WO2012008443A1 - 転写用ドナー基板およびこれを用いたデバイスの製造方法、ならびに有機el素子 - Google Patents
転写用ドナー基板およびこれを用いたデバイスの製造方法、ならびに有機el素子 Download PDFInfo
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- WO2012008443A1 WO2012008443A1 PCT/JP2011/065874 JP2011065874W WO2012008443A1 WO 2012008443 A1 WO2012008443 A1 WO 2012008443A1 JP 2011065874 W JP2011065874 W JP 2011065874W WO 2012008443 A1 WO2012008443 A1 WO 2012008443A1
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/04—Coating on selected surface areas, e.g. using masks
- C23C14/048—Coating on selected surface areas, e.g. using masks using irradiation by energy or particles
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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
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
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- 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
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- 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
- H10K71/18—Deposition of organic active material using non-liquid printing techniques, e.g. thermal transfer printing from a donor sheet
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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
- H10K2102/351—Thickness
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/35—Devices specially adapted for multicolour light emission comprising red-green-blue [RGB] subpixels
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a thin film transfer donor substrate constituting an organic EL element, a device manufacturing method using such a transfer donor substrate, and an organic EL element.
- An organic EL element is one in which electrons injected from a cathode and holes injected from an anode are recombined in an organic light emitting layer sandwiched between both electrodes.
- the organic EL element that emits light as described above has been thin and capable of high luminance under a low driving voltage since the research results shown in Non-Patent Document 1 have been shown, and various organic materials can be used for the light emitting layer. By using, it is possible to obtain various emission colors including the three primary colors of red (R), green (G), and blue (B). As a result, various technologies have been required.
- One of them is a technology for forming a light-emitting layer that is a thin film with a typical film thickness of 0.1 ⁇ m or less and finely patterned for each of the three primary colors on a device substrate on which an organic EL element is formed as a final product. .
- the mask vapor deposition method is a method in which a vapor deposition mask having a precise hole is adhered to a metal plate, and each light emitting material is vapor-deposited on a device substrate using the mask as a mask. In this method, it is difficult to achieve both the enlargement of the color display and the accuracy of the holes, and the adhesion between the device substrate and the vapor deposition mask tends to be lost as the size of the color display increases.
- a transfer material is formed by applying R, G, and B light emitting materials to a transfer donor sheet (donor film or donor substrate) and then finely patterning the transfer material.
- a material for transferring a transfer material onto a device substrate by vapor deposition has been developed.
- a photothermal conversion layer is formed on a donor substrate, and organic EL materials of R, G, and B are separately applied thereon by a printing method, and the photothermal conversion layer is irradiated with a laser to perform batch transfer.
- a method is disclosed.
- Patent Documents 2 and 3 a partition pattern is provided on the photothermal conversion layer of the donor substrate, an organic EL material of R, G, and B is applied thereon by a method such as an ink jet method, and the photothermal conversion layer is irradiated with a laser. And a method of batch-transferring organic EL materials.
- Patent Document 4 the organic EL material is transferred to the donor substrate by selectively irradiating only the portion of the organic EL material formed on the donor substrate by a method such as an inkjet method with little film thickness unevenness, thereby forming the device substrate.
- a method for reducing the unevenness of the film thickness of the organic EL material is described.
- the partition pattern is not formed on the donor substrate in the method described in Patent Document 1, when RGB is applied in a solution state, it is mixed with the adjacent material, or the solvent vapor at the time of drying is adjacent to the adjacent substrate. There is a problem that the material is redissolved, and it is difficult to coat the organic EL material with high accuracy. Further, in the methods described in Patent Documents 2 and 3, when a transfer material is formed in each partition pattern by an ink jet method, a so-called “coffee stain” -like local film thickness unevenness occurs, resulting in a device substrate. There is also a problem that local film thickness unevenness is copied even when transferring to a film.
- Patent Document 4 discloses a method of creating a device substrate with less film thickness unevenness by transferring only a portion with less film thickness unevenness of the organic EL material formed on the donor substrate as shown in FIG. Has been.
- a device substrate with a high aperture ratio as shown in FIG. 17B even if only a portion where the film thickness unevenness of the organic EL material formed on the donor substrate is small is transferred to the pixel region of the device substrate.
- the transfer area of the donor substrate is small, there is a problem that the film is extremely thinned near the insulating layer around the pixel.
- the organic EL material that has been extremely thickened near the partition wall of the donor substrate is also transferred, so that the organic EL transferred to the device substrate is transferred. There was a problem that the film thickness of the material became non-uniform.
- the present invention solves such a problem, and an object thereof is a donor substrate that transfers a transfer material to a device substrate by irradiating light typified by a laser, and can form a uniform transfer material film.
- An object of the present invention is to provide a donor substrate capable of accurate fine patterning and a method for producing a device typified by an organic EL element using the donor substrate. It is another object of the present invention to provide an organic EL element that has less unevenness in light emission luminance and film thickness in the light emitting region and is excellent in durability.
- the present inventors have been able to eliminate unevenness in film thickness that occurs in the drying process of the solvent by adjusting the surface roughness of the photothermal conversion layer of the donor substrate, and have a high aperture ratio device substrate
- the inventors have found that an organic EL element with little unevenness in light emission luminance can be produced, and the present invention has been achieved.
- one configuration of the present invention relates to a transfer donor substrate, which is a transfer donor substrate having a substrate and a photothermal conversion layer formed on the substrate, wherein the surface of the photothermal conversion layer is rough. It is a surface.
- Another configuration of the present invention relates to an organic EL element, which includes an organic compound layer including a light emitting layer sandwiched between at least a pair of electrodes, and at least a part of the organic compound layer uses a transfer method.
- the width of the insulating layer of the subpixel is less than 40 ⁇ m, and the light emission luminance unevenness of the light emitting region in the subpixel is ⁇ 20% or less.
- an organic EL element having an organic compound layer including a light emitting layer sandwiched between at least a pair of electrodes, and at least a part of the organic compound layer is formed using a transfer method, the width of the insulating layer of the subpixel Is less than 40 ⁇ m, and in the organic compound layer formed by using the transfer method, the thickness unevenness of the light emitting region in the sub-pixel is ⁇ 10% or less.
- a transfer donor substrate on which a transfer material having a uniform film thickness is formed can be produced by a coating method.
- a device is obtained. It is possible to manufacture a device that is finely patterned with high accuracy without deteriorating performance.
- the organic EL element of the present invention it is possible to realize a display device having high image quality display and excellent durability since there is little unevenness in light emission luminance.
- the expanded sectional view which shows the example of the typical structure of the device substrate in which the organic EL element was formed.
- the expanded sectional view which shows the example of the method of forming a transfer film in a device substrate using the donor substrate in embodiment of this invention.
- the enlarged plan view in FIG. Sectional drawing explaining formation of the transfer material in embodiment of this invention.
- Sectional drawing which shows an example of formation of the transfer material in embodiment of this invention.
- Sectional drawing which shows an example of the patterning method in embodiment of this invention.
- the top view photograph of the formation process of the transfer material in the Example of this invention.
- the enlarged sectional view and the enlarged plan view used in this specification show RGB sub-pixels constituting a pixel which is a minimum unit of a color display. Further, in order to help understanding, the magnification in the vertical direction (direction perpendicular to the substrate surface) is enlarged as compared with the horizontal direction (direction in the substrate surface) of the enlarged sectional view.
- a device substrate 10 having a typical structure in which an organic EL element is formed will be described as a typical example of a device, and then, an embodiment of the present invention suitable for forming a device on the device substrate 10 by transfer will be described.
- the donor substrate 30 will be described, and then a device manufacturing method will be described focusing on a transfer process using the donor substrate 30.
- FIG. 1 is an enlarged cross-sectional view showing an example of a typical structure of a device substrate 10 on which an organic EL element is formed.
- an active matrix circuit composed of TFTs 12 (including extraction electrodes), a planarizing layer 13, and the like is formed on a support 11 such as a glass plate.
- a first electrode 15 / hole transporting layer 16 / light emitting layer 17 / electron transporting layer 18 / second electrode 19 constituting the organic EL element are formed thereon.
- the light emitting layer 17 is composed of three types of RGB light emitting layers 17R, 17G, and 17B, which are partitioned in the horizontal direction.
- an insulating layer 14 that prevents a short circuit from occurring at the electrode end and defines a light emitting region is formed.
- the element configuration of the organic EL element is not limited to this example.
- only one light emitting layer 17 having a hole transport function and an electron transport function is provided between the first electrode 15 and the second electrode 19.
- the hole transport layer 16 may be formed of a hole injection layer and a hole transport layer
- the electron transport layer 18 may be a multilayer structure of an electron transport layer and an electron injection layer
- the electron transport layer 18 may be omitted.
- the first electrode 15 / electron transport layer 18 / light emitting layer 17 / hole transport layer 16 / second electrode 19 may be laminated in this order.
- these layers may be a single layer or a plurality of layers.
- a protective layer, a color filter, sealing, or the like may be performed using a known technique or a transfer process of this embodiment described later. .
- the light emitting layer 17 may be a single layer or a plurality of layers, and the light emitting material of each layer may be a single material or a mixture of a plurality of materials. From the viewpoint of luminous efficiency, color purity, and durability, the light emitting layer 17 preferably has a single layer structure of a mixture of a host material and a dopant material.
- the hole transport layer 16 may be a single layer or a plurality of layers, and each layer may be a single material or a mixture of a plurality of materials.
- a layer called a hole injection layer is also included in the hole transport layer 16. From the viewpoint of hole transportability (low driving voltage) and durability, the hole transport layer 16 may be mixed with an acceptor material that promotes hole transportability.
- the electron transport layer 18 may be a single layer or a plurality of layers, and each layer may be a single material or a mixture of a plurality of materials.
