig. 2.At this moment, be purpose with the alternately distortion that prevents 21 at electrode, it is topped preferably will to form between electrode 21 marginal portions of pattern and the electrode 21 usefulness insulating barrier 39.
The wetability that Fig. 4 is provided with on base material 46 in Fig. 2 EL element is varied to layering 42, and the pattern precision is good equally.Also wetability can be varied to layering 42 and be located on the luminescent layer 43, be varied to the configuration of layering, only limit to not hinder the electric charge injection about wetability, unqualified to its configuration, can be 1 layer, also can be multilayer.
EL element shown in Fig. 4 is after evenly forming wetability on the base material 46 and being varied to layering 42, after will forming electrode again and partly carrying out pattern exposure, electrode material is carried out the pattern evaporation with metallikon.Then, utilize even rubbing method to be coated with when forming the material of sending out luminescent layer, can on electrode, only form luminescent layer.Subsequently, carry out pattern exposure, the boundary member between luminescent layer is transformed into the rayed position after, utilize coating such as ink-jet method to form the material of next door layers, form the next door layer, make the EL element the same with Fig. 2.EL element shown in Figure 4, the same with Fig. 2, EL element shown in Figure 3, have good pattern precision, simultaneously, to inject goodly to the electric charge of luminescent layer by electrode 41,44, luminous efficiency is very high.
Luminescent layer for example can be monochromatic and form pattern, also can be varied to and form lamination in the layering in each wetability, and alternately assortment R, G, the various luminescent layers of B successively, and form panchromatic structure.Each luminescent layer can form following form, and (1) anode/wetability is varied to layering/hole injection layer (resilient coating)/luminescent layer/electron supplying layer/electron injecting layer (resilient coating)/negative electrode, (2) anode/hole injection layer (resilient coating)/luminescent layer/electron supplying layer/electron injecting layer (resilient coating)/wetability is varied to layering/negative electrode.
In the form of above-mentioned (1), (2), can be that combination has each materials with function, each layer of double as electric charge injection layer, charge transport layer, luminescent layer, and each layer needn't be set respectively, also can dual-purpose as mixed style with each functional material.
3 kinds of styles of-Di-
EL element of the present invention can be carried out the pattern luminous demonstration different with any one pattern form in the opposite electrode.At this moment, electrode there is no need to form pattern, but makes easy.EL element of the present invention, can have 1 layer at least and contain photocatalyst layer between opposite electrode, this layer is to make the layer that designs for simplifying, though situation about being formed by the insulating properties material is also arranged, but, even under unexpected situation, also can not damage the luminescent properties of EL element.
The pattern of EL element of the present invention is luminous, and first can be the EL layer to be formed pattern containing on the photocatalyst layer, makes the luminous mode of EL layer of patterning.This EL layer as its subordinate concept, is to contain electric charge injection layer (hole and electron injecting layer), charge transport layer (hole and electron supplying layer) and luminescent layer, and what form pattern can be in electric charge injection layer, charge transport layer or the luminescent layer at least 1 layer.For example, have the photocatalyst layer of containing on the anode, the above-mentioned hole injection layer that has pattern-like on the photocatalyst layer that contains is not only above-mentioned pattern but is had the EL element of luminescent layer comprehensively on above-mentioned hole injection layer.By making a part of luminescent layer form pattern, form the luminescent layer that forms the luminescent layer different colours of pattern with this simultaneously comprehensively, both can be luminous comprehensively, the pattern that can make up wherein is luminous again.
The pattern of EL element of the present invention is luminous, and second also can be insulating barrier to be formed pattern containing on the photocatalyst layer, and making does not have the luminous mode of the EL of insulated part layer.
Fig. 5 is a routine structural representation sectional drawing of EL element of the present invention, sets gradually the 1st electrode 52 on base material 1, contains photocatalyst layer 53 and the 2nd electrode 55, at the 2nd electrode 55 with contain between the photocatalyst layer 53, luminescent layer 54 only is set on the pattern luminous component.In such EL element, contain conditions such as the thickness of photocatalyst layer 53 and material by suitable selection, both can prevent the unexpected conducting between the 1st electrode 52 and the 2nd electrode 55, can make again electric charge by contain photocatalyst layer inject carry out in the luminescent layer luminous.
Fig. 6 is another routine structural representation sectional drawing of EL element of the present invention, on base material 61, set gradually the 1st electrode 62, contain photocatalyst layer 63, luminescent layer 64 and the 2nd electrode 65, at luminescent layer 64 with contain between the photocatalyst layer 63, electric charge injection layer 66 only is set on the pattern luminous component.In such EL element, the part that forms electric charge injection layer typically is luminous, does not have the non-luminous EL element of part that forms, also can be that to form the part of electric charge injection layer luminous, not have the part of formation to send out the EL element of faint light.
If form other luminescent layer, replace the electric charge injection layer of the formation pattern of Fig. 6, also can on this luminescent layer and the luminescent layer that comprehensively forms, carry out the luminous demonstration of 2 kinds of colors.
Fig. 7 is the another routine structural representation sectional drawing of EL element of the present invention, on base material 71, set gradually the 1st electrode 72, contain photocatalyst layer 73 and the 2nd electrode 75, at the 2nd electrode 75 with contain between the photocatalyst layer 73, pattern-like insulating barrier 79 only is set on non-luminous part, luminescent layer 74 is set comprehensively.
Purposes as EL element of the present invention, various purposes are arranged, for example, doorplate, bulletin board, show tags shows the way, the urgent warning mark, road markings, clock and instrument show uses fixedly literal, price tickets, menu, the advertisement at sunshine, postcard, greeting card (グ リ one テ ィ Application グ カ one De), prepayment (プ リ ペ ィ De) card, stationery shows, the electronics book, illumination, toy in recreation facility and the party field, the demonstration of word marking, plate and calendar are looked in advertisement, display, area map or map label etc., display pattern particularly, or pattern (mask) shape, can effectively show certain meaning thereon.
4 kinds of styles of-Di-
EL element of the present invention, in the 1st kind of style, the above-mentioned photocatalyst layer that contains also can contain the material that improves the characteristics of luminescence.
Produce wetability by rayed and be varied to layering
That uses among the present invention produces wetability by rayed and is varied to layering, illustrate for example contain with photosemiconductors such as titanium oxide be representative the narrow sense photochemical catalyst contain photocatalyst layer and specific organic polymer layer etc.In this specification,, use sometimes to contain this word of photocatalyst layer as containing these and being varied to the same generalized concept of layering by rayed generation wetability.
Contain photocatalyst layer
(containing photocatalyst layer)
Among the present invention, what is called contains photocatalyst layer, is meant to utilize rayed, can make wetability layer that changed afterwards and the layer that has changed.So-called photochemical catalyst, so long as can cause this variation, any material can.Contain photocatalyst layer,, can form pattern because of wetability changes by the pattern-like exposure.Say that typically not carrying out the rayed position is hydrophobicity and grease proofness, light-struck position then forms very high hydrophily and/or lipophile.Among the present invention, utilize to contain the pattern that photocatalyst layer wettability of the surface difference produces, can contain the superior in quality pattern that layer (EL layer, the 1st electrode, the 2nd electrode etc.) is set of formation on the photocatalyst layer easily.
-Di 1-3 kind scheme-
The photocatalyst layer that contains of the present invention if between base material and the 2nd electrode, can be arranged on any position, for example, and between base material and the 1st electrode, between the 1st electrode and the EL layer, when forming, between these EL interlayers or EL layer and the 2nd electrode by several layers of EL layer.Wherein, contain photocatalyst layer and be preferably disposed between the 1st electrode and the EL layer, the EL layer is formed pattern.Contain not only 1 layer of photocatalyst layer, also can form several layers, at this moment, be easy to containing formation number layer pattern on the photocatalyst layer, and can guarantee high-quality.
The thickness that contains photocatalyst layer has served as when approaching, and can not clearly find the difference of wetability, is difficult to form pattern, and when blocked up, the conveying of overslaugh hole or electronics again dislikes strong influence can for luminous the bringing of EL element, so be preferably
More preferably
Contain the thickness of photocatalyst layer, though can be taken as
Scope, but in the 1st kind of EL element shown in Figure 2, contain the formation patterned layer of photocatalyst layer 22, and the performance function simultaneously, is utilized its insulating properties as luminescent layer 23, as the layer that prevents conducting between the electrode 21,24, also bring into play function.General situation, in EL element, the thickness of luminescent layer is compared with electrode layer, is extremely thin film, though existing problems, the electrode layer that is formed by evaporation for example is because of uneven being easy to produces conducting between electrode 21,24.But be varied to layering by wetability is set, can prevent this problem.Yet, when considering the luminous efficiency of luminescent layer 23, when applying voltage, must guarantee from the electric charge injection of electrode 21,24 to luminescent layer 23, therefore, the thickness that wetability is varied to layering is the film thickness of energy iunjected charge, is preferably in
Below, can be taken as
Between.As following, by resilient coating and charge transport layer, when making luminescent layer on electrode, form pattern, resilient coating, charge transport layer are varied in wetability respectively form pattern in the layering, though form the same with luminescent layer, but in the case, consider to set the total film thickness that each wetability is varied to layering by the electric charge mobility of electrode to luminescent layer.
4 kinds of schemes of-Di-
Among the present invention, contain photocatalyst layer and can contain the material that improves the characteristics of luminescence.
The thickness that contains photocatalyst layer is crossed when approaching, and can not clearly find the difference of wetability, is difficult to form pattern, when blocked up, can hinder the conveying of hole or electronics again, strong influence is disliked in the luminous generation of EL element, so be preferably
More preferably
(principle that wetability changes)
Among the present invention, the photochemical catalyst of use can cause chemical change near material (adhesive etc.) by the irradiation of light, at the patterns that are subjected to forming on light-struck part by the different generations of wetability.Utilize the machine matter of photochemical catalyst generation effect, may not be exactly clear and definite, but can think, irradiation by light, the carrier that generates on photochemical catalyst has directly changed the chemical constitution of adhesive etc., perhaps, in the presence of oxygen, water, changed the chemical constitution of adhesive etc., wettability of the surface is changed by the active oxygen source that generates.
