CN103190012A - Support for organic-light-emitting-diode device, such an organic-light-emitting-diode device and process for manufacturing said device - Google Patents
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
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- 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
- H05B33/02—Details
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- 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
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/302—Details of OLEDs of OLED structures
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/816—Multilayers, e.g. transparent multilayers
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- H—ELECTRICITY
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Abstract
The invention relates to a support (10) for an organic-light-emitting-diode device (1000) comprising a transparent substrate (1) of given first optical refractive index n1, comprising: a dielectric grating (3) in the form of one or more layers arranged discontinuously so as to form an array of what are called low-index patterns (30), the grating having a second optical refractive index n2 of 1.6 or less, the low-index patterns being submicron-sized in height, the average pattern width A1 being 6 [mu]m or less and the distance B1 between micron-sized patterns being larger than the width A1; and a first electrode (4), with a given third optical refractive index n3 of 1.7 or more. The distance B1 is aperiodic. At least some of the thickness of the first electrode (4) is above said grating (3) and makes contact with the surface of the grating (3) which is furthest from that substrate (1), or is spaced apart from the grating (3) of low-index patterns. The grating (3) is buried in a high-index medium (100) and is therefore inside the high-index medium, the high-index medium comprising the first electrode (4) in the form of the one or more layers furthest from the substrate, the high-index medium having a fourth refractive index n4 of 1.7 or more. The invention also relates to the process for manufacturing such a support.
Description
The present invention relates to Organic Light Emitting Diode holder, described device with and make.
The OLED(Organic Light Emitting Diode) device comprises piling up of luminous organic material or luminous organic material, and comprises two electrodes, one of electrode, be generally anode, constituted by the electrode relevant with glass baseplate, another electrode, be generally negative electrode, be arranged on the organic material of anode.
Use is by the anode injected holes with by the binding energy of negative electrode injected electrons, and by electroluminescence, OLED is luminous.Under the electrode relevant with base material was transparent situation, the photon of emission passed this transparency electrode and supports the glass baseplate of OLED, so that the outside of light to device to be provided.
The common application of OLED is display screen or is lighting device recently.
For luminescent system, from OLED, extract light and be preferably some or even " in vain " light of all launching under the wavelength at visible spectrum.It also must be homogeneous.In this field, the term of more specific use is that lambert launches, and namely follows the emission of Lambert law, and this law is characterised in that the photometer brightness that equates in all directions.
OLED shows low light extraction efficiency: the actual light that leaves glass baseplate and quite low by the ratio between the light of luminous organic material emission, and about 0.25.This phenomenon is special in following facts explain, and between negative electrode and anode, the photon of some is hunted down.
Thereby, need find one's way out to strengthen the efficient of OLED, namely increase and extract income, provide the light of homogeneous as far as possible simultaneously, preferred white light.Term " homogeneous " is understood that the homogeneous on intensity and the space in following specification.
Perhaps add by adhesive and the granuloplastic diffusing layer of diffusion at the glass anode surface, perhaps adding the structure with periodicity protrusion also is known practice, and it forms diffraction lattice, thereby can increase the extraction income.
For this reason, document US 2004/0227462 has shown a kind of OLED, supports anode with transparent base, and organic layer is grain surface.Thereby show to protrude on the surface of base material and depression alternately, its profile is followed anode and deposition organic layer thereon.Apply the profile that the photoresist mask obtains base material by the surface at base material, the pattern that the pattern of mask is pursued corresponding to protrusion, thus come etched surfaces by mask.Yet described method is not easy to the application of plant-scale big base material area, and is expensive especially after all, more particularly for illumination is used.
Extraction income that the network of prior art has centered on the specific wavelength optimization still, on the other hand, can not be given the emission of white light; On the contrary, its tendency is selected specific wavelength and emission, for example, is more prone to blueness or redness.
For this part, document US 2006/0192483 proposes to arrange at glass baseplate the two-dimentional diffraction network of silica, and it has unique cycle according to the zone along given translation vector, with the shortage of the homogeneity that relaxes light.
The possible top advantage of this diffraction network is to have the high index ZnO layer of plane surface, avoiding electric fault, thereby and is the transparent anode of ITO.Periodic length is between the 80%-120% of average cycle length.Periodic length is 0.1 μ m-5 μ m.The height of network is the 80%-120% of average height.The height of network is 50nm-20 μ m.
Again, the extraction of white light is not satisfied.
At last, document WO 2008/121414 proposes a kind of structure, is included in refraction index and is that to insert optical index between the organic light emission system of 1.7-1.8 and first electrode be the grid of 1-1.5.This grid according to embodiment is hexagon or rectangle.Low index material is selected from silica, TiO
2, aeroge (silica, carbon, aluminium oxide, etc.), PTFE.
According to test, grid is that 0.5-1.2 μ m is wide; Grid has the interval of 4-8 μ m.In a preferred embodiment, grid is that 0.8 μ m is wide, is spaced apart 5 μ m, and first electrode is the thick ITO of 100nm.
This suggestion structure has strengthened the extraction of light really, but luminous power is unsatisfactory.
Target of the present invention provides a kind of optional holder that is used for the OLED device, have and gratifyingly extract income and the satisfied luminous power of light (particularly white) by OLED, especially can on commercial scale, simply make, and reliable and cheap holder.
First theme of the present invention is the holder of oled device, comprises:
The transparent base of-the first given optics refraction index n1 has first interarea, is called inner face and second interarea, is called the outside, and inner face comprises:
-(basically) dielectric network, especially nonmetallic, with discontinuous mode arrange the layer form, thereby form a picture group case, be called low index, network has the second optics refraction index n2, it is less than or equal to 1.6, low index pattern is the sub-micron height, and average pattern width A1 is less than or equal to 6 μ m, and pattern separates, thereby adjacent patterns is by given pattern-pitch spaced apart, and/or pattern is interconnective, especially in grid, has distance in the given pattern, apart from B1, its be between pattern and/or pattern in the mean value of distance, trickle greater than width A1 and be less than or equal to 50 μ m, be acyclic apart from B1.
-the first electrode, especially transparent, with the form of layer, have the 3rd given optical index n3 more than or equal to 1.7, first electrode has the square resistance less than 30 ohms per squares, preferably less than 10 ohms per squares, even is more preferably less than 5 ohms per squares.
And,
First electrode of-at least a portion thickness and contacts with the surface away from the network of base material on described network, perhaps opens (passing through lower floor) with the network compartments of low index pattern,
-network is embedded in the high-index medium, high-index medium comprise first electrode as away from the layer of base material, high-index medium has the 4th refraction index n4 more than or equal to 1.7.
On the one hand, about the OLED that proposes in the document WO 2008/121414, it is comparable extracting from foundation OLED of the present invention, or even strengthen, because being positioned at the high index guide structure, low index pattern (comprises OLED system and foundation high-index medium of the present invention, it comprises first electrode) core, thereby diffused light effectively.
The application finds that also because the signal portion of the anode of prior-art devices is covered by the low index material of electric insulation, therefore all surfaces of final prior art OLED is sluggish.The spacing that reduces the thickness of streakline significantly or significantly increase between streakline can make the active surface that increases OLED become possibility, but like this can be unfavorable to extraction efficiency.Therefore, the balance that can the optimization active surface keeps appropriate light to extract simultaneously can not recover whole active surfaces.
According to the present invention, low index pattern (index is opposite with high-index medium) is under the OLED system, covered by first electrode, so that whole foundations OLED of the present invention is electroactive, its light that makes the luminous power of increase emission keep brilliance simultaneously extracts performance level becomes possibility.
The conduction of low-down upward pattern (on pattern) is enough for distributing electric current.
And, about the OLED of suggestion in the document US 2006/0192483, extract according to the light of OLED of the present invention and to be enhanced, no matter be polychromatic light (especially white light, especially for general lighting) or monochromatic light (for example being used for decorative lighting).This be because, the diffraction grid of prior art can not only optionally strengthen light and extract, increased photoemissive strong angle dependence (light for any kind all is disadvantageous) and colourity and relied on (be disadvantageous for white light), different diffraction orders has the angle of departure profile of highly significant.
Therefore, become possibility in the radiative angle distribution that obtains accurate lambert according to the aperiodic or even random attribute apart from B1 between the pattern on the whole low index network of the present invention and the extraction income (not having the courseware luminosity effect) of broadband wavelength.There is not diffraction effect.
And the span of the pattern of network can strengthen extractability and need not to worry diffraction.
Mean breadth A1(or even the Breadth Maximum of the pattern of network) preferably be less than or equal to 3 μ m and greater than 100nm.