- a layer called a hole blocking layer or an electron injection layer is also included in the electron transport layer 18.
- the electron transport layer 18 may be mixed with a donor material that promotes electron transport properties.
- a layer called the electron injection layer is often discussed as this donor material.
- the transfer material for forming the electron transport layer 18 may be made of a single material or a mixture of a plurality of materials.
- Donor materials include lithium, cesium, magnesium, calcium and other alkali metals and alkaline earth metals, their quinolinol complexes and other metal complexes, lithium fluoride and cesium oxide, their oxides and fluorides, tetrathia
- An electron donating low molecular weight material such as fuvalene (TTF) can be exemplified.
- An electron transport material or a donor material is one of the materials in which performance changes easily occur in combination with the light emitting layer 17.
- the first electrode 15 and the second electrode 19 are transparent in order to extract light emitted from the light emitting layer 17.
- the first electrode 15 is transparent
- the second electrode 19 is transparent.
- the transparent electrode material and the other electrode conventionally known materials can be used as described in JP-A-11-214154, for example.
- Such an organic EL element is not generally limited to an active matrix type in which the second electrode 19 is formed as a common electrode.
- a stripe in which the first electrode 15 and the second electrode 19 intersect each other is used.
- It may be a simple matrix type composed of electrode-like electrodes, or a segment type in which the display unit is patterned so as to display predetermined information. Examples of these applications include televisions, personal computers, monitors, watches, thermometers, audio equipment, automobile display panels, and the like.
- the donor substrate 30 includes a support 31, a photothermal conversion layer 33 formed on the support 31, a partition pattern 34 formed by being stacked on the photothermal conversion layer 33, and a transfer material 37 partitioned by the partition pattern 34. And comprising.
- the transfer material 37 of the donor substrate 30 is composed of transfer materials 37R, 37G, and 37B of three types of light emitting materials of RGB divided in the lateral direction. It corresponds to the types of light emitting layers 17R, 17G, and 17B.
- 3 is a view of the state of light irradiation in FIG. 2 as viewed from the support 31 side of the donor substrate 30.
- FIG. Since there is the photothermal conversion layer 33 formed on the entire surface, the partition pattern 34 and the transfer materials 37R, 37G, and 37B are not actually visible from the support 31 side, but a dotted line is used to explain the positional relationship with light irradiation. This is illustrated in FIG.
- the irradiated light has a rectangular shape, is irradiated so as to straddle the transfer materials 37R, 37G, and 37B, and is scanned in a direction perpendicular to the arrangement of the transfer materials 37R, 37G, and 37B.
- the irradiated light may be scanned relatively, and the light itself may be moved, the set of the donor substrate 30 and the device substrate 10 may be moved, or both.
- the support 31, the photothermal conversion layer 33, the transfer material 37, and the partition pattern 34 will be described in this order.
- the support 31 of the donor substrate 30 is not particularly limited as long as it has a low light absorption rate and can stably form the photothermal conversion layer 33, the partition pattern 34, and the transfer material 37 thereon.
- a film of a resin material Polyester, polyethylene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyacryl, polysulfone, polyethersulfone, polyphenylene sulfide, polyimide, polyamide, polybenzoxazole, polyepoxy, polypropylene, polyolefin, aramid resin, silicone Resin etc. can be illustrated.
- a glass plate can be cited as a preferred support 31 in terms of chemical / thermal stability, dimensional stability, mechanical strength, and transparency. Soda lime glass, alkali-free glass, lead-containing glass, borosilicate glass, aluminosilicate glass, low expansion glass, quartz glass and the like can be selected according to the conditions. As will be described later, when the transfer process is performed in a vacuum, since it is required that the gas release from the support 31 is small, a glass plate is particularly preferable also in this respect.
- the support 11 of the device substrate 10 and the donor substrate 30 When transferring the transfer material with the device substrate 10 and the donor substrate 30 facing each other, in order to prevent the patterning accuracy from deteriorating due to a difference in thermal expansion due to a temperature change, the support 11 of the device substrate 10 and the donor substrate 30,
- the difference in thermal expansion coefficient between 31 is preferably 10 ppm / ° C. or less, and it is more preferable that these supports 11 and 31 are made of the same material.
- the difference in thickness between the two is not particularly limited.
- the temperature rise (thermal expansion) of the support 31 itself needs to be within an allowable range, so that the heat capacity of the support 31 is sufficiently larger than that of the photothermal conversion layer 33.
- the thickness of the support 31 is preferably 10 times or more the thickness of the photothermal conversion layer 33.
- the allowable range depends on the size of the transfer region, the required accuracy of patterning, and the like.
- the photothermal conversion layer 33 rises by 300 ° C. from room temperature, and the temperature rise of the support 31 is reduced to 1/100 of that.
- the thickness of the support 31 should be at least 100 times the thickness of the photothermal conversion layer 33.
- the thickness of the support 31 is 300 times or more the thickness of the photothermal conversion layer 33.
- the thickness of the support is preferably 200 times or more, and more than 600 times the thickness of the light-to-heat conversion layer. Is more preferable.
- the photothermal conversion layer 33 of the donor substrate 30 is not particularly limited as long as it is a material and configuration that efficiently absorbs light to generate heat and is stable against the generated heat.
- a thin film in which carbon black, graphite, titanium black, organic pigment, metal particles or the like are dispersed in a resin, or an inorganic thin film such as a metal thin film can be used.
- the photothermal conversion layer 33 since the photothermal conversion layer 33 may be heated to about 300 ° C., the photothermal conversion layer 33 is preferably made of an inorganic thin film having excellent heat resistance. It is particularly preferable that the thin film is made of a material.
- metal materials include tungsten, tantalum, molybdenum, titanium, chromium, gold, silver, copper, platinum, iron, zinc, aluminum, cobalt, nickel, magnesium, vanadium, zirconium, silicon, carbon, and the like, or alloys thereof. Can be used. If necessary, an antireflection layer can be formed on the support 31 side of the photothermal conversion layer 33. Further, an antireflection layer may be formed on the surface of the support 31 on the light incident side. These antireflective layers are preferably optical interference thin films using the difference in refractive index, and simple or mixed thin films such as silicon, silicon oxide, silicon nitride, zinc oxide, magnesium oxide, and titanium oxide, and laminated thin films thereof are used. it can.
- the photothermal conversion layer 33 has a fine uneven structure on the surface, that is, the surface is rough.
- the rough surface in the present invention is roughened to the extent that local film thickness unevenness does not occur in the dried film when a solution containing a transfer material is applied to the donor substrate as described later.
- FIG. 4 is a diagram for explaining the formation of a dry film of the transfer material 37 when the application to the donor substrate 30 is performed.
- the film thickness unevenness of the transfer material 37 shown in FIG. 4A is caused by the solidification of the solute locally. Therefore, the transfer film 27 after transfer to the device substrate 10 tends to remain as the same film thickness unevenness. Even when an EL element is manufactured, uneven light emission luminance is unevenly distributed in a part of the section.
- the film thickness of the transfer material 37 is made more uniform than in FIG. 4A, and the film thickness unevenness of the transfer film 27 can be suppressed even after transfer to the device substrate 10.
- the uniform film thickness means that the dissolved mass on the substrate is substantially uniform.
- the transfer material is brought to the molecular (atomic) level during transfer by using the vapor deposition mode described later. Since the film is deposited on the device substrate 20 after sublimation in a loose state, the film thickness unevenness of the transfer film 27 is made uniform, and the light emission luminance unevenness when the organic EL element is manufactured does not become a problem.
- the surface of the photothermal conversion layer 33 is rough, thereby reducing the movement of the transfer material 37 due to the dry vapor of the solvent, and causing film thickness unevenness. Can also be suppressed.
- FIG. 5 is a diagram illustrating the occurrence of film thickness unevenness when the transfer material 37 is applied.
- a substrate having a light-to-heat conversion layer 33 having a smooth surface as shown in FIG. A solution of the transfer material 37R is applied and dried.
- a solution of the transfer material 37G is applied and dried.
- a solution of the transfer material 37B is applied and dried.
- the transfer material 37R previously formed is affected by the vapor of the solvent that volatilizes when the transfer material 37G is dried, and the movement is likely to occur.
- Such movement causes film thickness unevenness in the transfer materials 37R and 37G.
- the transfer material 37R solution is applied and dried, and then the transfer material 37G solution is applied. Even if the transfer material 37R is affected by the vapor of the solvent that volatilizes when the material 37G is dried, the transfer material 37R is prevented from moving due to the unevenness of the surface of the photothermal conversion layer 33, so that the film thickness is reduced. Unevenness can be greatly reduced. The same applies to the transfer material 37G (or 37R) when the transfer material 37B is applied.
- FIG. 6 is a diagram illustrating the occurrence of coating unevenness when RGB is applied to a plurality of sections on a smooth donor substrate.
- the transfer area 38 a lot of RGB sections are arranged.
- the RGB transfer material 37 is collectively applied to these sections, a vapor flow from the center toward the outside is generated due to the vapor pressure difference on the donor substrate 30, and the transfer material near the outer periphery of the donor substrate 30 is affected by the vapor.
- the film is biased to the outside.
- At least one type of transfer material 37 is made of a low molecular material having a molecular weight of less than 1000, and the film thickness after drying of the film made of the low molecular material is 100 nm or less, and further 50 nm or less.
- This is particularly effective in the production of an organic EL thin film. This is because such a low-molecular material has a small intermolecular interaction, and therefore, it is much easier to move than a high-molecular material having a large intermolecular interaction due to entanglement between molecules.
- the film thickness of the transfer material can be obtained from a step with the photothermal conversion layer by measuring the surface shape with a stylus method such as an atomic force microscope.
