WO2002041400A1 - Organic electroluminescent device and a method of manufacturing thereof - Google Patents
Organic electroluminescent device and a method of manufacturing thereof Download PDFInfo
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- WO2002041400A1 WO2002041400A1 PCT/EP2001/012589 EP0112589W WO0241400A1 WO 2002041400 A1 WO2002041400 A1 WO 2002041400A1 EP 0112589 W EP0112589 W EP 0112589W WO 0241400 A1 WO0241400 A1 WO 0241400A1
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- relief pattern
- layer
- electrode layer
- pattern
- fluid
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/122—Pixel-defining structures or layers, e.g. banks
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/17—Passive-matrix OLED displays
- H10K59/173—Passive-matrix OLED displays comprising banks or shadow masks
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/805—Electrodes
Definitions
- an electroluminescent (EL) device is a device comprising EL material capable of emitting light when a current is passed through it, the current being supplied by means of electrodes. If the EL material or any other functional material, if present, disposed between the electrodes is of organic or polymeric nature the device is referred to as an organic or polymer(ic) EL device respectively. In the context of the invention, the term organic includes polymeric.
- wet deposition methods such as spin-coating and ink-jet printing would be a significant improvement.
- efforts to provide the organic layers in the known EL device by means of wet deposition methods gave unsatisfactory results.
- the color separation was found to be unsatisfactory.
- inhomogeneities in brightness between pixels, and, in case of large pixels, also within pixels are sometimes observed.
- cross-talk and/or leakage current between neighboring pixels is observed in particular if the EL device comprises a charge transport layer deposited by a wet deposition method.
- an electroluminescent device comprising: a first and a second electrode layer, at least the second electrode layer being provided in accordance with a desired pattern, one or more functional layers, the one or at least one of said functional layers being an electroluminescent layer, a relief pattern having one or more overhanging sections for defining the desired pattern of the second electrode layer, and means for hindering the transport of fluid along a capillary channel formed by an overhanging section and a surface supporting that overhanging section.
- the EL device in accordance with the invention if of the multi-color type, shows satisfactory color separation even and in particular if the one or at least one of the functional layers is provided using a wet deposition method such as spin-coating or ink-jet printing.
- the EL pixels of the device if the EL device is of the multi-pixel type, emit substantially uniformly across the entire light emitting surface and no or at least an insignificant amount of leakage current between independently addressable neighboring electrodes is observed when only one these electrodes is driven and the other is maintained at a constant voltage corresponding to the off-state of the pixel(s) addressable therewith. This is even and in particular the case if the EL device comprises a charge transport layer provided by means of a wet deposition method.
- the fluid containing electroluminescent layer material is drained from and redeposited in pixels arranged to emit different colors, a process referred to as color bleeding.
- the pixels of the EL device do not emit the desired colors but mixed colors.
- the drained fluid contains electroconductive (precursor) material such as charge transport material or electroluminescent material, an electrical connection via the capillary channel is established between neighboring pixels leading to a leakage current between neighboring pixels.
- the capillary causes fluid to be redeposited in the wrong areas, a situation which is to be prevented.
- Means for hindering the transport of fluid may be provided in a number of ways.
- the surfaces constituting the channel may be subjected to an anti- wetting treatment to increase the contact angle between fluid and the surfaces.
- Anti- wetting treatments and agents for use in such treatments are well known in the art and include plasma treatments, corona discharge, surfactants and the like.
- protrusions to hinder the drainage of fluid are attractive in that it does not render the manufacturing process more complex as the protrusion(s) can be provided together and simultaneous with the relief pattern as an integral part thereof.
- the protrusion extends transversely to the boundary of the relief pattern at the position of the protrusion.
- the means for hindering the transport described hereinabove may be used separate to or in combination with each other.
- the protrusion is extra in the sense that it is not essential for the definition of the pattern of the second electrode. As the protrusion occupies space which would have been available to the second electrode layer the protrusion reduces the conductivity of the electrode layer, its size should therefore be kept as small as possible yet sufficient to interrupt or reroute the capillary effectively.
- a special type of protrusion may be provided to prevent leakage of fluid from any free end of a capillary channel. Such free ends are typically found at the periphery of the light emitting area of the display.
- the protrusion then functions as an end-stop. If a single protrusion is not enough to prevent the transport of fluid several may be provided in series.
- One embodiment of such an end-stop is a protrusion joining different, possibly mutually separate, parts of the relief pattern. For example, in a passive matrix display comprising a relief pattern of rows of overhanging sections the rows may be joined together at their free ends by a protrusion to prevent fluid form leaking out.
