CN101536608B - For substrate, its Use and preparation method of organic light emitting apparatus, and organic light emitting apparatus - Google Patents

Abstract

The present invention relates to a kind of substrate (1) for organic light emitting apparatus (10), particularly transparent glass substrate, it comprises, be positioned at the bottom electrode film (3) on the first interarea (11), described electrode film (3) is by thin-film multilayer coating formation, and described laminated coating comprises following layer at least continuously :-based on the contact layer (31) of metal oxide and/or metal nitride;-there is the 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, described substrate (1) comprises basic unit (2), and described basic unit (2) covers described interarea (11).

Description

For substrate, its Use and preparation method of organic light emitting apparatus, and organic light emitting apparatus

Technical field

Theme of the present invention is multi-layered electrode, its acid etching and comprise its organic light emitting apparatus.

Background technology

Known organic light emission system or OLED include the laminated coating of electroluminescent material or electroluminescent organic material, make it charged by electrode, usually adopt two conductive layers to be positioned at the form of its both sides.

These conductive layers generally comprise based on indium oxide, the layer of the indium oxide of normally tin-doping, and the abbreviation ITO of the indium oxide of tin-doping is more common.In depth have studied ITO layer especially.Them can be made easily to deposit by magnetron sputter, wherein, use oxide target (non-reacted sputtering) or use the target (reactive sputtering under oxygen type oxidant exists) based on indium and tin, and their thickness is about 100-150nm.But this ITO layer has many shortcomings.First, for improving conductive material and high temperature (350 DEG C) deposition process generation fringe cost.Unless be increased to by layer thickness and be greater than 150nm, otherwise sheet resistance keeps relatively high (10 Ω/ level), and transparency thickness increase can be caused to reduce and surface roughness increase.

Therefore, new electrode structure is developed.Such as, the luminous flat screen of JP2005-038642 teaches TFT (thin-film transistor)-drive, it comprises the electro-luminescent systems of top light emitting, described electro-luminescent systems produces ruddiness, green glow and blue light respectively, to form active matrix (activematrix).

Each organic light emitting apparatus is all equipped with so-called back electrode or hearth electrode, and described electrode comprises:

-adhesion layer, such as, be made up of ITO;

-(partly) reflective metal layer, particularly based on silver or aluminium, or to be made up of the silver containing aluminium, its thickness is at least 50nm; With

-work function matching cover layer (work-function-matchingoverlayer), such as, be made up of ITO.

Summary of the invention

The object of the invention is to obtain conductive layer assembly, to form reliable electrode, described electrode durable (particularly in 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 comprising it, more can not cause the difficulty in production yet.

Object of the present invention particularly can obtain conductive layer assembly, and it for the formation of the hearth electrode of reliability and durability electro-luminescent systems, and does not sacrifice its electric conductivity, its optical quality or oled light performance, does not also produce the difficulty in production.

In content of the present invention, term " hearth electrode " is construed as the electrode referring to and be inserted between carrier substrate and OLED system.

In addition, this purpose will be realized with least cost, and not upset the known structure of organic light emission system related to the present invention.

This relate to exploitation as bottom electrode: as described in electrode be substantial transparent, or be transparent and reflection-type or reflection-type substantially, and described electrode is equal compatibly for OLED, form active matrix and passive matrix OLED screen, or form video recording screen back lighting device, or be generally used for the device of (building and/or decoration) illumination application, or be used to indicate in application, or in other electronic application.

This novel electrode film particularly can have the optical property being 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 the conduction of sufficient light, also has minimum possible light absorption simultaneously.Its reason seems the possible the highest light conduction of unnecessary pursuit to obtain maximum luminous energy in the outlet of OLED device, meanwhile, on the other hand, for panel, must have minimum possible absorption.

Therefore, the present invention is also to select the thin-film multilayer coating compatible with making the method for organic light emitting apparatus, particularly with deposit in OLED system before compatible by the step etching to be formed hearth electrode.

The object of the invention is to the shortcoming by proposing to remedy for the preparation of the new solution of the bottom electrode film of organic light emitting apparatus prior art.

In order to realize this object, theme of the present invention is: a kind of substrate as claimed in claim 1; A purposes for substrate, the particularly purposes of substrate as claimed in claim 22; Comprise the organic light emitting apparatus that described substrate person adopts described substrate as claimed in claim 24; With the method for making described substrate as claimed in claim 29.

Those being subordinated to above claim claims defines favourable selection of the present invention.

Therefore, most broadly say, a theme of the present invention is, a kind of substrate for organic light emitting apparatus, particularly transparent glass substrate, it comprises, and is positioned at the bottom electrode film on the first first type surface, described electrode film is by thin-film multilayer coating formation, and described laminated coating comprises following layer at least continuously:

-based on the contact layer of metal oxide and/or metal nitride,

-there is the metal function layer of intrinsic conduction performance, and

-based on the cover layer of metal oxide and/or metal nitride, described cover layer especially for the work function of the described electrode film of coupling,

Described substrate comprises basic unit (baselayer), and described basic unit covers the first type surface of described substrate.

Basic unit of the present invention has two effects: it had both been formed the alkali-metal barrier from substrate, also forms the requisite anti-reflecting layer of the micropore for OLED system simultaneously.

Therefore, electrode film of the present invention is made up of thin-film multilayer coating, described thin-film multilayer coating comprises at least one metal function layer, particularly based on silver (that is, be made from silver or be made up of the main metal alloy containing silver), with at least one is placed in the end anti-reflective film between substrate and described metal function layer, described anti-reflective film comprises at least one antireflection dielectric layer, i.e. basic unit.

In content of the present invention, term " film " is construed as and refers to, can have the layer be made up of homogenous material, or is made from a variety of materials many layers separately.

Be positioned at and only depend on visual angle in the face of substrate and with the object of the described anti-reflective film of substrate contacts to be the light making OLED system send be only wavelength-optionally under metal function layer.

This is because, if there is no described anti-reflective film, on the one hand, the light that OLED system sends very concentrates on emission wavelength, or concentrate in the very narrow scope of the emission wavelength of OLED system, and on the other hand, the color of described light and energy greatly change along with visual angle.

This thin-film multilayer coating is known in building or vehicle glass (automotiveglazing) field, for the preparation of the heat-intercepting glass of the enhancing of " low-emissivity or low-E " and/or " sunlight control " type.

Therefore, inventor notices that some laminated coating for low-E glass (glazing) may be used for preparing basic unit and the electrode film of organic light emitting apparatus especially, and especially for the basic unit of the panel of these devices and electrode film.

The laminated coating being called " can malleableize " laminated coating or " treating malleableize " coating is particularly suitable, that is, when hope preparation has the substrate of laminated coating, carries out malleableize heat treatment to those adopted laminated coatings.This is just more amazing, this is because be without heat treated when being used for this device for the substrate of organic light emitting apparatus, or do not need to carry out patent on the glass substrate in any case, and carry out sufficient heat treatment and cooling fast fully.

Therefore, theme of the present invention is also the purposes of thin-film multilayer coating for building glass (glazing), or a kind of purposes of substrate for building glass scribbling thin-film multilayer coating, particularly low-E laminated coating or coated substrate and/or particularly " can malleableize " laminated coating or coated substrate or " treating malleableize " laminated coating, to prepare the substrate for organic light emitting apparatus of the present invention.

In content of the present invention, term " can malleableize " laminated coating or substrate are construed as and refer to keep necessary optical property and hot property (represented by the patience (resistance) of every quadrature, this is directly related with emissivity) in heat treatment process.

Therefore, can in a building and the front of same building, such as the face glass of the substrate of the substrate and non-malleableize that combine malleableize is closely put together, described substrate all scribbles same laminated coating, they can not be distinguished from each other by the reflection of visualization of color simply and/or light reflection/transmission.

Such as, have the laminated coating of following change or scribble the substrate of laminated coating before 0 after the heat treatment, will be considered to can malleableize, this is because these changes are not that eyes can be discovered:

-be less than 3%, or the little change Delta T that the light being even less than 2% conducts _l; And/or

-be less than 3%, or the little changes delta R that the light being even less than 2% reflects _l; And/or

-be less than 3 or be even less than 2 the little change of color $\mathrm{\ΔE}=\sqrt{({(\mathrm{\ΔL}*)}^2+{(\mathrm{\Δa}*)}^2+{(\mathrm{\Δb}*)}^2)}.$

In the present invention, " treating malleableize " laminated coating or substrate are construed as the optical property that refers to coated substrate and hot property is acceptable after the heat treatment, but not, or be not under any circumstance all before the heat treatment.