(photocatalyst material)
As the photocatalyst material that uses among the present invention, for example,, can enumerate known titanium oxide (TiO as photosemiconductor
2), zinc oxide (ZnO), tin oxide (SnO
2) strontium titanates (SrTiO
3) tungsten oxide (WO3), bismuth oxide (Bi
2O
3), iron oxide (Fe
2O
3) metal oxide of a class, good especially is titanium oxide.Titanium oxide has very high band-gap energy, chemical stabilization, avirulence, advantages such as easy acquisition.
In titanium oxide as photochemical catalyst, can use any in Detitanium-ore-type and the rutile-type, preferably use the titanium oxide of Detitanium-ore-type.Specifically, the anatase type TiO 2 sol (the former industry of stone (strain) STS-02, average crystallite particle footpath 7nm) of hydrochloric acid peptization formulation, anatase type TiO 2 sol (the daily output chemistry of nitric acid peptization formulation are for example arranged, TA-15, average crystallite particle footpath 12nm).The excitation wavelength of this titanium oxide is preferably below 380nm.
The photocatalysis dosage that contains in the photocatalyst layer is preferably 5-90 weight %, more preferably 20-60 weight %.
The photochemical catalyst particle diameter is more little to cause effectively that more light-catalyzed reaction is ideal, so average grain diameter is below 50nm, the better photochemical catalyst that uses below the 20nm, and then the particle diameter of photochemical catalyst is more little, the roughness that contains the photochemical catalyst laminar surface that forms is more little, ideal, when the surface roughness that contains photocatalyst layer surpassed 10nm, the hydrophobicity that contains the non-rayed part of photocatalyst layer reduced, the hydrophily performance of rayed part is insufficient, so not ideal.
(adhesive ingredients)
The present invention contains spendable adhesive in the photocatalyst layer, best is that main framing is subjected to the optical excitation of above-mentioned photochemical catalyst not resolvent, has very high adhesive in conjunction with energy, for example, can enumerate (1) and utilize solgel reaction etc.,, carry out polycondensation the hydrolysis such as wash of chlorine or alcoxyl silicon, bring into play the very organopolysiloxane of hard intensity, or (2) carry out crosslinked organopolysiloxane etc. with hydrophobicity and the good reactive silicone of grease proofness.
The situation of above-mentioned (1), the compound that can make main body are general expression YnSiX
4-n(n=1-3) expression silicon compound in hydrolytie polycondensation thing, cohydrolysis compound more than a kind or 2 kinds.In the above-mentioned general expression, Y for example can be alkyl, fluoroalkyl, vinyl, amino or epoxy radicals, and X for example can be halogen, methoxyl group, ethyoxyl or acetyl group.
Methyl trichlorosilane, methyl tribromosilane, methyl trimethoxy oxosilane, methyl three ethoxy silane, methyl three different third oxosilanes, methyl three uncle's fourth oxosilanes specifically can have been enumerated; Ethyl trichlorosilane, ethyl tribromosilane, ethyl trimethoxy silane, ethyl three ethoxy silane, ethyl three different third oxosilanes, ethyl three uncle's fourth oxosilanes; N-propyltrichlorosilan, n-pro-pyl tribromosilane, n-pro-pyl trimethoxy silane, n-pro-pyl three ethoxy silane, n-pro-pyl three different third oxosilanes, n-pro-pyl three uncle's fourth oxosilanes; N-hexyl trichlorosilane, n-hexyl tribromosilane, n-hexyl trimethoxy silane, n-hexyl three ethoxy silane, n-hexyl three different third oxosilanes, n-hexyl three uncle's fourth oxosilanes; Positive decyltrichlorosilane, positive decyl tribromosilane, positive decyl trimethoxy silane, positive decyl three ethoxy silane, positive decyl three different third oxosilanes, positive decyl three uncle's fourth oxosilanes; N-octadecane base trichlorosilane, n-octadecane base tribromosilane, n-octadecane base trimethoxy silane, n-octadecane base three ethoxy silane, n-octadecane base three different third oxosilanes, n-octadecane base three uncle's fourth oxosilanes; Phenyl trichlorosilane, phenyl tribromo silicon are washed, phenyl trimethoxy silane, phenyl three ethoxy silane, phenyl three different third oxosilanes, phenyl three uncle's fourth oxosilanes; Tetrachloro silicane, tetrabromo silane, tetramethyl oxosilane, tetrem oxosilane, four fourth oxosilanes, dimethoxy diethoxy silane; Dimethyldichlorosilane, dimethyl two bromo-silicanes, dimethylformamide dimethyl oxosilane, dimethyl diethoxy silane; Diphenyl dichlorosilane, diphenyl dibromo silicon are washed, diphenyl dimethoxy silane, diphenyl diethoxy silane; Benzyl dichlorosilane, benzyl two bromo-silicanes, benzyl dimethoxy silane, benzyl diethoxy silane; Trichlorosilane alkane, tribromo hydrogen silane, trimethoxy hydrogen silane, three ethoxy hydrogen silanes, the three different third oxygen hydrogen silanes, three uncle's fourth oxygen hydrogen silanes; Vinyl trichlorosilane, ethene tribromosilane, ethene trimethoxy silane, ethene three ethoxy silane, ethene three different third oxosilanes, ethene three uncle's fourth oxosilanes; Trifluoro propyl trichlorosilane, trifluoro propyl tribromosilane, trifluoro propyl trimethoxy silane, trifluoro propyl three ethoxy silane, trifluoro propyl three different third oxosilanes, trifluoro propyl three uncle's fourth oxosilanes; γ-glycidol oxygen propyl group methyl dimethoxy oxosilane, γ-glycidol oxygen propyl group methyl diethoxy silane, γ-glycidol oxygen propyl group methyl trimethoxy oxosilane, γ-glycidol oxygen propyl group three ethoxy silane, γ-glycidol oxygen propyl group three different third oxosilanes, γ-glycidol oxygen propyl group three uncle's fourth oxosilanes; γ-metering system oxygen propyl group methyl dimethoxy oxosilane, γ-metering system oxygen propyl group methyl diethoxy silane, γ-metering system oxygen propyl group trimethoxy silane, γ-metering system oxygen propyl group three ethoxy silane, γ-metering system oxygen propyl group three different third oxosilanes, γ-metering system oxygen propyl group three uncle's fourth oxosilanes; γ-aminopropyl methyl dimethoxy oxosilane, γ-aminopropyl methyl diethoxy silane, γ-aminopropyl trimethoxy silane, γ-aminopropyl three ethoxy silane, γ-aminopropyl three different third oxosilanes, γ-aminopropyl three uncle's fourth oxosilanes; γ-mercapto propyl group methyl dimethoxy oxosilane, γ-mercapto propyl group methyl diethoxy silane, γ-mercapto propyl group trimethoxy silane, γ-mercapto propyl group three ethoxy silane, γ-mercapto propyl group three different third oxosilanes, γ-mercapto propyl group three uncle's fourth oxosilanes; β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl three ethoxy silane; With their partial hydrolysate; With their mixture.
As adhesive, preferably use the polysiloxanes that contains fluoroalkyl, specifically, the hydrolytie polycondensation thing more than a kind or 2 kinds, the cohydrolysis condensation polymer of following fluoroalkyl silane arranged, be silane coupling agent as fluorine, generally can use known.
CF
3(CF
2)
3CH
2CH
2Si(OCH
3)
3
CF
3(CF
2)
6CH
2CH
2Si(OCH
3)
3
CF
3(CF
2)
7CH
2CH
2Si(OCH
3)
3
CF
3(CF
2)
3CH
2CH
2Si(OCH
3)
3
(CF
3)
2CF(CF
2)
4CH
2CH
2Si(OCH
3)
3
(CF
3)
2CF(CF
2)
6CH
2CH
2Si(OCH
3)
3
(CF
3)
2CF(CF
2)
3CH
2CH
2Si(OCH
3)
3
CF
3(C
6H
4)C
2H
4Si(OCH
3)
3
CF
3(CF
2)
3(C
6H
4)C
2H
4Si(OCH
3)
3
CF
3(CF
2)
5(C
6H
4)C
2H
4Si(OCH
3)
3
CF
3(CF
2)
7(C
6H
4)C
2H
4Si(OCH
3)
3
CF
3(CF
2)
3CH
2CH
2SiCH
3(OCH
3)
2
CF
3(CF
2)
5CH
2CH
2SiCH
3(OCH
3)
2
CF
3(CF
2)
7CH
2CH
2SiCH
3(OCH
3)
2
CF
3(CF
2)
3CH
2CH
2SiCH
3(OCH
3)
2
(CF
3)
2CF(CF
2)
4CH
2CH
2SiCH
3(OCH
3)
2
(CF
3)
2CF(CF
2)
6CH
2CH
2SiCH
3(OCH
3)
2
(CF
3)
2CF(CF
2)
6CH
2CH
2SiCH
3(OCH
3)
2
CF
3(C
6H
4)C
2H
4SiCH
3(OCH
3)
2
CF
3(CF
2)
3(C
6H
4)C
2H
4SiCH
3(OCH
3)
2
CF
3(CF
2)
6(C
6H
4)C
2H
4SiCH
3(OCH
3)
2
CF
3(CF
2)
7(C
6H
4)C
2H
4SiCH
3(OCH
3)
2
CF
3(CF
2)
3CH
2CH
2Si(OCH
2CH
3)
3
CF
3(CF
2)
5CH
2CH
2Si(OCH
2CH
3)
3
CF
3(CF
2)
7CH
2CH
2Si(OCH
2CH
3)
3
CF
3(CF
2)
6CH
2CH
2Si(OCH
2CH
3)
3
CF
3(CF
2)
7SO
2N(C
2H
5)C
2H
4CH
2Si(OCH
8)
3
The polysiloxanes that contains above-mentioned fluoroalkyl can improve the hydrophobicity and the grease proofness that contain the non-rayed part of photocatalyst layer greatly as adhesive.
As the reactive silicone of above-mentioned (2), can enumerate and have the compound that following general expression is represented skeleton.