In the present invention, express " being embedded in the network in the high-index medium basically " and should be understood that the network of high-index medium inboard basically, and express the network that " being embedded in the network in the high-index medium " should be understood that the high-index medium inboard.
In the present invention, express " optics refraction index " and should be understood to be in the refraction index that the 550nm place is measured.
Under the situation of continuous multilayer (multilayer bottom and/or multitiered network and/or multi-layered electrode and/or multilayer organic light emission system, etc.), it can be average index.The average index of continuous multilayer is defined as index n
iMultiply by every layer thickness e
iDivided by the gross thickness e of medium, i.e. ∑ n
i.e
i/ e.
High-index medium is essentially high index, can (in the network outside, naturally) comprise and do not have an adverse effect:
-low index layer, continuous basically, occupation rate〉90%, refraction index is less than 1.7, and thickness is more than or equal to 20nm, even 10nm,
-or a plurality of so-called low index layer, each is continuous basically, occupation rate〉90%, refraction index is less than 1.7, thickness is more than or equal to 20nm, especially spacing distance is less than 40nm, even 20nm, or even 10nm,
The thickness of low index layer (under the multilayer situation for adding up to) is less than 0.20 times of the thickness of high-index medium.
In the present invention, lack precision, high index layer (or coating) is defined as refraction index more than or equal to 1.7.
In a structure, high-index medium can comprise the first so-called complanation grid that is formed by discrete metal level, be arranged on the network, and on the space between pattern, occupation rate＜20%, especially be arranged in the grid, covered by so-called high index plane conductive coating, with the form of hyaline layer.
Especially, the index n3 of this first complanation grid is defined as the index of high index coating (if the latter has sandwich construction, being the average index of complanation coating).
Preferably:
The light transmittance (LT) that-transparent (blank) base material shows is at least 70%, in addition 80% and more than,
-have (totally) LT that the transparent base of high-index medium shows to be at least 70%, even 80% reach more than, network preferably has transparent material.
In first structure, can be less than or equal to 1.6 according to the first optics refraction index n1 of base material of the present invention, high-index medium is on so-called low index base material and be stratiform.
In second structure, can be more than or equal to 1.7 according to the first optics refraction index n1 of base material of the present invention, high-index medium comprises so-called high index base material, especially unorganic glass.
High-index medium comprises so-called bottom, transparent, especially (basically) is continuous, directly on the inner face of base material, layer (preferably directly under network) and may between low index pattern, (cross a part of thickness or cross whole thickness) under network, or even overlay network, high index layer has the 5th refraction index n5 more than or equal to 1.7.
According to functional, the thickness of (directly on base material) bottom is 50nm-1 μ m.
When being particularly useful for overlay pattern, preferred gross thickness is at least 150nm, preferably regulates according to the thickness of photoconduction, especially the thickness of organic light emission system.
Transparent base (even also having network and first electrode) with transparent underlayer can show at least 70% LT, in addition 80% and more than.
The index of the bottom of any other high-index medium layer can be near the first high index electrode, and deviation is preferably less than 0.2.
High-index medium can comprise directly at the high index bottom on the base material and/or under network and the high index layer on bottom (high index or low index are directly on the base material), is selected from:
-basic species barrier layer is selected from glass baseplate, especially silicon nitride SI
3N
4, can be doped; Silicon oxide carbide; Silicon oxynitride, oxygen carbonitride of silicium, zinc oxide and tin, especially thickness are 5-1000nm, even less than 500nm, even 150nm, preferably comprise 50-150nm,
-and/or etching stopping layer, especially bottom, be used for first electrode, especially based on tin oxide SnO
2, Si
3N
4, especially thickness comprises 5-300nm,
-and/or hydrophilic layer, especially bottom on the plastic basis material of selecting, is selected from layer, the especially silicon nitride of nitride layer, and/or oxide skin(coating), especially titanium oxide, zirconia,
-and/or bottom, only under network, it is the smooth layer of base substrate, is selected from
(basically) noncrystalline layer of-single or mixed oxide, for example vacuum-deposited, the layer of selecting based on mixed oxide especially, described mixed oxide is based on zinc and tin (Sn
xZn
yO
zOr ZTO), based on the mixed oxide (ITO) of indium and tin, or based on the mixed oxide (IZO) of indium and zinc, thickness is 5-1000nm, and preferred thickness is less than or equal to 500nm, even 150nm,
-sol-gel layer, especially ZrO
2, TiO
2, thickness is 5-1000nm, preferred thickness is less than or equal to 500nm, even 150nm,
-and/or glass bottom, melten glass material for example is on the unorganic glass base material of selecting.
For simple overlay network, high-index medium can comprise (basically) high index layer, and is especially transparent, be deposited between the pattern, and the layer of the whole height of preferred overlay network, it is single or multiple lift.First electrode is on this high index layer (or comprising this layer) for example.First electrode can have the complanation outside surface of base material (away from).First electrode can have the outside surface of base material (away from) in addition, and it is especially undulatory, for example follows the network of pattern basically, has difference in height at least between the high surface on the so-called pattern and the low surface between so-called pattern.High index layer can be deposited on the network by gas deposition, without planarization steps first electrode directly is deposited on this layer and goes up (or comprising this layer).
For simple overlay network, the space between pattern can be filled by first electrode at least in part, and first electrode is overlay network directly.First electrode can have the complanation outside surface of base material (away from).First electrode can have the outside surface of base material (away from) in addition, and it is especially undulatory, for example follows the network of pattern basically, has difference in height at least between the high surface on the so-called pattern and the low surface between so-called pattern.This first electrode thereby can be deposited on the network by gas deposition directly is deposited on organic layer on first electrode without planarization steps.
For simple overlay network, under network, high-index medium can comprise the high index individual layer that can form bottom.
Preferably, network (basically) is inorganic, and/or first electrode (basically) is inorganic.
(on average) index n3 of first electrode can be 1.8-2.2.
First electrode can be for example by gas deposition, especially by magnetron sputtering, the form of thin layer by hydatogenesis.
First electrode can mainly comprise (at least 80% thickness of electrode), even by (continuously) individual layer formation based at least one conductive, transparent oxide, especially be selected from based on special with the zinc oxide (AZO) of aluminium doping or the zinc oxide (GZO) that mixes with gallium, based on the mixed oxide (ITO) of indium and tin or based on the mixed oxide (IZO) of indium and zinc, the mixed oxide of indium, gallium and zinc (IGZO), especially have and equal 100nm at least and less than the thickness of 1500nm, even be less than or equal to 500nm.
First electrode can also comprise piling up of (thin, continuous) layer, is essentially high index and especially transparent, particularly thickness less than 500nm, even less than 300nm, comprises in proper order with this:
-the first high index subgrade based on the conductive, transparent oxide,
-have first a metal function layer of the intrinsic property of conductivity, this functional layer is based on pure material, preferred silver, or based on alloy or the doping of this pure material and another kind of material, described another kind of material is selected from: Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co, Sn, particularly thickness is 3-20nm
-based on the high index cover layer of conductive, transparent oxide,
-and possible, between the first metal function layer and cover layer, in the following order at least one times:
-based on the high index separator of conductive, transparent oxide,
-another metal function layer.
Naturally, this (on average) index n3 that piles up with metal function layer keeps high index, even has thin metal function layer and possible ultra-thin the isolation down or covering isolating metal layer.
Have the lower floor of piling up of metal function layer or the enhancing that cover layer helps the electrical property level of first electrode (conductivity and/or the adaptability by the difference in functionality output work):
-growth (or contact) lower floor its objective is and gives metal level degree of crystallinity,
-smooth layer, reducing the electrons spread that the interface goes out,
The layer of-protection external attack, described external attack comprises: the ion bombardment between the depositional stage of another layer, humidity, the migration of burn into alkalescence.
In order to select the contact layer of smooth layer, so-called covering isolation or following separator, can referenced patent application WO2008/029060, WO2008/059185 and WO2009/083693.
Preferably, owing to the cost reason, the gross thickness with the material that contains indium of the form of piling up of metal function layer in first electrode can be less than or equal to 60nm, preferably is less than or equal to 50nm.Widely, the gross thickness that preferably contains the material of indium in high-index medium can be less than or equal to 60nm, preferably is less than or equal to 50nm.
Preferably, electric current injects and/or the restriction operating voltage level in order to give, cover layer, even the separator that piles up with metal function layer shows that under bulk state, resistance coefficient is less than or equal to 10
7Ohm.cm preferably is less than or equal to 10
6Ohm.cm, or even be less than or equal to 10
4Ohm.cm.