In content of the present invention, such as, there is the laminated coating of following characteristic after the heat treatment or scribble the substrate of laminated coating, " treating malleableize " will be considered to but at least one that do not have before the heat treatment in these characteristics:

The high light conduction T of-at least 50% _l, or even at least 60% or 65%, or even 70%, or even at least 75% and more preferably at least 80%; And/or

The patience R of-at least equally good with the ITO with usual thickness every quadrature _□, be particularly less than 20 Ω/ or be even less than 15 Ω/.

The important point is, the electrode film for panel is also fully transparent, thus before OLED system deposition, it has the light conduction of at least 50% and preferred 60-70%, and on the other hand, has low-down absorption, thus before OLED system deposition, it is defined as 1-R _l-T _labsorption be equal to or less than 15%, or be even equal to or less than 10%, or be even equal to or less than 8%, or be even equal to or less than 5%.

The light conduction being greater than 70% should be avoided, this means, if reach this value, the thickness being positioned at the film coating between metal function layer and OLED system (cover layer and other layer optionally existed) is too large, metal function layer distance OLED system is too far away, is easy to the performance weakening 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), and especially based on Si ₃n ₄;

-based on silicon-oxygen nitride (general formula is SiON);

-based on silicon oxy carbo nitride (general formula is SiONC).

The nitrogenize of basic unit may be slightly substoichiometric.

Preferably, the thickness of basic unit is 10-150nm, even more preferably 20-100nm.

Basic unit gives electrode of the present invention many advantages.First, basic unit forms barrier to the alkali metal of base part.The upper contact layer of its protection is not polluted (described pollution can cause mechanical defect, such as layering), and it also keeps the conductivity of metal function layer simultaneously.Basic unit also prevents the organic structure of OLED device from being polluted by alkali metal, but, cause the life-span of greatly reducing OLED.

Alkali-metal migration may be there is in the preparation process of device, thus cause lacking reliability, and/or and then reduce its life-span.

Basic unit improves the grappling performance (anchoringproperties) of contact layer, and can not cause the increase of a little to the roughness of whole laminated coating, even if insert one or more layers between basic unit and contact layer.

Certainly, the present invention for being extremely beneficial with being easy to discharge alkali-metal carrier substrate electrode close as far as possible, such as particularly transparent or super clear soda-lime glass.

In addition, this special laminated coating structure also can obtain reliable electrode, thus 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 adjustment by the thickness of change metal level or other layer and/or sedimentary condition.

For the organic structure of given OLED device, compared with the ITO electrode of usual thickness, for being greater than 500cd/m ²brightness, electrode of the present invention can make the unit of OLED be the improved efficiency 5-10% of lm/W, and height 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, and the thickness particularly 10-100nm of described etching stopping layer, even more preferably 20-60nm.

Most particularly, in order to simply, etching stopping layer can form a part for basic unit or can be basic unit: preferably, it can based on silicon nitride, or can be the layer based on Si oxide, or based on the layer of silicon-oxygen nitride, or based on the layer of silicon oxycarbide, or or even based on the layer of silicon oxy carbo nitride, be used for strengthening anti-etching performance containing tin, the general formula of layer is SnSiOCN simultaneously.

Etching stopping layer is used for the protective substrate when chemical etching or reactive plasma etching.

Due to etching stopping layer, basic unit keep exist, even quarter figuratum region also like this.Therefore, by edge effect, can stop alkali metal the quarter of substrate figuratum region and adjacent electrode part (or even organic structure) between migration.

Particularly preferably be most (mainly) by that adulterate or unadulterated silicon nitride Si ₃n ₄basic unit/the etching stopping layer made.Silicon nitride very rapidly deposits and forms excellent alkali metal barrier.And because it is relative to the high optical index of carrier substrate, it allows the optical property changing electrode, realizes preferably by the thickness changing described basic unit/etching stopping layer.Therefore, such as, when electrode is transparent, transmitted colors can be regulated by this way, or when the opposite face of carrier substrate is mirror, can accommodation reflex color by this way.

Preferably, functional layer is based on the pure material being selected from silver, gold, aluminium and copper, or 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 forming electrode film is preferably function monofilm, that is simple function layer.But it can be the coating comprising many functional layers and particularly two functional layers.

In order to prepare the electrode film being included in and basic unit and the optional etching stopping layer existed depositing many functional layers of n time, wherein, n be equal to or greater than 1 integer, adopt following structure: contact layer and function metal level, on described structure, have the stratose comprising following pantostrat, described pantostrat is at least made up of contact layer/function metal level/cover layer.

Electrode of the present invention can have large area, such as, be equal to or greater than 0.02m ², or be even equal to or greater than 0.5m ², or be equal to or greater than 1m ².

Advantageously, electrode of the present invention can have:

-be the functional layer of more than 6nm for thickness, electrode of the present invention has the patience of the every quadrature being equal to or less than 10 Ω/, be 10nm and above functional layer for thickness, there is the patience of the every quadrature being preferably equal to or less than 5 Ω/, preferably there is following optical property simultaneously:

-be equal to or greater than 50% light conduction T _l, preferred 60%-70%, or even higher, and prerequisite is that this does not weaken the luminescent properties of OLED, and

-be equal to or less than 15% absorption, or be equal to or less than 10%, or be even more preferably equal to or less than 8%, or even 5%,

Thus, electrode of the present invention is made to be used as transparency electrode satisfactory especially,

-be 50nm and above functional layer for thickness, the patience of every quadrature is equal to or less than 1 Ω/, is preferably equal to or less than 0.6 Ω/, preferably simultaneously, light conduction R _lbe equal to or greater than 70%, even more preferably 80%, thus, make electrode of the present invention be used as transparency electrode satisfactory especially,

-be 20nm and above functional layer for thickness, the patience of every quadrature is equal to or less than 3 Ω/, is preferably equal to or less than 1.8 Ω/, preferably simultaneously, T _l/ R _lthan being 0.1-0.7, thus, electrode of the present invention is made to be used as transparent/reflecting electrode satisfactory especially.

The thickness of the silver selected by electrode-Base Metal functional layer (or all these layers) can be 3-20nm (gross thickness), preferred 5-15nm.In this thickness range, due to the anti-reflective film under silver-Base Metal functional layer (or 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.

But it is not favourable that selected silver-Base Metal functional layer (or all these layers) has significantly larger thickness, if particularly organic light emission system is with reflective operation or top light emitting.In this case, the thickness of the Yin-Ji functional layer (or all these layers) selected by electrode can be 50-150nm (gross thickness), preferred 80-100nm, thus gratifying especially reflecting electrode can be prepared, as mentioned above.

In addition, the thickness of the Yin-Ji functional layer (or all these layers) selected by electrode can be 20-50nm (gross thickness), so that electrode is simultaneously with transmittance and reflectance operation, thus can prepare gratifying especially transparent/reflecting electrode, as mentioned above.

Metal function layer (or each metal), particularly Yin-Ji functional layer, be preferably deposited on thin dielectric layer with crystallization mode, and thin dielectric layer is preferably crystallization also.Therefore, contact layer promotes that the metal level be deposited thereon carries out the crystal orientation be applicable to.

Therefore, functional layer is preferably deposited on oxide-Ji contact layer, even be deposited directly to above oxide-Ji contact layer, based on the contact layer of oxide particularly based on the contact layer of zinc oxide, zinc oxide is optionally doping, optionally adulterating with aluminium, (term " adulterates " and is interpreted as in due form and refers to contact described element in layer, described element is the metallic element of the amount being less than 10 % by weight, and term " based on " be interpreted as the material referring to that layer mainly contains in due form, that is, containing this material of at least 50 % by weight, therefore, term " based on " cover doping).

Geometry (or actual) thickness of contact layer is preferably 3-30nm, more preferably 4-20nm.

The effect of the contact layer be positioned under metal function layer in anti-reflective film sometimes may be out in the cold, particularly when index close to substrate of the index of this layer, and/or when the thickness hour of this layer, typically when the thickness of this layer is less than 10nm.

Contact layer can based on metal nitride, then can be consistent with basic unit, particularly when basic unit is based on silicon nitride.

Preferably, contact layer is based at least one in following metal oxide, wherein optional doping other metal oxide described: 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 (in order to simplify, thinking that silicon is metal here).

Typically, can by doped metallic oxide 0.5-5%.Especially, it can be Al-doped zinc oxide (AZO), Ga-doped zinc oxide (GZO), or or even B-adulterates, Sc-adulterates or Sb-doped zinc oxide, to realize the better stability of deposition process, or or even F-doping or S-doped tin oxide.

Contact layer can based on mixed oxide, especially, and normally non-stoichiometric mixed oxidization tin zinc Sn _xzn _yo _zas amorphous phase, or based on mixing indium tin oxide (ITO) or mixed oxidization indium zinc (IZO).