-(Si(R
1)(R
2)O)
n-
In the formula, n is the integer more than 2, R
1, R
2Be respectively alkyl, alkenyl, aryl or the cyanoalkyl of the replacement or the non-replacement of 1-10 carbon atom.Best is to be vinyl, phenyl, halogenophenyl below overall 40 moles of %.R
1And/or R
2Be methyl, ideal because the surface energy minimum, best is methyl on chain end or side chain, has the hydroxyl isoreactivity base more than at least 1 at 60 moles more than the % in the strand.
Can will not cause that the stable organo-silicon compound of the cross-linking reaction of dimethyl polysiloxane are mixed in the adhesive with above-mentioned organopolysiloxane.
(improve the material of the characteristics of luminescence, during 4 kinds of schemes of-Di-)
The material that contains the raising characteristics of luminescence that can contain in the photocatalyst layer of EL element of the present invention is the material that improves the EL layer characteristics of luminescence, for example, is the material that promotes to EL layer injected hole such as luminescent layer or electronics, this is not had particular determination.Among the present invention, contain in the photocatalyst layer even the material that improves the characteristics of luminescence added to, the almost not unexpected influence of the wetability that contains photocatalyst layer after the rayed.
In the time of will containing photocatalyst layer and be located between EL layer and the anode, material as effective raising characteristics of luminescence, the typical case says, added the material that improves the hole injection properties in the hole injection layer of EL layer or the anode buffer layer in the past to, oxide, amorphous carbon, polyaniline, polythiofuran derivatives etc. such as aniline system, ス one バ one ス ト type amine system, phthalocyanine dye system, vanadium oxide, molybdenum oxide, ruthenium-oxide, aluminium oxide were for example arranged.The addition that these improve hole injection properties material is not damaging under the function that contains photocatalyst layer, is 10-90 weight %, best 30-70 weight %.
Active principle when containing photocatalyst layer and be located between EL layer and the anode for example can be enumerated following hole transporting material.
The dimer of＜cavity conveying material〉oxadiazole Xi, oxazole system, triazole system, thiazole system, triphenylmenthane system, polystyrene, pyrazoline system, hydrazone system, aromatic amine system, carbazole system, polyvinylcarbazole system, Stilbene system, ェ Na ミ Application system, piperazine system, triphenylamine system, butadiene-based, polycyclc aromatic compound system, Stilbene etc., from the little aspect of ionization potential, be more preferably butadiene-based, ェ Na ミ Application system, hydrazone system, triphenylamine system.As pi-conjugated in the cavity conveying agent be macromolecule, polyacetylene, polydiacetylene (Port リ ジ ァ セ チ レ リ Application), poly-(to phenylene), poly-(to phenylene sulfoether), polyphenylene oxide, poly-(1 are arranged, the 6-heptadiyne), poly-(to the phenylene ethylidene), poly-(2,5 inferior thienyls), (poly-(2,5-pyrroles), poly-(to phenylene sulfoether), poly-(4,4 '-biphenylene) etc.Move high-molecular complex as electric charge, polystyrene, AgClO are arranged
4, polyethylene naphthalenedicarboxylate TCNE, polyethylene naphthalenedicarboxylate P-CA, polyphenylene naphthalene DDQ, polyethylene
TCNE, poly-naphthalene acetylene TCNE, polyethylene anthracene Br
2, polyethylene anthracene I
2, polyethylene (PVC ヌ Le) anthracene TNB, poly dimethyl aminobenzene ethene CA, polyvinyl imidazole CQ, polyparaphenylene I
2Poly--1-vinylpyridine I
2, poly--4-vinylpyridine I
2, poly--right-1-phenylene I
2, polyvinyl pyridine TCNQ etc.Moving complex compound as low branch charge of the electron has TCNQ-TTF etc., as the metal complex macromolecule poly-copper phthalocyaine dye etc. is arranged.The addition of these cavity conveying materials is not damaging under the function that contains photocatalyst layer, is 10-90 weight %, best 30-70 weight %.
As will contain photocatalyst layer and be located between EL layer and the negative electrode time, effectively improve the material of the characteristics of luminescence, the typical case says, to add the material that improves Electron Injection Characteristics in the electron injecting layer of forward direction EL layer or the cathode buffer layer, materials such as aluminium lithium, lithium fluoride, strontium, magnesium oxide, magnesium fluoride, strontium fluoride, calcirm-fluoride, barium fluoride, aluminium oxide, strontium oxide strontia, calcium, poly methyl methacrylate, kayexalate are for example arranged.The addition that these improve the Electron Injection Characteristics material is not damaging under the prerequisite that contains the photochemical catalyst layer function, is 10-90 weight %, is preferably 30-70 weight %.
The active principle that adds as the allocation position restriction that is not contained photocatalyst layer, the following chromonic materials that adds in the typical luminescent layer that also can enumerate with forward direction EL layer.
＜pigment system〉cyclopentadiene derivant, tetraphenylbutadiene derivative, triphenylamine derivative, oxadiazole derivative, pyrazolo quinoline, talan benzene derivative, the derivative of talan arylene, シ ロ one Le derivative, thiphene ring compound, pyridine ring compound, ペ リ ノ Application derivative, perylene derivative, Oligopoly thiophene derivative, three fumaramide derivative, oxadiazole dimers, pyrazoline dimer.
＜metal complex system〉aluminium oxyquinoline complex compound, benzene oxyquinoline beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azo methyl zinc complex, haematoporphyrin zinc complex, europium complex, etc., central metal has Al, Zn, Be etc. or rare earth metals such as Tb, Eu, Dy, part that the metal complex of oxadiazole, thiadiazoles, benzene pyridine, phenyl benzimidazole, quinoline structure etc. is arranged.
＜macromolecular〉poly (phenylenevinylene) derivative, polythiofuran derivative, poly radical derivative, polysilane derivative, polyacetylene derivative, polyvinylcarbazole etc., poly-fluorene derivative.
The addition of these chromonic materials is not damaging under the prerequisite that contains the photochemical catalyst layer function, is 10-90 weight %, is preferably 30-70 weight %.
As no matter the allocation position that contains photocatalyst layer how, the active principle of interpolation can be enumerated following dopant material.
＜dopant material〉perylene derivative, coumarin derivative, rubrene derivative, quinacridone derivative, ス Network ァ リ ゥ system derivative, hematoporphyrin derivative, polystyrene pigment, aphthacene derivative, pyrazoline derivative, デ カ シ Network レ Application, Fenoxazoline (Off ュ ノ キ サ ゾ Application).The addition of these dopant materials is not damaging under the prerequisite that contains photocatalyst layer, is 10-90 weight %, is preferably 30-70 weight %.
＜slaine 〉
As the material of effective raising characteristics of luminescence, also can enumerate following slaine.FeCl
2、FeCl
3、Cr(NO
3)
3、CrCl
3、NaNO
3、Ca(NO
3)
2、Sr(NO
3)
2、Co(NO
3)
2、CoCl
2、Cd(NO
3)
2、Mg(NO
3)
2、Cu(CH
3COO)
2、Cu(NO
3)
2、Ni(NO
3)
2、Mn(NO
3)
2、MnCl
2、PbNO
3、RuCl
3、IrCl
4、Ir(NO
3)
3、ScCl
3、Sc(NO
3)
3、H
2PtCl
6、RhCl
3、Tb(NO
3)
3、Pr(NO
3)
3、Dy(NO
3)
3、Sm(NO
3)
3、Ga(NO
3)
3、Gb(NO
3)
3、Yb(NO
3)
3、NbCl
5、ZrCl
4、Zr(NO
3)
2、KNO
3、LiNO
3、HAsCl
4、Pd(NO
3)
2、Eu(NO
3)
2、Nd(NO
3)
2、NiCl
3、Ce(NO
3)
3、CsNO
3、Er(NO
3)
3、Ba(NO
3)
2、La(NO
3)
3、AgCl、CH
3CH(OH)COOAg、AgNO
3、TlNO
3、Y(NO
3)
3、Pb(NO
3)
2、Ho(NO
3)
3、Bi(NO
3)
3。These are 0.01-50 weight % with respect to containing titanium oxide and adhesive sum in the photocatalyst layer, are preferably 0.1-10 weight %.
(containing other compositions that use in the photocatalyst layer)
That uses among the present invention contains in the photocatalyst layer, in order to reduce the wetability of unexposed portion, can contain surfactant.These surfactants are decomposed by photochemical catalyst to be removed, unqualified to this, specifically can enumerate preferred as Japanese サ one Off ァ Network Application ト industry system: NIKKOL BL, BC, BO, each serial hydrocarbon system surfactant such as BB, E.I.Du Pont Company's system: ZONYL FSN, FSO, Asahi Glass system: サ one Off ロ Application S-141,145, big Japanese ィ Application キ system: メ ガ Off ァ ッ Network F-141,144, ネ ォ ス system: Off one ジ ェ Application ト F-200, F251, ダ ィ キ Application industry system: ュ ニ ダ ィ Application DS-401,402, ス リ one ェ system system: Off ロ ラ one De FC-170, system such as 176 fluorine such as grade or silicone-based non-ionic surface active agent.Also can use cation, anion system, amphoteric surfactant.
In the present invention, contain other the most suitable in photocatalyst layer compositions, for example can contain polyvinyl alcohol, unsaturated polyester (UP), acrylic resin, polystyrene, two allyl phthalate esters, ethylene propylene diene monomer, epoxy resin, phenolic resins, poly-urethane, melamine resin, Merlon, polychlorostyrene ethene, polyamide, polyimides, styrene butadiene ribber, neoprene, polypropylene, polybutene, polystyrene, polyvinyl acetate, nylon, polyester, polybutadiene, polybenzimidazoles, polyacrylonitrile, chloropropylene oxide, poly-sulfite, oligomer such as poly-isoprene, polymer.
In containing in the photocatalyst layer that the present invention uses, also can contain the photoactive composition sensitizing coloring matter of sensitizing photochemical catalyst.By adding this sensitizing coloring matter, can use low exposure just can change wetability, perhaps use the exposure of different wave length just can change wetability.