Particularly, have piling up of metal function layer and can preferably not contain (always) thickness more than or equal to 15nm, even more than or equal to 10nm, even the cover layer of 5nm is based on silicon nitride, silica, silicon oxynitride, silicon oxide carbide, based on the oxygen carbonitride of silicium or even based on titanium oxide.
As has been described, first electrode can also comprise, and for example, metal level is become by silver or aluminium and/or copper, has the complanation coating, and this metal level is discontinuous at this, for example especially arrange to be grid, layer, preferably with non-chemically or the ion(ic) etching step make.
It can be made by mask especially, described in patent application WO2008/132397.For example use and form mask according to the used mask same type of low index network of the present invention (if necessary, the width by revising opening and the size of mask piece).
It should be noted, can also select to have the complanation electrode, be arranged as the high index grid of making as mentioned above, for example conductive, transparent oxide (ITO, AZO etc.).
For higher effectiveness, the filling rate of network, (pattern) coverage rate on the total surface of the network coverage just can comprise 1-40%, preferably comprises 3-20%, even comprises 5-15%, for example at for example at least 300 * 300 μ m
2Reference surface on the ratio of microscope (optics or electronics) measurement of comparison.
Pattern can be any form, especially how much, particularly have zigzag part basically, and summit be circle.
Pattern can be one dimension (piece, etc.) or two dimension: elongated pattern, and curve or straight-line pattern, etc.
As showing, pattern can be that disconnected (piece, the line that separate in the space, etc.) and/or (part) are communicated with, especially mesh form (mesh with possibility is destroyed), give the network as (random) grid arrangement aperiodic, thereby be interior screen distance apart from B1.
The deposition of the network of low index material can be undertaken by using conventional lithographic techniques.Yet in foundation advantage method of the present invention, the dimension of consideration (pattern with width of visible wavelength magnitude, preferably approximately 15% bigger substrate surface filling rate) is perfect compatible with the method for using any mask.Many advantages are arranged, especially:
-low cost,
-acyclic network (preventing diffraction effect).
Dimension about network:
-advantageously can be less than 50 μ m apart from B1, preferably be less than or equal to 30 μ m, even be less than or equal to 10 μ m, and even be less than or equal to 6 μ m, and the range distribution between the pattern that is preferably limited by standard deviation is for example passed through optical microscope measuring greater than 10% of mean value.
Between-preferred maximum non-period pattern or pattern in the distance advantageously can be less than or equal to 100 μ m, even 50 μ m, and for example the distance in the pattern is got rid of along first ultimate range with along 50% the deviation of surpassing between second distance, and two axles tilt, and especially meet at right angles.
And/or
The mean breadth A1 of-pattern can be less than or equal to 5 μ m, even is less than or equal to 2 μ m, and preferable width A1 is acyclic, and the distribution of the width A1 of the pattern that is limited by standard deviation is greater than 50% of mean value, for example by optical microscope measuring,
The Breadth Maximum of the pattern of-preferred network can advantageously be less than or equal to 10 μ m, even 5 μ m,
And/or
The average height of-pattern (and preferred maximum height) is less than or equal to 300nm, even be less than or equal to 200nm, even be less than or equal to 150nm---under the situation of deposition first electrode on the pattern or between pattern, limited significantly that electric fault---average height is preferably greater than 50nm, even more than or equal to 80nm.
The dielectric network can comprise silicon dioxide layer (even be made of it), sol-gel especially, and it is preferably porous layer (sol-gel), and n1 is less than or equal to 1.5, even is less than or equal to 1.4, even is less than or equal to 1.3.The dielectric network can comprise CaF2 layer (even be made of it).
On the outside (back to the surface of inner face) of so-called network, structurized low index layer (by stamp structuring, especially silica sol-gel layer, can be porous for example) can be born low index pattern.Therefore, the thickness of this layer stays the thickness of the solid layer under the network at the most less than 40nm greater than the height of pattern, in addition 20nm or even 10nm or 5nm, and less than 1/10 of the maximum height of network.
Optionally, network, especially silicon dioxide (porous), directly on the high index subgrade, high index bottom especially, or directly on the high index base material of selecting.
Transparent base can be unorganic glass, and 20 μ m-75 μ m, for example so-called ultra-thin glass that provided and described in patent application JP2010132347 by Nippon Electric Glass are provided for especially so-called film glass, thickness.Preferred industrial glass, the especially silicate selected is preferred cheap.Preferred soda-lime-silica glass.
Foundation transparent base of the present invention can be light base material.According to base material of the present invention for example for or comprise the thin polymer film that is constituted by the transparent thermoplastics with suitable character fully.The example of suitable thermoplastic polymer comprises, especially, PETG (PET), Polyethylene Naphthalate (PEN), Merlon, polyurethane, polymethyl methacrylate, polyamide, polyimides or or even fluorinated polymer, as ethene (ECTFE), fluorinated ethylene-propylene copolymer (FEP), polyester, the polyamide of ETFE (ETFE), Kynoar (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene.
On first electrode, holder comprises organic luminescent system, and especially thickness is 50-1000nm, organic light emission system preferred emission polychromatic light, especially white light.
Thereby (directly) deposition has the system of organic layer or high index oled layer, the normally layer between organic luminous layer or other organic layers on first electrode.
Index n4 can be 1.8, even above (1.9, even higher).Need not preferred, index n3 can less than, be equal to or greater than n4.
According to top electrode (second electrode) be reflection or respectively half reflection, perhaps or even transparent (especially have the LT suitable with first electrode, typically be 60% and be preferably greater than or equal 80%), OLED is bottom emission, also can be top-emission.
Advantageously, network, organic light emission system and the high-index medium (or optical medium) with given average height can form photoconduction (the possible thickness of not getting rid of low index layer of given thickness D1; Metal layer thickness), be defined as the centre of the network of semi-average height, away from distance B 2 places on the surface of the base material of organic light emission system, it calculates low index layer more than or equal to 0.3D1(), even more than or equal to 0.4D1, and be less than or equal to 0.7D1, even be less than or equal to 0.6D1, (directly) second electrode in the organic light emission system for example be reflection, metal.
In particular configuration, the organic light emission system, high-index medium (or optical medium) and (directly), second high index (translucent) electrode in the organic light emission system formed the photoconduction of given thickness D1, be defined as the centre of network of semi-average height in that (outside, away from base material) is distance B 2 places from the surface of second electrode, it is more than or equal to 0.3D1, even more than or equal to 0.4D1 be less than or equal to 0.7D1, even be less than or equal to 0.6D1.
Because foundation network of the present invention is positioned at the centre of high index guide structure just, on the strongest point of electric field, it is scattered beam very effectively.Photoconduction (especially having low index base material) is more thin, and the maximum intensity of electric field is more high, and network is advantageously at this peaked center, from but the most effective.
This position guarantee than directly on the low index base material or the network on low index bottom more effective because this network is at the more weak fringe region of electric field.
Under the situation of high index base material, photoconduction quite thick (even having ultra-thin base material), electric field extends more, and network can depart from the center and not lose efficacy.
Holder can be with the holder of the oled device that acts on illumination.
Oled device in particular for what throw light on, can comprise holder.
Because network has given average height, the thickness of foundation organic light emission of the present invention system can be less than or equal to 250nm, even 150nm, the thickness of the high-index medium in the part below network is less than 200nm, even 150nm, and the thickness of first electrode is less than 200nm, even 100nm, the average height of network equals 50nm at least, even 100nm, preferably less than 200nm.
The organic light emission system, in particular for what throw light on, its thickness can be greater than 250nm, even 400nm, with less than 1100nm, the thickness of the high-index medium in the part below network is less than 1100nm, even 800nm, but the thickness of the ergosphere between network first electrode beneath and streakline is greater than 250nm, even 400nm, and less than 1000nm, the average height of network equals 50nm at least, even 100nm, and preferably less than 200nm.
The OLED system is preferably designed for the emission polychromatic radiation, and (x1 y1) locates to determine for 0 ° reference axis that may be in the CIE1931XYZ chromatic diagram, is used for radiation thereby provide coordinate in normal direction.
The OLED system preferably is suitable for emission (basically) white light, as close as possible coordinate (0.33; 0.33) or coordinate (0.45; 0.41), especially locate at 0 °.
In order to produce the light of white basically, many possible methods are arranged, especially following method: mixing cpd in individual layer (red, green, blue emission), pile up three organic structures (red, green, blue emission) or two organic structures (Huang Helan) at electrode surface.
Can arrange OLED to produce the homogeneous polychromatic light at single area, be particularly useful for even illumination, perhaps produce the district of not sharing the same light with same intensity or varying strength.
