WO2011118654A1 - 発光装置の製造方法 - Google Patents
発光装置の製造方法 Download PDFInfo
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- WO2011118654A1 WO2011118654A1 PCT/JP2011/057033 JP2011057033W WO2011118654A1 WO 2011118654 A1 WO2011118654 A1 WO 2011118654A1 JP 2011057033 W JP2011057033 W JP 2011057033W WO 2011118654 A1 WO2011118654 A1 WO 2011118654A1
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
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- H—ELECTRICITY
- 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
- 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
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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
- 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
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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
- H10K71/12—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
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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
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
-
- 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
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
-
- 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
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
Definitions
- the present invention relates to a method for manufacturing a light emitting device.
- This display device includes a plurality of organic EL elements arranged on a support substrate.
- a partition in which the organic EL element is provided is set on the support substrate.
- a partition for defining a recess corresponding to the partition in which the organic EL element is provided is provided on the support substrate. That is, the plurality of organic EL elements are respectively arranged in the recesses defined by the partition walls.
- the organic EL element is composed of a pair of electrodes and an organic EL layer provided between the pair of electrodes, and is manufactured by sequentially laminating each component.
- the organic EL layer constituting the organic EL element can be formed by a coating method.
- a mode when the organic EL layer is formed by a coating method is shown in FIGS. 4A and 4B.
- FIG. 4A and FIG. 4B are diagrams showing an aspect when an organic EL layer is formed by a coating method.
- ink containing a material that becomes an organic EL layer is supplied to the concave portion 2 that is a region defined by the adjacent partition walls 1 on the support substrate 11.
- the supplied ink shrinks while drying.
- the organic EL layer 3 is formed in the recess 2 (see, for example, Patent Document 1).
- FIGS. 5 and 6 are diagrams schematically showing a display device in which an organic EL layer different from the intended shape is formed.
- the film thickness of the organic EL layer 3 is preferably uniform over the entire organic EL layer 3.
- an organic EL layer 3 having a very thin film thickness in the vicinity of the boundary between the partition wall 1 and the organic EL layer 3 may be formed.
- the ink supplied to the recess 2 defined by the partition wall 1 dries while spreading along the surface of the partition wall 1, and the organic EL layer 3 is formed on the side surface of the partition wall 1.
- the ink overflows to the adjacent concave portion 2 beyond the concave portion 2, and there is a problem of color mixture that the ink is mixed with the ink to be supplied to the adjacent concave portion 2.
- an object of the present invention is to provide a method for manufacturing a light emitting device capable of forming an organic EL layer having an intended shape.
- the present invention provides the following [1] to [10].
- [1] A support substrate, a partition wall provided on the support substrate and defining a recess set on the support substrate, a first electrode, a second electrode, A plurality of organic electroluminescence elements including an organic electroluminescence layer provided between one electrode and a second electrode, the method comprising: Preparing the support substrate provided with the first electrode and the partition; Supplying an ink containing a material to be an organic electroluminescence layer to the recess as a volume of 90% to 120% of the volume of the recess; Forming the organic electroluminescence layer by solidifying the supplied ink; and Forming the second electrode.
- a method for manufacturing a light emitting device is a light emitting device.
- the partition is composed of a plurality of partition members each extending in a predetermined row direction on the support substrate, The method for manufacturing a light-emitting device according to [1], wherein the plurality of partition members are arranged at a predetermined interval in a column direction different from the row direction.
- [5] The method for manufacturing a light-emitting device according to any one of [1] to [4], wherein a contact angle between the partition wall and the ink is 5 degrees or more and 50 degrees or less.
- [6] The method for manufacturing a light-emitting device according to [5], wherein oxygen plasma treatment is performed after the step of preparing the support substrate and before the step of supplying the ink.
- [7] The method for manufacturing a light-emitting device according to any one of [1] to [6], wherein the ink has a surface tension of 30 mN / m or more and 72 mN / m or less.
- the present invention it is possible to manufacture a light-emitting device in which an organic EL layer having an intended shape is formed while preventing formation of undesired holes and undesired color mixing. As a result, a light emitting device in which the occurrence of element defects is suppressed can be manufactured.
- FIG. 1 is a plan view schematically showing the light emitting device of this embodiment.
- FIG. 2 is a cross-sectional view schematically showing the light emitting device.
- FIG. 3 is a diagram showing the results of evaluating the film formation state.
- FIG. 4A is a diagram showing an aspect when an organic EL layer is formed by a coating method.