- a stylus method such as an atomic force microscope.
- a method of suppressing the film thickness unevenness of the transfer material is conceivable.
- this method has a problem that the amount of impurities mixed in the solution or solvent increases because the coating process occurs twice.
- Another example is a method in which three types of transfer materials 37R, 37G, and 37B are slowly and simultaneously dried using a high boiling point solvent.
- this method has a problem that the process time becomes long.
- the degree to which the photothermal conversion layer 33 is rough can be expressed by the arithmetic surface roughness (hereinafter referred to as Ra) of the surface of the photothermal conversion layer 33.
- the arithmetic average roughness in the present invention is a ten-point average roughness obtained when a measurement length of 1.0 mm is measured based on JIS B 0601-1994 with a surface roughness shape measuring instrument.
- the Ra of the surface of the photothermal conversion layer 33 is preferably 30 nm or more. If Ra on the surface of the photothermal conversion layer 33 is 30 nm or more, the effect can be exhibited by suppressing the film thickness unevenness. More preferably, it is 50 nm or more, More preferably, it is 100 nm or more, Most preferably, it is 150 nm or more.
- the thickness of the coating solution only needs to be larger than Ra on the surface of the photothermal conversion layer 33. That is, Ra on the surface of the photothermal conversion layer 33 may be larger than the value of the film thickness after drying.
- Ra of the photothermal conversion layer 33 is preferably 4 ⁇ m or less, more preferably 1 ⁇ m or less, still more preferably 500 nm or less, and particularly preferably 250 nm or less. Within this range, the thickness of the coating solution can be made larger than the Ra of the photothermal conversion layer 33 when a solution having a reasonable concentration is applied to obtain a transfer material having a desired thickness. .
- the unevenness average interval (hereinafter referred to as Sm) on the donor substrate surface is 20 ⁇ m or less.
- the arithmetic average roughness in the present invention is an average unevenness interval obtained when the surface roughness shape measuring instrument is measured at a measurement length of 1.0 mm based on JIS B0601-1994.
- a known technique such as spin coating, slit coating, vacuum deposition, EB deposition, sputtering, ion plating, or the like can be used.
- Ra on the surface of the support 31 can be copied to Ra on the surface of the photothermal conversion layer 33.
- the photothermal conversion layer can also adjust the Ra of the 33 surface to 30 nm or more. Therefore, Ra on the surface of the support on which the light-to-heat conversion layer is formed is preferably set to a value determined as Ra on the surface of the light-to-heat conversion layer 33. For example, it is preferably 30 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, and particularly preferably 150 nm or more.
- the method of roughening the surface of the support 31 is not particularly limited. Mechanical roughening by sandblasting, chemical etching by hydrofluoric acid, buffered hydrofluoric acid and mixed acids with other acids, and glass powder are applied to the surface. Well-known techniques such as a method of welding with high heat can be used. In these treatments, Ra increases as the conditions such as pressure and treatment time are increased, so that the desired Ra can be adjusted. Moreover, in order to make Sm into 20 micrometers or less, when performing mechanical surface roughening by sandblasting, it can adjust by making the particle size of a blast material small.
- a sputtering method is preferably exemplified.
- detailed conditions differ depending on the material, it cannot be generally stated, but as an example, in the case of tantalum, for example, it is preferable to form it in an Ar gas atmosphere with a gas pressure of 0.2 Pa and an input power of 1 kw.
- the condition is not limited to this.
- the other is a method of roughening the surface after forming the photothermal conversion layer 33 having a substantially smooth surface by a known method.
- the method is not particularly limited, and publicly known techniques such as mechanical surface roughening by sandblasting, chemical etching, and gas pressure / input power / film formation temperature change during sputtering film formation can be used.
- the surface temperature varies between the thick and thin portions of the photothermal conversion layer when light irradiation is performed, and the transfer material is uniformly heated.
- the former method in which the surface of the support 31 is roughened and the photothermal conversion layer 33 is uniformly formed according to the unevenness of the surface is preferable.
- the heat capacity of the photothermal conversion layer 33 is preferably larger than that of the transfer material 37. Therefore, the thickness of the photothermal conversion layer 33 is preferably thicker than the transfer material 37, and more preferably 5 times or more the thickness of the transfer material 37. The numerical value is preferably 0.02 to 2 ⁇ m, more preferably 0.1 to 1 ⁇ m. Since the photothermal conversion layer 33 preferably absorbs 90% or more of light, and more preferably 95% or more, the thickness of the photothermal conversion layer 33 is preferably designed so as to satisfy these conditions.
- the photothermal conversion layer 33 may be formed in a portion where the transfer material 37 exists, and may be patterned so as to be discontinuous at the lower portion of the partition pattern 34, for example.
- the partition pattern 34 has poor adhesion to the photothermal conversion layer 33, the adhesion can be improved by utilizing the adhesion to the support 31 in this manner.
- the photothermal conversion layer 33 is patterned, it is not necessary to have the same type of shape as the partition pattern 34, the partition pattern 34 may be a lattice shape, and the photothermal conversion layer 33 may be a stripe shape.
- the material of the photothermal conversion layer 33a is formed on the donor substrate 30 to cover the partition pattern 34 (photothermal It is also possible to prevent the partition pattern material from being mixed into the conversion layer 33b) and the donor substrate 30 as an impurity, thereby preventing the impurity of the partition pattern material from being transferred when transferring to the device substrate. No adverse effect.
- Ra on the surface of the support 31 roughened in advance is first copied to Ra on the surface of the photothermal conversion layer 33a, and Ra on the surface of the photothermal conversion layer 33a is further copied onto the surface of the photothermal conversion layer 33b.
- Ra of the surface of the photothermal conversion layer 33b can be adjusted to 30 nm or more.
- a material for the photothermal conversion layer 33 may be formed on the donor substrate 30 to cover the partition pattern 34.
- the photothermal conversion layer 33 is uniformly formed on the support 31 roughened in advance according to the unevenness of the surface of the support 31 or the photothermal conversion layer 33 having a smooth surface. A method of roughening the surface after forming can be used.
- the photothermal conversion layer 33 Since the photothermal conversion layer 33 has a high light absorption rate, it is preferable to form the position mark of the donor substrate 30 at an appropriate position inside and outside the transfer region using the photothermal conversion layer 33.
- the transfer material 37 formed on the donor substrate 30 will be described.
- the transfer material of the transfer material 37 either an organic material or an inorganic material including a metal may be sublimated (including ablation sublimation) when heated, and transferred from the donor substrate to the device substrate 10.
- the transfer material may be a precursor for thin film formation, and the transfer film 27 may be formed by being converted into a thin film formation material by heat or light before or during transfer.
- This transfer material can form not only organic EL elements but also thin films constituting devices such as organic TFTs, photoelectric conversion elements, and various sensors.
- the transfer material 37 for one transfer of a donor material (electron injection material) such as lithium fluoride has a typical thickness of 1 nm or less.
- the thickness of the transfer material 37 of the electrode material may be 100 nm or more.
- the thickness of the transfer material 37 for one transfer is preferably 10 to 100 nm, and more preferably 20 to 50 nm.
- the formation method of the transfer material 37 is not particularly limited, and a dry process such as vacuum deposition or sputtering can also be used.
- a coating method in which a solution comprising at least a transfer material and a solvent is applied in the partition pattern 34 and dried after the solvent is dried.
- Specific examples of the coating method include ink jet, nozzle coating, electropolymerization and electrodeposition, offset and flexographic printing, lithographic printing, relief printing, gravure, screen printing and the like.
- inkjet and nozzle coating can be exemplified as particularly preferable methods.
- the transfer materials 37 formed from the coating liquid are in contact with each other, and the boundary is not uniform, and a mixed layer is formed at least. In order to prevent this, it is difficult to make the film thickness of the boundary region the same as the center when the gap is formed so as not to contact each other. In any case, since this boundary region cannot be transferred because it degrades the performance of the device, it is necessary to selectively transfer a region narrower than the pattern of the transfer material 37 on the donor substrate 30. Therefore, the width of the transfer material 37 that can actually be used is narrowed, and when an organic EL display is manufactured, the pixel has a small aperture ratio (the area of the non-light emitting region is large).
- transfer since transfer is not possible because of the need to transfer except for the boundary region, if the type of transfer material of the transfer material 37 is different, they are sequentially lasered (for example, transfer materials 37R, 37G, and 37B). It is necessary to irradiate and transfer each independently, and high-precision alignment of high-intensity laser irradiation is required. Such a problem can be solved by performing batch transfer as described later using a donor substrate 30 having a transfer material 37 formed from a partition pattern 34 and a coating liquid.
- a solution consisting of a transfer material and a solvent When applying a solution consisting of a transfer material and a solvent to the coating method, generally adding a surfactant, dispersant, etc., adjusts the viscosity, surface tension, dispersibility, etc. of the solution to make an ink. Often to do. However, in the donor substrate 30, if these additives exist as a residue in the transfer material, there is a concern that the donor substrate 30 may be taken into the transfer film 27 during transfer and adversely affect device performance. Accordingly, it is preferable to prepare the solution so that the purity of the transfer material after drying is 95% or more, and further 98% or more. Such adjustment is possible by setting the ratio of the transfer material in the components other than the solvent in the ink to 95% by weight or more.
- the solvent known materials such as water, alcohol, hydrocarbons, aromatic compounds, heterocyclic compounds, esters, ethers, and ketones can be used.
- a relatively high boiling point solvent of 100 ° C. or higher, and further 150 ° C. or higher is used.
- suitable solvents include tetrahydronaphthalene), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), ⁇ -butyllactone ( ⁇ BL), cyclohexanone, ethyl benzoate, xylene and cumene.