OLED can be the part of compound glass unit, especially vacuum or air or other gas blade glass units.Device can also be whole, comprises single glazed unit, to save in packing and/or weight.
OLED can with the bonding or preferred lamination of other so-called overlay planes base materials, this overlay planes base material is preferably transparent, as glass, uses lamination to insert.
OLED can form luminescent panel, or backlight (white and/or homogeneous basically), and especially (solid) electrode surface is more than or equal to 1 * 1cm
2, even go up to 5 * 5cm
2, even 10 * 10cm
2And more than.
Therefore, OLED can be designed as the independent light-emitting block (having independent electrode surface) that forms in the polychromatic light (white basically), perhaps a plurality of light-emitting blocks (having the multiple electrode surface) in the polychromatic light (white light basically), each light-emitting block provides more than or equal to 1 * 1cm
2(solid) electrode surface, even 5 * 5cm
2, even 10 * 10cm
2And more than.
The invention still further relates to the various possible application of this OLED, form one or more or externally or arrange in inside transparent and/or reflection (mirror face function) optical surface.
Device can form (optional or accumulative total select) luminous, decorate, building or similarly system, signal display floater---for example drawing, logo, alphanumeric signal type, especially emergency exit panel.
When the electrode of the OLED that selects and organic structure when being transparent, the production light-emission window is especially possible.Thereby can not produce the enhancing of room light, and unfavorable to the light transmission.Also by the reflection of restriction light, especially in the outside of light-emission window, it can also make the control reflection levels become possibility, for example observes for the positive effective anti-glare standard of building.
Widely, device, especially all or part of transparent, can be:
-be used for building, as outside fluorescent glass, internal illumination cuts off or fluorescent glass door (part), especially sliding door,
-be used for transport vehicle, cut off as the luminous roof of land, waterborne or hole transatmospheric vehicle (car, rail truck, aircraft, steamer, etc.), luminous side window (part), internal illumination.
-be used for street or professional equipment, as bus waiting booth panel, showcase wall, jewellery exhibition or show window, greenhouse wall, illuminatian plate,
-be used for indoor furniture, the preceding facade of shelf or furnishing elements, furniture, illuminatian plate, ceiling light source, refrigerator luminous plaque, aquarium,
-being used for the backlight of electronic equipment, especially visual or display screen may be double screen, as TV or computer screen, or touch-screen.
According to the organic material that uses, OLED is divided into two main families usually.
If luminescent layer is little molecule, be the little molecule Organic Light Emitting Diode of SM-OLED().Usually, the structure of SM-OLED comprises the hole and injects piling up of thin layer or HIL, hole transmission layer or HTL, luminescent layer, electron transfer layer ETL.
For example, the example that organic light emission piles up is described in following document, be that people such as C.H.Jeong deliver at Organic Electronics8 (2007) 683-689 pages or leaves, exercise question is " using 4,4 '-two-[carbazole-(9)]-stilbene as four wavelength white OLEDs of navy blue emission layer ".
If organic luminous layer is polymer, be the PLED(polymer LED).
Therefore, piling up of the organic layer of OLED device comprises at least one center organic luminous layer, and to produce light, preferred white light is inserted in electron transfer layer and hole transport interlayer, and it then is inserted between electron injecting layer and the hole injection layer.
The OLED device comprises the strong doping htl layer of describing among the US7274141 (hole transmission layer), and for this reason, last one deck of first electrode needn't have the output work adaptive functions.
The thickness of OLED system is 100-500nm, typically be 350nm, or thicker OLED system, for example the exercise question of delivering at the relevant Philip Wellmann of luminous Korea S 2009 conferences (Lighting Korea2009conference) is " to be used for the luminous Novaled PIN of high-performance OLED
Technology (Novaled PIN
Technology for High PerformanceOLED Lighting) " 800nm that describes in the paper.
Second electrode of OLED, or top electrode, or even common negative electrode, be electric conducting material, preferred (partly) reflects, particularly the metal material of silver or aluminum type.
Each high-index medium layer preferably be not have very much absorbefacient, especially to the absorbance of visible light less than 10
-2Cm
-1
Preferably, high-index medium can comprise inorganic or hydridization (organic-inorganic) layer basically, even is made of it.
The invention still further relates to the method for the holder of a kind of manufacturing oled device as defined above, it comprises:
-low index transparent base, the especially bottom that the high index transparent base are provided or have the high index layer of at least one described high-index medium,
-be that part is positioned under the situation under the network at electrode, before being completed into first electrode, perhaps be positioned on the network at electrode (directly direct or non-) under the situation of (and may between pattern), before first electrode forms, the formation of the dielectric network of the low index pattern of stratiform has random distance B1, need not photoetching or etching (ion or chemistry) step
-especially (fully) for the network in the high-index medium embeds, the deposition of at least one high index layer (preferred non-selective deposition namely deposits with pattern between pattern).
The invention still further relates to the method for the holder of making aforementioned oled device, for this reason, the dielectric network with low index pattern of random distance B1 comprises:
-at the high index base material or on layer (high index of low index or high-index medium), especially on the high index bottom, deposit liquid mask layer (especially sol gel layer that can be cracked, for example silicon dioxide),
The drying of-mask layer has the gap up to the mask that obtains, and the random distance B between the gap is substantially equal to the random distance B1(expectation of the pattern of network),
-pass mask the gap and, preferred, at the layer of the material of the network of the low index pattern of mask deposition, be filled up at least a portion of the degree of depth in gap,
-remove mask, reveal up to the dielectric network that hangs down the index pattern.
The invention still further relates to a kind of method of making the holder of following defined oled device:
-liquid deposition is the deposition of stablizing and be dispersed in the solution of the colloidal solid in the solvent,
-particle has given glass transition temperature Tg, and the deposition of mask and dry implement being lower than under the temperature of described temperature T g especially forms the two-dimensional network in the screen cloth of straight flange, especially gap basically,
-pass the gap of gap, the especially silicon dioxide of layer, with the network of the low index pattern of gas deposition,
-preferably remove mask by the liquid mode.
After drying, obtain nano particle bunch, this cocooning tool has visible size, and isolates by the gap, itself thereby also be visible size.
In order to obtain opening in whole degree of depth, necessary:
-select the particle (nano particle) of finite size, to help its dispersion, preferred (on average) characteristic dimension comprises 10-300nm, even comprises 50-150nm,
Particle in the-solvent stability (especially handle by surface charge, for example pass through surfactant, pass through control pH) agglomerates to together to avoid it, makes its precipitation and/or makes its gravitational settling.
And, (always) concentration of regulating particle, preferably by volume comprises 5%-50%, even by volume comprises 10%-50%, even more preferably comprises 20%-40%.Under the situation that particle mixes, the concentration by volume of solution is that at least 80% Tg is greater than the particle of baking temperature.
The given glass transition temperature Tg of particle and the difference between baking temperature are preferably greater than 10 ℃, even 20 ℃.
The invention still further relates to a kind of method of making foregoing oled device, wherein the thickness of mask is less than 5 μ m, preferably be less than or equal to 3 μ m, especially comprise 0.5-3 μ m, and before the layer of the network that deposits low index pattern, mask is warming up to more than or equal to 0.8 times of Tg, thereby make gap enlargement be less than or equal to 5 μ m to mean breadth A1, even be less than or equal to 2 μ m and average distance B1 is less than or equal to 10 μ m, even be less than or equal to 6 μ m.
For described quite thin mask (and having narrow gap), preferably in water, fully dilute colloidal solution, be less than or equal to 35% to obtain particle (always) concentration.Thereby the size in crack reduces greatly, thereby by mask experience high temperature (for example baking) and fully widen the crack, produces the compression of mask.
The invention still further relates to a kind of method of making foregoing oled device, the base material of this device is glass, and wherein the formation of the network of silica sol-gel comprises the following steps:
-in solvent, especially water-based and/or alcohols solvent can mix with pore-foaming agent, and precursor colloidal sol, the especially hydrolyzable compound of the material that forms silicon dioxide layer is provided, as alkoxyl silicone,
The described silicon dioxide gel layer of-deposition,
The possible step of-elimination solvent,
-with the mask with the pattern that replenishes described low index pattern carry out a layer stamp (part, stay basic thickness less than 40nm, even 20nm or even 10 or 5nm, or preferably completely).
This silica sol-gel layer can be porous, by eliminating pore-foaming agent, especially solid and obtaining, this method comprises, and behind stamp, eliminates the network that pore-foaming agent forms the low index pattern of porous silica sol-gel by described use heat treatment, heat treatment is especially at 350 ℃, even 500 ℃, or even 600 ℃, preferably undertaken by (heat) tempering operation subsequently.