(the formation method that contains photocatalyst layer)
Do not have particular determination for the formation method that contains photocatalyst layer, for example by methods such as rotary coating, injection coating, dip coated, roller coating, curtain (PVC one De) coatings, the coating fluid that will contain photochemical catalyst is coated on the base material, can form.
When use contained coating fluids such as photochemical catalyst, as spendable solvent in the coating fluid, though there is not particular determination, for example can use alcohol such as ethanol, isopropyl alcohol was organic solvent.
When containing the ultraviolet hardening composition, be cured processing, also can form and contain photocatalyst layer by irradiation ultraviolet radiation as adhesive.
(acting on the irradiation light of photochemical catalyst)
Act on the irradiation light of photochemical catalyst, if can exciting light catalyst just can, unqualified to this.As such irradiation light, except ultraviolet ray, luminous ray, infrared ray, also can use electromagnetic wave shorter or more long wavelength, radioactive ray than these light.
For example, as photochemical catalyst, when using anatase titanium dioxide, because excitation wavelength is below 380nm, so can utilize ultraviolet ray to carry out the exciting light catalyst.As this ultraviolet light source of emission, mercury vapor lamp, metal halide lamp, xenon lamp, ェ キ シ マ レ one ザ one, and other ultraviolet light source are arranged.
Other produce wetability by rayed and be varied to layering.
Be varied to layering as wetability, contain the photocatalyst layer, also can use the organic polymer resin layer except above-mentioned.Organic polymers such as Merlon, polyethylene, poly-phthalic acid second diester, polyamide, polystyrene, pass through irradiation ultraviolet radiation, particularly irradiation contains the many ultraviolet rays of the following short wavelength's composition of a large amount of 250nm, can carry out the macromolecular chain cut-out degraded, as a result, produce surface roughening, change wetability, form high-hydrophilic, promptly with the compatibility of laminated material.Utilize this effect, illumination part is divided and non-rayed partly produces the very wetability of big-difference, thus can raising and laminated material and compatibility, can make laminated material formation pattern.
The EL layer
Be arranged on the EL layer on the EL element of the present invention, do not have particular determination, as long as it is just passable to produce electroluminescence.The EL layer is arranged on (between the 1st electrode and the 2nd electrode) on the 1st electrode, can be set directly on the 1st electrode, also can be as required, and setting contains photocatalyst layer or other layers between the 1st electrode and EL layer.
In the EL layer of the present invention,, can be provided with as lower floor as its inscape; As the luminescent layer of essential layer, as random layer, to luminescent layer carry the electron supplying layer (these are referred to as charge transport layer sometimes) of the hole transporting layer in hole and conveying electronic, and to the hole injection layer of luminescent layer or hole transporting layer injected hole with inject the electron injecting layer (these are referred to as electric charge injection layer sometimes) of electronics to luminescent layer or electron supplying layer.
As these materials that constitutes the EL layer, following material is for example arranged.
(luminescent layer)
＜pigment system〉cyclopentadiene derivant, tetraphenylbutadiene derivative, triphenylamine derivative, oxadiazole derivative, pyrazoles quinoline, talan benzene derivative, talan fragrance ene derivative, シ ロ one Le derivative, thiphene ring compound, pyridine ring compound, perylene derivative, Oligopoly thiophene derivative, three fumaramide derivative, oxadiazole dimers, pyrazoline dimer.
＜metal complex system〉aluminium oxyquinoline complex compound, benzo oxyquinoline beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azo methyl zinc complex, haematoporphyrin zinc complex, europium complex etc., central metal has Al, Zn, Be etc. or rare earth metals such as Tb, Eu, Dy, metal complexs such as ligand You oxadiazole, thiadiazoles, benzo pyridine, phenyl benzimidazole, quinoline structure.
＜macromolecular〉poly (phenylenevinylene) derivative, polythiofuran derivative, poly radical derivative, polysilane derivative, polyacetylene derivative, polyvinylcarbazole etc., poly-fluorene derivative.
(dopant material) perylene derivative, coumarin derivative, rubrene derivative, quinacridone derivative, ス Network ァ リ ゥ system derivative, hematoporphyrin derivative, polystyrene pigment, aphthacene derivative, pyrazoline derivative, デ カ シ Network レ Application, Fenoxazoline.
(hole injection layer (anode buffer material))
Oxide, amorphous carbon, polyaniline, polythiofuran derivatives such as aniline system, an array of stars formula type amine system, phthalocyanine dyestuff system, vanadium oxide, molybdenum oxide, ruthenium-oxide, aluminium oxide.
(electron injecting layer (negative electrode padded coaming))
Aluminium lithium, lithium fluoride, strontium, magnesium oxide, magnesium fluoride, strontium fluoride, calcirm-fluoride, barium fluoride, aluminium oxide, strontium oxide strontia, calcium, poly methyl methacrylate, kayexalate.
(the next door layer material in the EL layer)
Next door layer, this next door layer can be set in the EL layer, particularly useful when the EL layer combination that will send out different color light.As such material, there is photonasty to gather inferior acyl amide resin, acrylic resin, other also have light-cured type resin, thermohardening type resin, hydrophobic resin etc.
The 1st electrode and the 2nd electrode
In this specification, with the electrode that at first is provided be called the 1st electrode, the electrode that is provided with on the EL layer subsequently is called the 2nd electrode.Though these electrodes are unqualified, electrode preferably is made of anode and negative electrode, and the 1st electrode at this moment can be any in anode, the negative electrode.No matter be anode, or negative electrode in any, be transparent or semitransparent shape.When forming transparency electrode, can be the direct viewing type EL element,, can form the reflection-type EL element by either party is formed reflecting electrode.
As anode, preferably be easy to the big conductive material of worker's function of injected hole, otherwise, as negative electrode, preferably be easy to inject the little conductive material of worker's function of electronics.Also several materials can be mixed.Any electrode, its resistance is the smaller the better, generally uses metal material, also can use organic substance or inorganic compound.Specifically, best anode material has ITO, indium oxide, gold, polyaniline, as cathode material magnesium alloy (MgAg etc.), aluminium alloy (AlLi, AlCa, AlMg etc.), calcium metal is arranged.
When forming the 1st electrode and the 2nd electrode, by electrode pattern mask, electrode evaporation material formation on the pattern of square crossing mutually, thickness is 10nm-1 μ m usually, can form the EL element of simple matrix type.When on having the substrate of thin-film transistor, electrode being set, can form activity matrix type EL element.
Base material
Base material among so-called the present invention is the material that electrode and EL layer are set thereon, can also can be formed by opaque material by transparent material as required.In EL element of the present invention, base material though can be used as the 1st electrode, normally on the substrate surface that keeps intensity, directly or by the intermediate layer is provided with the 1st electrode.
As base material, can be tabular substrate, film, bulk etc., for example glass plate etc. is arranged.As base material, so long as can pay supportive material to EL element, just unqualified.
3 kinds of schemes of insulating barrier-Di and the 4th kind of scheme
In the best style of EL element of the present invention, can partly form 1 layer insulating at least containing on the photocatalyst layer.This insulating barrier is preferably formed by the material that contains light-cured resin such as ultraviolet curable resin or heat-curing resin, can stop supplying with electric charge by electrode to the EL layer, and this insulating barrier part as non-luminous component, can be formed pattern.
Among the present invention, when using ultraviolet curable resin, the most favourable in the manufacturing process as insulating barrier.For example, carry out pattern exposure on the photocatalyst layer containing, only utilizing exposure to improve the material that coating on the part of wetability forms insulating barrier, by going up irradiation ultraviolet radiation to whole, make the insulating barrier sclerosis, improve the wetability that contains the photocatalyst layer exposed portions serve that does not form insulating barrier simultaneously.Thereby, containing formation EL layer on the photocatalyst layer.At this moment, the EL layer only contain photocatalyst layer do not have form (promptly on the insulating barrier part, only be that pattern exposure partly forms the EL layer), also can on whole, form (promptly, contain photocatalyst layer do not have all forms on insulating barrier part and the insulating barrier), suitable selections such as goods that can be as requested and manufacturing expense.
Manufacture method
1 kind of scheme of-Di-
The manufacture method of EL element of the present invention, on containing photocatalyst layer, be provided with in the scheme of EL layer, manufacture method comprises following operation, promptly, in the operation that forms the 1st electrode on the base material, forming the operation that contains photocatalyst layer on above-mentioned the 1st electrode, will above-mentionedly contain photocatalyst layer carry out pattern exposure, utilize wetability difference form the operation of pattern, on the above-mentioned exposed portion that contains photocatalyst layer coating EL layer forming liquid, form the operation of the EL layer of above-mentioned formation pattern, the operation of formation the 2nd electrode on this EL layer.
The present invention is containing the EL element that the 1st electrode scheme is set on the photocatalyst layer, be in said method, be included in base material rather than on the 1st electrode, form and contain photocatalyst layer, be to contain above-mentioned the 1st electrode formation of coating liquid on the exposed portion of photocatalyst layer, form outside the 1st electrode operation of above-mentioned formation pattern other make the same with said method.
The present invention is containing the EL element that the 2nd electrode scheme is set on the photochemical catalyst, be in said method, to comprise following operation, on the EL layer on the 1st electrode, form and contain photocatalyst layer, above-mentioned the 2nd electrode of coating forms liquid on the exposed portion of photocatalyst layer containing, form the 2nd electrode of above-mentioned formation pattern, in addition, other make the same with said method.
Except containing photocatalyst layer and thereon the cambium layer, can carrying out according to common EL element manufacture method.
Be used at the coating liquid that contains each layer of formation on the photocatalyst layer, for example, EL layer forming liquid, the 1st electrode form liquid, the 2nd electrode forms liquid (these general designations are made coating fluid), solvent is water isopolarity solvent preferably, use the coating fluid of this polar solvent, just improving and contain the buffering tendency of wetability, enhancing and the unexposed portion of photocatalyst layer exposed portion, is very favourable to coating fluid being formed aspect such as pattern.
To containing photocatalyst layer coating coating fluid, method of spin coating, ink-jet method, dip coated method, scraper rubbing method are for example arranged and to the dripping method that contains photocatalyst layer.