- transfer material prototype When the transfer material satisfies all of the solubility, transfer resistance, and device performance after transfer, it is preferable to dissolve the transfer material itself (hereinafter referred to as “transfer material prototype”) in a solvent.
- solubility can be improved by introducing a soluble group in a solvent such as an alkyl group into the transfer material prototype.
- a soluble group When a soluble group is introduced into a prototype of a transfer material that excels in device performance, the performance may deteriorate. In that case, for example, the soluble material can be eliminated by heat at the time of transfer to deposit the original material on the device substrate 10.
- the transfer material When transferring a transfer material into which a soluble group has been introduced, the transfer material has a soluble group in the solvent at the time of application to prevent the generation of gas and the incorporation of desorbed material into the transfer film. It is preferable to transfer the transfer material after converting or eliminating the soluble group by. For example, taking a material having a benzene ring or an anthracene ring as an example, a material having a soluble group as shown in formulas (1) to (2) can be irradiated with light to be converted into a prototype material.
- an intramolecular cross-linking structure such as an ethylene group or a diketo group is introduced as a soluble group, and the original material is restored by a process of eliminating ethylene and carbon monoxide therefrom. It can also be made.
- the conversion or elimination of the soluble group may be in a solution state before drying or in a solid state after drying. However, in consideration of process stability, it is preferably performed in a solid state after drying. Since the original molecule of the transfer material is often nonpolar, the molecular weight of the desorbed material is small so that the desorbed material does not remain in the transfer material when the soluble group is removed in the solid state.
- the desorbed material In order to remove oxygen and water adsorbed in the transfer material together with the desorbed material, it is preferable that the desorbed material easily reacts with these molecules. From these viewpoints, it is particularly preferable to convert or eliminate the solubilizing group in the process of eliminating carbon monoxide.
- This technique can be applied to condensed polycyclic hydrocarbon compounds as well as condensed polycyclic hydrocarbon compounds such as naphthacene, pyrene, and perylene. Of course, these may be substituted or unsubstituted.
- the transfer material for forming the light emitting layer 17 is composed of the host material and the dopant material.
- a mixture is preferred.
- the transfer material 37 can be formed by applying and drying a mixed solution of the host material and the dopant material. You may apply
- the concentration of the dopant material in the light emitting layer 17 of the device substrate 10 can be changed in the film thickness direction by utilizing the difference in sublimation temperature between the host material and the dopant material during transfer.
- the organic semiconductor layer can be suitably patterned according to the present invention.
- the organic semiconductor layer can be suitably patterned according to the present invention.
- two or more kinds of transfer materials 37 are formed on the donor substrate 30, one set of circuit units consists of two or more TFT elements, and the size (or thickness) of the organic semiconductor layer required for them is the same.
- a group of transfer materials made of the same organic semiconductor material but different in shape (or thickness) can be exemplified.
- separate organic semiconductor layers can be patterned according to the present invention for two or more TFT elements.
- the source and drain, the gate electrode, the gate insulating layer, and the like constituting the organic TFT element may be patterned according to the present invention.
- the partition pattern 34 is not particularly limited as long as it is a material / configuration that defines the boundary of the transfer material 37 and is stable against the heat generated in the photothermal conversion layer 33. Further, the method for forming the partition pattern 34 and the patterning method are not particularly limited as long as fine patterning can be performed with high accuracy.
- the partition pattern 34 can be formed using a known material and manufacturing method described in Patent Document 2.
- the partition pattern 34 is prevented in order to prevent the solution from being mixed into another partition or climbing onto the upper surface of the partition pattern 34.
- Liquid repellent treatment surface energy control
- a liquid repellent material such as a fluorine-based material can be mixed with the resin material forming the partition pattern 34, or a high concentration region of the liquid repellent material can be selectively formed on the surface or the upper surface.
- the partition pattern 34 can be a multilayer structure of materials having different surface energies, and the surface energy state can be controlled by performing light irradiation, plasma treatment with a fluorine-containing material-containing gas, or UV ozone treatment after the partition pattern 34 is formed.
- a known technique can be used.
- the cross-sectional shape of the partition pattern 34 is preferably a forward tapered shape in order to facilitate the deposition of the sublimated transfer material uniformly on the device substrate 10. As illustrated in FIG. 2, when a pattern such as the insulating layer 14 exists on the device substrate 10, the width of the insulating layer 14 is preferably wider than the width of the partition pattern 34. Further, it is preferable to arrange the partition pattern 34 so that the width of the partition pattern 34 is within the width of the insulating layer 14 at the time of alignment.
- the partition pattern 34 needs to have a structure that suppresses the temperature rise of the device substrate 10, and its thermal conductivity is 1.0 W / mK or less, and further 0.3 W / mK or less.
- the thickness of the partition pattern 34 is preferably 5 ⁇ m or more from the viewpoint of suppressing the temperature rise of the device substrate 10 and from being hardly affected by each other when the transfer material is applied. On the other hand, from the viewpoint of forming the partition pattern 34 with high accuracy, the thickness is preferably 100 ⁇ m or less.
- the light emitting layer 17 In a color display, at least the light emitting layer 17 needs to be patterned, and the light emitting layer 17 is a thin film that is suitably patterned using the transfer process of this embodiment. Further, only the light emitting layers 17R and 17G of the light emitting layer 17 are patterned by using the transfer process of the present embodiment, and the light emitting layer 17B and the layer serving as the R and G electron transport layers 18 are formed on the entire surface thereof. You can also. When it is necessary to pattern at least one layer such as the hole transport layer 16, the electron transport layer 18, and the second electrode 19, the pattern may be patterned using the transfer process of the present embodiment.
- the electron transport layer 18 is preferably patterned using the transfer process of the present embodiment.
- the insulating layer 14, the first electrode 15, the TFT, and the like are often patterned by a known photolithography method, but may be patterned using the transfer process of this embodiment.
- the underlying layer already formed on the device substrate 10 varies depending on the thin film to be patterned.
- the first electrode 15 and the hole transport layer 16 are formed as a base layer.
- a structure such as the insulating layer 14 is not essential, the edge pattern of the first electrode 15 is protected, and when the device substrate 10 and the donor substrate 30 are opposed to each other, the partition pattern 34 of the donor substrate 30 is From the viewpoint of preventing contact with and damage to the underlying layer already formed on the device substrate 10, it is preferably formed in advance on the device substrate 10.
- the materials, film formation methods, and patterning methods exemplified as the partition pattern 34 of the donor substrate 30 can be used.
- the shape, thickness, and pitch of the insulating layer 14 the shape and numerical values exemplified for the partition pattern 34 of the donor substrate 30 can be exemplified.
- the substrates 10 and 30 are arranged to face each other in a state in which the partition pattern 34 of the donor substrate 30 and the insulating layer 14 of the device substrate 10 are aligned.
- the donor substrate 30 and the device substrate 10 can be opposed to each other in a vacuum, and the transfer space can be taken out into the atmosphere with the vacuum kept as it is.
- the region surrounded by the partition pattern 34 of the donor substrate and / or the insulating layer of the device substrate 10 can be held in a vacuum.
- a vacuum sealing function may be provided at the periphery of the donor substrate 30 and / or the device substrate 10.
- the donor substrate 30 When the base layer of the device substrate 10, for example, the hole transport layer 16 is formed by a vacuum process, the light emitting layer 17 is patterned by transfer, and the electron transport layer 18 is also formed by a vacuum process, the donor substrate 30, the device substrate 10, Are preferably opposed to each other in a vacuum, and transfer is performed in a vacuum.
- a method of aligning the donor substrate 30 and the device substrate 10 with high accuracy in a vacuum and maintaining the facing state for example, vacuum dropping of a liquid crystal material used in a manufacturing process of a liquid crystal display -Well-known techniques, such as a bonding process, can be used.
- the donor substrate 30 can be easily held by an electrostatic method by using the photothermal conversion layer 33 formed of a good conductor such as metal.
- the transfer atmosphere may be atmospheric pressure or reduced pressure.
- reactive transfer such as reacting a transfer material with an active gas such as oxygen can be performed.
- it is preferably in an inert gas such as nitrogen gas or in a vacuum. If it is in an inert gas, it is possible to promote uniformity of film thickness unevenness during transfer by appropriately controlling the pressure. If it is under vacuum, it is possible to particularly promote the reduction of impurities mixed into the transfer film 27 and the lowering of the sublimation temperature. Further, the donor substrate 30 can be radiated or cooled during the transfer regardless of the transfer atmosphere.
- the transfer In the transfer, light typified by laser is irradiated from the support 31 side of the donor substrate 30 to be absorbed by the photothermal conversion layer 33, and the transfer material 37 is heated and sublimated by the heat generated there, thereby transferring the transfer film to the device substrate 10. To deposit. When one scan is completed by irradiating light of a predetermined size, the next unirradiated portion is irradiated with light and scanned. By such scanning, the transfer area is finally irradiated.
- FIG. 9 is a cross-sectional view illustrating an example of a method of irradiating the donor substrate 30 with light.
- the donor substrate 30 is composed of a support 31, a photothermal conversion layer 33, a partition pattern 34, and a transfer material 37 of a transfer material existing in the partition pattern 34, and the device substrate 20 is composed of only the support 21.
- the transfer material 37 is heated and sublimated by light irradiation from the support 31 side, and is deposited as a transfer film 27 on the support 21 of the device substrate 20.
- an ablation mode in which the transfer material 37 reaches the support 21 of the device substrate 20 with the film shape maintained can be used.
- a vapor deposition mode in which the transfer material 37 is sublimated (evaporated) in a state of being loosened to 1 to 100 units of molecules (atoms) and transferred is preferable to use.
- the method of the present embodiment significantly reduces the burden on the light irradiation device.