Preferred zinc oxide ZnO _xlayer, preferred x is less than 1, even more preferably 0.88-0.98, particularly 0.90-0.95.This layer can be pure layer, or doped with Al or the layer doped with Ga.

Normally obtain stacking by continuous print electroless copper deposition operation, described continuous print electroless copper deposition operation is by vacuum technique, and such as sputter, optional magnetron sputter carries out.Also can provide a kind of or even two kinds be called the very thin film of " barrier film (blockingfilm) ", film described in thing is deposited directly under each metal function layer, or be deposited on each metal function layer, or in the every side being deposited on each metal function layer, metal function layer is particularly based on silver, described film is positioned under functional layer on the direction of substrate, as bonding, nucleation and/or diaphragm, and the described film in functional layer is as protection or " sacrifice " film, to prevent because oxygen is from the layer attack be positioned at metal function layer and/or migration, if or the layer be located thereon deposits by sputtering in the presence of oxygen, also be due to oxygen migration, thus weakening metal function layer.

Therefore, function metal level directly can being placed under at least one on barrier film and/or being directly placed at least one under barrier film, the thickness of each film is all preferably 0.5-5nm.

In content of the present invention, when explicitly pointing out directly under other deposit or when directly forming the deposition of layer or film (comprising one or more layers) on other deposit, can insert without any layer between these two kinds of deposits.

At least one barrier film preferably comprises metal, metal nitride and/or metal oxide layer, at least one based in following metal: Ti, V, Mn, Fe, Co, Cu, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta, W, or based on the alloy of material described at least one.

Such as, barrier film can comprise the layer based on following metal: niobium, tantalum, titanium, chromium or nickel, or such as, based on the alloy formed by least two kinds of described metals, nickel-chromium alloy.

Thin thermoprint layer forms protective layer or even " sacrifices " layer, and it prevents the metal of function metal level weakened, particularly when in constructing at following one or more:

If the layer on-functional layer deposits, if the oxide skin(coating) be such as located thereon deposits by sputtering by using reactive (oxygen, nitrogen etc.) plasmasphere;

If the composition of the layer on-functional layer is easy to change (the change of sedimentary condition in industrial manufacturing process, for 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, Transmission light 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 being selected from niobium Nb, tantalum Ta, titanium Ti, chromium Cr and nickel, or based on the alloy formed by 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 are particularly preferred.This layer is based at least one metal with gettering effect strong especially.

Easily can prepare thin metal thermoprint layer, and not weaken functional layer.Described metal level (that is, do not have a mind and wherein introduce oxygen or nitrogen) preferably can be deposited in the inert atmosphere be made up of inert gas (He, Ne, Xe, Ar, Kr).Subsequently based in the layer deposition process of metal oxide, the surface of this metal level is oxidized and is neither left out, also no problem.

Thin metal thermoprint layer so also provides excellent mechanical performance (particularly mar proof and marresistance).Especially true for the heat treated laminated coating of acceptance, therefore, in this processing procedure, oxygen or nitrogen fully spread.

But, for the purposes of metal thermoprint layer, be necessary the thickness of restriction metal level and and then limit light absorption, to keep sufficient light to conduct for transparency electrode.

Can by thin thermoprint layer segment oxidation.Deposit this layer with non-metaliic form, therefore, this layer can not stoichiometrically form deposit, but to deposit with the substoichiometric form of Types Below: MO _xtype, wherein M represents metal, and x is the truth of a matter compared with the stoichiometry of metal oxide; Or MNO _xtype, for the oxide of two kinds of metal M and N (or more than two kinds of metals).Such as, TiO can be mentioned _xand NiCrO _x.

Preferably, x is 0.75 times-0.99 times of the stoichiometric normal number of oxide.For monoxide, can x be selected especially to be 0.5-0.98, and for dioxide, x can be 1.5-1.98.

In a concrete variant, thin thermoprint layer is based on TiO _x, wherein, x can particularly 1.5≤x≤1.98, or 1.5 < x < 1.7, or even 1.7≤x≤1.95.

Can by the nitrogenize of thin thermoprint layer segment.Therefore, this layer can not stoichiometrically form deposit, but with MN _ythe substoichiometric form deposition of type, wherein M represents metal, and y is the numeral being less than metal nitride stoichiometric number.Y is preferably 0.75 times-0.99 times of the stoichiometric normal number of nitride.

Similarly, also can by thin thermoprint layer segment oxynitriding.

Easily can prepare described thin oxidation thermoprint layer and/or thin nitrogenize thermoprint layer, and not weaken functional layer.Preferably, in the non-oxide atmosphere be preferably made up of inert gas (He, Ne, Xe, Ar or Kr), use ceramic target deposition.

Thin thermoprint layer can be preferably made up of substoichiometric nitride and/or oxide, to increase the electrical property of electrode and the reproducibility of optical property further.

Selected thin substoichiometric oxide and/or nitride thermoprint layer can be preferably based on the metal of at least one be selected from following metal: Ti, V, Mn, Fe, Co, Cu, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta, W, or based on the oxide of substoichiometric alloy, described alloy is based at least one in these metals.

Particularly preferably be as lower floor: as described in layer based on the oxide or the oxynitride that are selected from following metal: niobium Nb, tantalum Ta, titanium Ti, chromium Cr or nickel, or based on the alloy formed by 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 be made up of following material: silicon nitride SiN _x, or aluminium AlN _x, or chromium nitride CrN _x, or titanium nitride TiN _x, or permitted polymetallic nitride, such as NiCrN _x.

Use special deposition atmosphere, thin thermoprint layer can have oxidation gradient, such as M (N) O _xi, wherein xi is change, and the degree of oxidation that the part thermoprint layer that contact with functional layer compares from functional layer layer is farthest low.

Barrier film can also be multilayer, particularly comprises:

-on the one hand, " interface " layer and described functional layer abutting contact, described boundary layer is made up of the material based on non-stoichiometric metal oxide, nitride or oxynitride, such as above-mentioned those;

-on the other hand, at least one layer is made up of metal material, such as above-mentioned those, this layer and described " interface " layer abutting contact.

Boundary layer can be the oxide of metal, nitride or oxynitride, and it is present in the optional adjacent metal level existed.

The cover layer of electrode film of the present invention is preferably based at least one in following metal oxide, wherein optional doping other metal oxide described: 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 such as doped with the tin-oxide of F, Sb, or aluminium-doped zinc oxide, or optional based on mixed oxide, particularly mixes indium tin oxide, mixed oxidization indium zinc or mixing zinc tin oxide.

Substrate of the present invention its roughness preferred scribbling basic unit and electrode film makes the peak on cover layer-paddy distance be equal to or less than 10nm.

For the substrate of the present invention scribbling basic unit and electrode film, preferably its supratectal RMS roughness is 3nm or less, be more preferably 2nm or less, even be more preferably 1.5nm or less, or more preferably 1nm or less, thus avoid the acupuncture defect that strongly can reduce the life and reliability of particularly OLED.

RMS roughness represents r.m.s. roughness.This is measuring of the RMS deviation of roughness.Therefore, this RMS roughness has particularly quantized the peak of the roughness relevant with average height and the average height of groove.Therefore, the RMS roughness of 2nm means bimodal mean amplitude of tide.

Can measure in every way: such as, by Atomic Force Microscopy, by mechanical pin type system (adopting the measuring instrument that such as VEECO sells with trade name DEKTAK) with pass through optical interference measurement.Usually, measured by atomic force microscopy at the area of 1 square micron, at larger area, namely take advantage of the area of 2 millimeters for about 50 microns, measured by mechanical pin type system.

Particularly obtain described low roughness when substrate comprises the amorphous smooth layer be made up of mixed oxide between basic unit and contact layer, described smooth layer is close to described contact layer and is directly placed under described contact layer, and is made up of the material being different from 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 mixing indium tin oxide (ITO) layer, or mixing indium-zinc oxide (IZO) layer.

Preferably, the geometry thickness of smooth layer is 0.1-30nm, is more preferably 0.2-10nm.

But substrate preferably includes the end bus electrode structure be positioned on bottom electrode film, described bus electrode structure and described electrode film electrical contact.

End bus electrode structure is the form of electric current active layer before etching.Preferably, its thickness is 0.5-10 μm, is preferably the form of the individual layer based on following a kind of metal or alloy: described metal is Mo, Al, Cr, Nd, described alloy such as MoCr, AlNd, or the form of multilayer, such as MoCr/Al/MoCr.

During for the preparation of OLED device, from the first first type surface of substrate, substrate comprises in the following order:

OLED system on-bottom electrode film;

Top electrode film on-described OLED system; With

Top bus electrode structure on-top electrode film, described bus electrode structure and the electrical contact of described top electrode film.

