CN101536608A - Substrate for an organic light-emitting device, use and process for manufacturing this substrate, and organic light-emitting device - Google Patents
Substrate for an organic light-emitting device, use and process for manufacturing this substrate, and organic light-emitting device Download PDFInfo
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- CN101536608A CN101536608A CNA2007800414429A CN200780041442A CN101536608A CN 101536608 A CN101536608 A CN 101536608A CN A2007800414429 A CNA2007800414429 A CN A2007800414429A CN 200780041442 A CN200780041442 A CN 200780041442A CN 101536608 A CN101536608 A CN 101536608A
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- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 125000006617 triphenylamine group Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/805—Electrodes
- H10K59/8051—Anodes
- H10K59/80517—Multilayers, e.g. transparent multilayers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/82—Interconnections, e.g. terminals
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/86—Series electrical configurations of multiple OLEDs
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- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a substrate (1) for an organic light-emitting device (10), especially a transparent glass substrate, comprising, on a first main face (11), a lower electrode coating (3), the electrode coating (3) consisting of a thin-film multilayer comprising, in succession, at least: a contact layer (31) based on a metal oxide and/or metal nitride; a metallic functional layer (32) having an intrinsic electrical conductivity property; and an overlayer (34) based on a metal oxide and/or metal nitride, especially for matching the work function of said electrode coating, said substrate including a bottom layer (2), said bottom layer (2) covering said main face (11).
Description
Technical field
Theme of the present invention is multi-layered electrode, its acid etching and the organic light emitting apparatus that comprises it.
Background technology
Known organic light emission system or OLED comprise the laminated coating of electroluminescent organic material or electroluminescent organic material, make it charged by electrode, adopt two conductive layers to be positioned at the form of its both sides usually.
These conductive layers generally comprise based on indium oxide, the layer of the indium oxide of tin-doping normally, and the abbreviation ITO of the indium oxide of tin-doping is more common.Especially in depth studied the ITO layer.Can make their depositions at an easy rate by the magnetron sputter, wherein, use oxide target (non-reacted sputter) or use target (reactive sputtering in the presence of oxygen type oxidant), and their thickness be about 100-150nm based on indium and tin.Yet this ITO layer has many shortcomings.At first, be used to improve conductive material and high temperature (350 ℃) deposition process and produce fringe cost.Unless layer thickness is increased to greater than 150nm, otherwise that sheet resistance keeps is high relatively (
Level), can cause transparency to reduce and the surface roughness increase bed thickness increase.
Therefore, developed new electrode structure.For example, the JP2005-038642 file has been instructed the luminous flat screen of TFT (thin-film transistor)-driving, it comprises the electroluminescence system of top light emitting, and described electroluminescence system produces ruddiness, green glow and blue light respectively, so that form active matrix (active matrix).
Each organic light emitting apparatus all is equipped with so-called back electrode or hearth electrode, and described electrode comprises:
-adhesion layer is for example made by ITO;
-(partly) reflective metal layer, particularly based on silver or aluminium, perhaps make by the silver that contains aluminium, its thickness is 50nm at least; With
-work function coupling cover layer (work-function-matching overlayer) is for example made by ITO.
Summary of the invention
The objective of the invention is to obtain the conductive layer assembly, so that form reliable electrode, described electrode durable (particularly aspect stability and/or mechanical endurance and thermal endurance), and do not sacrifice its electric conductivity or its optical quality, do not sacrifice the performance of the device that comprises it yet, more can not cause the difficulty in the production.
Purpose of the present invention particularly can obtain the conductive layer assembly, and it is used to form the hearth electrode of reliability and durability electroluminescence system, does not learn performance and do not sacrifice its electric conductivity, its optical quality or oled light, does not also produce the difficulty in the production.
In content of the present invention, term ＂ hearth electrode ＂ is construed as and refers to the electrode that is inserted between carrier substrate and the OLED system.
In addition, will realize this purpose with least cost, and not upset the known structure of organic light emission system related to the present invention.
This relates to exploitation as bottom electrode: as described in electrode be substantial transparent, perhaps be transparent be again reflection-type or reflection-type basically, and described electrode on an equal basis compatibly is used for OLED, form active matrix and passive matrix OLED screen, perhaps form video recording screen back lighting device, perhaps be generally used for the device that (building and/or decoration) illumination is used, perhaps be used for indication and use, perhaps be used for other electronic application.
This novel electrode film particularly can have the optical property that is suitable as panel, and described panel is the face of the light that sends of OLED system by its separating device.Especially, it can have sufficient light conduction, also has minimum possible light absorption simultaneously.Its reason is to seem the possible the highest light conduction of unnecessary pursuit so that obtain maximum luminous energy in the outlet of OLED device, simultaneously, on the other hand, for panel, must have minimum possible absorption.
Therefore, the present invention also is to select and make the compatible thin-film multilayer coating of method of organic light emitting apparatus, particularly with to form the step of hearth electrode by etching before OLED system deposition compatible.
The objective of the invention is to remedy the shortcoming of prior art by proposing new solution that preparation is used for the bottom electrode film of organic light emitting apparatus.
In order to realize this purpose, theme of the present invention is: a kind of substrate as claimed in claim 1; The purposes of a kind of purposes of substrate, particularly substrate as claimed in claim 22; As claimed in claim 24ly comprise that described substrate person adopts the organic light emitting apparatus of described substrate; With the method that is used to make described substrate as claimed in claim 29.
Those claims that are subordinated to above claim define favourable selection of the present invention.
Therefore, the most in a broad aspect, a theme of the present invention is, a kind of substrate that is used for organic light emitting apparatus, transparent glass substrate particularly, it comprises, is positioned at the bottom electrode film on first first type surface, described electrode film is formed by the thin-film multilayer coating, and described laminated coating comprises following each layer at least continuously:
-based on the contact layer of metal oxide and/or metal nitride,
-have the intrinsic conduction performance the metal function layer and
-based on the cover layer of metal oxide and/or metal nitride, described cover layer is especially for the work function of the described electrode film of coupling,
Described substrate comprises basic unit (base layer), and described basic unit covers the first type surface of described substrate.
Basic unit of the present invention has two effects: it had both formed the alkali-metal barrier from substrate, also formed the requisite anti-reflecting layer for the micropore of OLED system simultaneously.
Therefore, electrode film of the present invention is made of the thin-film multilayer coating, described thin-film multilayer coating comprises at least a metal function layer, particularly (that is to say based on silver, be made from silver or make) by the metal alloy that mainly contains silver, and at least a end anti-reflective film that places between substrate and the described metal function layer, described anti-reflective film comprises at least a antireflection dielectric layer, i.e. basic unit.
In content of the present invention, term ＂ film ＂ is construed as and is meant, the layer of being made by homogenous material can be arranged, and perhaps is made from a variety of materials many layers separately.
Be positioned under the metal function layer in the face of substrate and with the purpose of the described anti-reflective film of substrate contacts be that light that the OLED system is sent only is wavelength-optionally and only depend on visual angle.
This be because, if there is no described anti-reflective film, on the one hand, the light that the OLED system sends concentrates on emission wavelength very much, perhaps concentrate in the very narrow scope of emission wavelength of OLED system, and on the other hand, the color of described light and energy are along with the visual angle greatly changes.
This thin-film multilayer coating is known in building or vehicle glass (automotive glazing) field, be used to prepare ＂ low-heat-intercepting glass of the enhancing of emissivity or low-E ＂ and/or ＂ sunlight control ＂ type.
Therefore, the inventor notices that some laminated coating that is used for low-E glass (glazing) can be used to prepare the basic unit of organic light emitting apparatus and electrode film especially and especially for the basic unit and the electrode film of the panel of these devices.
But it is particularly suitable being called the ＂ laminated coating of ＂ malleableize or the laminated coating of the ＂ coating that ＂ treats malleableize, that is to say, when the hope preparation has the substrate of laminated coating, those laminated coatings that adopted is carried out malleableize heat treatment.This is just more amazing, this is because the substrate that is used for organic light emitting apparatus is without heat treated when being used for this device, perhaps need not cool off fast with sufficient and carry out sufficient heat treatment in any case in order on glass substrate, to carry out patent.
Therefore, theme of the present invention also is the purposes that the thin-film multilayer coating is used for building glass (glazing), perhaps a kind of substrate that scribbles the thin-film multilayer coating is used for the purposes of building glass, but the ＂ laminated coating of particularly low-E laminated coating or the substrate that was coated with and/or particularly ＂ malleableize or the substrate that was coated with or ＂ treat the ＂ laminated coating of malleableize, so that prepare the substrate that is used for organic light emitting apparatus of the present invention.
In content of the present invention, but the ＂ laminated coating of term ＂ malleableize or substrate are construed as and are meant optical property and the hot property (patience (resistance) by every quadrature represents that this is directly related with emissivity) that keeps necessity in heat treatment process.
Therefore, can be in the front of a building and same building, for example will combine the substrate of malleableize and not the face glass of the substrate of malleableize closely put together, described substrate all scribbles same laminated coating, and reflection that can not be by visualization of color simply and/or light reflection/transmission are distinguished from each other them and come.
For example, had the laminated coating of following variation before 0 or scribble the substrate of laminated coating after heat treatment, but will be considered to malleableize, this is not that eyes can be discovered because of these variations:
-less than 3%, perhaps even less than the little change Delta T of 2% light conduction
LAnd/or
-less than 3%, perhaps even less than the little changes delta R of 2% light reflection
LAnd/or
-less than 3 or even less than the little variation of 2 color
In the present invention, ＂ treats that it is acceptable that the ＂ laminated coating of malleableize or substrate are construed as the optical property and the hot property that are meant the substrate that was coated with after heat treatment, but is not perhaps under any circumstance not to be all before heat treatment.