- the end-stops may also be used to prevent fluid from being transported from the display area into a contact pad area used for connecting the electrodes to any circuits exterior the display area such as driver electronics.
- the protrusion needs to have sufficient positive curvature to be able to hinder the drainage of fluid by the capillary effectively. Provided such curvature is provided, the shape of the protrusion is not critical. Suitable shapes include a rectangular and a bulb shape.
- a protrusion may be arranged to have more than one sub-protrusions such as a fingered protrusion. Alternatively, a protrusion may be split into a number of mutually spaced protrusions of similar shape to increase its effectiveness for hindering flow along capillary channels.
- the size of the protrusion in the direction of the capillary can be anything from 0.1 ⁇ m upwards. Preferably, from 0.5 ⁇ m to 50 ⁇ m, or better from 1.0 to 20.0 ⁇ m.
- the size of the protrusion, in the direction of the capillary is typically small compared to the size of the protrusion in the direction normal to the relief pattern, also referred to as the length.
- the size along the capillary is about as large as the height of the relief pattern.
- the flow along a N-shaped capillary channel measuring at the top of the N 3 to 5 ⁇ m could be effectively hindered by a 20 ⁇ m wide protrusion extending a distance of 60 ⁇ m in the direction normal to the direction of the channel.
- the corners of the relief pattern should not have acute angles (the angle measured as sweeping space outside the relief pattern).
- the corners are rounded off or alternatively, relief pattern material is added.
- a joint defining a 90° corner as seen in a plan view can be rounded-off to a quarter circle or a quarter circle segment can be added to create a bulge.
- the specific size and shape of the protrusion needed to hinder the flow along the capillary depends on, inter alia, the size of the capillary, the rheological properties of the fluid and the physico-chemical surface properties of the relief pattern and supporting surface, the size and shape required for a particular application being simply a matter of straightforward experimentation.
- the second electrode layer can be patterned in a simple, cost-effective and reliable manner.
- a wet deposition method Such methods are reliable, simple and cost-effective, can be suitably used for covering large surfaces and do not require the use of expensive vacuum equipment.
- the EL device can be manufactured in a simple, reliable and cost-effective manner.
- Suitable wet deposition methods include spin-coating, web-coating, doctor blade, spray-coating, roller-coating, curtain-coating, dip-coating, painting or casting.
- Selective wet deposition techniques include printing methods such as ink-jet printing, silk- screen printing, off-set printing, flexo-printing, lithography and tampon printing.
- fluid is understood to mean any deformable mass capable of flowing under pressure and includes suspensions, solutions, dispersions, pastes, inks, lacquers, emulsions, sols and the like.
- the electroluminescent device in accordance with the invention comprises a plurality of light emitting areas. The protrusions are then used to prevent functional layer material from being deposited in the wrong light emitting areas and/or in areas where no light emission is to occur.
- the relief pattern has one or more overhanging sections.
- Such an overhanging section is formed wherever the side-wall of the relief pattern has a part which makes an angle of more than 90° with respect to its supporting surface, the angle being defined as passing through the relief pattern. In the case of curved side-walls it is the set of tangents of a side- wall part which is the relevant parameter.
- An overhanging section is, for example, formed wherever the relief pattern widens if traversed in the direction normal to and away from the supporting surface. The overhanging section creates a shadow region on the supporting surface which prevents second electrode material from being deposited there if, for example, the second electrode is provided by means of vacuum vapor deposition.
- Examples of relief patterns having an overhanging section are relief patterns having a T-, a mushroom-, or an inverse trapezoidal- or triangular-shaped transverse profile.
- overhanging sections creating shadow regions of 1 to 2 ⁇ m width or less the risk of two neighboring second electrodes being electrically connected unintentionally is relatively high.
- a suitable width of the overhanging section is 2 to 10 ⁇ m.
- a preferred relief pattern has an inverse trapezoidal transverse profile with a base of 5 to 10 ⁇ m and a top of 15 to 30 ⁇ m. If the substrate is not rotating during the deposition process of second electrode material, the overhanging section may be even smaller. The risk of circuited second electrodes can be further reduced by splitting an overhanging section into a number of spaced parallel overhanging sections.
- the EL device may be any type of display such as a monochrome or multicolor display device, a still image display, a segmented display device, or a matrix display of the passive or active type.
- the first and/or second electrode layer may comprise one or more common electrodes.