In a concrete scheme, the assembly formed by basic unit and bottom electrode film comprises the laminated coating for building glass, particularly " can malleableize " laminated coating, or " treating malleableize " laminated coating, and/or particularly low-E laminated coating, particularly with the laminated coating of Types Below:

-based on metal oxide and/or basic unit/(etching stopping layer)/(smooth layer)/oxide interface layer/(lower barrier film)/metal function layer/(upper barrier film)/based on the cover layer of metal oxide and/or metal nitride based on metal nitride;

-based on the base stage of metal nitride and contact layer/(lower barrier film)/metal function layer/(upper barrier film)/based on the cover layer of metal nitride.

In another embodiment, the substrate scribbling basic unit and bottom electrode film comprises the substrate for building glass, the particularly substrate of " can malleableize " building glass or the substrate of " treating malleableize " building glass, these substrates scribble thin-film multilayer coating and/or particularly low-E laminated coating, described substrate preferably after stringer not by malleableize.

In further embodiment, substrate of the present invention comprises, be positioned at the functional membrane on the 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, phosphorous layer, mirror layer and light extract fringe area.

Flat substrate can be transparent (launching especially for by substrate).Flat substrate can be rigidity, flexible or semiflexible.

Flat substrate is preferably made up of glass, particularly soda-lime glass.Advantageously, under the wavelength of oled light line, substrate can be that absorption coefficient is less than 2.5m ^-1, be preferably less than 0.7m ^-1glass.

Such as, FeIII or Fe containing being less than 0.05% is selected ₂o ₃soda-lime glass, particularly derive from the glass Diamant of Saint-Gobain glass, derive from the glass Optiwhite of Pilkington, or derive from the glass B270 of Schott.The all super clear glass compositions described in document WO04/025334 can be selected.

In the structure selected by being launched by transparency carrier thickness for OLED system, in a substrate the carrying out of some light sent is led.

In addition, in expedients of the present invention, the thickness of selected glass substrate can be at least 1mm, such as preferred at least 5mm.This makes the quantity of internal reflection reduce, and therefore, it is possible to extract the more light be directed in glass, thus increase the brightness of luminous zone.

In order to carry out optimum circulation to institute's guided ray, also can reflection substrate edge and preferably there is minute surface, and/or but the described edge first type surface that can be connected with OLED system is formed and is greater than 90 ° is less than or equal to angle in 135 °, preferably about 100 °, to lead again to light at wider extraction area.Therefore, can there be inclined-plane at the edge of substrate.

In document JP2005-038642, in order to carry out electrically separated to electrode, in the many etching steps carried out with various etch-rate using various acid, construct hearth electrode.Therefore, the layer of first etching coupling work function, then etch metal layers, final etch adhesion layer.

An object of the present invention is to obtain conductive layer assembly, thus form reliability and durability electrode (particularly in stability and/or thermal endurance and mechanical endurance), and do not sacrifice its electric conductivity or its optical quality, the performance of the device comprising it is not sacrificed yet, more can not cause the difficulty in production, particularly when for all the more so during wet etching.

Therefore, the invention provides on substrate, the multi-layered electrode particularly on glass substrate carries out 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 the method for making substrate of the present invention, wherein, basic unit and electrode film is at least deposited on substrate, preferably deposited by sputtering type vacuum technique at least at least in part, optional magnetron sputter, then described substrate is etched, thus in one step at least etched electrodes film.

Carry out all layers of depositing electrode film preferably by evaporating deposition technique, but do not get rid of the layer that can be deposited ground floor or laminated coating by other technology, such as pyrolysis-type pyrolysis technique.

In the context of the method for making described device, if electrode film does not directly have required electrode structure, it will carry out the etching step for the preparation of electrode structure, such as chemistry (preferred acid) screen printing step or laser-induced thermal etching step, such as, become known for those steps of ITO-base electrode film substantially.

Most particularly, RIE (reactive ion etching) can be passed through or etch electrode film of the present invention more particularly by wet etching (easily can be merged into preparatory phase and under atmospheric pressure carry out the method that operates).

Preferably etch from contact layer to tectal all layers with same etched pattern with preferably by single etching operation, comprise functional layer, that is, do not etch basic unit self.Etching stopping layer, if present, preferably also without etching, but can slight etching, such as etch 1/10th of its initial thickness.If there is no etching stopping layer, same be applicable to basic unit.

And, usually preferably before deposition OLED system, provide the electrode film with bus electrode.Preferably etch the layer that will form bus electrode with electrode film simultaneously.

Therefore, the invention provides on acid etching substrate, the method of the multi-layered electrode particularly on glass substrate, described substrate comprises acid etching stop-layer, be preferably based on the substrate of silicon nitride and/or Si oxide, in one step, adopt single acid solution to etch, described acid solution is selected from pure nitric acid HNO ₃, or the mixture of nitric acid and hydrochloric acid HCl or pure hydrochloric acid or hydrochloric acid and ferric trichloride FeCl ₃the mixture of (or being called FeIII chloride).

Therefore, can etch such etched pattern, wherein the width of moment pattern and spacing vary depending on the application.

Described etching is carried out under the existence of at least one metal current source band, 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 such as MoCr, AlNd, or the form of multilayer, such as MoCr/Al/MoCr.

The present invention also relates to organic light emitting apparatus, described organic light emitting apparatus comprises at least one carrier substrate, particularly glass substrate, prerequisite is that at least one organic electro luminescent layer is placed between aforementioned hearth electrode (namely closest to the electrode of carrier substrate) and top electrode.

OLED device can prepare monochromatic light, particularly blue and/or green and/or red light, or can adjust it thus produce white light.

In order to produce white light, can adopt in many ways: mixing cpd (red, green, blue-light-emitting) in simple layer; Stacking three organic structures (red, green and blue-light-emitting) or two organic structures (yellow and blue) at the electrode surface; The organic structure (red, green, blue-light-emitting) that continuous print three is adjacent; A surface of electrode arranges a kind of organic structure of color, applicable phosphorous layer is set on the other surface.

OLED device can comprise multiple adjacent organic light emission system, and these organic light emission systems emit white light separately, or comprises continuous print three organic light emission systems, and the rubescent look of these organic light emission systems, green and blue light, these systems are such as connected in series.

Device can form a part for compound glass unit, compound glass unit particularly vacuum glass unit or have the glass unit of air layer or other gas blanket.Device can be also monolithic integrated circuit, and comprises monolithic integrated circuit glass unit so that more closely knit compact and/or lighter.

OLED system can be flat with other substrate bonding, or preferably laminated, call it as covering, flat substrate is preferably transparent, and such as glass, uses laminated interlayer, particularly super lamina septum pellucidum.

Laminated glass unit is made up of two rigid substrates usually, is equipped with the laminates of thermoplastic polymer sheets or this between these two rigid substrates.The present invention also comprises the glass unit being 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 one spacing sheet, this spacing sheet based on the elastomeric-type of one-sided or bilateral sticky polymers (that is, described spacing sheet does not need traditional Lamination, that is, traditionally laminatedly usually need heated under pressure, thus softening thermoplastic barrier layer sheet and make it bond).

In the structure shown here, can be laminated interlayer for covering being fixed on the mode of carrier substrate, particularly thermal plasticity slice, such as polyurethane (PU), polyvinyl butyral resin (PVB) or ethylene/vinyl acetate (EVA), or thermal curable list-component or many-component resin (epoxy, or ultraviolet-curable list-component or many-component resin (epoxy, acrylic resin) PU).Preferably, sheet and covering and substrate (substantially) are same sizes.

Laminated interlayer can prevent covering from bending, and especially for large device, such as area is greater than 0.5m ²device.

Especially, EV has many advantages:

-it contains the water of very small size or not moisture;

-do not need in high voltage units process.

The laminated interlayer of thermoplasticity can preferably have the covering be made up of casting resin, because it is easier to operate, more economical and can more seal.

Interlayer optionally comprises the row's conductor wire be placed in interior surface thereof, and described conductor wire facing to top electrode, and/or comprises and is placed in conductive layer on covering interior surface or conducting strip.

Preferably OLED system can be placed in the inner side of two glass unit, there is gas blanket such as inert gas (such as argon).

Top electrode can be conductive layer, is advantageously selected from metal oxide, particularly following material:

The zinc oxide, particularly aluminium-doped zinc oxide ZnO:Al of-doping or gallium-doped zinc oxide ZnO:Ga;

-or doped indium oxide, particularly tin-doped indium oxide (ITO) or zinc-doped indium oxide (IZO).

More generally, can use the transparency conducting layer of any type, such as TCO (transparent conductive oxide) layer, such as its thickness is 20-1000nm.