- the transfer of the transfer material 37 in a plurality of times in the film thickness direction by irradiating light to the photothermal conversion layer 33 in a plurality of times with respect to one donor substrate 30 is a particularly important feature of the present embodiment. This is a preferred transfer method. As a result, the maximum temperature of not only the transfer material 37 but also the partition pattern 34 and the underlying layer formed on the device substrate 20 can be lowered, so that damage to the donor substrate and device performance can be prevented. .
- the organic EL device produced by the transfer method using the donor substrate of the present invention has the following characteristics.
- the transfer layer is a light emitting layer (R, G, B)
- the light emitting layer transferred to the device substrate by laser irradiation traces the pattern of the donor substrate. That is, as shown in FIG. 11A, when a donor substrate having light emitting layers patterned at regular intervals is used, the spacing between adjacent light emitting layers is substantially constant on the device substrate.
- broken lines extending to R, G, and B indicate the center positions of the respective light emitting layers in the width direction. The distance between the center positions of adjacent light emitting layers is substantially constant.
- FIG. 11 (a) an example in which laser irradiation is performed in the same manner as in FIG. 2 and FIG. 3 is illustrated. However, after other irradiation methods, for example, a partition pattern and a part of the transfer layer are irradiated with laser light. The same result is obtained even when the laser is scanned in the R, G, B alignment direction.
- FIG. 11B shows a case where a light emitting layer is formed by a vapor deposition method.
- alignment of the mask is necessary at the time of vapor deposition of each of R, G, and B, but it is difficult to complete the alignment.
- R, G, and B may not be at regular intervals at the part where the mask position error has occurred.
- FIG. 11 (c) shows a method of partially transferring R, G, and B light-emitting layers on three donor substrates having no partition pattern, respectively. In this case, it is difficult to completely align the positions of the three laser irradiations, and there are cases where R, G, and B are not at regular intervals as in the vapor deposition method. From this, it can be seen that the transfer method using the donor substrate of the present invention can perform patterning of R, G, and B with high accuracy and make the intervals substantially constant.
- the film thickness is gradually attenuated at the edge of the transfer film 27 at the transfer destination as shown in FIG. 12A (FIG. 12A at first glance, the edge of the pattern appears to be smaller than the center. Although it seems to be rising, there is a forward taper-shaped partition pattern at the edge, so that the film thickness of the transfer film is gradually attenuated toward the edge).
- FIG. 12B in the mask vapor deposition, the molecules of the light emitting layer fly linearly from the vapor deposition source and adhere to the substrate, so that the film thickness attenuation at the edge becomes steep. In this way, by observing the edge of the transfer film, it is possible to distinguish whether it is formed by vapor deposition or transfer.
- the organic EL device of the present invention is produced using a transfer method, and even if the device substrate has a high aperture ratio, a uniform transfer film is formed and exhibits excellent light emission performance.
- Such an organic EL device preferably has, for example, an organic compound layer including a light emitting layer sandwiched between at least a pair of electrodes, and at least a part of the organic compound layer is formed by using a transfer method.
- the EL element is an organic EL element satisfying any of the following. (1) The width of the insulating layer of the subpixel is less than 40 ⁇ m, and the light emission luminance unevenness of the light emitting region in the subpixel is ⁇ 20% or less. (2) The width of the insulating layer of the subpixel is less than 40 ⁇ m, and the thickness unevenness of the light emitting region in the subpixel is ⁇ 10% or less in the organic compound layer formed using the transfer method.
- the organic EL element satisfies both (1) and (2).
- the thickness of the transfer film on the device substrate due to the effect of suppressing the uneven thickness of the donor substrate, which is a rough surface, in the organic EL element in which the width of the insulating layer of the subpixel is less than 40 ⁇ m, more preferably 30 ⁇ m or less.
- An effect can be exhibited by the improvement, and an organic EL element having a thickness non-uniformity of ⁇ 10% or less in the light emitting region in the sub-pixel of the device substrate can be produced.
- the light emission luminance unevenness in the sub-pixel of the created organic EL element is ⁇ 20% or less.
- the sub-pixel refers to a portion indicated by reference numeral 47 in FIG. 13, that is, light emission of any one of the light-emitting regions 37R, 37G, 37B and the insulating layer 34 constituting the pixel of the device substrate.
- the width of the sub-pixel in the x direction or the y direction represents the pitch of the patterned insulating layer.
- the width of the insulating layer means a portion indicated by reference numeral 44 in FIG. 13, that is, the length of the insulating layer in the x direction (or y direction) of the pixel.
- film thickness unevenness and the light emission brightness unevenness are expressed as percentages of the film thickness and brightness errors in the light emitting region of the sub-pixel.
- film thickness unevenness is measured by measuring a two-dimensional film thickness profile in a sub-pixel using an optical interference film thickness meter, and substituting it into the formula (maximum film thickness ⁇ minimum film thickness) / film thickness average value ⁇ 100. This is the calculated value.
- the film thickness average value is a value obtained by dividing the sum of the film thickness measurement values at all measurement points in the sub-pixel by the number of film thickness measurement points. If it is difficult to measure the film thickness by the above method due to the difference in refractive index between layers, the cross-sectional shape of the organic EL element is observed with SEM, TEM, etc., and the film thickness of the light-emitting layer is determined from the cross-sectional profile. May be applied to the above equation to calculate the film thickness unevenness.
- the emission luminance unevenness is determined by using the FPD module inspection apparatus, points having a distance of 20 ⁇ m from the four corners of the subpixel in the x direction and the y direction (a total of four points), and the x direction, y direction, and diagonal lines of these points.
- Luminance is measured at a spot diameter of 30 ⁇ m for a total of 9 points (total 5 points) in the direction (total 5 points) in the direction, and assigned to the formula (maximum luminance ⁇ minimum luminance) / luminance average value ⁇ 100. This is the calculated value.
- the average luminance value is a value obtained by dividing the sum of luminance measurement values at nine points in the sub-pixel by 9 (the number of luminance measurement points 48 in FIG. 13).
- the design values are, for example, a subpixel width of 100 ⁇ m, a light emitting region width of 80 ⁇ m, and an insulating layer width of 20 ⁇ m (aperture width ratio 80%).
- the width of the partition pattern is smaller than the width of the insulating layer. Therefore, the emission region width of the donor substrate is designed to be 90 ⁇ m, for example, and the width of the partition pattern is 10 ⁇ m. It is possible.
- the light emitting region width is 95 ⁇ m and the partition pattern width to 5 ⁇ m.
- the width of the partition pattern of the donor substrate is too narrow, stress is generated in the partition pattern during the substrate preparation process or bonding / separation of the donor substrate and the device substrate, and the partition pattern is easily crushed or has defects. There is a problem.
- a part of the local deviation of the film may be transferred, there is a possibility that a part having a large film thickness unevenness is generated even in the device substrate.
- the insulating layer width of the device substrate is designed to 30 ⁇ m or 40 ⁇ m (opening width ratio 70% or 60%).
- the partition pattern width of the donor substrate is designed to be 10 ⁇ m, a device substrate with less film thickness unevenness can be produced by performing transfer while avoiding local film bias occurring in the range of 10 ⁇ m from the partition wall. be able to.
- the material utilization efficiency is remarkably lowered.
- a subpixel width which is a design value of a general display panel can be in a range of 30 ⁇ m or more and 1000 ⁇ m or less.
- the insulating layer width of the organic EL element is narrowed to increase the aperture ratio, the amount of current per unit area that flows when a constant voltage is applied to the element is reduced, so that element durability is improved. It is empirically known that the durability is inversely proportional to the 1.6 to 1.7 power of the current density. For example, when the aperture ratio is increased from 60% to 70%, the durability is improved by about 30%. In addition, by suppressing the film thickness unevenness to ⁇ 10%, the light emission unevenness and chromaticity unevenness in the pixel can be reduced, so that the display quality can be improved and the bias of the current density distribution can be improved. Also gets longer.
- FIG. 14 shows the width of each of two or more different transfer materials 37 (in this example, three types 37R, 37G, and 37B) and the partition pattern 34 (in this example, the partition pattern sandwiched between 37R and 37G, 37G and 37B).
- the partition pattern 34 in this example, the partition pattern sandwiched between 37R and 37G, 37G and 37B.
- transfer materials 37R, 37G When the set of 37B is repeatedly formed k times in the x direction and h times in the vertical y direction, for example, m sets (m is an integer of 2 or more and k or less) of transfer materials 37R, 37G, By scanning light in the y direction while simultaneously irradiating light to 37B, the transfer time can be shortened to about 1 / m.
- FIG. 15B when there are a plurality of transfer regions 38 on the substrate, it is also possible to transfer them all at once.
- This batch transfer can shorten the patterning time as compared with the method of sequentially irradiating the transfer materials 37R, 37G, and 37B with light. Since the light is sufficiently absorbed by the photothermal conversion layer 33, each of the transfer materials 37R, 37G, and 37B having different light absorption spectra can be heated to the same temperature using the same light source. There is no concern that the device substrate 10 is heated. Since the partition pattern 34 is present, different transfer materials of the adjacent transfer material 37 can be mixed, or the transfer of the portion where the boundary position fluctuates can be eliminated. Absent.
- the transfer materials 37R, 37G, and 37B have different sublimation temperatures (temperature dependency of vapor pressure)
- the light is irradiated once in accordance with the transfer material having the highest sublimation temperature.
- Batch transfer may be performed.
- the transfer material 37R has the lowest sublimation temperature
- the transfer material 37R is completely transferred by one light irradiation, and 37G and 37B are partially transferred, and the light irradiation is repeated 37G,
- the remainder of 37B may be transferred, or may be divided into three or more transfers. Since the transfer time can be shortened to about 1 / m, the damage to the transfer material 37 can be further reduced by dividing the transfer into m times over the same time.