Stamp preferably can be implemented down at 65 ℃-150 ℃, preferably between 100 ℃-120 ℃, and especially for the sol-gel based on silane, TEOS especially.
Before separating mask and product, can fully harden to the surface.
And after period of contact and/or contact, pattern for example preferably hardens (or beginning sclerosis at least) by at least one following processing: heat treatment, the width of cloth are penetrated processing, are exposed in the controlled atmosphere, and this handles the mechanical performance of improving the surface.
The present invention will describe by embodiment now, and described embodiment is used for illustrating purely, never limit the scope of the invention, and embodiment is based on accompanying drawing, wherein
-Fig. 1 represents in the first embodiment, the cross sectional representation of the holder of foundation OLED of the present invention,
-Fig. 2 a and 2b represent to have the plane graph according to the mask of the network of the low index pattern of the holder of OLED of the present invention, and image obtains by the scanning of microscope and this image,
Each representative of-Fig. 3 a-4b has the plane graph according to the dielectric network of the low index pattern of the holder of OLED of the present invention, and image obtains by the scanning of microscope and this image,
-Fig. 5 schematically shows another and has plane graph according to the network of the low index pattern of the holder of OLED of the present invention.
Fig. 1, it has schematically shown the cross-sectional view of the holder 10 of the oled device 100 that is used for first structure in order to understand better not in proportion, it comprises continuously:
-low index transparent base 1, for example plastics (preferred thickness is PET or the PEN of 50-250 μ m) or " low index " glass (especially soda-lime glass, thickness is 0.7mm-3mm, or film glass), it comprises in proper order with this on first interarea,
-being embedded into the high-index medium 10 of low index network 3, it comprises continuously:
-directly be deposited on the bottom 2 on the base material, its be high index layer, transparent and (basically) continuous, refraction index n5 is more than or equal to 1.7,
-other possible high index layer (not shown)s,
-have a dielectric network 3 of the low index pattern 30 that is less than or equal to 1.6 the second optics refraction index n2, network have between pattern or pattern in apart from B1, it is aperiodic, according to pattern width A1, pattern is 1D or 2D, do not connect or connect, for example be interconnected to form irregular grid
-between the acyclic network 3 and on the network, first transparency electrode is with the form of first conductive coating 4, and it is anode, has the optics refraction index n3 more than or equal to 1.7.
High index bottom 2 can be the Si by magnetron sputtering deposition
3N
4, more particularly by in argon/nitrogen, under the pressure of 0.25Pa, use the reactive sputter-deposition of aluminium doping silicon target.Its thickness for example is 100nm.
Bottom covering substrates (not comprising allowance for trim) and conduct:
-alkaline barrier under the situation of glass,
-and/or the hydrophilic layer under the situation of plastics,
-during etching, the especially acid etching of first electrode, stop etching.
High index layer, especially transparent, can be arranged under the network, on the bottom, even between pattern, be AlN, TCO for example, as have or SnZnO, ZnO, ITO, TiO that the reagent that do not mix exists
2, ZrO
2
For its part, low index network for example is silicon dioxide SiO
2Layer, preferred porous silica (sol-gel) layer is to reduce refraction index.
First electrode 4, preferred anodes comprises, and for example, the high index transparent conducting coating as the indium oxide (ITO) based on the usefulness tin dope, or has piling up of silver.
Having piling up of silver comprises:
The subgrade based on the mixed oxide of zinc and tin that – is possible may be doped, or mixed oxide (IZO) layer of the mixed oxide of indium and tin (ITO) layer or indium and zinc,
– is selected from and mixes or unadulterated ZnO based on the contact layer of metal oxide
x, Sn
yZn
zO
x, ITO or IZO,
– function metal level, for example silver has intrinsic conductivity,
The directly barrier layer on thin on the functional layer that – is possible, this thin upward barrier layer comprises thickness and is less than or equal to the metal level of 5nm and/or the layer that thickness is less than or equal to 10nm, it is based on substoichiometric metal oxide, substoichiometric metal oxynitride or substoichiometric metal nitride (and possible directly thin barrier layer down under functional layer)
– for example changes the output work function based on the cover layer of metal oxide.
On possible bottom and/or wet etch stop layer and/or subgrade, the following structure of arranging n time, n is the integer (especially n=2 is namely, silver-colored double-deck) more than or equal to 1:
-contact layer,
-possible thin barrier layer down,
-functional layer,
-thin the barrier layer of going up.
Final layer keeps cover layer.
Therefore can quote and have piling up of silver, for example document WO 2008/029060 and WO2008/059185 or even WO2009/083693 in describe.
Following table 1 summarized silver-colored bilayer and silver-colored single layer stack different instances attribute and in the geometric thickness of nanometer, with and main optics and electrical feature.
Table 1
The sedimentary condition of each first electrode layer is as follows:
-by reactive sputtering, the zinc target and the tin target that use antimony to mix comprise 65wt%Sn, 34wt%Zn and 1wt%Sb, and under the pressure and argon/oxygen atmosphere of 0.2Pa, deposition is based on SnZn:SbO
xLayer,
-use silver-colored target, under the pressure and straight argon atmosphere of 0.8Pa, deposit the layer based on silver,
-use the titanium target, under the pressure and straight argon atmosphere of 0.8Pa, the depositing Ti layer,
-by reactive sputtering, the zinc target that uses aluminium to mix under the pressure and argon/oxygen atmosphere of 0.2Pa, deposits the layer based on ZnO:Al,
– uses ceramic target, and under argon/oxygen atmosphere, under the pressure and argon/oxygen atmosphere of 0.2Pa, deposition is based on the cover layer of ITO.
As a variant, first electrode can comprise barrier coat down, especially comprise metal level conduct barrier coat down, preferably by having neutral plasma or obtaining such as the nitride of one or more metals of Ti, Ni, Cr and/or the metallic target of oxide, preferably obtain by the ceramic target with neutral plasma.
In order to form OLED, exist extra (not shown) to have the luminescent system of organic material, its optics refraction index n4 is more than or equal to 1.7, for example directly on first electrode, do not have planarization steps.
On organic system, existence form is second electrode of the second conductive coating (not shown), and it is reflexive, is used for returning opposite direction by the light of organic system emission, be the direction of transparent base 1, light leaves (top-emission) from transparent base 1.
The high-index medium 10 that compensates by the luminescent system with organic material forms given thickness D1(naturally, the thickness that does not comprise network) high index photoconduction 100, it comprises the metal grate of possible grid or the possible metal layer of electrodes of piling up with layer.
The preferred thickness of selecting is so that low index network places the center of fully close high index waveguide.
(network on the bottom, between network and directly first electrode of overlay network) has thickness to be in the structure of Fig. 1
High index bottom, the especially Si of-100nm
3N
4,
The first high index electrode of-Yue 100nm (multiple-level stack that for example has silver),
The average index of-100nm is 1.8 organic piling up,
-and have the high network of 80nm,
Light guide thickness D1 is about 300nm, and the centre of network (at the 40nm place) calculates the low index layer of metal at the distance B 2(from outside (surface of the organic system) 140nm of photoconduction best) center in the waveguide located.
Under the situation of thick OLED, the stacked organic that namely wherein has first electrode is stacked as hundreds of nm(especially because the remarkable htl layer of thickness, with the sensitiveness of restriction electrical defect), the thickness of bottom thereby must increase.
(network on the bottom, between network and directly first electrode of overlay network) has thickness to be in the structure of Fig. 1
The bottom of-800nm, especially Si
3N
4,
First electrode, the especially ITO of-Yue 150nm,
The average index of-650nm is 1.8 organic piling up,
-and be the network of 80nm highly,
Light guide thickness D1 is about 1600nm, and the centre of network (at the 40nm place) calculates low index layer at the distance B 2(from outside (surface of the organic system) 760nm of photoconduction best) center in the waveguide located.
(network on the bottom, between network and directly first electrode of overlay network) has thickness to be in the structure of Fig. 1
The bottom of-800nm, especially Si
3N
4,
First electrode of-Yue 100nm especially has silver-colored multiple-level stack,
The average index of-800nm is 1.8 organic piling up,
-and be the network of 80nm highly,
Light guide thickness D1 is about 1700nm, and the centre of network (at the 40nm place) calculates low index layer at the distance B 2(from outside (surface of the organic system) 860nm of photoconduction best) center in the waveguide located.
As first variant, for example 100-150nm is thick as high index layer (TCO etc.), especially ITO(if select second electrode), photoconduction comprises this second electrode, and its thickness must be included among thickness D1 and the valuation D2.