Containing the pattern that forms layers such as EL layer, the 1st electrode, the 2nd electrode on the photocatalyst layer,, also can under cambial state after the curing, only peel off the low part of wetability except forming the method for patterning with the coating fluid state before solidifying.Specifically, for example have, in the method that base material is tilted, the method that is blown into air, after solid shapeization, peel off the method that attaches adhesion zone etc.
When EL element of the present invention is the display unit of panchromatic demonstration, preferably form and the corresponding display element of pattern according to the wetability difference that contains photocatalyst layer.
2 kinds of schemes of-Di-
As be varied in the layering method that forms luminescent layer to wetability, utilize ink-jetting style, pattern printing, make luminescent material form the coating process, vapour deposition method etc. of pattern.When utilizing ink-jetting style, mode of printing, be varied to layering, make the formation position of single-color layer formation position or R, G, each luminescent layer of B carry out pattern exposure as wetability.Subsequently,, utilize ink discharge device, printing equipment, carry out pattern application with each chromatic ink according to this pattern.When doing like this, be varied in the layering in wetability, according to monochromatic or R, G, B trichromatic diagram case, owing to do not have the position of irradiates light to repel ink, so each chromatic ink can be exactly attached on the pattern form.Subsequently, utilize and common the same EL element manufacture method, can produce the good EL element of pattern precision.
Wetability is varied to the rayed position of layering, owing to improved wetability, ink is evenly expanded, and obtains to improve the effect of film thickness uniformity.
Generally say, macromolecular material is to utilize the rubbing method of ink-jet method, rubbing method, pattern print process, low molecular material, though utilize the vapour deposition method film forming, but, will hang down molecular material and be dispersed in resin etc., the same with macromolecular material, also can utilize the rubbing method film forming, otherwise, even macromolecular material system utilizes vapour deposition method also can form lamination.
By on wetability variation component layer evenly coating can form monochrome or R, G, B three looks.At R, G, during B three looks, be varied to layering as wetability, to R, G, after pattern exposure is carried out in the formation position of any look among the B, carry out dip coated with any ink of the same colour, at the position that does not have irradiates light, utilize the method for repelling ink, the pattern that carries out first look forms, then, evenly be coated with thereon after wetability is varied to layering, pattern exposure is carried out in formation position to second look, and is same, and the pattern that carries out second look forms, at last, evenly be coated with after wetability is varied to layering again, exposed in the formation position of the 3rd look, the pattern that carries out the 3rd look equally forms.Like this, but alternate configurations R, G, B three-colour light-emitting layer can make the good EL element of pattern precision.
Utilize even evaporation also can form monochrome or R, G, B three looks.This situation, the pattern that is varied to layering by wetability forms, at the position of irradiates light, very high with the associativity of evaporation layer, in the part of irradiates light not, very low with the associativity of evaporation layer, and utilize to peel off easily and remove the stickup band that is attached on the evaporation layer that does not have the irradiates light part.When forming the method for R, G, B three looks, the formation method with above-mentioned even rubbing method can form equally, obtains the good EL element of pattern precision.
Luminescent layer forms material, in ink-jetting style, pattern mode of printing, even coating method, can adopt formation such as water-soluble solution, organic solvent solution.When evaporation, also can use macromolecular material, but only to hang down molecular material as example, the thickness of luminescent layer is 1nm-2 μ m, is preferably 10nm-200nm.
Below, the manufacture method to the 1st kind of EL element of the 2nd kind of scheme of the present invention describes according to Fig. 8.The 1st kind of EL element, at first, shown in Fig. 8 (a), on pattern electrode 81, after being varied to layering with even rubbing method lamination wetability, shown in Fig. 8 (b), use and the mask of electrode pattern identical patterns or exposed portion is identical with electrode pattern or than its broader mask, carry out ultraviolet irradiation, the wetability on the electrode is varied to the layering surface forms the rayed position.At this moment, in order to prevent the short circuit of 81 at electrode, with insulating barrier 89 will form between electrode 81 marginal portions of pattern and the electrode 81 topped firmly.
Then, on electrode pattern top, with lamination luminescent layers such as ink-jetting styles.When using coating fluid to carry out lamination, the luminescent layer that does not have to repel coating on the rayed position that is varied to layering in wetability forms material, only lamination luminescent layer exactly on the rayed position on the electrode.When utilizing evaporation or comprehensively coating forms, the luminescent layer in not having the rayed position touch with adhesion zone etc., and can peel off removal.At last, omit in the diagram, relative pattern electrode and electrode 81 square crossings are carried out the pattern evaporation, manufacture the 1st kind of EL element.
The 2nd kind of EL element manufacture method to the 2nd kind of scheme describes according to Fig. 9.The 2nd kind of EL element shown in Fig. 9 (b), utilizes the negative patterned mask of electrode pattern or exposed portion than patterned mask narrower between electrode, carries out ultraviolet irradiation, the wetability in the boundary member between electrode is varied to layering forms the rayed position.At this moment, preventing that short circuit is a purpose between the electrode 91, will form with insulating barrier 99 between the marginal portion of electrode 91 of pattern and the electrode 91 topped firmly.
Then use ink-jetting style etc., lamination next door layer between electrode pattern.When utilizing coating method to form lamination, the next door layer that does not carry out repulsion coating on the rayed position that is varied to layering in wetability forms material, only forms pattern on the rayed position exactly.In addition, when utilizing evaporation to form, will not carry out the rayed position, and touch with pasting band etc., and can peel off removal.
Shown in Fig. 9 (c), irradiation ultraviolet radiation is varied to layering with wetability on the electrode and forms the rayed position, shown in Fig. 9 (d), between isolating, and on electrode, uses lamination luminescent layers such as ink jet mode.
At last, diagram is omitted, and with relative pattern electrode and electrode 91 square crossing evaporation patterns, manufactures the 2nd kind of EL element.
The 3rd kind of EL element manufacture method to the 2nd kind of scheme describes according to Figure 10.The 3rd kind of EL element at first, shown in Figure 10 (a), on base material 106, after the coating wetability is varied to layering 102, forms pattern electrode.At this moment, the wetability that preferably will form electrode 101 parts is varied to layering, gives and carries out pattern exposure earlier.Then, shown in Figure 10 (b), utilizing ink-jetting style etc., behind the lamination luminescent layer of pattern electrode top, shown in Figure 10 (c), is the boundary member between pattern electrode, wetability is varied to layering forms the rayed position by mask.Then, shown in Figure 10 (d), use lamination next door layers such as ink-jetting style.At last, diagram is omitted, and relative pattern electrode and electrode 101 square crossings are carried out the pattern evaporation, make the 3rd kind of EL element.
3 kinds of styles of-Di-
The manufacture method of EL element of the present invention, feature are to contain on the photocatalyst layer, utilizing rayed, form the different pattern of wetability, utilize the difference of this wetability, form EL layer or insulating barrier on the high part of wetability, it is luminous to form the pattern different with electrode pattern.
As concrete style is to comprise the EL element manufacture method that has the EL layer between comparative electrode and the above-mentioned comparative electrode, and the method for making EL element comprises following operation.Promptly, on above-mentioned side's electrode, formation contain photocatalyst layer operation, the above-mentioned photocatalyst layer that contains is carried out pattern-like exposure, form in electric charge injection layer, charge transport layer and the luminescent layer operation of one deck at least by the different operations that form pattern of wetability, on the above-mentioned exposed portion that contains photocatalyst layer, form the operation of the opposing party's electrode.
As another kind, can enumerate the method that contains following operation, promptly, contain utilize on the photocatalyst layer that wetability is different and form pattern after, containing the operation that forms insulating barrier on the exposed portion of photocatalyst layer, after part that insulating barrier is not set or blanket exposure, operation that forms the EL layer on the photocatalyst layer containing of insulating barrier and the operation that forms the opposing party's electrode are being set.
As another scheme scheme, can enumerate the method that contains following operation, promptly, contain utilize on the photocatalyst layer that wetability is different and form pattern after, contain on the exposed portion of photocatalyst layer form the operation that forms insulating barrier by ultraviolet curable resin, to after being provided with the containing photocatalyst layer and carry out blanket exposure of insulating barrier, form in electric charge injection layer, charge transport layer and the luminescent layer operation of one deck at least and form the operation of the opposing party's electrode.
In said method, as forming the method that forms EL layer or insulative resin layer on the photocatalyst layer that contains of pattern, for example utilize coating, ink-jet or evaporation, the material that makes EL layer or insulative resin layer is attached to containing on the photocatalyst layer.In this case, the best way is, adhering to constantly, forms pattern, as requested, before the solid shapeization back or solid shapeization after coating comprehensively, by applying physics or chemical energy, removes the low part of wetability, the formation pattern.As this removal method, for example there is utilization to paste peeling off of band and corrosion etc.
EL element of the present invention is made typically as stated above, also can with and above-mentioned diverse ways manufacturing, just with the said method diverse ways, also can produce the EL element of different structure, for example, at electrode with contain other layers of lamination between the photochemical catalyst.
4 kinds of schemes of-Di-
The present invention, the EL element contain the photochemical catalyst layered scheme is set between several layers of EL layer, with the 1st kind of method that scheme is identical in, contain following operation, promptly, not on the 1st electrode, contain photocatalyst layer, containing coating 2EL layer forming liquid on the exposed portion of photocatalyst layer but on the 1EL layer, form, form the 2EL layer of above-mentioned formation pattern, contain photocatalyst layer and contain the material that improves the characteristics of luminescence, in addition, other with the 1st kind scheme is the same makes.
The present invention, containing the EL element that insulator layer schemes is set on the photocatalyst layer, comprise following operation in the manufacture method, promptly be coated with layer of cloth on the exposed portion of photocatalyst layer and form liquid containing, utilize methods such as drying, hot curing, photocuring that insulating barrier is formed liquid-solidization, form insulating barrier, contain photocatalyst layer and contain the material that improves the characteristics of luminescence, in addition, other with the 1st kind scheme is the same makes.
Other EL element contains the material that improves the characteristics of luminescence except containing photocatalyst layer, and other are made with the 1st kind of method that scheme is identical.