- a common electrode is one which serves as the second electrode of more than one EL element.
- At least the first or second electrode layer comprises common electrodes.
- an active matrix device comprises a single common second (first) electrode and the (second) first electrodes are independently addressable.
- the first electrode layer may be electron-injecting and the second electrode layer hole-injecting.
- the first electrode layer is hole injecting and the second electrode layer is electron injecting.
- An electron-injecting electrode is suitably made of a metal(alloy) having a low work function, such as Yb, Ca, Mg:Ag Li: Al, Ba or is a laminate of different layers such as Ba/Al or Ba/Ag electrode.
- a metal(alloy) having a low work function such as Yb, Ca, Mg:Ag Li: Al, Ba or is a laminate of different layers such as Ba/Al or Ba/Ag electrode.
- a hole-injecting electrode is suitably made of a metal (alloy) having a high work function such as Au, Pt, Ag.
- a more transparent hole-injecting electrode material such as an indiumtinoxide (ITO)
- ITO indiumtinoxide
- Conductive polymers such as a polyaniline (PANT) and a poly-3,4-ethylenedioxythiophene (PEDOT) are also suitable transparent hole-injecting electrode materials.
- a PANI layer has a thickness of 50 to 200 nm, and a PEDOT layer 100 to 300 nm. If an ITO hole-injecting electrode is used, the first electrode is preferably the hole-injecting electrode.
- the EL device comprises one or more functional layers.
- the one or more functional layers are preferably provided using a wet deposition method as described hereinabove.
- the low molecular weight compounds can be embedded in a polymer matrix or chemically bonded to polymers, for example by inclusion in the main chain or as side-chains, an example being poly vinylcarbazole .
- Preferred high molecular weight materials contain EL polymers having a substantially conjugated backbone (main chain), such as polythiophenes, polyphenylenes, polythiophenevinylenes, or, more preferably, poly-p-phenylenevinylenes.
- poly(alkyl)fluorenes and poly-p-phenylenevinylenes which emit red, yellow or green light and are 2-, or 2,5- substituted poly-p-phenylenevinylenes, in particular those having solubility-improving side groups at the 2- and/or 2,5 position such as C ⁇ -C 2 o, preferably C 4 -C10, alkyl or alkoxy groups.
- side groups are methyl, methoxy, 3J-dimefhyloctyloxy, and 2-methylpropoxy.
- polymers including a 2-aryl-l,4-phenylenevinylene repeating unit, the aryl group being optionally substituted with alkyl and/or alkoxy groups of the type above, in particular methyl, methoxy, 3J-dimethyloctyloxy, or, better still, 2-methylpropoxy.
- the organic material may contain one or more of such compounds.
- Such EL polymers are suitably applied by wet deposition techniques.
- organic includes polymeric whereas the term polymer and affixes derived therefrom, includes homopolymer, copolymer, terpolymer and higher homologues as well as oligomer.
- the organic EL material contains further substances, organic or inorganic in nature, which may be homogeneously distributed on a molecular scale or present in the form of a particle distribution.
- compounds improving the charge-injecting and/or charge-transport capability of electrons and/or holes, compounds to improve and/or modify the intensity or color of the light emitted, stabilizers, and the like may be present.
- the organic EL layer preferably has an average thickness of 50 nm to 200 nm, in particular, 60 nm to 150 nm or, preferably, 70 nm to 100 nm.
- the EL device comprises further, preferably organic, functional layers disposed between the electrodes.
- Such further layers may be hole-injecting and/or transport (HTL) layers and electron-injecting and transport (ETL) layers.
- HTL hole-injecting and/or transport
- ETL electron-injecting and transport
- Examples of EL devices comprising more than one functional layer are a laminate of anode/HTL layer/EL layer/cathode, anode/EL layer/ETL layer/cathode, or anode/HTL layer/EL layer/ETL layer/cathode.
- Suitable materials for the hole-injecting and/or hole-transport layers include aromatic tertiary amines, in particular diamines or higher homologues, polyvinylcarbazole, quinacridone, porphyrins, phthalocyanines, poly-aniline and poly-3,4- ethylenedioxythiophene.
- the EL device preferably comprises a 50 to 300 nm thick layer of the hole-injecting/-transport layer material poly-3,4- ethylenedioxythiophene or a 50 to 200 nm thick layer of polyaniline.
- the EL device comprises a substrate.
- the substrate is transparent with respect to the light to be emitted. Suitable substrate materials include transparent synthetic resin which may or may not be flexible, quartz, ceramics and glass.