In content of the present invention, for example, after heat treatment, have the laminated coating of following characteristic or scribble the substrate of laminated coating, will be considered to ＂ and treat the ＂ of malleableize but before heat treatment, do not have at least a in these characteristics:
-at least 50% high light conduction T
L, perhaps even at least 60% or 65%, perhaps even 70%, perhaps even at least 75% and more preferably at least 80%; And/or
The patience of-the same with ITO at least good every quadrature with common thickness
, particularly less than
Perhaps in addition less than
The important point is, the electrode film that is used for panel is also fully transparent, thereby before OLED system deposition, it has at least 50% and the light conduction of preferred 60-70%, and on the other hand, has low-down absorption, thereby before OLED system deposition, it is defined as 1-R
L-T
LAbsorption be equal to or less than 15%, perhaps even be equal to or less than 10%, perhaps even be equal to or less than 8%, perhaps even be equal to or less than 5%.
Should avoid light conduction greater than 70%,
If reach this value, the thickness that is positioned at the film coating between metal function layer and the OLED system (cover layer and optional other layer that exists) is too big, and the metal function layer is too far away apart from the OLED system, is easy to weaken the performance of OLED.
Basic unit can:
-based on Si oxide (general formula is SiO);
-based on silicon oxycarbide (general formula is SiOC);
-based on silicon nitride (general formula is SiN) with especially based on Si
3N
4
-based on silicon-oxygen nitride (general formula is SiON);
-based on silica carbonitride (general formula is SiONC).
The nitrogenize of basic unit may be substoichiometric slightly.
Preferably, the thickness of basic unit is 10-150nm, even more preferably 20-100nm.
Basic unit gives electrode of the present invention many advantages.At first, basic unit forms barrier to the alkali metal of electrode below.Its protection is gone up contact layer and is not subjected to any pollution (described pollution can cause mechanical defect, for example layering), and it also keeps the conductivity of metal function layer simultaneously.Basic unit prevents that also the organic structure of OLED device from being polluted by alkali metal, still, causes greatly reducing the life-span of OLED.
In the preparation process of device alkali-metal migration may take place, thereby cause lacking reliability, and/or and then reduce its life-span.
Basic unit improves the grappling performance (anchoring properties) of contact layer, and can not cause the increase of a little to the roughness of whole laminated coating, even insert one or more layers between basic unit and contact layer.
Certainly, the present invention is for being extremely beneficial with being easy to discharge the approaching as far as possible electrode of alkali-metal carrier substrate, for example particularly transparent or super clear soda-lime glass.
In addition, this special laminated coating structure also can obtain reliable electrode, thereby can realize significantly improving of productivity ratio.
And, and lower cost obtains is as bottom electrode: as described in electrode demonstrate the compatibility of surface property and organic light emission system, still have simultaneously can be adjusted in suitable conductivity and/or transparency or reflecting properties, particularly carry out described adjusting by the thickness and/or the sedimentary condition that change metal level or other layer.
For the organic structure of given OLED device, compare with the ITO electrode of common thickness, for greater than 500cd/m
2Brightness, it is the improved efficiency 5-10% of 1m/W that electrode of the present invention can make the unit of OLED, and high to 15% or even 20%.
Electrode film can preferably include etching stopping layer between basic unit and contact layer, particularly based on the layer of tin-oxide, the thickness of described etching stopping layer is 10-100nm particularly, even more preferably 20-60nm.
Most particularly, for simply, etching stopping layer can form the part of basic unit or can be basic unit: preferably, it can be based on silicon nitride, perhaps can be based on the layer of Si oxide, or based on silicon-oxygen nitride the layer, or based on silicon oxycarbide the layer, perhaps or even based on the layer of silica carbonitride, contain tin simultaneously and be used for strengthening anti--etching performance, the general formula of layer is SnSiOCN.
Etching stopping layer is used for protective substrate under chemical etching or the etched situation of reactive plasma.
Because etching stopping layer, basic unit keeps existing, even also like this in the zone of being carved with pattern.Therefore, by edge effect, can stop the migration of alkali metal between the zone of being carved with pattern of substrate and adjacent electrode part (perhaps even organic structure).
Particularly preferably be most (mainly) by that mix or unadulterated silicon nitride Si
3N
4Basic unit/etching stopping layer of making.Silicon nitride very rapidly deposits and forms excellent alkali metal barrier.And because its high optical index with respect to carrier substrate, the optical property that it allows to change electrode preferably realizes by the thickness that changes described basic unit/etching stopping layer.Therefore, for example,, can regulate transmitted colors by this way when electrode when being transparent, perhaps when the opposite face of carrier substrate is mirror, accommodation reflex color by this way.
Preferably, functional layer is based on the pure material that is selected from silver, gold, aluminium and copper, perhaps based on described material and the alloy or the alloy that are selected from other following material: Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co and Sn, and particularly based on gold/silver alloy or based on gold/copper alloy.
The film coating of formation electrode film is the function monofilm preferably, that is to say the simple function layer.Yet it can be to comprise many functional layers and the particularly coating of two functional layers.
Be included in the electrode film that deposits many functional layers of n time on basic unit and the optional etching stopping layer that exists in order to prepare, wherein, n is equal to or greater than 1 integer, adopt following structure: contact layer and function metal level, the stratose that comprises following pantostrat is arranged on described structure, and described pantostrat is made of contact layer/function metal level/cover layer at least.
Electrode of the present invention can have big area, for example is equal to or greater than 0.02m
2, perhaps even be equal to or greater than 0.5m
2, perhaps be equal to or greater than 1m
2
Advantageously, electrode of the present invention can have:
-be functional layer more than the 6nm for thickness, electrode of the present invention have be equal to or less than 10 Ω/
The patience of every quadrature, be 10nm and above functional layer for thickness, have preferably be equal to or less than 5 Ω/
The patience of every quadrature, preferably have following optical property simultaneously:
-be equal to or greater than 50% light conduction T
L, preferred 60%-70%, perhaps even higher, prerequisite be this do not weaken OLED luminescent properties and
-be equal to or less than 15% absorption, perhaps be equal to or less than 10%, perhaps even more preferably be equal to or less than 8%, perhaps even 5%,
Thus, make electrode of the present invention satisfactory especially as transparency electrode,
-be 50nm and above functional layer for thickness, the patience of every quadrature be equal to or less than 1 Ω/
, preferably be equal to or less than 0.6 Ω/
, simultaneously preferred, light conduction R
LBe equal to or greater than 70%, even more preferably 80%, thus, make electrode of the present invention satisfactory especially as transparency electrode,
-be 20nm and above functional layer for thickness, the patience of every quadrature be equal to or less than 3 Ω/
, preferably be equal to or less than 1.8 Ω/
, simultaneously preferred, T
L/ R
LThan being 0.1-0.7, thus, make electrode of the present invention satisfactory especially as transparent/reflecting electrode.
For the thickness of the selected silver of electrode-Base Metal functional layer (perhaps all these layer) can be 3-20nm (gross thickness), preferred 5-15nm.In this thickness range, because the anti-reflective film under silver-Base Metal functional layer (perhaps each silver-Base Metal functional layer), electrode can be fully transparent, thus the gratifying especially transparency electrode of preparation, just as described in the previous paragraph.
Yet it is not favourable that selected silver-Base Metal functional layer (perhaps all these layers) has remarkable bigger thickness, if particularly the organic light emission system is with reflective operation or top light emitting.In this case, for the thickness of the selected Yin of electrode-Ji functional layer (perhaps all these layer) can be 50-150nm (gross thickness), preferred 80-100nm, thus can prepare gratifying especially reflecting electrode, as mentioned above.
In addition, for the thickness of the selected Yin of electrode-Ji functional layer (perhaps all these layer) can be 20-50nm (gross thickness) so that electrode is simultaneously with transmission and reflective operation, thus can prepare gratifying especially transparent/reflecting electrode, as mentioned above.
Metal function layer (perhaps each metal), particularly Yin-Ji functional layer preferably is deposited on the thin dielectric layer with crystallization mode, the also preferred crystallization of thin dielectric layer.Therefore, contact layer promotes the crystal orientation that deposition metal level thereon is fit to.
Therefore, the functional layer preferred deposition is on oxide-Ji contact layer, even directly be deposited on oxide-above the Ji contact layer, based on the contact layer of oxide particularly based on the contact layer of zinc oxide, zinc oxide is optional to mix, (term ＂ doping ＂ is interpreted as in due form and is meant contacts described element in layer for optional and aluminium doping, described element is the metallic element less than the amount of 10 weight %, and term ＂ is interpreted as the material that is meant that layer mainly contains in due form based on ＂, that is to say, this material that contains at least 50 weight %, therefore, term ＂ covers based on ＂ and mixes).
How much (perhaps actual) thickness of contact layer are preferably 3-30nm, more preferably 4-20nm.
The effect that is positioned at the contact layer under the metal function layer in the anti-reflective film sometimes may be out in the cold, particularly when the index of this layer approaches the index of substrate, and/or when the thickness of this layer hour, when being typically thickness when this layer less than 10nm.
Contact layer can be based on metal nitride, then can be consistent with basic unit, particularly work as basic unit based on silicon nitride.
Preferably, at least a based in the following metal oxide of contact layer, wherein optional described other metal oxide that mixes: chromated oxide, indium oxide, optional substoichiometric zinc oxide, aluminum oxide, titanium oxide, molybdenum oxide, Zirconium oxide, sb oxide, tin-oxide, tantalum pentoxide and Si oxide (, thinking that here silicon is metal) in order to simplify.
Typically, can be with doped metallic oxide 0.5-5%.Especially, it can be Al-doped zinc oxide (AZO), Ga-doped zinc oxide (GZO), perhaps or even B-mixes, Sc-mixes or the Sb-doped zinc oxide, to realize the better stability of deposition process, perhaps or even F-mix or the S-doped tin oxide.