- FIG. 4B is a diagram illustrating an aspect when an organic EL layer is formed by a coating method.
- FIG. 5 is a diagram schematically showing a display device in which an organic EL layer different from the intended shape is formed.
- FIG. 6 is a diagram schematically showing a display device in which an organic EL layer different from the intended shape is formed.
- a method of manufacturing a light emitting device includes a support substrate, a partition wall provided on the support substrate and defining a recess set on the support substrate, a first electrode provided on the recess, a first electrode, And a plurality of organic EL elements including an organic EL layer provided between the first electrode and the second electrode, wherein the first electrode, the partition, A step of preparing the support substrate provided thereon, a step of supplying ink containing a material to be an organic EL layer to the recess as a volume of 90% to 120% of the volume of the recess, A step of forming the organic EL layer by solidifying the formed ink and a step of forming the second electrode.
- the light emitting device is used as a display device, for example.
- the present invention can be applied to both drive-type display devices.
- a light emitting device applied to an active matrix driving display device will be described as an example.
- FIG. 1 is a plan view schematically showing the light emitting device of this embodiment.
- FIG. 2 is a cross-sectional view schematically showing the light emitting device.
- the light emitting device 21 is provided mainly on the support substrate 11, the partition wall 17 that defines the recess 18 that is a partition set on the support substrate 11, and a plurality of organic ELs provided in the recess 18.
- the organic EL element 22 is provided between the first electrode 12, the second electrode 16, and the first electrode 12 and the second electrode 16.
- the organic EL element 22 includes the element 22 (22 R, 22 G, 22 B).
- a hole injection layer 13 which is an EL layer and a light emitting layer 14 (14R, 14G, 14B) are included.
- the plurality of organic EL elements 22 are respectively arranged in predetermined recesses 18 set on the support substrate 11.
- the partition wall 17 is provided to define a predetermined recess 18 set on the support substrate 11, and the shape of the partition member 20 constituting the partition wall 17 is the shape of the recess 18 set on the support substrate 11. It depends on your needs. For example, when the matrix-shaped recess 18 is set on the support substrate 11, the support substrate 11 is provided with a lattice-shaped partition wall 17 that defines the matrix-shaped recess 18. When the stripe-shaped recess 18 is set on the support substrate 11, the support substrate 11 is provided with a stripe-shaped partition wall 17 that defines the stripe-shaped recess 18.
- the partition wall 17 is composed of a plurality of partition wall members 20 that extend substantially in parallel in the predetermined row direction X on the support substrate 11.
- the plurality of partition members 20 are arranged at a predetermined interval in the column direction Y, which is different from the row direction X.
- the row direction X and the column direction Y are directions orthogonal to each other, and the row direction X and the column direction Y are directions orthogonal to the thickness direction Z of the support substrate 11.
- a plurality of recesses 18 corresponding to the gaps between the plurality of partition wall members 20 are set on the support substrate 11.
- an insulating film 15 is further provided between the support substrate 11 and the partition wall 17.
- This insulating film 15 is provided, for example, to ensure electrical insulation between the organic EL elements 22 adjacent in the row direction X or the column direction Y.
- the insulating film 15 in this embodiment is formed in a lattice shape.
- the lattice-like insulating film 15 is configured by integrally forming a plurality of strip-shaped portions extending in the row direction X and a plurality of strip-shaped portions extending in the column direction Y.
- the insulating film 15 has a shape in which a large number of openings 15a are formed in a matrix in a thin film that exhibits electrical insulation.
- the opening 15 a of the insulating film 15 is formed at a position overlapping the organic EL element 22 when viewed from one side in the thickness direction of the support substrate (hereinafter, sometimes referred to as “plan view”).
- the opening 15a of the insulating film 15 is formed so as to substantially coincide with a first electrode 12 described later in a plan view, and is formed in, for example, a substantially rectangular shape, an oval shape, a substantially circular shape, or a substantially elliptical shape.
- the lattice-like insulating film 15 is formed so as to expose a part of the first electrode 12 in plan view, and a part of the insulating film 15 is formed so as to cover the periphery of the first electrode 12.
- the plurality of partition members 20 described above are provided on the plurality of strip-shaped portions of the insulating film 15.
- the organic EL element 22 is provided in the recess 18 defined by the partition wall 17.
- the plurality of organic EL elements 22 are provided between the partition wall members 20 adjacent to each other in the column direction Y (that is, the recess 18), and a predetermined interval is provided in the row direction X between the partition wall members 20.