In first variant that does not show, glass is high index, and for example, network directly is deposited on glass or the thin high index bottom.Network needn't be positioned at the center of waveguide, with effective as much as possible.
In second variant that does not show, Si
3N
4Layer along with solidify directly be deposited between the pattern and 30 in pattern and the low index network on it on, then first electrode 4 directly is deposited on this high index layer.
So, first electrode can be piling up of having described, or or even by for example by be deposited on break mask or even tco layer on the metal grate of the high index coating complanation that obtains.
In the structure of this second variant (network on the bottom, between network and the direct cured layer of overlay network, with and on first electrode), have thickness to be
The bottom 2 of-100nm, Si
3N
4,
The Si of-Yue 100nm
3N
4Cured layer,
The first high index electrode 4(of-Yue 20nm for example has the single layer stack of silver),
The average index of-100nm be 1.8 organicly pile up 5,
-and be the network of 80nm highly,
Light guide thickness D1 is about 320nm, and the centre of network (at the 40nm place) is best at the center in the waveguide at distance B 2 places of outside (surface of the organic system) 160nm of photoconduction.
The embodiment in more detail that makes low index dielectric network below is provided.
Make embodiment 1
The deposition of step 1. mask
On the base material of high index layer (preferred bottom) or especially high index unorganic glass, by using Wet technique, by " spin coating ", deposit two kinds of mixtures based on two solution of the colloidal solid of acrylic copolymer stable in water.
First solution contains first colloidal solid, and characteristic size is 80-100nm, is that DSM N. V. is with trade (brand) name
Product sold, glass transition temperature Tg 1 equals 115 ℃, is diluted to 40% in water.
Second solution contains second colloidal solid, and characteristic size is 190nm, is that DSM N. V. is with trade (brand) name
Product sold, glass transition temperature Tg 2 equals 30 ℃, is diluted to 52% in water.
First particle (hard particles) is given mask and can be ftractureed just, by selecting to be lower than the drying of Tg1, preferred normal temperature.
Second particle is given the adhesive force of mask to base material or lower floor.
Selection mixes first solution of 97 parts by volume with second solution of 3 parts by volume.The total concentration of particle in the mixture of two solution is about by volume 40%, and the volumetric concentration of mixture is greater than 95% first particle.The thickness of mask is 8-10 μ m.
Then, drying is sneaked into the layer of colloidal solid, with solvent flashing and form the gap.Described drying can be undertaken by suitable method, preferably is being lower than under the temperature of Tg (dry in hot-air etc.), for example at normal temperatures.
During this drying steps, system arranges with non-rule and arranges himself.Need not to toast and obtain stable mask.
Obtain the two-dimensional network in gap, around variable-sized piece, have closed contour.
Mask shows big variable, the aperiodic gap width of 1.5-5.7 μ m, and variable, the aperiodic block length of 15-65 μ m.
Length-width ratio also can be modified by the coefficient of friction between the surface that for example changes compression colloid and bottom, or even change the size of nano particle, also even change evaporation rate, perhaps granule density in fact, the perhaps attribute of solvent, perhaps according to the thickness of deposition technique, etc.
In second embodiment, deposit following mixing:
-characteristic dimension is less than first solution of the silicon dioxide colloid of 10nm, and for example the product sold TMA of Aldrich company is diluted to 40%, Tg greater than 1000 ℃ in water;
-with 30% second solution that is dissolved in the polyacrylamide in the water.
The total concentration by volume of the particle in the solution mixture is about 30%.Make a choice and mix with second solution of 10 parts by volume with first solution with 90 parts by volume.
The thickness of mask is about 5 μ m.Mask shows variable, the aperiodic gap width between 1-2 μ m, and variable, aperiodic length between 15-35 μ m.
Obtain the two-dimensional network 31 in gap, around variable-sized piece 32, have closed contour.
In the 3rd embodiment, the mixture of two solution of deposition, described mixing is described in first embodiment.
Make a choice again and mix with second solution of 3 parts by volume with first solution with 97 parts by volume, but by dilute with water so that the total concentration by volume of the particle in the solution mixture is about 30%.Mixture keeps the concentration of the first particle by volume to be higher than 95%.The thickness limits of mask is at about 2.5 μ m.
Then mask dry and be full of cracks is in heat treatment (140 ℃ of following 15min in air-oven), so that crackle is widened.
Mask shows variable, the aperiodic gap width between 0.5-1 μ m, and variable, aperiodic length between 3-8 μ m.
The morphology research (in all above-described embodiments) of mask shows that the gap shows straight crackle profile.
The crackle profile provides specific advantage:
-deposition, the especially very thick material of a step deposition,
-after removing mask, keep the pattern meet mask, very thick pattern particularly.
Step 2. has the deposition of material of the dielectric network of low index pattern
Have the material of the network of low index pattern by mask deposition, be filled up to a part of gap.
This deposition process can be implemented by the gas deposition mode, for example passes through magnetron sputtering.On mask and the inboard deposition materials of the network in gap, to fill crackle, a part of thickness of filling at least according to the network in gap carries out.
Like this, make a choice to reach 30nm-200nm by magnetron sputtering deposition silicon dioxide to thickness, preferably about 80-100nm.Low index dielectric network forms, and has the mean breadth A1 and be similar to average distance B1 aperiodic of mask dimension aperiodic of pattern.
In order from mask, to manifest lattice structure, implement " rise " operation.This operation is by following true the promotion, i.e. the cohesiveness of the colloid that is caused by weak Van der Waals force (rather than adhesive or bonding of being caused by baking).So, the colloid mask is immersed in the solution that contains water and acetone (attribute according to colloidal solid is selected cleaning solution), and afterflush, with the part that adopts the useful colloid of institute to be coated with.This phenomenon can be by using ultrasonic acceleration, decomposing the colloidal solid mask, and manifests the part (network in the gap of filling with material) of compensation, and it can produce grid.
The plane graph of the dielectric network of Fig. 3 a-4b by having low index pattern shows two morphology, and described network obtains (the second and the 3rd embodiment) with above-mentioned last two masks.
Finer and close according to the network (Fig. 4 a and 4b) that the 3rd embodiment obtains, be preferred.
The deposition of step 4. first electrode material
For the structure of Fig. 1, first electrode---example have as has been described silver multiple-level stack---be deposited between pattern and the pattern of low index network on.
Low index network is not subjected to the influence of the deposition of first electrode, and the Rsquare of first electrode is similar to those on the planar substrate.
For optional structure, the cured layer of deposition primer.Then, deposit first electrode, for example with the described first consistent electrode of first structure.
Make embodiment 2
In another embodiment, the network with low index pattern is the sol-gel layer of porous silica, obtains by stamp.
Obtain silica-based sols-gel layer with TEOS or MTEOS precursor, and give porousness by eliminating pore-foaming agent.
Therefore, the refraction index that reduces material to be lower than 1.5 or even 1.3 be possible, this has promoted index contrast, thereby has promoted light scattering efficiency.
Among the embodiment, the first step comprises the Si that deposits 100nm as described above
3N
4Layer is for example by the cathodic sputtering on the glass baseplate.
The manufacturing of the sol-gel type porous layer on the bottom at first comprises following consecutive steps:
-form preparation, the especially hydrolyzable compound of precursor colloidal sol of the material of silicon dioxide layer, as halide or alkoxyl silicone, in solvent, especially in water and/or the alcoholic solvent,
-mix with pore-foaming agent, solid especially, with the form of particle, the particle preferred size is more than or equal to 20nm, 40-100nm especially,
-deposited mixture on bottom.
The solid pore-foaming agent can advantageously comprise ball, preferred polymeric, especially PMMA type, methyl methacrylate/acrylic copolymer, polystyrene.
Base material deposition can by sputter, by dipping and from silicon dioxide gel, pull out (or " dip-coating "), by spin coating, pass through flow coat, implement by roller coat.
Then the mark stamp sedimentary deposit of pattern that has a low index pattern of the described expectation of compensation by use determines to hang down the pattern of index network.The method that is used for the stamp sol-gel layer is traditional.
Then, the heat treatment of layer experience under at least 500 ℃, even at least 600 ℃, continue preferably to be less than or equal to 15 minutes, even 5 minutes, tempering subsequently.This makes and toasts texture layer on the one hand that the organic nanometer granule that volatilizees on the other hand becomes possibility, to reduce the refraction index of low index network.
Porous sol-gel layer for example, the layer of describing in can referenced patent application WO 2008/059170 (embodiment in this application uses oil or particle base pore-foaming agent, or the embodiment that is provided by the prior art with traditional pore-foaming agent).
Fig. 5 schematically shows exemplary low index network 3, and by random distribution and have variable-sized piece and form, network for example forms by the stamp of silica sol-gel layer.