Contact layer can be based on mixed oxide, especially, and normally non-stoichiometric mixed oxidization tin zinc Sn
xZn
yO
zAs amorphous phase, perhaps based on mixing indium tin oxide (ITO) or mixed oxidization indium zinc (IZO).
Preferred zinc oxide ZnO
xLayer, preferred x be less than 1, even more preferably 0.88-0.98, particularly 0.90-0.95.This layer can be pure layer, or is doped with Al or is doped with the layer of Ga.
Normally obtain to pile up by continuous electroless copper deposition operation, described continuous electroless copper deposition operation is by vacuum technique, for example sputter, and optional magnetron sputter is carried out.Also can provide a kind of or even two kinds of extremely thin films that are called " barrier film (blocking film) "; the described film of thing directly is deposited under each metal function layer; or be deposited on each metal function layer; perhaps be deposited on each side of each metal function layer; the metal function layer is particularly based on silver; described film is positioned under the functional layer on the direction of substrate; as bonding; nucleation and/or diaphragm; and the described film on the functional layer is as protection or " sacrifice " film; to prevent since oxygen from being positioned at layer attack and/or the migration on the metal function layer; if perhaps position layer thereon deposits by sputter in the presence of oxygen; also be because oxygen moves, thereby weaken the metal function layer.
Therefore, the function metal level directly can be placed at least a down barrier film and/or directly place at least a going up under the barrier film, the thickness of each film all is preferably 0.5-5nm.
In content of the present invention, under other deposit or directly on other deposit, during the deposition of cambium layer or film (comprising one or more layers), between these two kinds of deposits, can insert without any layer when spelling out directly.
At least a barrier film preferably comprises metal, metal nitride and/or metal oxide layer, at least a based in the following metal: Ti, V, Mn, Fe, Co, Cu, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta, W, perhaps based on the alloy of at least a described material.
For example, barrier film can comprise the layer based on following metal: niobium, tantalum, titanium, chromium or nickel, and perhaps based on the alloy that forms by at least two kinds of described metals, for example nickel-chromium alloy.
Thin thermoprint layer form protective layer or even " sacrifices " layer, its metal that prevents the function metal level is weakened, particularly when in following one or more are constructed:
If the layer on-the functional layer deposits by using reactive (oxygen, nitrogen etc.) plasmasphere, if for example position oxide skin(coating) thereon deposits by sputter;
If the composition of the layer on-the functional layer is easy to change (the variation of sedimentary condition in industrial manufacture process, be target loss pattern etc.) words, if particularly stoichiometric oxide and/or nitride type layer change, change the quality of functional layer thus and change the performance (surface resistance, transmittance etc.) of electrode thus; With
If-after deposition, electrode coating is heat-treated.
Described protective layer or sacrifice layer improve the electrical property of electrode and the reproducibility of optical property significantly.This is very important for commercial run, and wherein, the only very little dispersion of electrode performance is acceptable.
Thin thermoprint layer is based on the metal that is selected from niobium Nb, tantalum Ta, titanium Ti, chromium Cr and nickel, be particularly preferred perhaps based on the alloy that forms by at least two kinds in these metals, particularly niobium/tantalum (Nb/Ta) alloy, niobium/chromium (Nb/Cr) alloy or tantalum/chromium (Ta/Cr) alloy or nickel/chromium (Ni/Cr) alloy.This layer is based at least a metal with strong especially gettering effect.
Can easily prepare thin metal thermoprint layer, and not weaken functional layer.Can be preferably in the inert atmosphere that constitutes by inert gas (He, Ne, Xe, Ar, Kr) the described metal level of deposition (that is, do not have a mind wherein introduce oxygen or nitrogen).In the layer deposition process based on metal oxide subsequently, oxidation neither is left out on the surface of this metal level, and is also no problem.
Thin metal thermoprint layer so also provides excellent mechanical performance (particularly mar proof and marresistance).Heat treated laminated coating is especially true for accepting, and therefore, oxygen or nitrogen fully spread in this processing procedure.
Yet, for the purposes of metal thermoprint layer, be necessary to limit metal layer thickness and and then the restriction light absorption so that keep the conduction of sufficient light for transparency electrode.
Can the oxidation of thermoprint layer segment will be approached.Deposit this layer with nonmetal form, therefore, this layer can not deposit with stoichiometric form, but deposits with the substoichiometric form of following type: MO
xType, wherein M represents metal, and x is the truth of a matter of comparing with the stoichiometry of metal oxide; Perhaps MNO
xType is used for the oxide of two kinds of metal M and N (perhaps more than two kinds of metals).For example, can mention TiO
xAnd NiCrO
x
Preferably, x is 0.75 times-0.99 times of stoichiometric positive constant of oxide.For monoxide, can select x to be 0.5-0.98 especially, and for dioxide, x can be 1.5-1.98.
In a concrete variant, thin thermoprint layer is based on TiO
x, wherein, x is 1.5≤x≤1.98 particularly, perhaps 1.5＜x＜1.7, perhaps even 1.7≤x≤1.95.
Can the nitrogenize of thermoprint layer segment will be approached.Therefore, this layer can not deposit with stoichiometric form, but with MN
yThe substoichiometric form deposition of type, wherein M represents metal, and y is the numeral less than the metal nitride stoichiometric number.Y is preferably 0.75 times-0.99 times of stoichiometric positive constant of nitride.
Similarly, also can thermoprint layer segment oxynitriding will be approached.
Can easily prepare described thin oxidation thermoprint layer and/or thin nitrogenize thermoprint layer, and not weaken functional layer.Preferably, in the non-oxide atmosphere that preferably constitutes, use the ceramic target deposition by inert gas (He, Ne, Xe, Ar or Kr).
Thin thermoprint layer can preferably be made by substoichiometric nitride and/or oxide, so that further increase the electrical property of electrode and the reproducibility of optical property.
Selected thin substoichiometric oxide and/or nitride thermoprint layer can be preferably based at least a metal that is selected from the following metal: Ti, V, Mn, Fe, Co, Cu, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta, W, perhaps based on the oxide of substoichiometric alloy, at least a based in these metals of described alloy.
Particularly preferably be as lower floor: as described in layer based on oxide that is selected from following metal or oxynitride: niobium Nb, tantalum Ta, titanium Ti, chromium Cr or nickel, perhaps based on the alloy that forms by at least two kinds in these metals, particularly niobium/tantalum (Nb/Ta) alloy, niobium/chromium (Nb/Cr) alloy, tantalum/chromium (Ta/Cr) alloy or nickel/chromium (Ni/Cr) alloy.
As substoichiometric metal nitride, also can select the layer of making by following material: silicon nitride SiN
x, or aluminium AlN
x, or chromium nitride CrN
x, or titanium nitride TiN
x, or the nitride of many metals, for example NiCrN
x
Use special deposition atmosphere, thin thermoprint layer can have the oxidation gradient, for example M (N) O
Xi, wherein xi changes, and that part of thermoprint layer that contacts with functional layer is than low from the degree of oxidation of functional layer layer farthest.
Barrier film can also be a multilayer, particularly comprises:
-on the one hand, " interface " layer is close to described functional layer and contacts, described boundary layer is by making based on the material of non-stoichiometric metal oxide, nitride or oxynitride, for example above-mentioned those;
-on the other hand, at least a layer is made by metal material, for example above-mentioned those, this layer and described " interface " layer are close to and contact.
Boundary layer can be oxide, nitride or the oxynitride of metal, and it is present in the optional adjacent metal layer that exists.
The cover layer of electrode film of the present invention is preferably based at least a in the following metal oxide, wherein optional described other metal oxide that mixes: chromated oxide, indium oxide, optional substoichiometric zinc oxide, aluminum oxide, titanium oxide, molybdenum oxide, Zirconium oxide, sb oxide, tin-oxide, tantalum pentoxide and Si oxide, and described tectal thickness is preferably 3-50nm.
Described cover layer can be the tin-oxide that for example is doped with F, Sb, and perhaps aluminium-doped zinc oxide is perhaps optional based on mixed oxide, particularly mixes indium tin oxide, mixed oxidization indium zinc or mixes zinc tin oxide.
Preferred its roughness of substrate of the present invention that scribbles basic unit and electrode film makes the peak-paddy distance on the cover layer be equal to or less than 10nm.
For the substrate of the present invention that scribbles basic unit and electrode film, preferred its supratectal RMS roughness is 3nm or littler, 2nm or littler more preferably, even 1.5nm or littler more preferably, perhaps more preferably 1nm or littler, thus avoid reducing strongly the particularly life-span of OLED and the acupuncture defective of reliability.
The RMS roughness is represented r.m.s. roughness.This is the measuring of RMS deviation of roughness.Therefore, this RMS roughness has particularly quantized the average height of the peak and the groove of the roughness relevant with average height.Therefore, the RMS roughness of 2nm means bimodal mean amplitude of tide.
Can measure in every way: for example, by the atomic force microscope method, by mechanical pin type system (measuring instrument that adopts VEECO for example to sell) with pass through optical interference measurement with trade name DEKTAK.Usually, measure by atomic force microscopy at the area of 1 square micron, at bigger area, promptly about 50 microns areas of taking advantage of 2 millimeters are measured by mechanical pin type system.
Particularly when comprising the amorphous smooth layer of being made by mixed oxide between basic unit and contact layer, substrate obtains described low roughness, described smooth layer is close to described contact layer and directly places under the described contact layer, and is made by the material that is different from the contact layer material.
Preferably, it is mixed oxide layer, described mixed oxide layer is based on the oxide of one or more following metals: Sn, Si, Ti, Zr, Hf, Zn, Ga and In, particularly based on the mixed oxide layer of the optional doping of zinc and tin, or mix indium tin oxide (ITO) layer, or mix indium-zinc oxide (IZO) layer.
Preferably, the geometry thickness of smooth layer is 0.1-30nm, more preferably 0.2-10nm.