- the plurality of organic EL elements 22 are arranged in a matrix on the support substrate 11, and are arranged with a predetermined interval in the row direction X and also with a predetermined interval in the column direction Y.
- the organic EL elements 22 do not need to be physically separated from each other, and may be electrically insulated from each other so that they can be individually driven. Therefore, some layers (the first electrode 12, the second electrode 16, and the organic EL layer) constituting the organic EL element 22 may be physically connected to other organic EL elements 22.
- the organic EL element 22 includes the first electrode 12, the organic EL layer (the hole injection layer 13 and the light emitting layer 14), and the second electrode 16 in this order so that the first electrode 12 is closer to the support substrate 11. Arranged and configured.
- the first electrode 12 and the second electrode 16 constitute a pair of electrodes composed of an anode and a cathode. That is, one of the first electrode 12 and the second electrode 16 is provided as an anode, and the other is provided as a cathode. Further, the first electrode 12 out of the first electrode 12 and the second electrode 16 is disposed closer to the support substrate 11, and the second electrode 16 is closer to the support substrate 11 than the first electrode 12. It arrange
- the organic EL element 22 includes one or more organic EL layers.
- the organic EL layer means all layers sandwiched between the first electrode 12 and the second electrode 16 and containing an organic material.
- the organic EL element includes at least one light emitting layer 14 as an organic EL layer.
- a predetermined layer is provided between the first electrode 12 and the second electrode 16 as needed, not limited to the light emitting layer 14.
- a hole injection layer, a hole transport layer, an electron blocking layer, and the like are provided as an organic EL layer between the anode and the light emitting layer 14, and an organic EL layer is provided between the light emitting layer 14 and the cathode, A hole blocking layer, an electron transport layer, an electron injection layer, and the like are provided.
- the organic EL element 22 of this embodiment includes a hole injection layer 13 as an organic EL layer between the first electrode 12 and the light emitting layer 14.
- the first electrode 12 is supported by the first electrode 12 functioning as an anode, the hole injection layer 13, the light-emitting layer 14, and the second electrode 16 functioning as a cathode.
- the organic EL element 22 stacked in this order so as to be closer to the substrate 11 will be described.
- the first electrode 12 is provided for each organic EL element 22 individually. That is, the same number of first electrodes 12 as the number of organic EL elements 22 are provided on the support substrate 11.
- the first electrode 12 has a thin film shape and is formed in a substantially rectangular shape in plan view.
- the first electrodes 12 are provided in a matrix on the support substrate 11 corresponding to the positions where the respective organic EL elements 22 are provided.
- the plurality of first electrodes 12 are arranged at predetermined intervals in the row direction X and at predetermined intervals in the column direction Y.
- the first electrodes 12 are provided between the partition wall members 20 adjacent to each other in the column direction Y in a plan view, and are arranged at predetermined intervals in the row direction X between the partition wall members 20. .
- the lattice-like insulating film 15 is formed so as to expose a part of the first electrode 12 in plan view, and a part of the insulating film 15 is formed so as to cover the periphery of the first electrode 12. . That is, an opening 15 a is formed in the insulating film 15 so as to expose a part of the first electrode 12.
- the hole injection layer 13 is disposed so as to extend in the row direction X in a recess 18 sandwiched between adjacent partition wall members 20. That is, the hole injection layer 13 is formed in a strip shape in the recess 18 defined by the partition members 20 adjacent in the column direction Y, and continuously extends across the organic EL elements 22 adjacent in the row direction X. Is formed.
- the light emitting layer 14 is arranged extending in the row direction X in a region sandwiched between adjacent partition wall members 20.
- the light emitting layer 14 is formed in a strip shape in the recess 18 defined by the partition members 20 adjacent to each other in the column direction Y, and continuously extends over a plurality of organic EL elements 22 adjacent in the row direction X. Is formed.
- the band-shaped light emitting layer 14 is laminated on the band-shaped hole injection layer 13.
- the organic EL element according to the embodiment of the present invention can also be applied to a monochrome display device.
- a color display device will be described as an example.
- three types of organic EL elements that emit any one of red, green, and blue light are provided on the support substrate 11.
- the color display device can be realized, for example, by repeatedly arranging the following rows (I), (II), and (III) in the column direction Y in this order.
- a plurality of organic EL elements 22R that emit red light are arranged at predetermined intervals in the row direction X.