- the optimum one can be selected from a variety of transfer conditions in consideration of the time available for the transfer process and damage to the transfer material 37.
- the batch transfer has another effect.
- the lateral thermal diffusion that has become a problem in laser transfer does not occur, so it is possible to irradiate light for a relatively long time, such as by scanning the laser at a relatively low speed. It becomes possible. Therefore, it becomes easier to control the maximum temperature of the transfer material 37 and fine patterning can be performed with high accuracy.
- the damage to the transfer material 37 is reduced, the damage to the partition pattern 34 is also reduced at the same time, and even if the partition pattern 34 is formed of an organic material, the deterioration hardly occurs.
- the cost required for patterning can be reduced because the donor substrate can be reused a plurality of times.
- the mechanism of the light irradiation apparatus can be simplified.
- a laser that can easily obtain high intensity and excellent in shape control of irradiation light can be exemplified as a preferable light source, but a light source such as an infrared lamp, a tungsten lamp, a halogen lamp, a xenon lamp, or a flash lamp is used.
- a known laser such as a semiconductor laser, a fiber laser, a YAG laser, an argon ion laser, a nitrogen laser, an excimer laser, or a pulse laser can be used.
- the wavelength of the irradiation light is not particularly limited as long as the irradiation atmosphere and the donor substrate support 31 have low absorption and are efficiently absorbed by the photothermal conversion layer 33. Therefore, not only visible light region but also ultraviolet light to infrared light can be used.
- 300 nm to 5 ⁇ m can be exemplified as a preferable wavelength region, and 380 nm to 2 ⁇ m can be illustrated as a more preferable wavelength region.
- the irradiation light irradiation method and the scanning method are not particularly limited.
- the method disclosed in Patent Document 2 may be used.
- Ra and Sm on the surfaces of the support and the photothermal conversion layer were measured based on JIS B0601-1994 using a surface roughness shape measuring instrument (manufactured by Tokyo Seimitsu Co., Ltd.)
- the ten-point average roughness obtained when measuring at a measurement length of 1.0 mm was used.
- the film thickness is measured using a light interference type film thickness measuring device SP-700 (Toray Engineering Co., Ltd.), and the two-dimensional film thickness profile in the sub-pixel is measured, and the emission luminance is measured using an FPD module inspection device (Otsuka Electronics Co., Ltd.). And measured.
- the film thickness unevenness is a value calculated by substituting into the formula of (maximum film thickness ⁇ minimum film thickness) / film thickness average value ⁇ 100 in the subpixel, and the light emission brightness unevenness is x from the four corners of the subpixel.
- Is a value calculated by substituting into the formula (maximum luminance ⁇ minimum luminance) / luminance average value ⁇ 100.
- the film thickness average value is a value obtained by dividing the sum of the film thickness measurement values at all measurement points in the sub-pixel by the number of film thickness measurement points.
- the luminance average value is a value obtained by dividing the sum of the luminance measurement values at nine points in the sub-pixel by 9 (the number of luminance measurement points 48 in FIG. 13).
- Durability was evaluated by measuring the time (luminance half-life) until the luminance decreased to half from the initial luminance by continuously applying a constant current of 10 mA / cm 2 . At this time, the spot diameter was set to 5 mm so that at least an area including the sub-pixel where the light emission luminance unevenness was measured could be measured.
- Example 1 The donor substrate 30 was produced as follows. A non-alkali glass substrate of 38 ⁇ 46 mm and a thickness of 0.7 mm was used as the support 31, and the support 31 was etched with hydrofluoric acid to roughen the surface on which the photothermal conversion layer 33 was formed. Ra of the surface of the support 31 was 30 nm, and Sm was 15 ⁇ m. After cleaning / UV ozone treatment, a tantalum film having a thickness of 0.2 ⁇ m was formed as the photothermal conversion layer 33 by sputtering (gas type: Ar, gas pressure: 0.2 Pa, power: 1 kW). Ra on the surface of the photothermal conversion layer 33 was also 30 nm.
- a fluorine-based positive polyimide photosensitive coating agent is spin-coated thereon, pre-baked and UV exposed, and then the exposed portion is dissolved by a developer. -Removed.
- the polyimide precursor film thus patterned was baked on a hot plate at 350 ° C. for 10 minutes to form a polyimide-based partition pattern 34.
- the partition pattern 34 had a thickness of 7 ⁇ m, a width of 20 ⁇ m, and a cross section of a forward tapered shape.
- a tantalum film having a thickness of 0.2 ⁇ m is formed on the entire surface of the donor substrate 30 by a sputtering method having a thickness of 0.2 ⁇ m, so that the transfer material 37R and the transfer material 37G to be applied later are not mixed with each other. Fluorine-based liquid repellency treatment was applied.
- the contact angle of the partition pattern 34 was approximately 60 degrees with respect to xylene.
- Each solution of transfer materials 37R and 37G having a viscosity of about 0.75 mPa ⁇ s using xylene as a solvent was prepared.
- a pyrene-based red host material RH-1 and a pyromethene-based red dopant material RD-1 are dissolved in xylene at 0.5 wt% and 0.01 wt%, respectively, and a transfer material 37G is formed.
- the solution to be prepared is obtained by dissolving pyrene-based green host material GH-1 and coumarin-based green dopant material (C545T) in xylene at 0.5 wt% and 0.04 wt%, respectively.
- the 37G solution is applied to the section corresponding to G by the inkjet method so that the transfer materials 37R and 37G on the donor substrate 30 repeat RGB and form an RGB pattern with the RGB3 section as one unit. Then, the solution of 37R was applied to the section corresponding to R by an inkjet method.
- the blue light emitting layer also serves as an electron transport layer that is subsequently deposited on the device substrate, the blue transfer material 37B is not applied here.
- Fig. 16 (a) shows a planar photograph of the donor substrate after xylene is naturally dried.
- the thicknesses of the transfer materials 37R and 37G in the sections are about 40 nm and about 30 nm, respectively, and there is no local bias of the transfer material in the surface and in the sections, and the film is a good film with very little film thickness unevenness. It was.
- Example 2 Inkjet coating was performed using a donor substrate 30 having the same configuration as in Example 1 except that Ra on the surfaces of the support 31 and the photothermal conversion layer 33 was 150 nm. The Sm on the surfaces of the support 31 and the photothermal conversion layer 33 was 15 ⁇ m.
- a solution of the transfer material 37 was prepared by dissolving 0.5 wt% of the pyrene-based green host material GH-1 in cyclohexanone, and application by an ink jet method was performed on all the sections of the donor substrate 30.
- FIG. 16 (b) shows a planar photograph of the donor substrate after natural drying of cyclohexanone.
- the thickness of the transfer material 37 in the compartment is about 40 nm and adheres according to the unevenness of the surface of the photothermal conversion layer 33 (shading in FIG. 16B), the in-plane and compartment are the same as in Example 1. There was no local bias of the transfer material inside, and the film was a good film with very little film thickness unevenness.
- Example 3 Inkjet coating was carried out in the same manner as in Example 2 except that the donor substrate 30 having a surface roughness Ra of 250 nm was used for the support 31 and the photothermal conversion layer 33.
- the Sm on the surfaces of the support 31 and the photothermal conversion layer 33 was 15 ⁇ m.
- FIG. 16 (c) shows a planar photograph of the donor substrate after natural drying of cyclohexanone.
- the thickness of the transfer material 37 in the compartment is about 40 nm and adheres according to the unevenness of the surface of the photothermal conversion layer 33 (shading in FIG. 16C), it is in-plane as in Examples 1 and 2.
- the transfer material in the compartments was not locally biased, and the film was a good film with very little film thickness unevenness.
- Example 4 An organic EL device was produced using the donor substrate of Example 1.
- the device substrate was produced as follows.
- a non-alkali glass substrate manufactured by Geomatech Co., Ltd., sputtering film-formed product
- ITO transparent conductive film
- the polyimide precursor film patterned similarly to the donor substrate was baked at 300 ° C. for 10 minutes to form a polyimide-based insulating layer.
- the insulating layer had a height of 1.8 ⁇ m, a width of 30 ⁇ m, and a cross-sectional shape with a forward taper.
- This substrate was subjected to UV ozone treatment, installed in a vacuum deposition apparatus, and evacuated until the degree of vacuum in the apparatus became 3 ⁇ 10 ⁇ 4 Pa or less.
- 50 nm of an amine compound and 10 nm of NPD were vapor-deposited as a hole transport layer on the entire light emitting region of the substrate.
- the position of the partition pattern of the donor substrate prepared in Example 1 and the insulating layer of the device substrate are aligned to face each other, and the outer peripheral portion is sealed after being held in a vacuum of 3 ⁇ 10 ⁇ 4 Pa or less. Removed from the atmosphere.
- the transfer space partitioned by the insulating layer and the partition pattern was kept in a vacuum.
- light having a center wavelength of 940 nm and an irradiation shape formed into a rectangle of 340 ⁇ m wide and 50 ⁇ m long was used.
- the co-deposited film as the transfer material was transferred onto the hole transport layer as the underlying layer of the device substrate.
- the laser intensity was 148 W / mm 2 and the scan speed was 0.6 m / s. While the light was overlapped in the horizontal direction at a pitch of about 300 ⁇ m, scanning was repeatedly performed so that the number of times of transfer was 24 so that the light was transferred to the entire light emitting region. As a result, the film thickness unevenness of the RG light emitting layer was ⁇ 10% or less.
- the device substrate after the transfer of the RG light emitting layer was placed in the vacuum deposition apparatus again and evacuated until the degree of vacuum in the apparatus became 3 ⁇ 10 ⁇ 4 Pa or less.