- the substrate provides the supporting surface for the relief pattern. Apart from defining the pattern of the second electrode layer, the relief pattern may, if desired, also serve to define the pattern of the one or more functional layers.
- a positively-sloped section is the opposite of an overhanging section.
- the tangents of the boundary of the transverse profile of the positively-sloped section all make angle of less than 90° with the supporting surface, the angle being defined as passing through the relief pattern.
- a section having straight slopes (side-walls) is considered either positively- sloped or overhanging.
- the height, width and shape of the relief pattern is chosen such that the fluid layer breaks up into fluid areas in accordance with the desired pattern each area being then converted into a corresponding area of functional material.
- the transverse profile of the positively-sloped section is preferably rounded.
- the relief pattern is a composite relief pattern comprising a first relief pattern having overhanging sections overlaying or underlying a second relief pattern having positively-sloped sections.
- the relief pattern is preferably provided as a first relief pattern having overhanging section overlying or underlying a second relief pattern having positively-sloped sections because such a composite pattern can be conveniently manufactured by using two photolithographic steps in succession.
- the layout of the first and second relief pattern is mutually different.
- the first relief pattern by itself determines the pattern of the second electrode layer while the combined first and second relief pattern defines the pattern of any functional layer to be patterned and defines the boundary of the pixel in the case of a multi-pixel device.
- the composite relief has a first relief pattern which overlays the second relief pattern.
- the capillary channel formed by the first relief pattern has to go uphill to pass to cross the second relief pattern thus reducing the capillary effect of the channel.
- the capillary effect is not sufficiently suppressed and protrusions extending transversely from the boundary of the first relief pattern are provided at those locations where the first relief pattern crosses the second relief pattern to further reduce the capillary effect of the channels.
- the second relief pattern may overlay the first relief pattern. This has the advantage that the second relief pattern may provide the protrusions needed to block the capillary channels of the first relief pattern at the desired locations but may increase of the risk of inadvertently connecting second electrodes of the second electrode layer.
- the first and second relief pattern are directly supported by a same substrate surface, except where the first and the second relief pattern cross each other.
- the average height of the composite relief pattern is reduced and more uniform across the display area of the device. This makes it more simple to deposit a functional layer having a uniform thickness across the device (within and between the pixels, in case of a multi-pixel device) if provided by means of a wet, in particular non-selective, deposition method.
- the second relief pattern provides the supporting surface of the first relief pattern.
- the composite relief pattern according to this embodiment has the advantage that the first and second relief pattern are provided on a substantially level supporting surface.
- the transverse profile of the first relief pattern is selected to be narrower than the transverse profile of the second relief pattern.
- the projection of the first relief pattern onto the surface supporting the composite relief pattern is a sub-area of the corresponding projection of the second relief pattern. If this is the case, the first relief pattern does not contribute to the definition of any functional layer to be patterned by wet deposition method but the second relief pattern alone defines the outline of such functional layer.
- the outline of the pixels of a multi-pixel EL device is provided by the second relief pattern.
- the protrusions blocking the capillary channels are provided on top of the second relief pattern and extend from the boundary of the first relief pattern.
- the EL device is a matrix display device of the passive type comprising row electrodes as the first electrode layer, column electrodes as the second electrode layer, independently addressable electroluminescent elements formed at crossings of row and column electrodes, and the relief pattern having overhanging sections in the form of strips extending along and between the column electrodes.
- a protrusion extends transversely to the overhanging sections and is positioned in the boundary areas between pixels.
- the size of the EL elements is selected in accordance with the application. For high definition pixels of 10 to 75 ⁇ m can be used. For less demanding applications a pixel size of 100 to 300 ⁇ m may be sufficient.
- a red, a green and a blue light-emitting pixel is grouped in an RGB pixel. For example, the red, green and blue each measures 100 by 300 ⁇ m giving an RGB pixel of 300 by 300 ⁇ m.
- the width of the strips of relief pattern defines the distance between the EL elements (pixels) along the column electrodes. This distance is preferably selected as small as possible to maximize the fill- factor, defined as the total area available for light emission divided by the total area of the display. Typically, the width of the strips is 10 to 40 ⁇ m or better 15 to 30 ⁇ m.
- the width of the protrusion that is the dimension in the longitudinal direction of the column electrodes, is not critical but in order to maximize the fill-factor needs to be as small as possible.