Yet substrate preferably includes the end bus electrode structure that is positioned on the bottom electrode film, and described bus electrode structure and described electrode film electrically contact.
End bus electrode structure was the form of current source layer before etching.Preferably, its thickness is 0.5-10 μ m, is preferably the form based on the individual layer of following a kind of metal or alloy: described metal is Mo, Al, Cr, Nd, and described alloy is MoCr, AlNd for example, or the form of multilayer, for example MoCr/Al/MoCr.
When being used to prepare the OLED device, from first first type surface of substrate, substrate comprises in the following order:
OLED system on the-bottom electrode film;
Top electrode film on the-described OLED system; With
Top bus electrode structure on the-top electrode film, described bus electrode structure and described top electrode film electrically contact.
In a concrete scheme, comprise the laminated coating that is used for building glass by basic unit and the film formed assembly of hearth electrode, but the ＂ laminated coating of ＂ malleableize particularly, and perhaps ＂ treats the ＂ laminated coating of malleableize, and/or the laminated coating of particularly low-E laminated coating, particularly following type:
-based on metal oxide and/or based on basic unit/(etching stopping layer)/(smooth layer)/oxide contact layer/(following the barrier film)/metal function layer of metal nitride/(going up barrier film)/based on the cover layer of metal oxide and/or metal nitride;
-based on the base stage of metal nitride and contact layer/(following barrier film)/metal function layer/(going up barrier film)/based on the cover layer of metal nitride.
In another embodiment, the substrate that scribbles basic unit and bottom electrode film comprises the substrate that is used for building glass, but the substrate of the substrate of the ＂ building glass of ＂ malleableize or the ＂ ＂ building glass for the treatment of malleableize particularly, these substrates scribble thin-film multilayer coating and/or particularly low-E laminated coating, described substrate preferably after stringer not by malleableize.
In other embodiments, substrate of the present invention comprises, be positioned at the functional membrane on second first type surface, described functional membrane is selected from: antireflection multilayer, anti-fog layer or stain-proofing layer, ultraviolet filter, particularly titanium oxide layer, phosphorus layer, mirror layer and light extraction fringe area.
Flat substrate can be transparent (especially for launching by substrate).Flat substrate can be rigidity, flexibility or semiflexible.
Flat substrate is preferably made by glass, particularly soda-lime glass.Advantageously, under the wavelength of oled light line, substrate can be that absorption coefficient is less than 2.5rm
-1, preferably less than 0.7m
-1Glass.
For example, selection contains Fe III or the Fe less than 0.05%
2O
3Soda-lime glass, particularly derive from the glass Diamant of Saint-Gobain glass, derive from the glass Optiwhite of Pilkington, perhaps derive from the glass B270 of Schott.Can select the super clear glass composition of all described in the document WO 04/025334.
Be used for the selected structure of OLED system, leading in substrate to some light that sends by transparency carrier thickness emission.
In addition, in the favourable design of the present invention, the thickness of selected glass substrate can be 1mm at least, for example preferred 5mm at least.This makes the quantity of internal reflection reduce, and therefore can extract the more light that are directed in glass, thereby increases the brightness of luminous zone.
For institute's guided ray being carried out the optimum circulation, edge that also can reflection substrate and preferably have minute surface, and/or the first type surface that described edge can be connected with the OLED system forms the interior angle that still is less than or equal to 135 ° greater than 90 °, preferred about 100 °, so that light is led again at the extraction area of broad.Therefore, can there be the inclined-plane at the edge of substrate.
In document JP 2005-038642, separate for electrode being carried out electricity, in using the many etching steps that carry out with various etch-rates of various acid, construct hearth electrode.Therefore, the layer of etching coupling work function at first, etch metal layers then, final etch adhesion layer..
An object of the present invention is to obtain the conductive layer assembly, thereby form reliability and durability electrode (particularly aspect stability and/or thermal endurance and mechanical endurance), and do not sacrifice its electric conductivity or its optical quality, do not sacrifice the performance of the device that comprises it yet, more can not cause the difficulty in the production, particularly all the more so when being used for wet etching.
Therefore, the invention provides on the substrate, particularly the multi-layered electrode on the glass substrate carries out the acid etching method, and described substrate comprises basic unit, is preferably based on silicon nitride, Si oxide or silicon-oxygen nitride.
The present invention also relates to be used to make the method for substrate of the present invention, wherein, on substrate, deposit basic unit and electrode film at least, preferably deposit by sputter type vacuum technique at least at least in part, optional magnetron sputter, then described substrate is carried out etching, thus in one step etched electrodes film at least.
Preferably come all layers of depositing electrode film, yet do not get rid of the layer that can deposit ground floor or laminated coating, for example pyrolysis-type pyrolysis technique by other technology by evaporating deposition technique.
Context in the method that is used for making described device, if electrode film does not directly have essential electrode structure, it will be used to prepare the etching step of electrode structure, chemistry (preferred acid) silk screen printing step or laser-induced thermal etching step for example for example becomes known for those steps of ITO-base electrode film substantially.
Most particularly, can be by RIE (reactive ion etching) or more preferably come etching electrode film of the present invention by wet etching (can easily merge to preparatory phase and under atmospheric pressure carry out method of operating).
Preferably with same etched pattern and preferably by single etching operation come etching from contact layer to tectal all the layer, comprise functional layer, that is to say not etching basic unit self.Etching stopping layer, if present, preferably also without etching, but can slight etching, for example 1/10th of its initial thickness of etching.If there is no etching stopping layer, the same basic unit of being applicable to.
And, preferably before deposition OLED system, provide electrode film usually with bus electrode.Preferably with the layer of electrode film etching simultaneously will formation bus electrode.
Therefore, the invention provides and be used on the acid etching substrate, the method of the multi-layered electrode on the glass substrate particularly, described substrate comprises that acid etching stops layer, be preferably based on the substrate of silicon nitride and/or Si oxide, adopt single acid solution to carry out etching in one step, described acid solution is selected from pure nitric acid HNO
3, or mixture or pure hydrochloric acid or hydrochloric acid and the ferric trichloride FeCl of nitric acid and hydrochloric acid HCl
3The mixture of (perhaps being called Fe III chloride).
Therefore, can the such etched pattern of etching, wherein the width and the spacing of pattern vary depending on the application constantly.
In the presence of at least a metal current source band, carry out described etching, described metal current source band is preferably based on the form of the individual layer of following a kind of metal or alloy: described metal is Mo, Al, Cr, Nd, described alloy is MoCr, AlNd for example, or the form of multilayer, for example MoCr/Al/MoCr.
The present invention also relates to organic light emitting apparatus, described organic light emitting apparatus comprises at least a carrier substrate, particularly glass substrate, and prerequisite is that at least a organic electro luminescent layer places between aforementioned hearth electrode (promptly near the electrode of carrier substrate) and the top electrode.
The OLED device can prepare monochromatic light, particularly blueness and/or green and/or red light, produces white light thereby perhaps can adjust it.
In order to produce white light, can adopt many methods: mixing cpd in simple layer (red, green, blue-light-emitting); On electrode surface, pile up three organic structures (redness, green and blue-light-emitting) or two organic structures (yellow and blue); Three continuous adjacent organic structures (red, green, blue-light-emitting); A kind of organic structure of color is set on a surface of electrode, suitable phosphorus layer is set on another surface.
The OLED device can comprise a plurality of adjacent organic light emission systems, and these organic light emission systems emit white light separately, perhaps comprises three continuous organic light emission systems, these rubescent looks of organic light emission system, green and blue light, and these systems for example are connected in series.
Device can form the part of compound glass unit, and the compound glass unit is vacuum glass unit or have air layer or the glass unit of other gas blanket particularly.Device can be a monolithic integrated circuit also, and comprises the monolithic integrated circuit glass unit so that more closely knit compactness and/or lighter.
The OLED system can with other flat substrate bonding, perhaps preferably laminated, it is called covering, flat substrate is preferably transparent, for example glass uses laminated interlayer, particularly super lamina septum pellucidum.
The laminated glass unit is made up of two rigid substrates usually, is equipped with thermoplastic polymer sheets or this laminated thing between these two rigid substrates.The present invention also comprises the glass unit that is called " asymmetric " laminated glass unit, particularly uses glass mould rigid carrier substrate, and uses one or more protection polymer sheets as covered substrate.
The present invention also comprises such laminated glass unit, described laminated glass unit has at least a interlayer sheet, this interlayer sheet (that is to say based on the sticky polymers of elastomeric-type one-sided or bilateral, described interlayer sheet does not need traditional laminated operation, that is to say, traditional laminated common needs add depresses heating, thus softening thermoplasticity interlayer sheet and make that it is bonding).
In this structure, the mode that is used for covering is fixed in carrier substrate can be laminated interlayer, thermal plasticity slice particularly, for example polyurethane (PU), polyvinyl butyral resin (PVB) or ethylene/vinyl acetate (EVA), perhaps thermal curable list-component or many-component resin (epoxy, PU) or ultraviolet ray-curable list-component or many-component resin (epoxy, acrylic resin).Preferably, sheet and covering and substrate (basically) are same sizes.
Laminated interlayer can prevent covering generation deflection, and especially for big device, for example area is greater than 0.5m
2Device.
Especially, EV has many advantages:
-it contains the water of small size very or not moisture;
-need be in the high pressure processed.
The laminated interlayer of thermoplasticity can preferably have the covering of being made by casting resin, and is because it is easier to operate, more economical and can seal more.
The optional row's conductor wire that places in the interior surface thereof that comprises of interlayer, described conductor wire faces toward top electrode, and/or comprises conductive layer or the conducting strip that places on the inner surface of covering.
Can preferably the OLED system be placed the inboard of two glass units, have for example inert gas (for example argon) of gas blanket.