- E-1 was deposited as an electron transport layer to a thickness of 25 nm over the entire emission region by resistance heating.
- 0.5 nm of lithium fluoride was deposited as a donor material (electron injection layer), and 100 nm of aluminum was deposited as a second electrode.
- aluminum was patterned into 200 stripes at 300 ⁇ m pitch by mask vapor deposition, and the longitudinal direction of the stripe electrodes was made to coincide with the width direction of the insulating layer.
- the produced organic EL element has a simple matrix display structure in which the first electrode made of ITO stripe and the second electrode made of aluminum stripe are orthogonal to each other, and R, G, B are formed at the intersections of both electrodes. 256 ⁇ 200 pixels composed of the sub-pixels are arranged.
- Example 5 An organic EL element was produced in the same manner as in Example 4 except that the width of the insulating layer of the device substrate of Example 4 was 25 ⁇ m. Then, as in Example 4, clear R, G, and B light emission was confirmed from each subpixel, the film thickness unevenness was ⁇ 10% or less for each color, and the light emission luminance unevenness was ⁇ 20% or less for each color. There was no color mixing between them. Further, the durability was improved by 10% or more compared to Example 4.
- Example 6 An organic EL element was produced in the same manner as in Example 4 except that the width of the insulating layer of the device substrate in Example 4 was 35 ⁇ m. Then, as in Example 4, clear R, G, and B light emission was confirmed from each subpixel, the film thickness unevenness was ⁇ 10% or less for each color, and the light emission luminance unevenness was ⁇ 20% or less for each color. There was no color mixing between them. Further, the durability decreased by 10% or more compared to Example 4.
- Example 7 An organic EL element was produced in the same manner as in Example 4 except that the width of the insulating layer of the device substrate in Example 4 was 40 ⁇ m. Then, as in Example 4, clear R, G, and B light emission was confirmed from each subpixel, the film thickness unevenness was ⁇ 10% or less for each color, and the light emission luminance unevenness was ⁇ 20% or less for each color. There was no color mixing between them. Further, the durability decreased by 20% or more compared to Example 4.
- Example 8 Using the donor substrate prepared in Examples 2 and 3, transfer was performed on the device substrate prepared by the same method as in Example 4 under the same transfer conditions as in Example 4. However, in this embodiment, the hole transport layer is not provided on the device substrate, and the pyrene-based green host material GH-1 formed in all the sections of the donor substrate is used as the opening of the insulating layer on the device substrate. The film after transfer was observed with an optical microscope. The transfer material adhered according to the unevenness of the surface of the photothermal conversion layer 33 was made uniform, and a good film with very little film thickness unevenness in the surface and in the section was obtained.
- Comparative Example 1 A donor substrate 30 was produced in the same manner as in Example 1 except that the support 31 was not etched with hydrofluoric acid. The surfaces of the support 31 and the photothermal conversion layer 33 were smooth.
- Comparative Example 2 An organic EL element was produced in the same manner as in Example 4, using a donor substrate having a smooth surface in Comparative Example 1 and a device substrate in which the width of the insulating layer in Example 4 was 30 ⁇ m.
- Comparative Example 3 An organic EL element was produced in the same manner as in Example 4 using a donor substrate having a smooth surface in Comparative Example 1 and a device substrate in which the width of the insulating layer in Example 5 was 25 ⁇ m.
- Comparative Example 4 An organic EL element was produced by the same method as in Example 4 using a donor substrate having a smooth surface in Comparative Example 1 and a device substrate in which the width of the insulating layer in Example 6 was 35 ⁇ m.
- Comparative Example 5 An organic EL element was produced in the same manner as in Example 4 using a donor substrate having a smooth surface in Comparative Example 1 and a device substrate in which the width of the insulating layer in Example 7 was 40 ⁇ m.
- the present invention is a thin film patterning technology for organic EL elements, organic TFTs, photoelectric conversion elements, various sensors, and other devices, and is used for display panels used in mobile phones, personal computers, televisions, image scanners, etc. It can be used for manufacturing touch panels, image sensors, and the like.
- Organic EL elements (device substrates) 11 Support 12 TFT (including extraction electrode) DESCRIPTION OF SYMBOLS 13 Flattening layer 14 Insulating layer 15 1st electrode 16 Hole transport layer 17 Light emitting layer 18 Electron transport layer 19 Second electrode 20 Device substrate 21 Support body 27 Transfer film 30 Donor substrate 31 Support body 33 Photothermal conversion layer 34 Partition pattern 37 Transfer material 38 Transfer area 40 Mask 44 Insulating layer width 47 Subpixel 48 Luminance measurement point
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Abstract
Description
図1は、有機EL素子が形成されたデバイス基板10の典型的な構造の例を示す拡大断面図である。デバイス基板10は、ガラス板等の支持体11上にTFT12(取出電極込み)や平坦化層13などで構成されるアクティブマトリクス回路が構成されている。それらの上には、有機EL素子を構成する第一電極15/正孔輸送層16/発光層17/電子輸送層18/第二電極19が形成されている。この図1の例では、発光層17は、RGBの3種類の発光層17R、17G、17Bからなり、それらは横方向に区画されてなる。第一電極15の端部には、電極端における短絡発生を防止し、発光領域を規定する絶縁層14が形成される。有機EL素子の素子構成はこの例に限定されるものではなく、例えば、第一電極15と第二電極19との間に正孔輸送機能と電子輸送機能とを合わせもつ発光層17が一層だけ形成されていてもよく、正孔輸送層16は正孔注入層と正孔輸送層との、電子輸送層18は電子輸送層と電子注入層との複数層の積層構造であってもよく、発光層17が電子輸送機能をもつ場合には電子輸送層18が省略されてもよい。また、第一電極15/電子輸送層18/発光層17/正孔輸送層16/第二電極19の順に積層されていてもよい。また、これらの層はいずれも単層であっても複数層であってもよい。なお、図示されていないが、第二電極19の形成後に、公知技術あるいは後述の本実施形態の転写プロセスを用いて、保護層の形成やカラーフィルターの形成、封止などが行われてもよい。