- the width of the protrusion is 2 to 50 ⁇ m, or better, 3 to 30 or preferably, 5 to 20 ⁇ m.
- the length (dimension in the direction normal to the column electrodes) of the protrusion must be less than the dimension of the pixel in the longitudinal direction of the row electrodes because otherwise the column electrode will be interrupted and the pixel cannot be addressed.
- a suitable length is 2 to 100 ⁇ m or, better, 5 to 75 or still better 10 to 60 ⁇ m. Below 2 ⁇ m the protrusion becomes unstable due to the overhang at its free end. Above 100 ⁇ m the extent to which fluid flow along channel is hindered does not increase anymore.
- the passive matrix display may comprise a composite relief pattern, for example a stack of a first relief pattern in the form of strips having overhanging sections which extend between and along the second electrodes, that is the column electrodes, and a second relief pattern in the form of strips extending along and between the row electrodes of the first electrode layer.
- the matrix display has a composite relief pattern in which the second relief pattern is in the form of a mesh which extends between and along both the row and column electrodes and a first relief pattern extending along the row electrodes provided on top of the second relief pattern, the second relief pattern defining the outline of the pixels of the device.
- Acute corners (90° or less) enhance capillary effects. Therefore, in order to reduce the acuity of the corners formed by the relief pattern, the corners of the first and second relief pattern are preferably rounded.
- the EL device in accordance with the invention requires a potential of only a few volts to provide a brightness suitable for display purposes and/or consumes a small amount of power
- the EL device is particularly suitable for displays of battery operated and/or portable, in particular hand-held, electronic equipment such as lap top computers, palm top computers, personal organizers, mobile phones optionally provided with internet access or other services requiring the presentation of (video) images.
- the EL device allows internet data and image data to be displayed at video rates.
- the invention also relates to a method of manufacturing an electroluminescent device comprising a first and a second electrode layer, at least the second electrode layer being provided in accordance with a desired pattern, one or more functional layers, the one or at least one of said functional layers being an electroluminescent layer, a relief pattern having one or more overhanging sections for defining the desired pattern of the second electrode layer, and means for hindering the transport of fluid along a capillary channel formed by an overhanging section and a surface supporting that overhanging section, said method comprising the step of providing the functional layer or at least one of the functional layers by means of a wet deposition method.
- Providing means for hindering the transport of fluid along the channels allows the one or more functional layers to be deposited by a wet deposition methods without resulting in a leakage current and or cross-talk between neighboring pixels. Also, in case of a multi-color device, color bleeding between light emitting areas arranged to emit different colors is significantly reduced.
- the use of the wet deposition methods to deposit the functional layers leads to a simple and cost-effective manufacturing methods suitable for mass-production and large areas.
- the method in accordance with the invention is a method which comprises providing, in succession, substrate (optional), a first electrode layer, a relief pattern having one or more overhanging sections for defining the second electrode layer, one or more functional layers by means of a wet deposition method, and a second electrode layer patterned by means of the relief pattern.
- the method includes the step of providing the means for hindering the transport of fluid along the capillary channel(s). As demonstrated by the embodiments presented hereinbelow, generally, this step is performed as part of and simultaneous to one of the other method steps.
- the step of providing the means for hindering the transport of fluid is implemented by providing a relief pattern having overhanging sections of which the side-walls are poorly wetting on a poorly wetting supporting surface, where poorly wetting is understood to mean poorly wetting with respect to the fluid of which the transport is to be prevented and as determined by a contact angle measurement of the fluid and the surface concerned. Poorly wetting corresponds to a contact angle having a value as defined hereinabove.
- poorly-wetting side-walls and/or supporting surface may be provided by manufacturing the relief pattern and the supporting surface of poorly-wetting bulk material.
- bulk material can be rendered poorly-wetting by subjecting it to an anti-wetting treatment. Such anti-wetting treatments are well-known to those skilled in the art.
- the anti-wetting treatment may comprise exposing the photoresist surface to fluorinated hydrocarbons.
- a preferred embodiment of the method in accordance with the invention comprises the step of providing a relief pattern comprising at least one protrusion blocking and/or rerouting a channel formed by an overhanging section and a surface supporting that overhanging section.
- the protrusions serve as the hindering means.
- the means of hindering the transport of fluid along the channels is incorporated in the fluid used in wet deposition method.
- One embodiment of such a method comprises using a fluid which is poorly wetting with respect to the surfaces from which the channel is formed.
- a simple one being changing the polarity of the fluid by changing the solvent composition.