Top electrode can be a conductive layer, advantageously is selected from metal oxide, particularly following material:
Zinc oxide, particularly aluminium-doped zinc oxide ZnO:Al or the gallium-doped zinc oxide ZnO:Ga of-doping;
-or doped indium oxide, particularly tin-doped indium oxide (ITO) or zinc-doped indium oxide (IZO).
More generally be, can use the transparency conducting layer of any type, for example TCO (transparent conductive oxide) layer, for example its thickness is 20-1000nm.
Also can use the thin metal layer that is called TCC (transparent conducting coating), for example be made by Ag, Al, Pd, Cu, Pd, Pt In, Mo, Au, typically, its thickness is 5-150nm, and this thickness depends on the transmittance/reflection of hope.
It is continuous that electrode needs not be.Top electrode can comprise a plurality of conducting strips or conductor wire (silk screen).
And, can be on the opposite face of substrate or on other substrate, advantageously add the film of given function with electrode of the present invention.This can be anti-fog layer (an employing hydrophilic layer), and stain-proofing layer (comprises TiO
2Photocatalysis coating, at least with the form partially crystallizable of anatase), perhaps antireflection multilayer coating Si for example
3N
4/ SiO
2/ Si
3N
4/ SiO
2Type, the coating of perhaps filtering UV, for example, titanium oxide (TiO
2) layer.Also can be that one or more phosphorus floor, mirror floor or at least a scattered light extract the district.
The present invention also relates to adopt the various application of these OLED devices, described device forms one or more multiple optical surface, and described surface is transparent and/or (mirror face function) reflection, can be used for outdoor simultaneously and indoor application.
Device can be optionally or the mode of combination form systems such as illumination, decoration, building, perhaps indication is with display panel-for example display panel of picture, sign or alphanumeric indicator type, particularly emergency exit panel.
Thereby the OLED device can be set produce uniform light,, perhaps prepare the various luminous zones of same intensity or varying strength especially for even illumination.
Conversely, can search the illumination that to distinguish.Organic light emission system (OLED) produces direct light district, and other luminous zone obtains by extracting the oled light line, and described oled light line is selected to make substrate by glass by total reflection guiding of substrate thickness.
In order to form this another luminous zone, it is can be with the OLED system adjacent or be positioned on the opposite side with respect to substrate to extract the district.Extract the district and can be used for for example increasing the illumination that the direct sunshine district provides,, perhaps be used to indicate luminescent panel especially for architectural lighting.Extract the form that the district is preferably one or more light belts, light belt uniformly particularly, they preferably place on one of described the periphery.These bands can for example form the picture of highly luminescent.
Extract by placing at least a of following mode of extracting the district: diffusion layer, be preferably based on inorganic particle and the preferred inorganic bond that uses, that makes has diffusible substrate, a particularly textured or coarse substrate.
Two first type surfaces can have the direct sunshine district separately.
When the electrode of selecting the OLED system and organic structure when being transparent, especially, can prepare illuminated window.At this moment, the illumination in improvement house just is not the infringement transmittance.Also, also can control degree of reflection, for example in order to meet the standard of prevent-dazzling the eyes of building masonry wall effectively by the light reflection in the reflection of restriction light, particularly the illuminated window outside.
More widely, device, particularly some or all of transparent unit, can:
-be used for the building, for example outside fluorescent glass, internal illumination dividing plate or fluorescent glass door (perhaps Men a part), particularly slidably those;
-be used for the vehicles, for example luminous top, luminous side window (the perhaps part of window), land, under water or the internal illumination dividing plate of transatmospheric vehicle;
-be used for city furniture or professional furniture, for example bus shelter panel, exhibition booth wall or shopper window, greenhouse wall perhaps throw light on and use brick and tile;
-be used for furnishings, for example the front of the element of shelf or cabinet, cabinet, illumination with brick and tile, ceiling, illumination with refrigerator shelf, fish jar wall;
-be used for the backlight of electronic equipment, particularly display screen, choose double screen, for example video screen or computer screen, touch screen wantonly.
For example, can be designed for bilateral screen backlight of different size, the small screen is preferably united use to concentrate light with the Fresnel lens.
In order to form illuminated mirror, if wish preferably only to illuminate a side in direct sunshine district, one of electrode can be a reflection-type, perhaps mirror can be placed on the OLED system opposite face.
It also can be mirror.Luminescent panel can be used to throw light on shower wall or kitchen worktop, perhaps can be ceiling.
Usually, according to used organic material, OLED is divided into two big classes.
If electroluminescence layer is formed by micromolecule, device is called SM-OLED (micromolecule Organic Light Emitting Diode).The electroluminescent organic material of thin layer comprises the molecule of dehydration, for example the molecule of following material: compound AlQ
3(three (oxine) aluminium), DPVBi (4,4 '-(diphenyl ethenylidene) biphenyl), DMQA (dimethyl quinoline a word used for translation) or DCM (4-(dicyano methylene)-2-methyl-6-(4-dimethylamino styryl)-4H-pyrans).Emission layer also can be for example 4,4 ', 4 " three (N-carbazyl) triphenylamines (TCTA) are doped with fac-three (2-phenylpyridine) iridium (Ir (ppy)
3) layer.
Usually, the structure of SM-OLED comprises piling up of HIL (hole injection layer) and hole transmission layer (HTL), emission layer and ETL (electron transfer layer).
The example of hole injection layer is that copper phthalocyanine (CuPC) and hole transmission layer can be N for example, N '-two (naphthalene-1-yl)-N, N '-two (phenyl) benzidine (α-NPB).
Electron transfer layer can be by three-(oxine) aluminium (AlQ
3) or phenanthrolene (BPhen) formation.
Top electrode can be Mg/Al or LiF/Al layer.
The example that organic light emission piles up is for example described in the document US 6 645 645.
If organic electro luminescent layer is a polymer, device is called PLED (polymer LED).
The electroluminescent organic material of thin layer for example comprises polymer (PLED), PPV, representative poly-(right-phenylene vinylidene), PPP (poly-(right-phenylene)), DO-PPP (poly-(2-Oxy-1 in the last of the ten Heavenly stems, the 4-phenylene)), MEH-PPV (poly-[2-(2 '-ethyl hexyl oxy)-5-methoxyl group-1, the 4-phenylene vinylidene]), CN-PPV (poly-[2, two (the own oxygen bases)-1 of 5-, 4-phenylene-(1-cyano group ethenylidene)]) or PDAF (poly-diakyl fluorenes), also be used in combination with polymeric layer with the layer that promotes hole injection (HIL), the hole injection layer for example is made of PEDT/PSS (poly-(3,4-ethenylidene-dioxy thiophene)/poly-(4-styrene sulfonate)).
The example of the PLED that constitutes by following stacking material:
-poly-(2,4-vinyl dioxy thiophene) are doped with poly-(styrene sulfonate) layer (PEDOT:PSS), and its thickness is 50nm; With
The layer of poly-(right-phenylene vinylidene) Ph-PPV of-phenyl, its thickness is 50nm.
Top electrode can be the layer of Ca.
Description of drawings
Now, will the present invention be described in more detail by non-limiting example and accompanying drawing:
-Fig. 1 is used for the evenly schematic sectional view of (back of the body) light-struck organic light emitting apparatus, and it comprises the hearth electrode of first embodiment of the present invention;
-Fig. 2 is the partial view that more specifically shows described hearth electrode;
-Fig. 3 has illustrated the method that is used to make with the described electrode of etching;
-Fig. 4 has illustrated and has been used for the evenly schematic sectional view of (back of the body) light-struck organic light emitting apparatus that it is arranged in many zones and comprises the hearth electrode of second embodiment of the present invention;
-Fig. 5 and 6 has illustrated schematic top view, has shown that two charts are used for being electrically connected the similar electrode used to second embodiment; With
-Fig. 7 is the schematic side elevational view that is used for the organic light emitting apparatus of the illumination that can distinguish.
Should be noted that,, do not need to make in proportion schematic diagram in order to describe the various elements (comprising angle) of object in detail.
Embodiment
Fig. 1 is intended to highly schematic.Fig. 1 has shown the cross section of organic light emitting apparatus 10 (end-light-emitting device that is to say that it is luminous to pass substrate), and organic light emitting apparatus 10 comprises continuously:
The flat substrate 1 of-transparent or super clear soda-lime glass, its thickness is 2.1mm, has first and second first type surfaces, 11,12, the first first type surfaces 11 and has:
-directly be deposited on the basic unit 2 on first first type surface 11, also as etching stopping layer, it is made by silicon nitride, and thickness is 10nm-80nm, and covers the whole of all first first type surfaces 11 basically;
-directly be deposited on the hearth electrode (or electrode film) 3 on the basic unit 2, etching, and to select it be transparent, and it comprises the laminated coating (referring to Fig. 2) of following type, laminated coating comprises:
-contact layer 31, it is selected from ZnO
x(doping or unadulterated), Sn
yZn
zO
x, ITO or IZO;
-the functional layer 32 that is made from silver, preferred fine silver;
-optional exist be located immediately at last barrier film 32 on the functional layer 32 ';
-be selected from ZnO
x, Sn
yZn
zO
x, ITO or IZO protective layer 33, contact layer and protective layer, it is used to protect the influence that is not subjected to water and/or oxygen, and character is identical;
-cover layer 34 particularly mates the cover layer of work function;
That is to say that it is 5-20nm that preferred laminated coating ZnO:Al/Ag/Ti or NiCr/ZnO:Al/ITO have following thickness: ZnO:Al respectively; Silver is 5-15nm; Ti or NiCr are 0.5-2nm; ZnO:Al is 5-20nm; ITO is 5-20nm;
-organic light emission system 4, for example SM-OLED of following structure:
-α-NPD layer;
-TCT+Ir (ppy)
3Layer;
-BPhen layer;
-LiF layer;
-reflection, metal particularly, top electrode 5 is especially based on silver or aluminium.
By magnetron sputter at room temperature, normally sputter on the substrate of 1-4mm thickness is used to prepare a series of deposition example of the laminated coating of basic unit 2 and film 3.