Also can use the thin metal layer being called TCC (transparent conducting coating), such as, be made up of Ag, Al, Pd, Cu, Pd, PtIn, Mo, Au, typically, its thickness is 5-150nm, and this thickness depends on the Transmission light/reflection of hope.

Electrode needs not be continuous print.Top electrode can comprise multiple conducting strip or conductor wire (silk screen).

And, or can advantageously add the film of given function on the opposite face of substrate with electrode of the present invention on other substrate.This can be anti-fog layer (employing hydrophilic layer), and stain-proofing layer (comprises TiO ₂photocatalysis coating, at least with the form partially crystallizable of anatase), or antireflection multilayer coating such as Si ₃n ₄/ SiO ₂/ Si ₃n ₄/ SiO ₂type, or the coating of filter UV, such as, titanium oxide (TiO ₂) layer.Also can be that one or more phosphorous layer, mirror layer or at least one scattered light extract district.

The present invention also relates to the various application that can adopt these OLED device, described device forms one or more light-emitting area, and described surface is transparent and/or reflection (mirror face function), can simultaneously for outdoor and indoor application.

Device can optionally or combination mode form the systems such as illumination, decoration, building, or indicate use display panel-such as picture, mark or alphanumeric indicator type display panel, particularly emergency exit panel.

Can OLED device be set thus produce uniform light, especially for Uniform Illumination, or preparing the various luminous zones of same intensity or varying strength.

Conversely, the illumination that can distinguish can be searched.Organic light emission system (OLED) produces direct light district, and other luminous zone obtains by extracting oled light line, and described oled light line, by total reflection guiding of substrate thickness, is selected to make substrate by glass.

In order to form this another luminous zone, extracting district can be adjacent with OLED system or on being positioned at relative to substrate opposite side.Extract district and can be used for such as increasing the illumination that direct light district provides, especially for architectural lighting, or be used to indicate luminescent panel.Extract district and be preferably the form of one or more light belts, particularly uniform light belt, on the periphery that they are preferably placed in one of described.These bands can the picture of such as height of formation luminescence.

Extracting with at least one of under type of district is extracted: diffusion layer, is preferably based on inorganic particle and preferably uses inorganic bond, and that makes has diffusible substrate, particularly textured or coarse substrate by being placed in.

Two first type surfaces can have direct light district separately.

When being transparent when selecting the electrode of OLED system and organic structure, especially, illuminated window can be prepared.At this moment, the illumination improving house is not just infringement Transmission light.Also by the reflection of restriction light, the light reflection on particularly outside illuminated window, also can control degree of reflection, such as, prevent-dazzle the eyes standard in order to what effectively meet building masonry wall.

Broadly, device, particularly some or all of transparent unit, can:

-for building, such as outer blaze glass, internal illumination dividing plate or fluorescent glass door (or part of door), particularly slidably those;

-for the vehicles, such as luminous top, luminous side window (or part of window), land, under water or the internal illumination dividing plate of transatmospheric vehicle;

-for urban furniture or professional furniture, such as bus shelter panel, exhibition booth wall or shopper window, greenhouse wall, or illumination brick and tile;

-for furnishings, the element of such as shelf or cabinet, the front of cabinet, illumination brick and tile, ceiling, illumination refrigerator shelf, fish bowl wall;

-for the backlight, particularly display screen of electronic equipment, optional double screen, such as video screen or computer screen, touch screen.

Such as, the backlight of the bilateral screen of different size can be designed for, the small screen preferably with Fresnel lens conbined usage with concentrated light.

In order to form illuminated mirror, if wish the side preferably only illuminating direct light district, one of electrode can be reflection-type, or mirror can be placed on OLED system opposite face.

Also can be mirror.Luminescent panel may be used for illumination shower wall or kitchen worktop, or can be ceiling.

Usually, according to organic material used, OLED is divided into two large classes.

If electroluminescence layer is formed by Small molecular, device is called SM-OLED (Small molecular Organic Light Emitting Diode).The electroluminescent organic material of thin layer comprises the molecule of dehydration, such as 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-dimethylaminostyryl)-4H-pyrans).Emission layer also can be such as 4,4 ', 4, and "-three (N-carbazyl) triphenylamine (TCTA) are doped with fac-tri-(2-phenylpyridine) iridium (Ir (ppy) ₃) layer.

Usually, the structure of SM-OLED comprises the stacking of HIL (hole injection layers) and hole transmission layer (HTL), emission layer and ETL (electron transfer layer).

The example of hole injection layers is copper phthalocyanine (CuPC) and hole transmission layer can be such as N, N '-bis-(naphthalene-1-base)-N, N '-bis-(phenyl) benzidine (α-NPB).

Electron transfer layer can by three-(oxine) aluminium (AlQ ₃) or phenanthrolene (BPhen) formation.

Top electrode can be Mg/Al or LiF/Al layer.

Organic light emission stacking example is such as described in document US6645645.

If organic electro luminescent layer is polymer, device is called PLED (polymer LED).

The electroluminescent organic material of thin layer comprises polymer (PLED) such as, PPV, representative poly-(p-phenylene vinylidene), PPP (poly-(p-phenylene)), DO-PPP (poly-(2-Oxy-1 in the last of the ten Heavenly stems, 4-phenylene)), MEH-PPV (poly-[2-(2 '-ethyl hexyl oxy)-5-methoxyl group-1, 4-phenylene vinylidene]), CN-PPV (poly-[2, two (the own oxygen base)-1 of 5-, 4-phenylene-(1-cyano group ethenylidene)]) or PDAF (poly-diakyl fluorenes), also be combined with the layer of promotion hole injection (HIL) with polymeric layer, hole injection layers is such as by PEDT/PSS (poly-(3, 4-ethenylidene-dioxy thiophene)/poly-(4-styrene sulfonate)) form.

An example of the PLED be made up of following stacking material:

-poly-(2,4-ethylenedioxythiophene) is doped with the layer of poly-(styrene sulfonate) (PEDOT:PSS), and its thickness is 50nm; With

The layer of poly-(p-phenylene vinylidene) Ph-PPV of-phenyl, its thickness is 50nm.

Top electrode can be the layer of Ca.

Accompanying drawing explanation

Now, in more detail the present invention will be described by non-limiting example and accompanying drawing:

-Fig. 1 is the schematic sectional view for even (back of the body) light-struck organic light emitting apparatus, and it comprises the hearth electrode of first embodiment of the invention;

-Fig. 2 is the partial view more specifically showing described hearth electrode;

-Fig. 3 describes the method for making and etch described electrode;

-Fig. 4 describes the schematic sectional view for even (back of the body) light-struck organic light emitting apparatus, and it to be arranged in many regions and to comprise the hearth electrode of second embodiment of the invention;

-Fig. 5 and 6 describes schematic top view, shows two charts for being electrically connected and similar electrode used in the second embodiment; With

-Fig. 7 is the schematic side elevational view of the organic light emitting apparatus for the illumination that can distinguish.

It should be noted that, in order to describe the various elements (comprising angle) of object in detail, not needing to make schematic diagram in proportion.

Embodiment

Fig. 1 is intended to high-level schematic.Fig. 1 shows the cross section of organic light emitting apparatus 10 (end-light-emitting device, that is, luminous through 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 the first and second first type surface 11,12, first first type surfaces 11 and has:

-be deposited directly to basic unit 2 on the first first type surface 11, be also used as etching stopping layer, it is made up of silicon nitride, and thickness is 10nm-80nm, and substantially covers the whole of all first first type surfaces 11;

-be deposited directly to hearth electrode (or electrode film) 3 on basic unit 2, etching, and select it to be transparent, it comprises with the laminated coating of Types Below (see Fig. 2), and 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 upper the barrier film 32 ' be located immediately on functional layer 32 existed;

-be selected from ZnO _x, Sn _yzn _zo _x, the protective layer 33 of ITO or IZO, contact layer and protective layer, it is for the protection of the impact not by water and/or oxygen, and character is identical;

-cover layer 34, particularly mates the cover layer of work function;

That is, preferred laminated coating ZnO:Al/Ag/Ti or NiCr/ZnO:Al/ITO has following thickness respectively: ZnO:Al is 5-20nm; Silver is 5-15nm; Ti or NiCr is 0.5-2nm; ZnO:Al is 5-20nm; ITO is 5-20nm;

-organic light emission system 4, the such as SM-OLED of following structure:

-α-NPD layer;

-TCT+Ir (ppy) ₃layer;

-BPhen layer;

-LiF layer;

-reflection, particularly metal, top electrode 5, especially based on silver or aluminium.

By magnetron sputter at room temperature, normally sputter on the substrate of 1-4mm thickness, carry out a series of deposition example of the laminated coating for the preparation of basic unit 2 and film 3.

Following table shows the character of each layer of these embodiments and unit is the thickness of nanometer, and the key property of these embodiments.