- the viscosity of the fluid is adapted such that, on the time scale of the deposition of the functional layer, fluid is transported over distances less than the distances separating pixels.
- first and second electrode layers, functional layers and relief patterns have already been described hereinabove.
- each of the method steps required to manufacture the EL device is conventional and well-known to those skilled in the art.
- a composite relief pattern can be conveniently manufactured by performing two photolithographic steps in succession.
- the wet deposition method step involves providing a layer of fluid containing functional layer material or precursor material thereof, which layer of fluid is then converted into a functional layer.
- functional layers include a hole transport layer, hole injecting layer, an electroluminescent layer, an electron injecting layer an electron transport layer.
- the fluid layer has fluid in a form as defined hereinabove. After the fluid layer is deposited it is converted to the functional layer.
- the conversion may involve exposing, if required in an inert atmosphere, the fluid layer to increased or reduced temperatures, increased or reduced pressure, and/or radiation. Preferably, the conversion is performed at an elevated temperature.
- the functional layer material is present as such in the fluid layer, it may be sufficient to evaporate a solvent and/or other volatile components. If the fluid layer contains a precursor material of the functional material the conversion also involves a chemical reaction. The wealth of chemical reactions known to those skilled in the art of chemistry may be exploited to derive suitable precursor materials. A preferred precursor material contains leaving groups which are eliminated during the conversion.
- the fluid layer may contain further substances.
- substances which modulate its rheological properties such as viscosity, (visco)elasticity, contact angle and/or wettability.
- Wetting agents, or anti-wetting agents, leveling agents, surfactants, thickening agents, diluents and the like may be added.
- a preferred method of coating is ink-jet printing using a jet consisting of ink drops or a continuous jet (also referred to as dispensing).
- a jet consisting of ink drops or a continuous jet (also referred to as dispensing).
- the use of multi-nozzle ink-jet printing heads is preferred.
- inkjet printing is performed at constant frequency and the inkjet printing head is moved at constant velocity resulting in a series of ink drops deposited equidistantly on the substrate.
- a preferred method comprises moving the ink jetting printing head in a direction at right angles to the second electrodes which after conversion of the fluid layer results in an array of pixels of the same color extending parallel to the first electrode.
- the equidistantly placed ink drops merge into an uninterrupted line of fluid thus automatically ensuring that electroluminescent layer material is evenly distributed among the pixels arranged to emit the same color even if the periodicity is not an integral number of times the pixel periodicity.
- the line of fluid is not interrupted by the first relief pattern because typically the fluid level is arranged to be initially higher than the total height of the relief pattern.
- the relief pattern having overhanging sections is, apart from patterning the second electrode, used for patterning the one or more functional layers.
- the inkjet head is moved parallel to the overhanging sections to fill the spaces defined by the overhanging sections of the relief pattern.
- a separate relief pattern for defining the outline of the functional layers is not required. Because in this embodiment there is no barrier against the transport of fluid along the capillary channels, the use of protrusions and/or end-stops as described hereinabove is particularly relevant. Furthermore, it has been observed that in the spaces near the free ends of the overhanging sections evaporation of fluid may proceed faster because the surface area available for evaporation is larger near such a free end.
- the protrusion should be at least half the height of the fluid layer thickness if transport of fluid is to be effectively hindered.
- the device in accordance with the invention can be any electroluminescent device. It may be of the inorganic type but preferably is of the organic type. It may be a unipolar electroluminescent device, that is a device in which injection of charge carriers of only one polarity is sufficient to generate light. It may also be of the bipolar type which requires injection of both holes and electrons to generate light.
- the latter type includes the light emitting cell (LEG) as disclosed in US 5,682,043 which does not require electrodes of different work function to get observable light emission and the light emitting diode (LED) which requires electrodes of high work function to inject holes and an electrodes of low work function to inject electrons. Also included are electroluminescent devices where the charge injecting electrodes are arranged subjacent or, alternatively, adjacent with respect to each other.
- Fig. 1 shows, drawn to scale and in a plan view, a part of an EL device not in accordance with the invention at a stage of manufacture obtained after pattern-wise deposition of an electroluminescent layer,
- Fig. 1 A shows a cross-sectional view along the line I-I of Fig. 1,
- Fig. 2 shows, drawn to scale and in a plan view, a part of an EL device in accordance with the invention at a stage of manufacture after deposition of a electroluminescent layer
- Figs. 2A, 2B and 2C show enlarged cross-sectional views along the lines II-II, m-m and IN-IV respectively of Fig. 2,
- Fig. 3 schematically shows, in a perspective plan view, a part of an organic EL matrix display device in accordance with the invention
- Fig. 4 schematically shows a mobile phone provided with an EL device in accordance with the invention.