According to the present invention, provide can easy manufacturing EL element and manufacture method thereof.
EL element of the present invention can obtain the luminescent layer of accurate pattern precision, and display performance is good simultaneously, does not also have the problem of conducting between said electrode.
And then, can provide the EL element that can carry out the easy manufacture method of the luminous EL element of pattern and utilize this method to make according to the present invention.
The EL element that the pattern formation easiness and the good characteristics of luminescence have both in the time of can providing manufacturing according to the present invention, and manufacture method.
Embodiment
Below with implementing to further specify the present invention.The numbering of embodiment, corresponding with 1-4 kind scheme of the present invention, pay the symbol of A, B, C, D respectively.
Example A-1-1
Contain photochemical catalyst layer forming liquid and EL layer forming liquid by following composition modulation.
(containing photochemical catalyst layer forming liquid A-1)
Anatase type TiO 2 sol (the former industry of stone (strain) system
ST-K03) 6 weight portions
Fluothane oxosilane (ト one ケ system プ ロ ダ Network ッ
(strain) system MF-160E) 1.26 weight portions
1N hydrochloric acid 12 weight portions
Isopropyl alcohol 58.5 weight portions
(about the formation that contains photocatalyst layer, the affirmation that reaches the wetability variation)
Above-mentioned composition contained the photocatalyst layer coating fluid, be coated on the washed glass substrate with spin coater, carry out 10 minutes dried under 150 ℃, be hydrolyzed, polycondensation reaction, photochemical catalyst is firmly fixed in the organosiloxane, forms the transparent photocatalyst layer that contains of thickness 20nm.
To the photocatalyst layer that contains that obtains, by mask, with mercury vapor lamp (wavelength 365nm), with 70mW/cm
2Illumination carry out 50 second patterned illumination.Use contact angle determination device (consonance interface science (strain) system CA-Z type), drip water droplet by micro syringe, after 30 seconds, measure rayed position and the non-irradiated site contact angle to water, the result is, in non-irradiated site, the contact angle of water is 142 °, in contrast, and in irradiated site, the contact angle of water is below 10 °, thereby can confirm to utilize the wetability difference of irradiated site and non-irradiated site to form pattern.
(EL layer forming liquid A-1)
Polyvinylcarbazole (ァ Na Application (strain) system .Lot.k81127) 70 weight portions
Oxadiazole compound (with the pure pharmaceutical worker's industry of light (strain) system) 30 weight portions
Coumarin 6 (Aldrich.Chem.Co system) 1 weight portion
1,2-dichloroethanes (pure chemistry system) 3367 weight portions
At first, at interval with 24 μ m, 162 μ m live widths form on the ito glass substrate of pattern, rotary coating Port ジ レ ジ ス (ZPP-1850: Japanese ゼ ォ Application (strain) system), form 1 μ m thick film, after under 110 ℃ dry 90 seconds, with 150mJ, the light of illumination wavelength 365nm between the live width of ITO is with the video picture of organic amine imaging liquid.Under 130 ℃, it was baked 10 minutes, between ITO, form insulating barrier., utilize rotary coating thereon, be coated with the above-mentioned photochemical catalyst layer forming liquid A-1 that contains comprehensively, 150 ℃ of following dried were hydrolyzed and polycondensation reaction after 10 minutes, and photochemical catalyst is securely fixed in the organosiloxane, formed thickness
The transparent photocatalyst layer that contains.Then, by mask, with mercury vapor lamp (wavelength 365nm), with 70mW/cm
2Illumination shone for 50 seconds, only on the ITO live width, contain in the 170 wide μ m zones of 4 μ m about the photocatalyst layer position and carry out patterned illumination.
Then, utilize spin coater, in containing on the photocatalyst layer of patterned illumination, coating poly-(3 comprehensively, 4) ethene dioxythiophene/polystyrolsulfon acid ester (being called for short PEDOT/PSS, trade name Baytron PTP AI4083, バ ィ ェ Le society), be dried under 100 ℃, only the irradiated site coating film thickness on the ITO live width approximately
PEDOT.Be coated with above-mentioned EL layer forming liquid A-1 with spin coater more comprehensively.At last, use mask equally, with the pattern square crossing formation upper electrode of ITO and organic EL layer, evaporation LiF, thickness
AM aluminum metallization, thickness
ITO electrode and top Al electrode as address electrode, by driving, are obtained green emitting.
Example A-1-2
Except the weight portion of the solvent isopropyl alcohol that will contain photochemical catalyst layer forming liquid A-1 reduces, form thickness
Contain outside the photocatalyst layer, other the same EL element made from routine A-1-1 obtain green emitting.
Example A-1-3
Except not being provided with the PEDOT, other the same EL element made from routine A-1-1 obtain green emitting.
Example A-1-4
Except not being provided with the PEDOT, other the same EL element made from routine A-1-2 obtain green emitting.
Example A-1-5
Except containing the photochemical catalyst layer forming liquid A-2 by following composition modulation, other the same EL element made from routine A-1-3 obtain green emitting.
(containing photochemical catalyst layer forming liquid A-2)
The inorganic smears of photochemical catalyst (the former industry of stone (strain) system ST-K03) 2 weight portions
Fluothane oxosilane (ト one ケ system Block ロ ダ Network ッ
(strain) system MF-160E) 0.001 weight portion
2N hydrochloric acid 4 weight portions
Isopropyl alcohol 7.5 weight portions
Example B-1-1
Modulate following coating fluid, replace the organic EL layer coating fluid among the routine A-1-3.
The green light emitting layer coating fluid ... (the organic EL layer coating fluid identical) with routine A-1-3
The red light emitting layer coating fluid ... (replacing coumarin 6 among the routine A-1-3) with Na ィ Le レ ッ De
Cyan luminescent layer coating fluid ... (Yong perylene compound replaces the coumarin 6 among the routine A-1-3)
The structural formula of above-mentioned each composition is as follows.
Na ィ Le レ ッ De structural formula
The perylene structural formula
Use ink discharge device, above-mentioned coating fluid of all kinds is coated on the corresponding position of R, G, B three looks, carry out patterned illumination, make with the method identical with routine A-1-3.Containing on the photocatalyst layer on the ITO electrode live width of the ITO electrode base board that forms insulating barrier, alternately assortment separately after the coating, 80 ℃ dry 30 minutes down, only forming respectively at the illumination part bit interleaving, thickness is the 3 look luminescent layers of 100nm.
And then, use mask, form upper electrode like that with ITO electrode and the square crossing of organic EL layer pattern, evaporating Al Li alloy forms the 150nm thickness, makes EL element.
ITO electrode and top AlLi alloy electrode are driven as address electrode, obtain 3 look EL element of the good simple matrix type of display performance.
Example B-1-2
Except using intaglio printing to replace ink discharge device among the routine B-1-1, alternately separately outside the coating, other the same EL element made from routine B-1-1.
ITO electrode and top AlLi alloy electrode are driven as address electrode, obtain the good simple matrix type of display performance 3 look EL element.
Example B-1-3
Will be at interval, and in 200 μ m live widths with 200 μ m, after the ito substrate that forms pattern with thickness 0.15 μ m is cleaned, utilize the method identical with the above-mentioned comprehensive film forming of photocatalyst layer, the thickness 20nm of containing with routine B-1-1.Then, use mask, with mercury vapor lamp (wavelength 365nm), with 70mW/cm
2Illumination, shone 50 seconds, only on the ITO electrode does not have the live width of film forming, contain the photocatalyst layer position and carry out patterned illumination.
Utilize the dip coated method, the ultraviolet curable resin of 5 weight % initators (the different chemicals of vapour Bart (strain) system ダ ロ キ ュ ァ 1173) is added in coating for ultraviolet curing resin (Japanese chemical drug (strain) system PEG400DA), only do not contain photocatalyst layer position, coating lamination ultraviolet curable resin liquid on the live width of film forming at light-struck ITO electrode.
It is used mercury vapor lamp (wavelength 365nm), with 70mW/cm
2Comprehensively irradiation 50 seconds of illumination, ultraviolet curable resin is solidified, form thickness 0.2 μ m, 200 μ m next door layer at interval simultaneously, for containing the wetability at photochemical catalyst position on the live width that improves ITO electrode film forming, makes contact angle be roughly 0 °.
Under this state, use ink discharge device, with green, redness, each the organic EL layer coating fluid of cyan that uses among the routine B-1-1, on ITO electrode live width, contain alternately separately coating on the photocatalyst layer.It is dry under 80 ℃, to form the organic EL layer of thickness 100nm between isolating.
And then, the same with routine B-1-1, use same mask, with the pattern square crossing formation upper electrode of ITO electrode and organic EL layer, with 200 μ m live widths, 200 μ m at interval, evaporating Al Li alloy forms the 150nm thickness, makes EL element.
ITO electrode and top AlLi alloy electrode are driven as address electrode, obtain the good simple matrix type of display performance 3 look EL element.
Example B-1-4
On the washed glass substrate, use method of spin coating, be coated with put down in writing among the routine B-1-1 contain the photocatalyst layer masking liquid, under 150 ℃, dried 10 minutes is hydrolyzed, and carries out polycondensation reaction, photochemical catalyst is firmly fixed in the organosiloxane, forms the transparent photocatalyst layer that contains of thickness 20nm.Contain on the photocatalyst layer at this, use mask, with 200 μ m live widths, 200 μ m at interval, with mercury vapor lamp (wavelength 365nm), with 70mW/cm
2Illumination, shine after 50 seconds, ITO is sprayed the film that forms 0.15 μ m.
Then, utilize the drop spreader to be coated with organic EL layer coating fluid among the routine B-1-1, only coating lamination organic EL layer coating fluid on the ITO layer.It 80 ℃ baker inner drying 30 minutes, is obtained organic EL pattern cambium layer of 100nm thickness.