Claims (28)
1. be used for the holder (10) of oled device (1000), it comprises:
The transparent base (1) of-the first given optics refraction index n1 has first interarea, is called inner face and second interarea, is called the outside, and inner face comprises:
-dielectric network (3), with discontinuous mode arrange the layer form, thereby form a picture group case (30), be called low index pattern, network has and is less than or equal to 1.6 the second optics refraction index n2, low index pattern has the sub-micron height, and average pattern width A1 is less than or equal to 6 μ m, and pattern separates, thereby adjacent patterns by given pattern-pitch from and spaced apart, and/or pattern is interconnective, especially in grid, has distance in the given pattern, apart from B1, its be between pattern and/or pattern in the mean value of distance, trickle greater than width A1 and be less than or equal to 50 μ m
-the first electrode (4), especially transparent, with the form of layer, have the 3rd given optical index n3 more than or equal to 1.7, first electrode has the square resistance less than 30 ohms per squares,
Be characterised in that
-be acyclic apart from B1,
First electrode (4) of-at least a portion thickness and contacts with the surface away from the network (3) of base material (1) on described network (3), and is perhaps spaced apart with the network (3) of low index pattern,
-network (3) is embedded in the high-index medium (100), network therefore in high-index medium, high-index medium comprise first electrode (4) as away from the layer of base material, high-index medium has the 4th refraction index n4 more than or equal to 1.7.
2. the described holder for oled device (1000) of claim 1 (10), the first optics refraction index n1 that is characterised in that base material (1) is less than or equal to 1.6, high-index medium (100) and is stratiform on so-called low index base material (1).
3. the described holder for oled device of claim 1 is characterised in that the first optics refraction index n1 of base material more than or equal to 1.7, and high-index medium comprises so-called high index base material, is especially made by unorganic glass.
4. the described holder for oled device (1000) of one of aforementioned claim (10), be characterised in that high-index medium (100) comprises the directly so-called transparent underlayer (2) on the inner face of base material, under the network (3) and may be between low index pattern or even the layer of embedding network, the high index bottom has the 5th refraction index n5 more than or equal to 1.7.
5. the described holder for oled device (1000) of one of aforementioned claim (10), be characterised in that structurized low index layer is on so-called outside, back to the base material inner face, network with low index pattern, thereby the thickness of layer is greater than the height of pattern, the solid layer thickness that stays under the network is at the most less than 40nm, even 20nm and less than 1/10 of the maximum height of network.
6. the described holder for oled device (1000) of one of claim 1-4 (10) is characterised in that network is directly on high index layer, especially on the high index bottom, perhaps directly on the high index base material of selecting.
7. the described holder for oled device (1000) of one of aforementioned claim (10), be characterised in that high-index medium (100) comprises directly at the high index bottom (2) on the base material inner face and/or under the network, or comprise high index layer under the network and on the bottom, high index layer is selected from:
-basic species barrier layer (2), especially bottom are selected from glass baseplate, and especially silicon nitride may be doped; Silicon oxide carbide, silicon oxynitride, oxygen carbonitride of silicium, zinc oxide and tin,
-and/or etching stopping layer (2), especially bottom, be used for first electrode (4), especially based on tin oxide, silicon nitride,
-and/or hydrophilic high index layer, especially bottom on the plastic basis material of selecting, is selected from bottom, the especially silicon nitride of nitride layer, and/or oxide skin(coating), especially titanium oxide, zirconia,
-and/or bottom, only under network, it is for the smooth layer of following base material, is selected from:
The noncrystalline layer of-single or mixed oxide, the layer of especially selecting based on mixed oxide, described mixed oxide be based on zinc and tin, based on the mixed oxide of indium and tin, or based on the mixed oxide of indium and zinc,
-sol-gel layer, especially ZrO
2Sol-gel layer; TiO
2Sol-gel layer,
-and/or high index nature of glass bottom, melten glass material for example is on the unorganic glass base material of selecting.
8. the described holder for oled device (1000) of one of aforementioned claim (10), be characterised in that high-index medium comprises high index layer (4), especially transparent, be deposited on the pattern or between, preferably on the whole height of network.
9. the described holder for oled device (1000) of one of aforementioned claim (10) is characterised in that the direct overlay network of first electrode is filled in the space between pattern (30) at least in part by first electrode (4).
10. the described holder for oled device (1000) of one of aforementioned claim (10) is characterised in that first electrode (4) comprises:
-mainly be based on the high index individual layer of at least one conductive, transparent oxide, especially be selected from the zinc oxide that mixes based on aluminium, based on the mixed oxide of indium and tin or based on the mixed oxide of indium and zinc, especially have and equal 100nm at least and less than the thickness of 1500nm
-and/or basically high index pile up the layer of (4), especially transparent, comprise in the following order:
-based on high index first subgrade of conductive, transparent oxide,
-have first a metal function layer of the intrinsic property of conductivity, this functional layer is based on pure material, preferred silver, or based on the alloy of described pure material and another kind of material or by its doping, described another kind of material is selected from: Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co, Sn
-based on the high index cover layer of conductive, transparent oxide,
-and possible, between the first metal function layer and cover layer, in the following order at least one times:
-based on the high index separator of conductive, transparent oxide,
-another metal function layer.
11. the described holder for oled device (1000) of one of aforementioned claim (10), the filling rate that is characterised in that network (3) is 1-40%, preferred 3-20%.
12. the described holder for oled device (1000) of one of aforementioned claim (10) is characterised in that the average height of pattern (30) is less than or equal to 300nm, even is less than or equal to 200nm and average height is preferably greater than 50nm.
13. the described holder for oled device (1000) of one of aforementioned claim (10), be characterised in that apart from B1 and be less than or equal to 30 μ m, even be less than or equal to 10 μ m, preferably the range distribution that limits by standard deviation is greater than 10% of mean value, and be, preferably, ultimate range aperiodic between the pattern of network (3) is less than or equal to 100 μ m.
14. the described holder for oled device (1000) of one of aforementioned claim (10), the mean breadth A1 that is characterised in that pattern (30) is less than or equal to 5 μ m, even be less than or equal to 2 μ m, with preferable width A1 be aperiodic, the distribution of the pattern width that limits by standard deviation is greater than 50% of mean value, and is, and is preferred, the Breadth Maximum of the pattern of network is less than or equal to 10 μ m, even 5 μ m.
15. the described holder for oled device (1000) of one of aforementioned claim (10), be characterised in that network is inorganic, especially comprise CaF2 layer or silicon dioxide layer (3), especially sol-gel layer, it is porous layer preferably, index n1 is less than or equal to 1.5, even is less than or equal to 1.4.
16. the described holder for oled device (1000) of one of aforementioned claim (10) is characterised in that base material (1) has unorganic glass, especially so-called film glass, thickness are 20 μ m-75 μ m, or are that base material has plastics.
17. the described holder for oled device (1000) of one of aforementioned claim (10) is characterised in that high-index medium (100) is made of inorganic layer basically.
18. the described holder for oled device (1000) of one of aforementioned claim (10), be characterised in that on first electrode (4), it comprises organic luminescent system (5), especially the thickness that has 50-1000nm, organic light emission system preferred emission polychromatic light, especially white light.
19. the described holder for oled device (1000) of last claim (10), be characterised in that, network with given average height, organic light emission system (5) and high-index medium form the photoconduction (110) of given thickness D1, be defined as the centre of network (3) of semi-average height of network away from distance B 2 places on the surface of the base material of organic light emission system (5), it is more than or equal to 0.3D1, even more than or equal to 0.4D1, and be less than or equal to 0.7D1, even be less than or equal to 0.6D1, second electrode in the organic light emission system is reflexive, especially metal
Or be, the second high index electrode in organic light emission system (5), high-index medium and the organic light emission system forms the photoconduction of given thickness D1, be defined as the centre of network (3) of semi-average height of network at distance B 2 places on the surface of distance second electrode, it is more than or equal to 0.3D1, even more than or equal to 0.4D1, and be less than or equal to 0.7D1, even be less than or equal to 0.6D1.
20. oled device (1000) is particularly useful for luminously, comprises the arbitrary described holder of aforementioned holder claim (10).
21. the described oled device of claim 20 (1000), the thickness that is characterised in that organic light emission system (5) is less than or equal to 250nm, the thickness of the high-index medium (110) in the part under network (2) is less than 200nm, the thickness of first electrode (4) is less than 200nm, the average height of network equals 50nm at least, and preferably less than 200nm.