- FIG. 1 shows, drawn to scale and in a plan view, a part of an EL device not in accordance with the invention at a stage of manufacture obtained after pattern-wise deposition of an electroluminescent layer.
- Fig. 1 is drawn to scale and represents an image when the EL device 1 is inspected through an optical microscope.
- Fig. 1A shows a cross-sectional view along the line I-I of Fig. 1.
- the direction normal to the substrate is not drawn at a different scale than the directions in the plane of the substrate.
- the EL device 1 is a multi-color passive matrix display device having 300 ⁇ m by 300 ⁇ m EL elements (pixels) 10, 11 and 12 and comprises a glass substrate 2 provided with a first electrode layer 3 in the form of ITO hole-injecting row electrodes. It further comprises a composite relief pattern 7 of a first relief pattern 9 which has overhanging sections for defining the pattern of a second electrode layer (not shown) and a second relief pattern 8 having positive-sloped sections underlying the first relief pattern 9. The angle of inclination of the overhanging sections is 45°, the height of the relief pattern 9 is about 2.5 ⁇ m and the height of the second relief pattern 8 is 4.5 ⁇ m.
- Indicated with reference sign 5 is a pattern-wise deposited electroluminescent layer arranged to emit light of a first color.
- Fig. 1 clearly shows that, despite the selective deposition into pixels 10 and 12, EL material is, after conversion, present in areas 11 as well. Apparently, fluid has bled into the pixel areas 1 l. The bleeding is caused by the capillary action of the channels 13 formed by side-walls 9a of the overhanging sections of the first relief pattern 9 and the supporting surface 8a provided by the second relief pattern 8. The channels 13 drain fluid from the pixel areas 10 and 12 and redeposit the drained fluid in the neighboring pixel areas 11.
- the pattern of the EL layer 5 in the region between pixels 12 and 11 on the one hand and the region between pixels 10 and 11 on the other hand is asymmetric. This is a result of the fact that the EL layer in pixels 10 and 12 is deposited in succession. Apparently, the presence of EL material as such affects the transport of fluid along the capillary channel as well in that it modifies the wettability of the relief pattern. If the EL layer 5 renders the surface of the relief pattern less wettable the transport of fluid along the channels 13 is hindered.
- Fig. 2 shows, drawn to scale and in a plan view, a part of an EL device in accordance with the invention at a stage of manufacture after deposition of a electroluminescent layer
- the relief pattern 109 has protrusions 115, each extending, at the position of the protrusion, transversely to the boundary of the first relief pattern 109.
- the protrusions 115 block and/or reroute the channels 113 formed by the overhanging section of the first relief pattern 109 and its supporting surface 108a provided by the second relief pattern 108 and thus serve as means for hindering the transport of fluid along the capillary channel(s) 113.
- each pixel 110, 111, 112 is about 600 pi. After conversion by evaporating the solvent each of the pixels 110, 111 and 112 is provided with a 200 nm thick charge transport layer 104. As is clear from Figs 2A and 2B, charge transport layer material is deposited in the capillary channels 113. Referring to Fig. 2, the charge transport areas of the pixels 110 are not completely separated from those of pixels 111. Just beyond the free ends of the protrusions 115, the pixels 110 are connected via a narrow path of charge transport material.
- Fig. 3 schematically shows, in a perspective plan view, a part of an organic EL matrix display device 21 in accordance with the invention.
- Fig. 4 schematically shows a mobile phone 101 provided with the EL device
- the device 21 has EL multi-color pixels 31R, 31G and 3 IB and comprises a glass substrate 22 covered with a patterned first electrode layer in the form of hole-injecting row electrodes 23.
- a composite relief pattern 27 extending at least between and along the row electrodes 23 comprises a first relief pattern 29 having overhanging sections which is supported by a second relief pattern 28 having positively-sloped sections.
- the first relief pattern 29 is used to define the pattern of the second electrode layer 26.
- the purpose of the second relief pattern 28 is to define the outline of the pattern of the EL layers and of the pixels 31R, 31G, 3 IB of the EL device.
- the relief pattern has protrusions 35 which each extend, at the position of the protrusion, transversely to the boundary of the first relief pattern 29.
- the protrusions 35 block and/or reroute the channels 33 formed by the side-walls 29a of the overhanging sections of the relief pattern 29 and the surface 28a supporting that relief pattern.