RMS roughness (or Rq) is measured by atomic force microscopy.

Sedimentary condition 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 % by weight Sn, and 34 % by weight Zn and 1 % by weight Sb, deposit SnZn:SbO by reactive sputtering _x-basic unit;

Under the pressure of 0.8Pa, in straight argon atmosphere, silver-colored target is used to carry out depositing silver-basic unit e;

Under the pressure of 0.8Pa, in straight argon atmosphere, titanium target is used to carry out 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, ceramic target is used to deposit ITO-base cover layer.

Embodiment	1	2	3	4	5*	6*	7
								Layer
SiO 2						150nm
								ITO						90nm
2:Si 3N 4:Al	20	25	26	21	21		20
								30:SnZn: SbO x				5	5
31:ZnO:Al	20	10	5	5	5		20
								32:Ag	12	12	12	12	12		30
32′:Ti		1	1	1	0.5
								33:ZnO:Al	40	20	20	20			40
34:ITO	20	20	20	20	10		20
T L(％)	75	83	85	85	65	85	16
								R L(％)	15	8	5	8	29	10	81
Abs(％)	10	9	10	7	6	5	3
								The patience (Ω/) of sheet	4. 5	4. 4	3. 5	3. 3	3.5	20	0. 9
RMS roughness (nm)	1. 2	1. 3	0. 9	0. 7	0.7	1	1. 3
								OLED performance (x and y coordinate) * *					20 (0.43； 0.45)	15 (0.43； 0.43)
At 1000cd/m 2Under life-span (hour)					25000	15000

* on the substrate made at the soda-lime glass thick by 0.7mm;

*: at 1000cd/m ²under, adopt and be used for the OLED system (unit lm/W) with the optimization of x and y coordinate of transmitting white, measure in xyCIE colorimetric method system, it is close to the luminous A wished, that is, and x=0.45 and y=0.41.

In the structure shown here, electrode of the present invention make the unit of OLED be the power reforming of lm/W at least 5-10%, or 15%, not even more than 20%, compared with ITO electrode, brightness is greater than 500cd/m ².

As variant, first (end) electrode can comprise lower barrier film 31 ', be similar to barrier film 32 ', especially, comprise metal level, preferably use the metallic target with neutral plasma to obtain, or the layer be made up of nitride and/or the oxide of one or more of metal, described metal such as Ti, Ni and Cr, preferably use the ceramic target with neutral plasma to obtain.

In embodiment 1-6, electrode is transparency electrode, the light conduction >=50% of coated substrate, and is 50% and 90%.According in embodiments of the invention 1-4, described light conduction is high, this is because light conduction is 75-85%.In example 5 in accordance with the invention, light conduction is admittedly very low, although it is still greater than 50%, this is exactly not necessarily shortcoming, because its absorption is very low.These embodiment 1-6 can not be used as reflecting electrode, this is because their light reflection is 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.Described smooth layer makes the roughness of whole laminated coating decrease about 10%, and this measures on cover layer 34, and the laminated coating of sheet resistance is improved about 5% simultaneously.

Embodiment 5 constructs and mutually p-embodiment, and namely embodiment 6 compares the embodiment of optimization, and embodiment 5 has TCO (ITO) electrode.As can be seen from the above table, the sheet resistance of embodiment 5, roughness, performance and life characteristic are all better than embodiment 6.

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 0.1-0.7.In addition, the conduction of the light of the substrate of described coating is less than 50%, therefore, and can not for the preparation of transparency electrode, but it may be used for preparing reflecting electrode, because the reflection of its light is greater than 70%.

First electrode can be also reflecting electrode substantially.

Hearth electrode 3 extends along the side of substrate 1.Therefore, the first metal current source band 61 is had on the edge of and then cover layer 34, preferably its thickness is 0.5-10 μm, such as 5 μm, and be the form of the layer be made up of one of following metal or alloy: metal is Mo, Al, Cr, Nd, alloy is MoCr, AlNd such as, or the form of multilayer such as MoCr/Al/MoCr.

As variant, hearth electrode 3 can have the structure of repetition n time, wherein n be equal to or greater than 1 integer, described structure is as follows: contact layer/functional layer/(thin thermoprint layer)/(water and/or oxygen barrier layer).

For comprising contact layer/functional layer/(water and/or oxygen barrier layer)/described tectal stratose on described structure.

When organic structure stacking, such as rubescent look, green and blue light, to prepare white light, also all elements can be repeated 3,4,5 three times, or use multilayer simply, described multilayer comprises: thin similar thermoprint layer/ZnO/ITO that thin similar thermoprint layer/ITO or Ag/ that Al/ITO or Ag/ optionally exists optionally exists, for other hearth electrode.

Top electrode extends along the opposite side of substrate 1.Optional on the edge of and then top electrode 5 exist the second metal current source band, preferably similar to the first sheet metal.If the thickness of top electrode is 50nm or less, preferably described second.

As variant, the second electrode is in fact also transparent or translucent electrode, such as can be identical with the first electrode or similar.In this case, optionally, reflector is added to the second face 12, such as metal layer thickness is 150nm.

EVA sheet can be used to substrate 1 to be laminated on other pane, and the preferred glass of other pane glass has the characteristic identical with substrate 1.Optionally, the face 12 towards EV sheet of pane 1 provides the laminated coating with aftermentioned given function.

Hearth electrode 3 is made two parts of being separated by etching region 310.

Adopt wet etching with by electrically separated to the top electrode 5 of device 10 and hearth electrode 3.

In order in an etching scheme and in same etched pattern; etch whole hearth electrode (the upper barrier film of contact layer, functional layer, optional existence or layer, the protective layer optionally existed and cover layer) in one operation; each layer is exposed to one of following acid solution; the acidproof adhesive tape of prior employing carries out part to described layer and shelters; or as variant, use lithoprinting mask:

-HCl (such as 40% concentration);

-or HCl (such as 4% concentration);

-or HCl (such as 4% concentration)/HNO ₃(such as 7% concentration) mixture;

-or HCl/FeCl ₃mixture; Or

-HNO ₃, concentration is 10-18%.

Very uniform etching outline is obtained with hydrochloric acid.Also useful result is obtained with nitric acid/hydrochloric acid mixture etching.When for ITO, conventional employing HCl/FeCl ₃mixture.

Use described two kinds of sour mixtures and by changing concentration, etching outline, etching period and resolution can be regulated.

Therefore, can the pattern that changes with application of etched width and spacing.

For little passive-array OLED screen curtain (display for electronic equipment-mobile phone, display, the private secretary, MP3 reader etc.), the width of each etching region can typically be 10-20 μm, each etching region separates 10-50 μm, such as 35 μm (width corresponding to each electrode district).

When large passive-array OLED screen curtain, such as, for advertisement or instruction display, the width of each etching region can be about 0.5mm and the width of each electrode district can be several millimeters, several centimetres or larger.

For uniform illumination, the width of each etching region can be equal to or less than 100 μm, is more preferably equal to or less than 50 μm, and has nothing to do with the size of screen.

Fig. 3 describes the method for making and etch described electrode.

After deposited basic unit 2, electrode 3 and metal electric current active layer 6 (no matter being individual layer or multilayer), employing the solution of etched electrodes can not etch described layer 6, described solution such as NaOH (step e 1) and, then as already explained, hearth electrode 3 (step e 2) is etched in one step, then deposit OLED system 4 and top electrode 5 thereon, such as, make thereon (step e 3) by Al.

Fig. 4 describes the schematic sectional view of the organic light emitting apparatus 10 for even (back of the body) optical illumination, and it is arranged in many regions, and comprises the hearth electrode of second embodiment of the invention.

In following element, described second device is different from first device.

Device 10 shown in Fig. 4 comprises two adjacent organic light emission systems 4 and 4b, they preferably emit white light separately or, as variant, continuous print three organic light emission systems, they are rubescent look separately, green and blue light.System 4 and 4b are connected in series.Hearth electrode is mainly divided into two rectangles or square 3a, 3b, and its length of side is about 10cm, stretches out on (left side in the drawings) on the side of each comfortable OLED system.These electrode zones are separated by etching region 310.By the second electrode district 3b, hearth electrode distinguishes (the right in the drawings) with " remaining " in etching region 320.First metal sheet portions ground covers the first hearth electrode district 3, forms bus bars, obtains bus electrode structure 61.

Top electrode is also separated.First top electrode district 5 extends to the right and covers the leftmost edge of the second hearth electrode district 3b.Second top electrode district 5b extends to right hand edge and covers the leftmost edge in remaining hearth electrode district, and is covered by the second sheet metal, forms bus bars, obtains bus electrode structure 62.

Etching region 310,320 is such as the ribbon of width 20-50 μm, and therefore naked eyes are almost visible.