次に、デバイス基板10にデバイスを形成する薄膜層を転写により形成するのに好適な本発明の実施形態に係るドナー基板30を説明する。図2及び図3は、ドナー基板30を用いてデバイス基板10に発光層17を形成する方法の例を示す拡大断面図と拡大平面図である。ドナー基板30は、支持体31と、支持体31上に形成された光熱変換層33と、光熱変換層33に積層して形成された区画パターン34と、区画パターン34により区画された転写材料37とを備えてなる。これらの図2及び図3の例では、ドナー基板30の転写材料37は横方向に区画されたRGBの3種類の発光材料の転写材料37R、37G、37Bからなり、デバイス基板10のRGBの3種類の発光層17R、17G、17Bに対応している。なお、図3は、図2における光照射の様子をドナー基板30の支持体31側から見た図である。全面に形成された光熱変換層33があるために、支持体31側から区画パターン34や転写材料37R、37G、37Bは実際には見えないが、光照射との位置関係を説明するために点線にて図示した。照射される光は矩形をしており、転写材料37R、37G、37Bを跨ぐようにして照射され、かつ、転写材料37R、37G、37Bの並びに対して垂直方向にスキャンされる。照射される光は相対的にスキャンされればよく、光自体を移動させても、ドナー基板30とデバイス基板10とのセットを移動させても、その両方でもよい。以下、支持体31、光熱変換層33、転写材料37、区画パターン34の順に説明する。
光熱変換層33の支持体31側には必要に応じて反射防止層を形成することができる。さらに、支持体31の光入射側の表面にも反射防止層を形成してもよい。これらの反射防止層は屈折率差を利用した光学干渉薄膜が好適に使用され、シリコン、酸化ケイ素、窒化ケイ素、酸化亜鉛、酸化マグネシウム、酸化チタンなどの単体や混合薄膜、それらの積層薄膜を使用できる。
次に、ドナー基板30を用いた転写プロセスを中心にして有機EL素子を代表とするデバイスの製造方法を説明する。
転写材料37は支持体31側からの光照射により加熱されて昇華し、デバイス基板20の支持体21に転写膜27として堆積する。
(1)副画素の絶縁層の幅が40μm未満であり、かつ副画素内の発光領域の発光輝度ムラが±20%以下であること。
(2)副画素の絶縁層の幅が40μm未満であり、かつ転写法を用いて形成された有機化合物層のうち、副画素内の発光領域の膜厚ムラが±10%以下であること。
ドナー基板30を以下のとおり作製した。支持体31として38×46mmで厚さ0.7mmの無アルカリガラス基板を用い、支持体31をフッ酸でエッチングを行い、光熱変換層33を形成する側の表面を粗面化した。支持体31の表面のRaは30nmであり、Smは15μmであった。洗浄/UVオゾン処理後に、光熱変換層33として厚さ0.2μmのタンタル膜をスパッタリング法(ガス種類:Ar、ガス圧:0.2Pa、電力:1kw)により全面形成した。光熱変換層33の表面のRaも30nmであった。次に、光熱変換層33を上記と同様のUVオゾン処理した後に、上にフッ素系ポジ型ポリイミド感光性コーティング剤をスピンコート塗布し、プリベーキング、UV露光した後に、現像液により露光部を溶解・除去した。このようにパターニングしたポリイミド前駆体膜をホットプレートで350℃、10分間ベーキングして、ポリイミド系の区画パターン34を形成した。この区画パターン34の厚さは7μm、幅は20μmで、断面は順テーパー形状であった。区画パターン34内部には幅80μm、長さ280μmの光熱変換層33を露出する開口部が、幅方向に100μmピッチで768個、長さ方向に300μmのピッチで200個配置されていた。次に、厚さ0.2μmのタンタル膜をドナー基板30の全面に厚さ0.2μmスパッタリング法により形成し、後に塗布する転写材料37Rと転写材料37Gが混色しないように、区画パターン34の上面にフッ素系の撥液処理を施した。区画パターン34の接触角はキシレンに対しほぼ60度であった。キシレンを溶媒とした粘度約0.75mPa・sの転写材料37R、37Gの各溶液を用意した。転写材料37Rを形成する溶液は、ピレン系赤色ホスト材料RH-1とピロメテン系赤色ドーパント材料RD-1とをキシレンにそれぞれ0.5wt%、0.01wt%溶解させたもの、転写材料37Gを形成する溶液は、ピレン系緑色ホスト材料GH-1とクマリン系緑色ドーパント材料(C545T)とをキシレンにそれぞれ0.5wt%、0.04wt%溶解させたものである。
支持体31及び光熱変換層33の表面のRaが150nmであること以外は、実施例1と同様の構成のドナー基板30を用いてインクジェット塗布を行った。支持体31及び光熱変換層33の表面のSmは15μmであった。転写材料37の溶液は、ピレン系緑色ホスト材料GH-1をシクロヘキサノンに0.5wt%溶解させて作製し、インクジェット法による塗布は、ドナー基板30の全ての区画に対して行った。
支持体31及び光熱変換層33の表面のRaが250nmのドナー基板30を用いた以外は、実施例2と同様の方法でインクジェット塗布を行った。支持体31及び光熱変換層33の表面のSmは15μmであった。
実施例1のドナー基板を用いて有機EL素子を作製した。
デバイス基板は以下のとおり作製した。ITO透明導電膜を140nm堆積させた無アルカリガラス基板(ジオマテック株式会社製、スパッタリング成膜品)を切断し、フォトリソグラフィー法によりITOを100μmピッチで768本のストライプ形状にパターニングした。次に、ドナー基板と同様にパターニングされたポリイミド前駆体膜を、300℃、10分間ベーキングして、ポリイミド系の絶縁層を形成した。この絶縁層の高さは1.8μm、幅は30μmで、断面は順テーパー形状であった。絶縁層のパターン内部には幅70μm、長さ250μmのITOを露出する開口部が、幅方向に100μmピッチで768個、長さ方向に300μmのピッチで200個配置されていた。ITOストライプ電極の長手方向を絶縁層の長さ方向に一致させた。
実施例4のデバイス基板の絶縁層の幅が25μmであること以外は、実施例4と同じ方法で有機EL素子を作成した。すると、実施例4と同様に各副画素からは、それぞれ明瞭なR、G、B発光が確認され、膜厚ムラは各色±10%以下、発光輝度ムラは各色±20%以下となり、副画素間の色混じりは認められなかった。また実施例4に比べ耐久性は10%以上向上した。
実施例4のデバイス基板の絶縁層の幅が35μmであること以外は、実施例4と同じ方法で有機EL素子を作成した。すると、実施例4と同様に各副画素からは、それぞれ明瞭なR、G、B発光が確認され、膜厚ムラは各色±10%以下、発光輝度ムラは各色±20%以下となり、副画素間の色混じりは認められなかった。また実施例4に比べ耐久性は10%以上減少した。
実施例4のデバイス基板の絶縁層の幅が40μmであること以外は、実施例4と同じ方法で有機EL素子を作成した。すると、実施例4と同様に各副画素からは、それぞれ明瞭なR、G、B発光が確認され、膜厚ムラは各色±10%以下、発光輝度ムラは各色±20%以下となり、副画素間の色混じりは認められなかった。また実施例4に比べ耐久性は20%以上減少した。
実施例2および3で作製したドナー基板を用いて、実施例4と同様の方法で作製したデバイス基板に、実施例4と同様の転写条件で転写を行った。ただし、本実施例においてはデバイス基板に正孔輸送層は設けられておらず、ドナー基板の全ての区画に形成されているピレン系緑色ホスト材料GH-1をデバイス基板上の絶縁層の開口部のすべてに転写し、転写後の膜を光学顕微鏡で観察した。光熱変換層33の表面の凹凸に応じて付着した転写材料は均一化され、面内および区画内の膜厚ムラが非常に少ない良好な膜となった。
支持体31をフッ酸でエッチングを行わなかった以外は、実施例1と同じ方法でドナー基板30を作製した。支持体31及び光熱変換層33の表面は平滑であった。
比較例1の表面が平滑なドナー基板と、実施例4の絶縁層の幅が30μmデバイス基板を用いて、実施例4と同様の方法で有機EL素子を作製した。
比較例1の表面が平滑なドナー基板と、実施例5の絶縁層の幅が25μmデバイス基板を用いて、実施例4と同じ方法で有機EL素子を作成した。
比較例1の表面が平滑なドナー基板と、実施例6の絶縁層の幅が35μmデバイス基板を用いて、実施例4と同じ方法で有機EL素子を作成した。
比較例1の表面が平滑なドナー基板と、実施例7の絶縁層の幅が40μmデバイス基板を用いて、実施例4と同じ方法で有機EL素子を作成した。
11 支持体
12 TFT(取り出し電極含む)
13 平坦化層
14 絶縁層
15 第一電極
16 正孔輸送層
17 発光層
18 電子輸送層
19 第二電極
20 デバイス基板
21 支持体
27 転写膜
30 ドナー基板
31 支持体
33 光熱変換層
34 区画パターン
37 転写材料
38 転写領域
40 マスク
44 絶縁層の幅
47 副画素
48 輝度測定点
Claims (10)
- 基板と、前記基板上に形成された光熱変換層とを有する転写用ドナー基板であって、前記光熱変換層の表面が粗面であることを特徴とする転写用ドナー基板。
- 前記光熱変換層の表面の算術平均粗さが30nm以上である請求項1記載の転写用ドナー基板。
- 前記基板の光熱変換層が形成される側の表面の算術平均粗さが30nm以上である請求項1または2記載の転写用ドナー基板。
- 請求項1~3記載の転写用ドナー基板において、表面の凹凸平均間隔が20μm以下である転写用ドナー基板。
- 前記光熱変換層の上面に区画パターンが形成されている請求項1~4記載の転写用ドナー基板。
- 請求項1~5のいずれかに記載された転写用ドナー基板をデバイス基板と対向させる工程と、前記光熱変換層に光を照射することで転写層を前記デバイス基板に転写する工程を有するデバイスの製造方法。
- 少なくとも一対の電極間に挟持された発光層を含む有機化合物層を有し、有機化合物層の少なくとも一部が転写法を用いて形成された有機EL素子において、副画素の絶縁層の幅が40μm未満であり、かつ副画素内の発光領域の発光輝度ムラが±20%以下であることを特徴とする有機EL素子。
- 前記副画素の絶縁層の幅が30μm以下である請求項7記載の有機EL素子。
- 少なくとも一対の電極間に挟持された発光層を含む有機化合物層を有し、有機化合物層の少なくとも一部が転写法を用いて形成された有機EL素子において、副画素の絶縁層の幅が40μm未満であり、かつ転写法を用いて形成された有機化合物層のうち、副画素内の発光領域の膜厚ムラが±10%以下であることを特徴とする有機EL素子。
- 前記副画素の絶縁層の幅が30μm以下である請求項9記載の有機EL素子。
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KR1020137002216A KR20130138174A (ko) | 2010-07-15 | 2011-07-12 | 전사용 도너 기판과 이것을 사용한 디바이스의 제조 방법, 및 유기 el 소자 |
CN2011800350071A CN103004291A (zh) | 2010-07-15 | 2011-07-12 | 转印用施主基板及使用其的器件的制造方法、及有机el元件 |
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JP2000351279A (ja) * | 1999-06-11 | 2000-12-19 | Fuji Photo Film Co Ltd | 熱転写シート |
JP2002178657A (ja) * | 2000-12-18 | 2002-06-26 | Fuji Photo Film Co Ltd | 感熱性平版印刷用原板 |
JP2005088330A (ja) * | 2003-09-17 | 2005-04-07 | Konica Minolta Medical & Graphic Inc | 印刷版材料及び印刷方法 |
JP2005173239A (ja) * | 2003-12-11 | 2005-06-30 | Dainippon Printing Co Ltd | 遮光層付き光学シート及びカラーフィルタ |
WO2009154156A1 (ja) * | 2008-06-16 | 2009-12-23 | 東レ株式会社 | パターニング方法およびこれを用いたデバイスの製造方法ならびにデバイス |
JP2010086840A (ja) * | 2008-10-01 | 2010-04-15 | Toray Ind Inc | パターニング方法およびこれを用いたデバイスの製造方法 |
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US20080036367A1 (en) * | 2004-08-26 | 2008-02-14 | Idemitsu Kosan Co., Ltd. | Organic El Display Device |
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JP2000351279A (ja) * | 1999-06-11 | 2000-12-19 | Fuji Photo Film Co Ltd | 熱転写シート |
JP2002178657A (ja) * | 2000-12-18 | 2002-06-26 | Fuji Photo Film Co Ltd | 感熱性平版印刷用原板 |
JP2005088330A (ja) * | 2003-09-17 | 2005-04-07 | Konica Minolta Medical & Graphic Inc | 印刷版材料及び印刷方法 |
JP2005173239A (ja) * | 2003-12-11 | 2005-06-30 | Dainippon Printing Co Ltd | 遮光層付き光学シート及びカラーフィルタ |
WO2009154156A1 (ja) * | 2008-06-16 | 2009-12-23 | 東レ株式会社 | パターニング方法およびこれを用いたデバイスの製造方法ならびにデバイス |
JP2010086840A (ja) * | 2008-10-01 | 2010-04-15 | Toray Ind Inc | パターニング方法およびこれを用いたデバイスの製造方法 |
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KR20130138174A (ko) | 2013-12-18 |
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