- the protrusions 35 are also overhanging sections which for the purpose of hindering the transport of fluid along the capillary channels 33 is by no means essential but is convenient for manufacturing purposes as they can be provided at the same time and using the same process as used for the first relief pattern 29.
- the strands of charge transport material present in the channels 33 are interrupted, thereby allowing a charge transport layer of mutually separate charge transport areas 24 to be provided using a wet deposition method such as spin-coating or ink-jet printing without the charge transport areas 24 being connected via charge transport material present in the channels.
- the protrusions 35 also prevent color bleeding in that, during for example ink-jet printing, the protrusions 35 block or least reroute the capillary channels 33 which without the protrusions 35 transport fluid containing electroluminescent layer material used for the EL layers 25R, 25G or 25B from one pixel to another.
- the substrate is then spin-coated (1000 rpm) with a layer of the image reversal photoresist AZ5218-e (AZ Hoechst).
- the photoresist is exposed pattern-wise using a mask in proximity (40 ⁇ m gap) with a dose of 32 mJ/cm , hard-baked at 110 °C for 10 min, flood exposed with a dose of 400 mJ/cm 2 , developed using a 1:1 AZ-developer:deionized- water developer for a time sufficient to obtain a negative slope of 45°, and post-baked at 100 °C for 15 min.
- Each of the overhanging sections has an inverted trapezoidal shape.
- the height of the relief pattern 29 is 2.0 ⁇ m.
- the total height of the relief pattern 27 is 6.0 ⁇ m.
- the transverse profile of the second relief pattern 28 can be made more rounded by hard-baking the relief pattern 28, before applying the first relief pattern 29, at a temperature above its softening point for an extended period of time so that it is able flow somewhat.
- a charge transport layer 24 of poly-3,4-ethylenedioxythiophene (PEDOT) is then ink-jetted according to the method described in embodiment 2 resulting in mutually separate areas each 250 nm thick and having a square resistance of 100 M ⁇ /square.
- PEDOT poly-3,4-ethylenedioxythiophene
- Fig. 3 shows ITO electrodes 23 to be separated along each pixel.
- ITO electrodes 23 it is sufficient to have a single common ITO track 23 for each aggregate RGB-pixel 25R, 25G and 25B in order to be able to address each pixel individually.
Abstract
Description
Claims
Priority Applications (5)
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AT01996886T ATE475198T1 (en) | 2000-11-17 | 2001-10-29 | ORGANIC ELECTROLUMINENCE COMPONENT AND METHOD FOR THE PRODUCTION THEREOF |
JP2002543702A JP4308522B2 (en) | 2000-11-17 | 2001-10-29 | Organic electroluminescent device and manufacturing method thereof |
EP01996886A EP1340261B1 (en) | 2000-11-17 | 2001-10-29 | Organic electroluminescent device and a method of manufacturing thereof |
KR1020027009137A KR20020073173A (en) | 2000-11-17 | 2001-10-29 | Organic electroluminescent device and a method of manufacturing thereof |
DE60142629T DE60142629D1 (en) | 2000-11-17 | 2001-10-29 | ORGANIC ELECTROLUMINESCENCE ELEMENT AND METHOD FOR THE PRODUCTION THEREOF |
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EP (1) | EP1340261B1 (en) |
JP (1) | JP4308522B2 (en) |
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- 2001-10-29 KR KR1020027009137A patent/KR20020073173A/en not_active Application Discontinuation
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- 2001-10-29 JP JP2002543702A patent/JP4308522B2/en not_active Expired - Fee Related
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US8207667B2 (en) | 2007-08-31 | 2012-06-26 | Sharp Kabushiki Kaisha | Organic EL display and manufacturing method thereof |
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Also Published As
Publication number | Publication date |
---|---|
CN1418375A (en) | 2003-05-14 |
JP4308522B2 (en) | 2009-08-05 |
US7122957B2 (en) | 2006-10-17 |
EP1340261A1 (en) | 2003-09-03 |
CN100353548C (en) | 2007-12-05 |
JP2004514256A (en) | 2004-05-13 |
US20020060518A1 (en) | 2002-05-23 |
KR20020073173A (en) | 2002-09-19 |
EP1340261B1 (en) | 2010-07-21 |
DE60142629D1 (en) | 2010-09-02 |
ATE475198T1 (en) | 2010-08-15 |
TW548856B (en) | 2003-08-21 |
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