Following table shows character of these each layers of embodiment and the key property of thickness and these embodiment that unit is nanometer.
By atomic force microscopy measure R MS roughness (perhaps Rq).
The sedimentary condition that is used for each layer is as follows:
Under the pressure of 0.25Pa, in argon/blanket of nitrogen, use the silicon target of aluminium-doping, deposit Si by reactive sputtering
3N
4: Al-basic unit;
Under the pressure of 0.2Pa, in argon/oxygen atmosphere, use the zinc tin oxide target of antimony-doping, described target comprises 65 weight %Sn, 34 weight %Zn and 1 weight %Sb deposit SnZn:SbO by reactive sputtering
x-basic unit;
Under the pressure of 0.8Pa, in straight argon atmosphere, use silver-colored target to come depositing silver-e of basic unit;
Under the pressure of 0.8Pa, in straight argon atmosphere, use the titanium target to come the depositing Ti layer;
Under the pressure of 0.2Pa, in argon/oxygen atmosphere, use aluminium-doping zinc target, deposit ZnO:Al-basic unit by reactive sputtering; With
In argon/oxygen atmosphere, under the pressure of 0.2Pa, in argon/oxygen atmosphere, use ceramic target to deposit ITO-base cover layer.
* on the substrate that the soda-lime glass thick by 0.7mm made;
*: at 1000cd/m
2Down, be used to launch the OLED system (1m/W of unit) of the optimization with x and y coordinate of white light, measure in xy CIE colorimetric method system, it that is to say x=0.45 and y=0.41 near luminous A of hope.
In this structure, electrode of the present invention make the unit of OLED be 1m/W power reforming 5-10% at least, perhaps 15%, even surpass 20%, compare with the ITO electrode, brightness is greater than 500cd/m
2
As variant, barrier film 31 under first (end) electrode can comprise ', be similar to barrier film 32 ', especially, comprise metal level, the preferred metallic target with neutral plasma that uses obtains, and perhaps plants the nitride of metal and/or the layer that oxide is made by one or more, described metal is Ti, Ni and Cr for example, and the preferred ceramic target with neutral plasma of using obtains.
In embodiment 1-6, electrode is a transparency electrode, the light conduction 〉=50% of the substrate that applied, and be 50% and 90%.In according to embodiments of the invention 1-4, described light conduction is high, and this is because the light conduction is 75-85%.In embodiments of the invention 5, the light conduction can't deny that ground is very low, although it is still greater than 50%, this not necessarily is exactly a shortcoming, because its absorption is very low.These embodiment 1-6 can not be used as reflecting electrode, and this is because the reflection of their light less than 70%, can not be used as transparent/reflecting electrode, because their T
L/ R
LThan not between 0.1-0.7.
In embodiment 4 and 5, transparency electrode comprises smooth layer 30, and in embodiment 1-3, does not have such smooth layer.It is about 10% that the roughness of whole laminated coating that makes described smooth layer has reduced, and this measures on cover layer 34, and simultaneously the laminated coating of sheet resistance has been improved about 5%.
In embodiment 7, the substrate of coating can be used as transparent/reflecting electrode, because the T of the substrate of described coating
L/ R
LThan being 0.2, it is between the 0.1-0.7.In addition, the light of the substrate of described coating conducts less than 50%, therefore, can not be used to prepare transparency electrode, but it can be used to prepare reflecting electrode, because its light reflection is greater than 70%.
First electrode can be a reflecting electrode also basically.
As variant, hearth electrode 3 can have the structure of repetition n time, and wherein n is equal to or greater than 1 integer, and described structure is as follows: contact layer/functional layer/(thin thermoprint layer)/(water and/or oxygen barrier layer).
On the described structure for comprising contact layer/functional layer/(water and/or oxygen barrier layer)/described tectal stratose.
In the situation of piling up of organic structure, for example rubescent look, green and blue light, so that preparation white light, also can repeat all elements 3,4,5 three times, perhaps use multilayer simply, described multilayer comprises: optional thin similar thermoprint layer/ITO that exists of Al/ITO or Ag/ or the optional thin similar thermoprint layer/ZnO/ITO that exists of Ag/ are used for other hearth electrode.
Top electrode extends along the opposite side of substrate 1.And then the optional second metal current source band that exists on the edge of top electrode 5 is preferably similar to first sheet metal.If the thickness of top electrode is 50nm or littler, preferred described second.
As variant, second electrode in fact also is transparent or translucent electrode, for example can be identical with first electrode or similar.In this case, randomly, add reflector to second 12, for example metal layer thickness is 150nrm.
The EVA sheet can be used to substrate 1 is laminated on other pane, and the preferred glass of other pane glass has the characteristic identical with substrate 1.Randomly, the face 12 towards the EV sheet of pane 1 provides the laminated coating with the given function of aftermentioned.
Adopt wet etching to separate with hearth electrode 3 electricity with the top electrode 5 that will install 10.
For in an etching scheme and in same etched pattern; the whole hearth electrode of etching in an operation (contact layer, functional layer, the optional last barrier film that exists or layer, optional protective layer and the cover layer that exists); each layer is exposed to one of following acid solution; adopting acidproof adhesive tape that described layer is carried out part in advance shelters; perhaps, use the lithoprinting mask as variant:
-HCl (for example 40% concentration);
-or HCl (for example 4% concentration);
-or HCl (for example 4% concentration)/HNO
3(for example 7% concentration) mixture;
-or HCl/FeCl
3Mixture; Perhaps
-HNO
3, concentration is 10-18%.
Obtain etching outline very uniformly with the salt acid etching.Also obtain useful results with nitric acid/hydrochloric acid mixture etching.Under the situation that is ITO, the conventional HCl/FeCl that adopts
3Mixture.
Use the mixture of described two kinds of acid and, can regulate etching outline, etching period and resolution by changing concentration.
Therefore, can etched width and the pattern that changes with application of spacing.
For little passive-array OLED screen (display that is used for electronic equipment-mobile phone, display, the private secretary, MP3 reader etc.), the width of each etching region can typically be 10-20 μ m, each etching region separates 10-50 μ m, for example 35 μ m (corresponding to the width of each electrode district).
Under the situation of big passive-array OLED screen, for example be used for advertisement or the indication use display, the width of each etching region can be several millimeters, several centimetres or bigger for the width of about 0.5mm and each electrode district.
Be used for even illumination, the width of each etching region can be equal to or less than 100 μ m, more preferably is equal to or less than 50 μ m, and irrelevant with the size of screen.
Fig. 3 has illustrated the method that is used to make with the described electrode of etching.
Depositing basic unit 2, electrode 3 and metal current source layer 6 (no matter being individual layer or multilayer) afterwards, adopt not can etched electrodes solution come the described layer 6 of etching, described solution for example NaOH (step e 1) and, such as explained then, etching hearth electrode 3 in one step (step e 2), deposit OLED system 4 and top electrode 5 then thereon, for example make thereon (step e 3) by Al.
Fig. 4 has illustrated and has been used for the evenly schematic sectional view of the organic light emitting apparatus 10 of (back of the body) optical illumination that it is arranged in many zones, and comprises the hearth electrode of second embodiment of the present invention.
Aspect following element, described second device is different from first device.
Top electrode also is separated.The leftmost edge of the second hearth electrode district 3b is extended and covers in the first top electrode district 5 to the right.The second top electrode district 5b extends and covers the leftmost edge in remaining hearth electrode district to right hand edge, and by the covering of second sheet metal, forms bus bars, obtains bus electrode structure 62.
Etching region 310,320 for example is the ribbon of width 20-50 μ m, so naked eyes almost as seen.
Fig. 5 and 6 has illustrated schematic top view, and it has shown two schemes that are used to connect the electrode similar to the used electrode of second embodiment.
In Fig. 5, three 4-4c of organic light emission system are connected in series.Etching region 310 and 320 is ribbons of width 20-50 μ m, so naked eyes almost as seen.
Hearth electrode is divided into three rectangles, and the width length of side is about 10cm separately, extends on each comfortable side on (left side in the drawings).They opened in etched regional 310,320 minutes.Top electrode 5-5c also is divided into three parts.First sheet metal partly covers the first hearth electrode district, forms bus bars, obtains bus electrode structure 61.
Two top electrode district 5a, 5b extend and cover the leftmost edge in adjacent hearth electrode district to the right.The 3rd top electrode district 5c extends and covers the leftmost edge in remaining hearth electrode district to right hand edge, and by the covering of second sheet metal, forms bus bars, obtains bus electrode structure 62.
In Fig. 6, connect six 4-4c of organic light emission system, 4 '-4 ' c (three continuous 4-4c of system are positioned at the top of figure, and three the continuous 4a ' of system-4c ' are positioned at the bottom of figure) with two series systems that are parallel to each other.In etching region 310-330,310,320 all is horizontal, and 330 be longitudinally, and is that width is the bar of 20-50 μ m, thereby naked eyes almost as seen.
Hearth electrode is divided into six squares, and the about 10cm of the length of side extends on each comfortable side on (left side in the drawings).Etched district, hearth electrode district 310-330 separately.Cutting forms first of bus bars, perhaps adopt the bus electrode structure 61,61 on the left side in the drawings ' two sheets, thereby form current-collector.
Top electrode 5-5c, 5 '-5 ' c also is divided into six parts.Top electrode district 5, two tops and 5b (being positioned at the figure top left) extend to the right, and cover the left side edge in the 3rd district of adjacent hearth electrode.
The 3rd top top electrode district 5c extends and covers the leftmost edge in remaining hearth electrode district to right hand edge, and covered by sheet metal, form bus bars, obtain bus electrode structure 62, and between the 3rd top electrode district 5c and 5c ', form and be electrically connected (being positioned on the right of the figure).
Fig. 7 is used for the schematic side elevational view of the organic light emitting apparatus of the illumination that can distinguish.