22. claim 20 is described for oled device, it is luminous being particularly useful for, be characterised in that the thickness of organic light emission system is greater than 250nm, even 400nm, with less than 1100nm, the thickness of the high-index medium in the part under network is less than 1100nm, the thickness of the layer between first electrode under the network and possible line is greater than 250nm and less than 1000nm, the average height of network equals 50nm at least, and preferably less than 200nm.
23. a method of making the described holder for oled device (1000) of aforementioned holder claim (10) is characterised in that it comprises:
-low index transparent base (1), the especially bottom that the high index transparent base are provided or have the high index layer (2) of at least one described high-index medium (100),
-be that part is positioned under the situation under the network at electrode, first electrode (3) is preceding being completed into, perhaps under electrode is positioned at situation on the network, first electrode (3) is preceding forming, formation has the dielectric network of the low index pattern (3) of stratiform of random distance B1, need not photoetching or etching step.
24. a method of making the described holder for oled device (1000) of last claim to a method is characterised in that forming the dielectric network with random distance B1 comprises:
-on the high index base material or on the layer (2) in high-index medium (100), especially on the high index bottom, the deposit liquid mask layer,
-dry mask layer has gap (31) up to the mask that obtains, and the random distance B between the gap is substantially equal to the random distance B1 of the pattern (30) of network (3),
-pass the layer of material of network of the low index pattern of gap (31) deposition of mask, be filled up at least a portion of the degree of depth in gap,
-remove mask, reveal up to the dielectric network (3) that hangs down index pattern (30).
25. make the method for the described holder for oled device (1000) of last claim to a method, be characterised in that
-liquid deposition is the deposition of stablizing and be dispersed in the solution of the colloidal solid in the solvent,
-particle has given glass transition temperature Tg, the deposition of mask and dry implement being lower than under the temperature of described temperature T g,
-the network that passes the low index pattern of gap deposition of layer carries out with the gas phase form,
-preferably remove mask by the liquid mode.
26. make the method for the described oled device of last claim to a method (1000), be characterised in that the thickness of mask is less than 5 μ m, preferably be less than or equal to 3 μ m, and be, before the layer of the network that deposits low index pattern, mask is warming up to more than or equal to 0.8 times of Tg, thereby make gap enlargement be less than or equal to 5 μ m to mean breadth A1, even be less than or equal to 2 μ m and average distance B1 is less than or equal to 10 μ m, even be less than or equal to 6 μ m.
27. make the method for the described oled device of claim 23 (1000), be characterised in that base material has glass, and be that the formation of the network of the silica sol-gel selected comprises following steps:
-the precursor colloidal sol of material in solvent that forms silicon dioxide layer is provided, described material is hydrolyzable compound especially, as alkoxyl silicone, water-based and/or alcohols solvent that described solvent especially may mix with pore-foaming agent,
The described silicon dioxide gel layer of-deposition,
The possible step of-elimination solvent,
-carry out a layer stamp with the mask with the pattern that replenishes described low index pattern.
28. make the described method for oled device (1000) of preceding method claim, be characterised in that the silica sol-gel layer is porous, obtain by eliminating pore-foaming agent, especially solid, this method comprises, and behind stamp, forms the network of the low index pattern of porous silica sol-gel by using heat treated described elimination pore-foaming agent, heat treatment under 350 ℃, is preferably carried out tempering operation especially subsequently.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1056861 | 2010-08-30 | ||
| FR1056861A FR2964254B1 (en) | 2010-08-30 | 2010-08-30 | ORGANIC ELECTROLUMINESCENT DIODE DEVICE HOLDER, ORGANIC ELECTROLUMINESCENT DIODE DEVICE, AND MANUFACTURING METHOD THEREOF |
| PCT/FR2011/051972 WO2012028809A1 (en) | 2010-08-30 | 2011-08-29 | Support for organic-light-emitting-diode device, such an organic-light-emitting-diode device and process for manufacturing said device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103190012A true CN103190012A (en) | 2013-07-03 |
Family
ID=43821819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180051794.9A Pending CN103190012A (en) | 2010-08-30 | 2011-08-29 | Support for organic-light-emitting-diode device, such an organic-light-emitting-diode device and process for manufacturing said device |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2612379A1 (en) |
| JP (1) | JP2013536977A (en) |
| KR (1) | KR20130106832A (en) |
| CN (1) | CN103190012A (en) |
| FR (1) | FR2964254B1 (en) |
| WO (1) | WO2012028809A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2999807B1 (en) * | 2012-12-13 | 2015-01-02 | Saint Gobain | CONDUCTIVE BRACKET FOR OLED DEVICE AND INCORPORATING OLED DEVICE |
| KR101493612B1 (en) * | 2013-10-08 | 2015-02-13 | 쌩-고벵 글래스 프랑스 | A laminate for a light emitting device and process for preparing thereof |
| FR3015926B1 (en) | 2013-12-31 | 2017-03-24 | Saint Gobain | LUMINOUS GLAZING WITH OPTICAL ISOLATOR |
| FR3019941A1 (en) * | 2014-04-09 | 2015-10-16 | Saint Gobain | LIGHT EXTRACTING BRACKET AND OLED DEVICE INCORPORATING SAME |
| US10197804B2 (en) | 2016-04-25 | 2019-02-05 | Microsoft Technology Licensing, Llc | Refractive coating for diffractive optical elements |
| DE102017004562A1 (en) | 2017-05-14 | 2018-11-15 | Docter Optics Se | Method of manufacturing a micro projector and a projection display |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10135513B4 (en) | 2001-07-20 | 2005-02-24 | Novaled Gmbh | Light-emitting component with organic layers |
| TWI260945B (en) | 2003-05-16 | 2006-08-21 | Toyota Ind Corp | Light-emitting apparatus and method for forming the same |
| JP4253302B2 (en) | 2005-01-06 | 2009-04-08 | 株式会社東芝 | Organic electroluminescence device and method for producing the same |
| JP2006269163A (en) * | 2005-03-23 | 2006-10-05 | Konica Minolta Holdings Inc | Organic electroluminescent element |
| WO2006120610A1 (en) * | 2005-05-12 | 2006-11-16 | Philips Intellectual Property & Standards Gmbh | Electroluminescence light source |
| JP2007287486A (en) * | 2006-04-17 | 2007-11-01 | Aitesu:Kk | Organic electroluminescence element having fine structure between transparent substrate and electrode |
| WO2008029060A2 (en) | 2006-09-07 | 2008-03-13 | Saint-Gobain Glass France | Substrate for an organic light-emitting device, use and process for manufacturing this substrate, and organic light-emitting device |
| FR2908406B1 (en) * | 2006-11-14 | 2012-08-24 | Saint Gobain | POROUS LAYER, METHOD FOR MANUFACTURING THE SAME, AND APPLICATIONS THEREOF |
| US9099673B2 (en) * | 2006-11-17 | 2015-08-04 | Saint-Gobain Glass France | Electrode for an organic light-emitting device, acid etching thereof and also organic light-emitting device incorporating it |
| FR2913972B1 (en) | 2007-03-21 | 2011-11-18 | Saint Gobain | METHOD FOR MANUFACTURING A MASK FOR CARRYING OUT A GRID |
| EP2132802B1 (en) | 2007-03-30 | 2013-01-09 | The Regents of the University of Michigan | Oled with improved light outcoupling |
| FR2925981B1 (en) * | 2007-12-27 | 2010-02-19 | Saint Gobain | CARRIER SUBSTRATE OF AN ELECTRODE, ORGANIC ELECTROLUMINESCENT DEVICE INCORPORATING IT. |
| JP5691148B2 (en) | 2008-10-01 | 2015-04-01 | 日本電気硝子株式会社 | Glass roll, glass roll manufacturing apparatus, and glass roll manufacturing method |
-
2010
- 2010-08-30 FR FR1056861A patent/FR2964254B1/en not_active Expired - Fee Related
-
2011
- 2011-08-29 JP JP2013526529A patent/JP2013536977A/en not_active Withdrawn
- 2011-08-29 EP EP11761675.5A patent/EP2612379A1/en not_active Withdrawn
- 2011-08-29 CN CN201180051794.9A patent/CN103190012A/en active Pending
- 2011-08-29 WO PCT/FR2011/051972 patent/WO2012028809A1/en active Application Filing
- 2011-08-29 KR KR1020137008184A patent/KR20130106832A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2964254B1 (en) | 2013-06-14 |
| WO2012028809A1 (en) | 2012-03-08 |
| KR20130106832A (en) | 2013-09-30 |
| JP2013536977A (en) | 2013-09-26 |
| FR2964254A1 (en) | 2012-03-02 |
| EP2612379A1 (en) | 2013-07-10 |
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Application publication date: 20130703 |