Then, from forming a side of organic EL layer, by the mask pattern of 200 μ m live widths, to not forming the containing on the photocatalyst layer of organic EL layer position, with mercury vapor lamp (wavelength 365nm), with 70mW/cm
2Illumination, shine after 50 seconds, use ink jet device to be coated with the ultraviolet hardening resin liquid of routine B-1-5 record, use mercury vapor lamp (wavelength 365nm) again, with 70mW/cm
2Illumination, by mask,, shone 50 seconds only to ultraviolet hardening resin liquid coated portion, the next door layer of 0.2 μ m thickness is set.
The same with routine B-1-1, use same mask, with the pattern square crossing formation upper electrode of ITO electrode and organic EL layer, with 200 μ m live widths, 200 μ m at interval, evaporating Al Li alloy forms the thick film of 150nm, makes EL element.
Electrode and top AlLi alloy electrode are driven as address electrode, obtain the monochromatic EL element of the good simple matrix type of display performance.
Example B-1-5
Except using ink discharge device, separately be coated with green, redness, the cyan organic EL layer coating fluid put down in writing among the routine B-1-1, replace that monochromatic organic EL layer is with outside the coating fluid among the routine B-1-4, other the same EL element made from routine B-1-4 obtain the good simple matrix type of display performance 3 look EL element.
Example B-2-1
Except forming thickness
Contain outside the photocatalyst layer, other the same EL element made from routine B-1-1 can not get 3 colo(u)r streak patterns of EL layer.
Example B-2-2
Except forming thickness
Contain outside the photocatalyst layer, other the same EL element made from routine B-1-1 do not obtain luminous.
Example B-2-3
Except not containing the photocatalyst layer, other the same EL element made from routine B-1-1 do not obtain 3 colo(u)r streak patterns of EL layer.
Example B-2-4
Except PEDOT is set, replace and contain outside the photocatalyst layer, other the same EL element made from routine B-1-1 do not obtain 3 colo(u)r streak patterns of EL layer.
Example C-1-1
(modulation contains the photocatalyst layer coating fluid)
At first contain the coating fluid that photocatalyst layer is used by following composition modulation.
The inorganic smears of photochemical catalyst (the former industry of stone (strain) system ST-K03) 6 weight portions
Fluothane oxosilane (ト one ケ system Block ロ ダ Network ッ
(strain) system MF-160E) 1.26 weight portions
1N hydrochloric acid 12 weight portions
Isopropyl alcohol 58.5 weight portions
(film forming that contains photocatalyst layer)
On the washed glass substrate, with the above-mentioned photocatalyst layer masking liquid that contains of method of spin coating coating, 150 ℃ of following dried were hydrolyzed and polycondensation reaction after 10 minutes.Photochemical catalyst is firmly fixed in organic quarrel oxygen alkane, forms the thick photocatalyst layer that contains of transparent 20nm.
(utilization contains the different patterns that form of wetability in the photocatalyst layer)
By mask, with mercury vapor lamp (wavelength 365nm), with 70mW/cm
2Illumination, the above-mentioned photocatalyst layer that contains is carried out 50 seconds patterned illuminations, (consonance interface science (strain) system (CA-Z) is measured irradiated site and the non-irradiated site contact angle to water with the contact angle determination device.Mensuration is to drip water droplet with microsyringe to carry out after 30 seconds.As a result, the water contact angle in the non-irradiated site is 142 °, and is opposite with it, and the water contact angle in the irradiated site is below 10 °, thereby affirmation can utilize the difference of irradiated site and non-irradiated site wetability to form pattern.
(the luminescent layer modulation of coating fluid)
Form the masking liquid that luminescent layer is used by following composition modulation organic EL.
Polyvinylcarbazole 70 weight portions
Coumarin 61 weight portion
Oxadiazole compound 30 weight portions
1,1,2 trichloroethanes, 663 weight portions
(making of organic EL)
After ito substrate cleaned, with the above-mentioned comprehensive film forming of photocatalyst layer that contains, formation 20nm thick film.Then, by 5mm quadrangle cave mask at interval, with mercury vapor lamp (wavelength 365nm), with 70mW/cm
2Illumination carry out 50 seconds the irradiation.
Utilize method of spin coating again, be coated with the masking liquid that organic EL layer is used on the photocatalyst layer comprehensively, only on the dimetric irradiated site of 5mm, be coated with organic EL layer in containing of patterned illumination.It is carried out drying under 80 ℃, only form the luminescent layer of thickness 100nm at irradiated site.
Thereon, as upper electrode, evaporating Al Li alloy forms the thick film of 500nm comprehensively, makes EL element, and when luminous, it is luminous to obtain pattern.
Example C-1-2
The same with routine C-1-1, after ito substrate cleaned, with the above-mentioned comprehensive film forming of photocatalyst layer that contains, the thick film of formation 20nm.Then, by the spacing mask in 5mm quadrangle cave, with mercury vapor lamp (wavelength 365nm), with 70 mW/cm
2Illumination irradiation after 50 seconds, rotary coating is as the commercially available conductivity coating fluid (PEDOT: Baeyer society system), only in 5mm dimetric rayed partly be coated with coating fluid of hole injection layer with coating fluid.It in 80 ℃ of bakers, was heated 30 minutes, form the hole injection layer of thickness 50nm with the dimetric pattern of 5mm.Be coated with the luminescent layer of routine C-1-1 thereon, it is dry under 80 ℃, and holomorphism becomes the luminescent layer of thickness 100nm comprehensively.
As upper electrode, evaporating Al Li alloy forms the thick film of 500nm comprehensively, makes EL element thereon, and when luminous, it is luminous to obtain pattern.
Example C-1-3
After ito substrate cleaned, with the above-mentioned comprehensive film forming of photocatalyst layer that contains, the thick film of formation 20nm.Then, the dimetric part of 5mm is formed mask, other parts are with mercury vapor lamp (wavelength 365nm), with 70mW/cm
2Illumination, shine after 50 seconds, add the ultraviolet curable resin liquid of 5 weight % initators (the different chemicals of vapour Bart (strain) system trade name ダ ロ キ ュ ァ 1173) for commercially available ultraviolet curable resin (Japanese chemical drug (strain) system, trade name PEG400DA) with the rotary process coating, except that 5mm quadrangle part, the coating ultraviolet curable resin.Subsequently, to comprehensively, utilize mercury vapor lamp (wavelength 365nm) with 70mW/cm
2Illumination irradiation 50 seconds, ultraviolet curable resin is solidified, improve the wetability of 5mm quadrangle part simultaneously.Be coated with the luminescent layer of routine C-1-1-2 thereon, after 80 ℃ of following dryings, as upper electrode, evaporating Al Li alloy forms the thick film of 500nm comprehensively, makes EL element comprehensively, and when luminous, it is luminous to obtain pattern.
Example D-1-1
Modulate following coating solution
(coating fluid D-1, contain the photochemical catalyst layer forming liquid)
The inorganic smears of photochemical catalyst (the former industry of stone (strain) system ST-K03) 6 weight portions
Fluothane oxosilane (ト one ケ system プ ロ ダ Network ッ
(strain) system MF-160E) 1.26 weight portions
1N hydrochloric acid 12 weight portions
Isopropyl alcohol 58.5 weight portions
Mix above-mentioned each material successively, added thermal agitation 20 minutes under 100 ℃, use 10 weight portion isopropanol again, with it as coating fluid D-1 (be called for short make DSR with photochemical catalyst).
(coating fluid D-2 and coating fluid D-3, add to improve characteristics of luminescence material contain the photochemical catalyst layer forming liquid)
With above-mentioned coating fluid D-1 and poly-3,4-ethene dioxythiophene/polystyrolsulfon acid ester aqueous dispersions (being called for short PEDOT/PSS, trade name Baytron PTPAI4083, バ ィ ェ Le society) by weight, be respectively and mixed in 2: 1,1: 2, it is taken as coating fluid D-2,3 respectively.
(coating fluid D-4-6)
With 0.0324gFeCl
3Be dissolved in the 20g isopropyl alcohol, this solution of 0.157g and 4g coating fluid D-1 are mixed, the coating fluid that obtains is taken as D-4.
In coating fluid D-4, replace FeCl with 0.0483g nitric acid ketone (II) trihydrate
3Outward, other are identical with D-4, are taken as coating fluid D-5.
In coating fluid D-4, replace FeCl with 0.056g manganese nitrate (II) 6 hydrates
3Outward, other are identical with D-4, are taken as coating fluid D-6.
(coating fluid D-7, EL layer forming liquid)
Poly-fluorene derivative 1 weight portion
Dimethylbenzene 66.67 weight portions
Synthetic by the following method poly-fluorene derivative.
Flow down at drying nitrogen, 5.0g (30m mol) fluorenes is dissolved in during dry tetrahydrochysene skin mutters, under-78 ℃, after wherein dripping 22ml (35mmol) 1.6M n-BuLi hexane solution ,-78 ℃ were stirred 1 hour down.Then,, stirred 1 hour down, at room temperature stirred again 1 hour at-78 ℃ toward wherein dripping 4.9ml (35 mM) n-hexyl bromine.Then, same, under-78 ℃, after wherein dripping 22ml (35mmol) n-BuLi hexane solution ,-78 ℃ were stirred 1 hour down.Then,, stirred 1 hour down, at room temperature stirred again 1 hour at-78 ℃ to wherein dripping 4.9ml (35mmol) 1.6M n-hexyl bromine.Behind the ice-cold water of dropping down, use ethyl acetate extraction, after dehydrating with magnesium sulfate, heat up in a steamer and desolvate.Again with hexane with its recrystallization, obtain 9.5g (95%) 9,9-dihexyl fluorenes.
With 2.0g (6.0m mol) 9,9-dihexyl fluorenes, 0.02g (0.12m mol) iron chloride (III) are dissolved in the 9ml chloroform, under the shading, stir down in 0 ℃, and dropping 1.2g is dissolved in the bromine in the 3ml chloroform.After it is at room temperature stirred 18 hours, clean with sodium thiosulfate solution, dehydrate with magnesium sulfate, heat up in a steamer and desolvate, (eluent: separation and purification hexane) obtains 2.4g (92%) 2,7-two bromo-9,9-dihexyl fluorenes to residue with column chromatography.