Described device 10 at first comprises flat transparency carrier 1, preferably is made of preferred heavy sheet glass sheet, and for example thickness is 4mm or 6mm, and its absorption coefficient at visible region is 2.5m
-1Perhaps littler.Preferred select super transparent sodium calcium quartz glass, its at the absorption coefficient of visible region less than 0.7m
-1For this glass provides the first and second parallel first type surfaces 12,11, and has bottom surface 13.By covering in the bottom of described device with its sealing (showing here).
The OLED-type is luminous-and device 10 comprises OLED system 4, and described OLED system 4 is at 25nmSi
3N
4Basic unit on have ZnO:Al
20nm/ Ag
12nm/ Ti
1nm/ ZnO:Al
20nm/ ITO
20nmThe type hearth electrode, described basic unit places on first first type surface 11.Define the first direct sunshine district 71,72 on substrate 1 either side.
Be positioned at the opposite side of OLED system 4 with respect to substrate 1, the first direct sunshine district 71, it has covered the core of second first type surface 12.The second direct sunshine district 72 is positioned at the same side of OLED system 4, extends under whole first first type surface 11.
The characteristic of adjusting device 10, thus the brightness L1 in the first direct sunshine district 71 is preferably greater than the brightness L2 (symbolically showing by thick arrow F1 and thin arrow F2) in the second direct sunshine district 72.
Therefore, in order to make L1 greater than L2, device 10 is main luminous by hearth electrode.For example, select L1 to make it equal about 1000cd/m
2And L2 equals about 500cd/m
2Thereby, euphorosia.
For the extraction of the light that promotes to be directed to, 11 one-tenth of each edge that forms bottom surface 13 and first first type surfaces greater than 90 ° with about 100 ° interior angle, and comprise minute surface, for example argent or copper layer.
The brightness L3 in San Guang district 73 is preferably greater than the brightness L1 (symbolically illustrating by very thick arrow F3) in the first direct sunshine district 71.
Install 10 and can be used for building, as illuminated window, illumination door, greenhouse wall or glass roof, perhaps the side window of the vehicles or illumination are pushed up.Second surface 12 is inner surface (faces that lighting level is the highest).
When illuminating 10 times of device, in night or the environment in dark, center direct sunshine district 71 can protect the privacy of the people in room or the private room.In order to reach this purpose, what all needed is exactly to equal at least by room reflections and the light beam that returns by the light beam that glass transmits.
Therefore, device 10 being designed to also can be as illumination lamina of septum pellucidum or the fish jar wall between the transparent shelf of illumination, luminous refrigerator shelf, two rooms.Therefore, characteristic that can adjusting device 10, thus make the brightness L1 in the direct sunshine district 71 that wins approximate the brightness L2 in the second direct sunshine district 72.
Light district the 71, the 72nd, uniformly.As variant, device 10 also can have at least a following direct sunshine district, and described direct sunshine district is discontinuous and/or forms pattern, sign or indication.
Additional function
Illustrating, is favourable with second surface (being positioned at the opposite side of the organic light emission system) functionalization of carrier substrate 1.
Therefore, stringer on the surface, mean to these thin layers specific performance properties is provided, for example purpose is to make substrate to keep cleaning as far as possible, and the influence that not attacked by environment, that is to say, be used for keeping for a long time ground surface performance and outward appearance, particularly when dust when substrate surface constantly increases, by achieving success aspect the removal dust, make clean operation further to separate and carry out, particularly the dust in organic source, for example impression of the hand or airborne volatile organic matter, perhaps or even sweat or pollute the dust of dust type.
In the substrate field with glass function, the known photocatalysis membrana that uses on substrate has the antifouling ＂ effect of significant ＂, and can commercial scale produce.These photocatalysis membranas usually in described film the form with particle contain the titanium oxide of partially crystallizable at least, particularly be of a size of several (3 or 4) nm to 100nm, the particle of preferred about 50nm, basically with anatase or anatase/rutile be crystallization form.
This is that under the effect of the light in visible light or ultraviolet light range, it can be degraded and be deposited on their lip-deep organic substance because titanium oxide is a kind of in the semiconductor.
Therefore, according to first embodiment, the film with photocatalysis performance derives from based on TiO
2Nano particle and mesoporous silica (SiO
2) solution of adhesive.
According to second embodiment, the film with photocatalysis performance derives from based on TiO
2Nano particle and non-structure silicon dioxide (SiO
2) solution of adhesive.
And, with about the photocatalysis membrana scheme of titanium oxide particle irrelevant be to have selected these titanium oxide particles, because demonstrate based on the titanium oxide of partially crystallizable at least, aspect photocatalysis performance, these titanium oxide particles are more much effective than amorphous titanium oxide.Preferably, described oxide is a crystalline state with the form of anatase form, rutile form or anatase/rutile mixture.
Except titanium oxide, film with photocatalysis performance also can comprise the inorganic material of at least a other type, the form of the oxide of particularly amorphous or partially crystallizable, for example Si oxide (perhaps hopcalite), titanium oxide, tin-oxide, Zirconium oxide or aluminum oxide.By himself having certain photocatalytic effect, described inorganic material also can participate in the photocatalytic effect of crystallization titanium oxide, though with crystallization TiO
2Compare, the photocatalytic effect of described inorganic material is less, and this is amorphous or the situation of the titanium oxide of partially crystallizable.
Film thickness can change between several nm and a few μ m, typically is 50nm-10 μ m.
In fact, can select thickness, particularly use, perhaps TiO in the film according to the expectation of substrate according to various parameters
2The size of crystallite.Also can selective membrane, make it have that more smooth relatively surface-this is that low surface roughness can be favourable because if low surface roughness allows bigger active photocatalyst area to develop.Yet roughness can be to be harmful to too significantly, because it can promote the crust and the accumulation of dust.
According to other variant, can be formed on the substrate another side by anti-reflective film function is provided.
Given below is the preferable range of the geometric thickness and the index of four multi-layer anti-reflection coatings, and described coating is called A:
-n
1And/or n
3Be 2.00-2.30, particularly 2.15-2.25, preferably near 2.20;
-n
2And/or n
4Be 1.35-1.65;
-e
1Being 5-50nm, particularly 10-30nm, perhaps is 15-25nm;
-e
2Be 5-50nm, particularly be equal to or less than 35nm or 30nm, in particular for 10-35nm;
-e
3Be 40-180nm, preferred 45-150nm; With
-e
4Be 45-110nm, preferred 70-105nm.
Be used to form first and/or the 3rd layer the most suitable material of antireflecting coating A, promptly have those of high index, be based on silicon nitride or zirconium nitride or based on the mixture of these nitride.As variant, these height-index layer are based on the mixture of silicon nitride or tantalum nitride or these nitride.All these materials that mix be can choose wantonly, thereby their chemical resistance and/or mechanical endurance and/or electric patience improved.
Be used to form second and/or the 4th layer the most suitable material of layer coating A, promptly have those of low index, be based on Si oxide, silicon-oxygen nitride and/or silicon oxycarbide or based on mixing sieve and silica-sesquioxide.This mixed oxide often has than pure SiO
2Good durability, particularly chemical durability (having provided embodiment among the patent EP 791 562).Can regulate these two kinds of oxides ratio separately,, and increase the refractive index of layer within bounds so that improve the durability of expectation.
The preferred version of described antireflecting coating is following form: substrate/Si
3N
4/ SiO
2/ Si
3N
4/ SiO
2
Much less, the present invention can same mode be used to adopt the light-emitting device that is different from luminous described in the embodiment-device system.
The present invention has been described by embodiment in the front.Certainly, those skilled in the art can make various optional form of the present invention, and can not deviate from the protection range of this patent that claim limits.
Claims (31)
1. substrate (1) that is used for organic light emitting apparatus (10), transparent glass substrate particularly, it comprises, is positioned at the bottom electrode film (3) on first interarea (11), described electrode film (3) is formed by the thin-film multilayer coating, and described laminated coating comprises following at least each layer continuously:
-based on the contact layer (31) of metal oxide and/or metal nitride;
-have a metal function layer (32) of intrinsic conduction performance; With
-based on the cover layer (34) of metal oxide and/or metal nitride, described cover layer (34) is especially for the work function of the described electrode film of coupling,
It is characterized in that described substrate (1) comprises basic unit (2), described basic unit (2) covers described interarea (11).
2. substrate as claimed in claim 1 (1), it is characterized in that, described basic unit (2) is by based on Si oxide or silicon oxycarbide or the layer made based on the material of silicon nitride, silicon-oxygen nitride or silica carbonitride, the material of the optional described basic unit of mixing, and described groundwork thickness is preferably 10-150nm.
3. substrate as claimed in claim 1 or 2 (1), it is characterized in that, described substrate (1) comprises the etching stopping layer that is positioned between basic unit (2) and the contact layer (31), described etching stopping layer particularly based on tin-oxide the layer, perhaps it is characterized in that, described etching stopping layer forms the part of basic unit (2) or forms basic unit (2), and described etching stopping layer is preferably based on silicon nitride, perhaps based on Si oxide, perhaps based on silicon-oxygen nitride, perhaps based on silicon oxycarbide, perhaps, form etching stopping layer optional and the tin dope or the formation alloy of described basic unit based on the silica carbonitride.
4. each described substrate (1) of claim as described above, it is characterized in that, will by described contact layer (31), described cover layer (34) and all layers between this is two-layer form the layer combination be etched in the same etched pattern, and preferably carry out etching at single etching step, the described layer that is positioned between described contact layer (31) and the described cover layer (34) comprises functional layer (32).
5. each described substrate (1) of claim as described above is characterized in that, on the one hand, and the light of described substrate (1) conduction T
LBe equal to or greater than 50%, and on the other hand, described substrate (1) is defined as 1-R
L-T
LAbsorption be equal to or less than 15%, perhaps it is characterized in that the light of described substrate (1) reflection R
LBe equal to or greater than 70%, perhaps it is characterized in that, the T of described substrate (1)
L/ R
LThan being 0.1-0.7.