Fig. 5 and 6 describes schematic top view, which show two schemes for connecting the similar electrode of the electrode used to the second embodiment.

In Figure 5, three organic light emission system 4-4c are connected in series.Etching region 310 and 320 is ribbons of width 20-50 μm, and therefore naked eyes are almost visible.

Hearth electrode is divided into three rectangles, and the respective width length of side is about 10cm, extends (left side in the drawings) on each comfortable side.They are opened by etching area 310,320 points.Top electrode 5-5c is also divided into three parts.First metal sheet portions ground covers the first hearth electrode district, forms bus bars, obtains bus electrode structure 61.

Tou Liangge top electrode district 5a, 5b extend to the right and cover the leftmost edge in adjacent hearth electrode district.3rd top electrode district 5c extends to right hand edge and covers the leftmost edge in remaining hearth electrode district, and is covered by the second sheet metal, forms bus bars, obtains bus electrode structure 62.

In figure 6, the series system be parallel to each other with two connects six organic light emission system 4-4c, 4 '-4 ' c (continuous print three system 4-4c are positioned at the top of figure, and a continuous print three system 4a '-4c ' are positioned at the bottom of figure).In the 310-330 of etching region, 310,320 is all horizontal, and 330 is longitudinal, and to be width the be bar of 20-50 μm, thus naked eyes are almost visible.

Hearth electrode is divided into six squares, and the length of side is about 10cm, extends (left side in the drawings) on each comfortable side.Hearth electrode district is separated by etching region 310-330.Cutting forms the first of bus bars, or adopts two sheets of bus electrode structure 61,61 ' on the left side in the drawings, thus forms current-collector.

Top electrode 5-5c, 5 '-5 ' c are also divided into six parts.Tou Lianggeding top electrode district 5 and 5b (being positioned at figure top left) extend to the right, and cover the left side edge in the 3rd district of adjacent hearth electrode.

3rd top top electrode district 5c extends to right hand edge and covers the leftmost edge in remaining hearth electrode district, and covered by sheet metal, form bus bars, obtain bus electrode structure 62, and form electrical connection (being positioned on the right of figure) between the 3rd top electrode district 5c and 5c '.

Tou Lianggedi top electrode district 5 ' and 5 ' b (being positioned at figure left bottom) right side extend and cover the leftmost edge of the 3rd hearth electrode district 3b of adjacent hearth electrode.

Fig. 7 is used for the schematic side elevational view of the organic light emitting apparatus of the illumination that can distinguish.

First described device 10 comprises flat transparency carrier 1, is preferably made up of preferred heavy sheet glass sheet, and such as thickness is 4mm or 6mm, and its absorption coefficient in visible region is 2.5m ^-1or it is less.The super transparent sodium calcium quartz glass of preferred selection, it is less than 0.7m at the absorption coefficient of visible region ^-1.For this glass provides the first and second parallel first type surfaces 12,11, and there is bottom surface 13.Closed (not showing here) in the bottom of described device by covering.

OLED-type luminescence-device 10 comprises OLED system 4, and described OLED system 4 is at 25nmSi ₃n ₄basic unit on there is ZnO:Al _20nm/ Ag _12nm/ Ti _1nm/ ZnO:Al _20nm/ ITO _20nmtype hearth electrode, described basic unit is placed on the first first type surface 11.Define the first direct light district 71,72 on substrate 1 either side.

Relative to substrate 1, the first direct light district 71 is positioned at the opposite side of OLED system 4, and it covers the core of the second first type surface 12.Second direct light district 72, is positioned at the same side of OLED system 4, to the downward-extension of whole first first type surface 11.

The characteristic of adjusting device 10, thus the brightness L1 in the first direct light district 71 is preferably greater than the brightness L2 (symbolically being shown by thick arrow F1 and thin arrow F2) in the second direct light district 72.

Therefore, in order to make L1 be greater than L2, device 10 is luminous mainly through hearth electrode.Such as, L1 is selected to make it equal about 1000cd/m ²and L2 equals about 500cd/m ², thus euphorosia.

Device 10 is also the light source led by total internal reflection in substrate 1 thickness.By diffusion layer 7, from the light that the edge extracting of second surface 12 is directed to, such as, based on the inorganic scattering particles disperseed in inorganic bond.Therefore, define the 3rd smooth district 73. of the peripheral light-emitting zone of formation as variant, diffusion layer 7 only forms transverse belt or peripheral longitudinal tape.

In order to promote the extraction of the light be directed to, each edge and first first type surface 11 one-tenth of formation bottom surface 13 are greater than the interior angle of 90 ° and about 100 °, and comprise minute surface, such as argent or layers of copper.

The brightness L3 in the 3rd smooth district 73 is preferably greater than the brightness L1 (symbolically being illustrated by very thick arrow F3) in the first direct light district 71.

Device 10 may be used for building, as illuminated window, illumination door, greenhouse wall or glass roof, or the side window of the vehicles or illumination top.Second surface 12 is inner surface (faces that lighting level is the highest).

When illuminating device 10 time, in night or the environment in dark, direct light district 71, center can protect the privacy of the people in room or private room.In order to reach this object, in need be exactly that the light beam that transmitted by glass is at least equaled by room reflections and the light beam that returns.

Device 10 can form two glass unit, and device 10 is preferably placed at the space of the internal gas-filling between substrate 1 and optional thinner other glass pane.

Therefore, device 10 is designed to also to be used as the illumination lamina of septum pellucidum between the transparent shelf of illumination, luminous refrigerator shelf, two rooms or fish bowl wall.Therefore, can the characteristic of adjusting device 10, thus make the brightness L1 in the first direct light district 71 approximate the brightness L2 in the second direct light district 72.

Light district 71,72 is uniform.As variant, device 10 also can have the following direct light district of at least one, and described direct light district is discontinuous and/or forms pattern, mark or instruction.

additional function

Illustrating, is favourable by second surface (being positioned at the opposite side of the organic light emission system) functionalization of carrier substrate 1.

Therefore, stringer on surface, mean as these thin layers provide specific performance, such as object is to make substrate keep clean as far as possible, and not by the impact of environmental assaults, that is, for long-time retentively surface property and outward appearance, particularly when dust constantly increases at substrate surface, by obtaining successfully in removal dust, clean operation can be separated further and carry out, the particularly dust in organic source, such as, volatile organic matter in impression of the hand or air, or or even sweat or pollute the dust of dust type.

In the substrate field with glass function, knownly on substrate, use photocatalysis membrana, there is significant " antifouling " effect, and can commercial scale produce.The titanium oxide of these photocatalysis membranas usually in the form of granules containing at least part of crystallization in described film, particularly be of a size of several (3 or 4) nm to 100nm, the preferably particle of about 50nm, substantially with the form that anatase or anatase/rutile are crystallization.

This is because titanium oxide is the one in semiconductor, under the effect of the light in visible ray or ultraviolet light range, it can be degraded deposition organic substance over their surface.

Therefore, according to the first embodiment, the film with photocatalysis performance derives from based on TiO ₂nano particle and mesoporous silica (SiO ₂) solution of adhesive.

According to the 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, have nothing to do with the photocatalysis membrana scheme about Titanium oxide particles, the titanium oxide based at least part of crystallization have selected these Titanium oxide particles, because demonstrate, in photocatalysis performance, these Titanium oxide particles are more much effective than amorphous titanium oxide.Preferably, described oxide is crystalline state with the form of anatase form, rutile form or anatase/rutile mixture.

Except titanium oxide, the film with photocatalysis performance also can comprise the inorganic material of other type of at least one, the particularly form of the oxide of amorphous or partially crystallizable, such as Si oxide (or 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, although 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 a few nm and several μm, typically is 50nm-10 μm.

In fact, according to various Selecting parameter thickness, particularly can apply according to the expectation of substrate, or TiO in film ₂the size of crystallite.Also can selective membrane, if make it have relatively smooth surface-this is because low surface roughness allows larger active photocatalyst area development, low surface roughness can be favourable.But roughness can be harmful too significantly, because it can promote crust and the accumulation of dust.

According to other variant, can be formed on substrate another side by anti-reflective film and function is provided.

Given below is the geometric thickness of four multi-layer anti-reflection coatings and the preferable range of index, and described coating is called A:

-n ₁and/or n ₃for 2.00-2.30, particularly 2.15-2.25, preferably close to 2.20;

-n ₂and/or n ₄for 1.35-1.65;

-e ₁for 5-50nm, particularly 10-30nm, or be 15-25nm;

-e ₂for 5-50nm, be particularly equal to or less than 35nm or 30nm, especially 10-35nm;

-e ₃for 40-180nm, preferred 45-150nm; With

-e ₄for 45-110nm, preferred 70-105nm.