Flow down at drying nitrogen, with 2.0g (4.0mmol) 2,7-two bromo-9,9-dihexyl fluorenes is dissolved in the 40ml dry tetrahydrofuran, ice-cold down, behind Dropwise 5 .3ml (8.4mmol) 1.6M n-BuLi hexane solution wherein, 0 ℃ was stirred 1 hour down.Then, to wherein dripping 2.0ml (10mmol) 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-two oxa-borines (ジ ォ キ サ ボ ラ Application) stirred 1 hour down for 0 ℃, at room temperature stirred 12 hours again.Behind the ice-cold water of dropping down, use extracted with diethyl ether, after dehydrating with magnesium sulfate, heat up in a steamer and desolvate.Residue is used ethanol/hexane mixed solution recrystallization after cleaning with ethanol again, obtains 2 of 1.4g (60%), two (4,4,5,5-tetramethyl-1,3,2-two oxa-s borine-2-yl)-9 of 7-, 9-dihexyl fluorenes.
Flow down at drying nitrogen, dissolving 0.53g 2 in the 18ml dry toluene, 7-two (4,4,5,5-tetramethyl-1,3,2-two oxa-s borine-2-yl)-9,9-dihexyl fluorenes, and 0.45g2,7-two bromo-9,9-dihexyl fluorenes and 0.02g tetrakis triphenylphosphine palladium, again after wherein adding 27ml 2M aqueous sodium carbonate, 100 ℃ of following agitating heating 48 hours.Be injected into after the cooling in the methyl alcohol, after with diluted hydrochloric acid aqueous solution solid constituent being cleaned, make solvent, remove solvent components, isolate insoluble part with the Soxhlet return channel with acetone.It is dissolved in the chloroform, precipitates again, obtain purpose and produce poly-fluorene derivative with methyl alcohol.
The ito glass substrate that the wide band shape of central 12mm is formed pattern is cleaned and surface treatment, with spin coater coating fluid D-1,2,3,4,5,6 is formed film thereon.These were heated 10 minutes in 150 ℃ purification stove, form the thick film of 50nm respectively by dry and sintering.Then, to the film that forms by coating fluid D-1,2,3,4,5,6, utilize high-pressure mercury-vapor lamp (dominant wavelength 365nm) to expose with the 5000mJ exposure.Utilize the above-mentioned coating fluid D-7 of rotary coating thereon, form the film of 100nm.At last, form upper electrode, mask evaporation 0.5nmLiF, 150nm aluminium with pattern square crossing with ITO.The top Al electrode of ITO electrode is driven as address electrode, observe luminous.
Measure the characteristics of luminescence of making element, obtain briliancy-voltage characteristic shown in Figure 11.Wherein will be taken as D-0 less than the test portion that contains photocatalyst layer is set.Because coating fluid D-4-6 and coating fluid D-3 are about the same, so by same curve representation.
As shown in figure 11, compare, contain photocatalyst layer by setting with D-0, reduce driving voltage, improved luminous efficiency, added the D-2, the D-3 that improve characteristics of luminescence material, the D-1 that reduction is arranged slightly with luminous efficiency relatively drives with low-voltage more, has very high briliancy as can be known.
In the following table, as can be known, added the D-4-6 that improves the luminescent layer characteristic material, compared, improved luminous efficiency with D-1.
Luminous efficiency (cd/A)
Coating fluid D-0 0.35
Coating fluid D-1 1.05
Coating fluid D-2 0.70
Coating fluid D-3 0.62
Coating fluid D-4 1.46
Coating fluid D-5 1.33
Coating fluid D-6 1.44
Claims (11)
1. the manufacture method of an EL element, it is characterized in that, at least by the 1st electrode, the 1EL layer that on the 1st electrode, forms, the rayed that forms on this 1EL layer causes wetability and is varied to layering, cause wetability in this rayed and be varied to the 2EL layer that forms in the layering, on this 2EL layer, form the manufacture method of the formed EL element of the 2nd electrode, comprise following operation: the operation that on above-mentioned the 1st electrode, forms above-mentioned 1EL layer, on above-mentioned 1EL layer, form above-mentioned rayed and cause the operation that wetability is varied to layering, above-mentioned rayed is caused wetability to be varied to layering and to expose by pattern-like, formation is produced the operation of pattern by wetability difference, cause in above-mentioned rayed that the above-mentioned 2EL layer forming liquid of coating forms pattern on the exposed portion that wetability is varied to layering, and form the operation of above-mentioned 2EL layer, with the operation that on above-mentioned 2EL layer, forms above-mentioned the 2nd electrode.
2. according to the manufacture method of the EL element of claim 1 record, it is characterized in that comprising the operation that on base material, forms above-mentioned the 1st electrode in advance.
3. according to the manufacture method of the EL element of claim 1 record, it is characterized in that rayed causing wetability, to be varied to layering be to contain photocatalyst layer.
4. according to the manufacture method of the EL element of claim 1 record, it is characterized in that, the pattern of the EL layer after the above-mentioned 2EL layer forming liquid coating forms and is undertaken by a kind of method that is selected from the following method: before the 2EL layer forming liquid solidifies, above-mentioned rayed is caused wetability be varied to the method that layering is tilted, brush the method for air and solidify the back and paste the method that splicing tape is peeled off again of paying.
5. according to the manufacture method of the EL element of claim 1 record, it is characterized in that utilizing vacuum film formation to form in the 1st electrode, the 2nd electrode, the EL layer at least 1 layer after, utilize to paste and pay the method that splicing tape peels off again and carry out the formation of pattern.
6. according to the manufacture method of the EL element of claim 1 record, it is characterized in that the above-mentioned photocatalyst layer that contains, not light-struck position is hydrophobicity and/or oleophobic property, and wetability has been improved at the rayed position.
7 manufacture methods according to the EL element of claim 1 record is characterized in that above-mentioned EL element is the display unit of panchromatic demonstration, and are corresponding with the pattern that the above-mentioned wetability difference that contains photocatalyst layer produces, and form display element.
8. according to the manufacture method of the EL element of claim 1 record, it is characterized in that above-mentioned the 1st electrode and the 2nd electrode are that the electrode of pattern-like, above-mentioned EL layer are luminescent layers, above-mentioned rayed is carried out pattern exposure corresponding to the pattern of above-mentioned the 1st electrode.
9. according to the manufacture method of the EL element of claim 1 record, the above-mentioned luminescent layer of at least 1 laminated layer in it is characterized in that being separated by resilient coating, the charge transport layer.
10. according to the manufacture method of the EL element of claim 1 record, the lamination operation utilization that it is characterized in that above-mentioned luminescent layer or above-mentioned next door layer is selected from ink-jet method, evenly a kind of method in rubbing method and the pattern print process is carried out.
11. the manufacture method according to the EL element of claim 1 record is characterized in that the lamination operation of above-mentioned luminescent layer or above-mentioned next door layer utilizes the vacuum film formation method to carry out, and, rayed is caused the film that wetability is varied to the not rayed position of layering strip down.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP45566/2000 | 2000-02-23 | ||
| JP2000045566A JP2001237069A (en) | 2000-02-23 | 2000-02-23 | El element and manufacturing method of the same |
| JP70493/2000 | 2000-03-14 | ||
| JP124063/2000 | 2000-04-25 |
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| CNB011173831A Division CN1263352C (en) | 2000-02-23 | 2001-02-23 | Electroluminescent element and its producing method |
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| CN100551186C true CN100551186C (en) | 2009-10-14 |
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| JP4617019B2 (en) * | 2000-04-25 | 2011-01-19 | 大日本印刷株式会社 | EL device having photocatalyst containing layer and method for producing the same |
| JP4165692B2 (en) | 2002-08-05 | 2008-10-15 | 大日本印刷株式会社 | Method for manufacturing electroluminescent device |
| JP4289852B2 (en) * | 2002-09-18 | 2009-07-01 | 大日本印刷株式会社 | Method for manufacturing electroluminescent device |
| JP4332360B2 (en) * | 2003-02-28 | 2009-09-16 | 大日本印刷株式会社 | Wetting pattern forming coating liquid and pattern forming body manufacturing method |
| JP4572370B2 (en) * | 2005-03-28 | 2010-11-04 | 国立大学法人 大阪教育大学 | Organic electronic device and manufacturing method thereof |
| JP2006310036A (en) * | 2005-04-27 | 2006-11-09 | Dainippon Printing Co Ltd | Substrate for organic electroluminescent element |
| EP1989818A4 (en) * | 2006-03-02 | 2011-05-18 | Du Pont | Process for making contained layers and devices made with same |
| US8124172B2 (en) * | 2006-03-02 | 2012-02-28 | E.I. Du Pont De Nemours And Company | Process for making contained layers and devices made with same |
| JP4975766B2 (en) * | 2006-03-07 | 2012-07-11 | エルジー・ケム・リミテッド | ORGANIC LIGHT EMITTING ELEMENT AND MANUFACTURING METHOD THEREOF |
| WO2009055628A1 (en) | 2007-10-26 | 2009-04-30 | E. I. Du Pont De Nemours And Company | Process and materials for making contained layers and devices made with same |
| TW201104357A (en) | 2009-07-27 | 2011-02-01 | Du Pont | Process and materials for making contained layers and devices made with same |
| US9444050B2 (en) | 2013-01-17 | 2016-09-13 | Kateeva, Inc. | High resolution organic light-emitting diode devices, displays, and related method |
| JP6494525B2 (en) * | 2013-01-17 | 2019-04-03 | カティーバ， インコーポレイテッド | High resolution organic light emitting diode devices, displays, and related methods |
| US9614191B2 (en) | 2013-01-17 | 2017-04-04 | Kateeva, Inc. | High resolution organic light-emitting diode devices, displays, and related methods |
| CN110289363B (en) * | 2019-06-28 | 2022-06-03 | 京东方科技集团股份有限公司 | Method for patterning nanoparticle layer, quantum dot light-emitting device and display device |
| CN110571362B (en) * | 2019-09-18 | 2022-02-22 | 云谷（固安）科技有限公司 | Flexible display panel and preparation method thereof |
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| CN1770938A (en) | 2006-05-10 |
| JP2001237069A (en) | 2001-08-31 |
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