6. each described substrate (1) of claim as described above is characterized in that the RMS roughness on the described cover layer (34) is equal to or less than 3nm, preferably is equal to or less than 2nm, perhaps more preferably is equal to or less than 1nm.
7. each described substrate (1) of claim as described above, it is characterized in that, described functional layer (32) is based on the pure material that is selected from silver, gold, aluminium and copper, perhaps based on described material and the alloy or the alloy that are selected from other following material: Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co and Sn, and particularly based on gold/silver alloy or based on gold/copper alloy.
8. each described substrate (1) of claim as described above, it is characterized in that, at least a based in the metal oxide of following optional doping of described contact layer (31): chromated oxide, indium oxide, optional substoichiometric zinc oxide, aluminum oxide, titanium oxide, molybdenum oxide, Zirconium oxide, sb oxide, tin-oxide, tantalum pentoxide and Si oxide, and it is characterized in that the thickness of described contact layer is preferably 3-30nm.
9. each described substrate (1) of claim as described above, it is characterized in that, at least a based in the metal oxide of following optional doping of described cover layer (34): chromated oxide, indium oxide, optional substoichiometric zinc oxide, aluminum oxide, titanium oxide, molybdenum oxide, Zirconium oxide, sb oxide, tin-oxide, tantalum pentoxide and Si oxide, and it is characterized in that described tectal thickness is preferably 3-50nm.
10. each described substrate (1) of claim as described above is characterized in that, described function metal level (32) is located immediately at least a barrier film (31 ') down and/or is located immediately at least a going up under the barrier film (32 ').
11. each described substrate (1) of claim as described above, it is characterized in that, at least a barrier film (31 ', 32 ') comprise metal level, metal nitride layer and/or metal oxide layer, wherein, at least a based in the following metal of these layers: Ti, V, Mn, Fe, Co, Cu, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta and W, perhaps based on the alloy of at least a described material.
12. each described substrate (1) of claim as described above, it is characterized in that, described substrate (1) comprises the amorphous smooth layer of being made by mixed oxide (30) between basic unit (2) and contact layer (31), described smooth layer (30) is close to described contact layer (31) and directly places under the described contact layer (31), and described smooth layer (30) is made by the material that is different from the contact layer material.
13. each described substrate (10) of claim as described above, it is characterized in that, described smooth layer (30) is based on the mixed oxide layer of the oxide of one or more following metals: Sn, Si, Ti, Zr, Hf, Zn, Ga, In, and described mixed oxide layer is particularly based on the mixed oxide layer of the optional doping of zinc and tin, or mix indium tin oxide (ITO) layer, or mix indium-zinc oxide (IZO) layer.
14. each described substrate (1) of claim as described above, it is characterized in that, following structure is deposited n time on basic unit (2) and the optional etching stopping layer that exists: contact layer (31) and function metal level (32), wherein, n is equal to or greater than 1 integer, the stratose that comprises following pantostrat is arranged on described structure, and described pantostrat is made of contact layer (31)/function metal level (32)/cover layer (34) at least.
15. each described substrate (1) of claim as described above, it is characterized in that described substrate (1) comprises the bottom bus electrode structure (61,61 ') that is positioned on the described bottom electrode film (3), described bus electrode structure (61,61 ') electrically contacts with described electrode film (3).
16. each described substrate (1) of claim is characterized in that as described above, described substrate (1) comprises the OLED system (4) that is positioned on the electrode film (3).
17. each described substrate (1) of claim is characterized in that as described above, described substrate (1) comprises the top electrode film (5) that is positioned on the described OLED system (4).
18. each described substrate (1) of claim as described above, it is characterized in that, described substrate (1) comprises the top bus electrode structure (62) that is positioned on the described top electrode film (5), and described bus electrode structure (62) electrically contacts with described top electrode film (5).
19. each described substrate (1) of claim as described above, it is characterized in that, the assembly that is formed by described basic unit (2) and described bottom electrode film (3) is made of the laminated coating that is used for building glass, particularly but the ＂ laminated coating by the ＂ malleableize constitutes, perhaps treat that by ＂ the ＂ laminated coating of malleableize constitutes, and/or particularly low-E laminated coating constitutes.
20. each described substrate (1) of claim as described above, it is characterized in that, the described substrate that scribbles described basic unit (2) and bottom electrode film (3) is made of the substrate that is used for building glass, particularly but the ＂ substrate for the treatment of malleableize by the ＂ substrate or the ＂ of ＂ malleableize constitutes, and these substrates scribble thin-film multilayer coating and/or particularly low-E laminated coating.
21. each described substrate (1) of claim as described above, it is characterized in that, described substrate (1) comprises the functional membrane that is positioned on second first type surface (12), and described functional membrane is selected from: antireflection multilayer, anti-fog layer or stain-proofing layer, ultraviolet filter, particularly titanium oxide layer, phosphorus layer, mirror layer and light extraction fringe area (73).
22. the thin-film multilayer coating is used for building glass, particularly low-the E laminated coating, but and/or particularly the ＂ laminated coating of ＂ malleableize or the purposes of the ＂ laminated coating that ＂ treats malleableize, so that prepare a kind of substrate (1) that is used for organic light emitting apparatus (10), each described substrate of claim as described above particularly, described substrate particularly transparent glass substrate comprises, be positioned at the bottom electrode film (3) on first interarea (11), described electrode film (3) is formed by the thin-film multilayer coating, and described laminated coating comprises following each layer at least continuously:
Contact layer (31) based on metal oxide and/or metal nitride;
Metal function layer (32) with intrinsic conduction performance; With
Based on the cover layer (34) of metal oxide and/or metal nitride, described cover layer (34) especially for the coupling described electrode film work function,
Described substrate comprises basic unit (2), and described basic unit (2) covers described interarea (11).
23. as the described purposes of last claim, wherein, described substrate (1) comprises bottom bus electrode structure (61,61 '), is positioned at oled layer (4) on the described bottom electrode film (3), is positioned at top electrode film (5) and top bus electrode structure (62) on the described OLED system (4).
24. an organic light emitting apparatus top light emitting and/or bottom-emission (10), it comprises each described substrate (1) of claim 1-21, perhaps the substrate (1) that uses in each of claim 22 and 23.
25. as the described organic light emitting apparatus of last claim (10), it is incorporated in the glass unit, particularly is incorporated in double glazed unit or the laminated glass unit.
26. as claim 24 or 25 described organic light emitting apparatus (10), it is characterized in that, described organic light emitting apparatus (10) comprises a plurality of adjacent organic light emission systems that emit white light separately, perhaps comprise a series ofly glow respectively, three systems of green glow and blue light, described these systems are connected in series.
27. as each described organic light emitting apparatus (10) of claim 24-26, it is characterized in that, described organic light emitting apparatus (10) forms one or more reflections and/or transparent luminescent surface, particularly throw light on, decoration or building system, the perhaps indication display panel of picture, sign or alphanumeric indicator type for example, luminous zone that described system produces even light or can distinguish is particularly extracted by the direct light in the glass substrate and is distinguished.
28., it is characterized in that described organic light emitting apparatus as each described organic light emitting apparatus (10) of claim 24-27:
-be used for the building, for example outside fluorescent glass, internal illumination dividing plate or fluorescent glass door (perhaps Men a part), particularly slidably those;
-be used for the vehicles, for example luminous top, luminous side window (the perhaps part of window), land, under water or the internal illumination dividing plate of transatmospheric vehicle;
-be used for city furniture or professional furniture, for example bus shelter panel, exhibition booth wall or shopper window, greenhouse wall perhaps throw light on and use brick and tile;
-be used for furnishings, for example the front of the element of shelf or cabinet, cabinet, illumination with brick and tile, ceiling, illumination with refrigerator shelf, fish jar wall;
-be used for the backlight of electronic equipment, particularly display screen, choose double screen, for example video screen or computer screen, touch screen wantonly; With
-illuminated mirror especially for illumination shower wall or kitchen worktop, perhaps is used for ceiling.
29. be used for making method as claim 1-21 substrate (1) as described in each, it is characterized in that, at least described basic unit (2) and described electrode film (3) are deposited on the described substrate, preferably deposit by sputter type vacuum technique at least in part, optional magnetron sputter, and, it is characterized in that, then described substrate is carried out etching.
30. the described method of claim is characterized in that as described above, described etching is acid etching operation, described be etched in the step and adopt be selected from following acid solution and carry out: pure nitric acid HNO
3, or mixture or pure hydrochloric acid or hydrochloric acid and the ferric trichloride FeCl of nitric acid and hydrochloric acid HCl
3Mixture.
31. as claim 29 or 30 described methods, it is characterized in that, in the presence of at least a metal current source band, carry out described etching, described metal current source band is preferably based on the form of the individual layer of following a kind of metal or alloy: described metal is Mo, Al, Cr, Nd, described alloy is MoCr, AlNd for example, or the form of multilayer, for example MoCr/Al/MoCr.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0653617 | 2006-09-07 | ||
| FR0653617 | 2006-09-07 | ||
| FR0654952 | 2006-11-17 | ||
| FR0654952 | 2006-11-17 | ||
| PCT/FR2007/051876 WO2008029060A2 (en) | 2006-09-07 | 2007-09-05 | Substrate for an organic light-emitting device, use and process for manufacturing this substrate, and organic light-emitting device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101536608A true CN101536608A (en) | 2009-09-16 |
| CN101536608B CN101536608B (en) | 2015-12-09 |
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|---|---|---|---|
| CN200780041442.9A Expired - Fee Related CN101536608B (en) | 2006-09-07 | 2007-09-05 | For substrate, its Use and preparation method of organic light emitting apparatus, and organic light emitting apparatus |
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