For the formation of first of antireflecting coating A and/or the most applicable material of third layer, namely having those of high index, is based on silicon nitride or zirconium nitride or the mixture based on these nitride.As variant, these height-index layer are based on the mixture of silicon nitride or tantalum nitride or these nitride.Optionally can be adulterated all these materials, thus improve their chemical resistance and/or mechanical endurance and/or electric patience.

For the formation of second of layer coating A and/or the most applicable material of the 4th layer, namely having those of low index, is 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 (in patent EP791562, giving embodiment).This two oxides ratio separately can be regulated, to improve the durability expected, and increase the refractive index of layer within bounds.

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 in the same manner for adopt the light-emitting device that is different from luminescence-device described in embodiment system.

Describe the present invention by embodiment above.Certainly, those skilled in the art can make various Alternative Form of the present invention, and can not deviate from the protection range of this patent that claim limits.

Claims (29)

1. the substrate for organic light emitting apparatus (10) (1), it comprises, be positioned at the bottom electrode film (3) on the first interarea (11), described electrode film (3) is by thin-film multilayer coating formation, and described laminated coating comprises at least following layer:

-based on the contact layer (31) of metal oxide, this contact layer (31) is optional doping, optional substoichiometric zinc oxide, or based on non-stoichiometric zinc and tin mixed oxide, mixing indium tin oxide, mixing indium-zinc oxide;

-there is the metal function layer (32) of intrinsic conduction performance, this functional layer (32) based on the pure material being selected from silver, or based on described material and the alloy or the alloy that are selected from other following material: Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co and Sn; With

-based on the cover layer (34) of metal oxide, described cover layer (34) is for mating the work function of described electrode film, and it is based on the oxide of doping optional below at least one: molybdenum oxide, indium oxide, mixing indium tin oxide (ITO) layer or mixing indium-zinc oxide (IZO) layer;

It is characterized in that, described substrate (1) comprises basic unit (2), described basic unit (2) covers described interarea (11), described substrate (1) comprises the etching stopping layer be positioned between basic unit (2) and contact layer (31), or it is characterized in that, etching stopping layer forms a part for basic unit (2) or forms basic unit (2), and described etching stopping layer is based on silicon nitride, or based on Si oxide, or based on silicon-oxygen nitride, or based on silicon oxycarbide, or based on silicon oxy carbo nitride, form the optional and tin dope of the etching stopping layer of described basic unit, described metal function layer (32) to be located immediately under at least one on barrier film (31 ') and/or to be located immediately at least one under barrier film (32 ').

2. substrate (1) as claimed in claim 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 silicon oxy carbo nitride, the material of the described basic unit of optional doping, and described groundwork thickness is 10-150nm.

3. substrate (1) as claimed in claim 1 or 2, it is characterized in that, the combination of the layer be made up of described contact layer (31), described cover layer (34) and all layers between this is two-layer is etched in same etched pattern, described in the layer be positioned between described contact layer (31) and described cover layer (34) comprise functional layer (32).

4. substrate (1) as claimed in claim 1 or 2, is characterized in that, the light conduction T of described substrate (1) _lbe equal to or greater than 50%, described substrate (1) is defined as 1-R _l-T _labsorption be equal to or less than 15%, or to it is characterized in that, the light reflection R of described substrate (1) _lbe equal to or greater than 70%, or it is characterized in that, the T of described substrate (1) _l/ R _lthan being 0.1-0.7.

5. substrate (1) as claimed in claim 1 or 2, it is characterized in that, the RMS roughness on described cover layer (34) is equal to or less than 3nm.

6. substrate (1) as claimed in claim 1 or 2, it is characterized in that, the thickness of described functional layer (32) is 3-20nm.

7. substrate (1) as claimed in claim 1 or 2, it is characterized in that, the thickness of described contact layer is 3-30nm.

8. substrate (1) as claimed in claim 1 or 2, it is characterized in that, the thickness of described cover layer (34) is 3-50nm.

9. substrate (1) as claimed in claim 8, it is characterized in that, at least one barrier film (31 ', 32 ') metal level, metal nitride layer and/or metal oxide layer is comprised, wherein, these layers are based at least one in following metal: Ti, V, Mn, Fe, Co, Cu, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta and W, or based on the alloy of material described at least one.

10. substrate (1) as claimed in claim 1 or 2, it is characterized in that, described substrate (1) comprises the amorphous smooth layer (30) be made up of mixed oxide between basic unit (2) and contact layer (31), described smooth layer (30) is close to described contact layer (31) and is directly placed under described contact layer (31), and described smooth layer (30) is made up of the material being different from contact layer material.

11. substrates (10) as claimed in claim 10, is characterized in that, described smooth layer (30) is the mixed oxide layer of the oxide based on one or more following elements: Sn, Si, Ti, Zr, Hf, Zn, Ga, In.

12. substrates (10) as claimed in claim 11, it is characterized in that, described mixed oxide layer is the mixed oxide layer of the optional doping based on zinc and tin, or mixing indium tin oxide (ITO) layer, or mixing indium-zinc oxide (IZO) layer.

13. substrates (10) as claimed in claim 11, is characterized in that, the thickness of described smooth layer is 0.1-30nm.

14. substrates (1) as claimed in claim 1 or 2, it is characterized in that, following structure is deposited n time in basic unit (2) and the optional etching stopping layer existed: contact layer (31) and function metal level (32), wherein, n be equal to or greater than 1 integer, on described structure, have the stratose comprising following pantostrat, described pantostrat is at least made up of contact layer (31)/function metal level (32)/cover layer (34).

15. substrates (1) as claimed in claim 1 or 2, it is characterized in that, described substrate (1) comprises the bottom bus electrode structure (61 be positioned on described bottom electrode film (3), 61 '), described bus electrode structure (61,61 ') and described electrode film (3) electrical contact.

16. substrates (1) as claimed in claim 1 or 2, is characterized in that, described substrate (1) comprises the OLED system (4) be positioned on electrode film (3).

17. substrates (1) as claimed in claim 16, is characterized in that, described substrate (1) comprises the top electrode film (5) be positioned on described OLED system (4).

18. substrates (1) as claimed in claim 17, it is characterized in that, described substrate (1) comprises top bus electrode structure (62) be positioned on described top electrode film (5), described bus electrode structure (62) and the electrical contact of described top electrode film (5).

19. substrates (1) as claimed in claim 1 or 2, it is characterized in that, described substrate (1) comprises the functional membrane be positioned on the second first type surface (12), and described functional membrane is selected from: antireflection multilayer, anti-fog layer or stain-proofing layer, ultraviolet filter, phosphorous layer, mirror layer and light extract fringe area (73).

20. 1 kinds of top light emittings and/or the organic light emitting apparatus (10) of bottom-emission, it comprises the substrate (1) described in any one of claim 1-19.

21. organic light emitting apparatus (10) as claimed in claim 20, it is incorporated in glass unit.

22. organic light emitting apparatus (10) as described in claim 20 or 21, it is characterized in that, described organic light emitting apparatus (10) comprises multiple adjacent organic light emission system emitted white light separately, or comprise a series ofly to glow respectively, three systems of green glow and blue light, these Cascade Systems described connect.

23. organic light emitting apparatus (10) as described in claim 20 or 21, is characterized in that, described organic light emitting apparatus (10) forms one or more reflection and/or transparent luminescent surface.

24. organic light emitting apparatus (10) as described in claim 20 or 21, is characterized in that, described organic light emitting apparatus:

-for building;

-for the vehicles;

-for urban furniture or professional furniture;

-for furnishings;

-for the backlight of electronic equipment; With

-illuminated mirror.

25., for making the method for substrate (1) as described in any one of claim 1-19, is characterized in that, at least described basic unit (2) and described bottom electrode film (3) deposition are on the substrate.

26. methods as claimed in claim 25, it is characterized in that, described deposition is undertaken by sputtering type vacuum technique at least in part, and, it is characterized in that, then described substrate is etched.

27. methods as claimed in claim 26, it is characterized in that, described vacuum technique is magnetron sputter.

28. methods as described in claim 25 or 26, is characterized in that, described etching is acid etching operation, described etching in one step and adopt and be selected from following acid solution to carry out: pure nitric acid HNO ₃, or the mixture of nitric acid and hydrochloric acid HCl or pure hydrochloric acid or hydrochloric acid and ferric trichloride FeCl ₃mixture.

29. methods as described in claim 25 or 26, it is characterized in that, described etching is carried out under the existence of at least one metal current source band, described metal current source band is the form of the individual layer based on following a kind of metal or alloy: described metal is Mo, Al, Cr, described alloy is MoCr, or the form of multilayer, described multilayer is MoCr/Al/MoCr.