- a plurality of organic EL elements 22G that emit green light are predetermined in the row direction X. Rows arranged at intervals
- III Rows in which a plurality of organic EL elements 22B emitting blue light are arranged at predetermined intervals in the row direction X
- a light emitting layer having a different emission color is usually provided for each type of element.
- the following rows (i), (ii), and (iii) are repeatedly arranged in the column direction Y in this order.
- strip-shaped light emitting layers 14 (14R, 14G, 14B) extending in the row direction X are sequentially stacked on the hole injection layer 13 with two rows in the column direction Y, respectively. .
- the second electrode 16 is provided on the light emitting layer 14.
- the second electrode 16 is continuously formed across the plurality of organic EL elements 22 arranged in a matrix, and is provided as a common electrode for the plurality of organic EL elements 22.
- the second electrode 16 is formed not only on the light emitting layer 14 but also on the partition wall 17, and is formed on the entire surface so that the electrode on the light emitting layer 14 and the electrode on the partition wall 17 are connected.
- the support substrate 11 on which the first electrode 12 and the partition wall 17 are provided is prepared.
- a substrate on which circuits for individually driving the plurality of organic EL elements 22 are formed in advance can be used as the support substrate 11.
- a substrate on which a TFT (Thin Film Transistor), a capacitor, and the like are formed in advance can be used as the support substrate 11.
- a substrate provided with the first electrode 12 and the partition wall 17 may be prepared as the support substrate 11 by forming the first electrode 12 and the partition wall 17 in this step as follows.
- the first electrode 12 is formed, for example, by forming a conductive thin film on one surface of the support substrate 11 and applying this to a photolithographic method (in the following description, “photolithographic method” includes a mask pattern forming step). A patterning step such as an etching step is included) and the conductive thin film is patterned in a matrix. Further, for example, a mask having an opening formed in a predetermined portion is disposed on the support substrate 11, and the conductive material is selectively deposited only on the predetermined portion on the support substrate 11 through the mask, thereby the first The electrode 12 may be patterned. The material of the first electrode 12 will be described later.
- the partition wall 17 is formed on the support substrate 11.
- the partition wall 17 composed of a plurality of partition wall members 20 is formed.
- the partition wall 17 is made of an organic material or an inorganic material.
- the organic material constituting the partition wall 17 include resins such as an acrylic resin, a phenol resin, and a polyimide resin.
- the partition walls are preferably made of organic materials.
- the partition wall 17 In order to hold the ink supplied to the recess 18 defined (enclosed) by the partition wall 17, the partition wall 17 preferably exhibits liquid repellency.
- an organic material is more lyophobic than an inorganic material, so that if the partition wall 17 is made of an organic material, the ability to retain ink in the recess 18 is enhanced.
- partition wall 17 made of an organic material When the partition wall 17 made of an organic material is formed, first, for example, a positive or negative photosensitive resin is applied on the support substrate 11, and a predetermined portion is exposed and developed. Further, by curing this, a plurality of partition members 20, that is, partition walls 17 are formed. Note that a photoresist can be used as the photosensitive resin.
- a thin film made of an inorganic material is formed on the support substrate 11 by plasma CVD, sputtering, or the like, and then a plurality of partition wall members 20 are formed by removing predetermined portions. Is done. The predetermined portion is removed by, for example, a photolithography method.
- the insulating film 15 is formed before the step of forming the partition wall 17.
- the insulating film 15 can be formed in a lattice shape in the same manner as the method of forming the partition wall 17 using, for example, the material exemplified as the material of the partition wall 17.
- the lattice-like insulating film 15 and the partition wall 17 may be described as an integral configuration.
- the “recess 18 defined by the partition wall 17” is defined by the insulating film 15 and the partition wall 17 and the exposed surface (bottom surface) between the support substrate 11 or the adjacent partition walls 17. May be referred to as an area).
- the insulating film 15 is preferably made of an inorganic material that is more lyophilic than an organic material.
- the ink supplied to the concave portion 18 defined by the partition wall 17 may be dried while being repelled by the insulating film 15, and the presence of the insulating film 15 is flat in the organic EL layer. It is because there exists a possibility that a flat organic electroluminescent layer may not be obtained as a result.
- the shape of the partition wall 17 and the arrangement thereof are appropriately set according to the specifications of the display device such as the number of pixels and resolution, the ease of manufacturing, and the like.
- the width L1 of the partition wall member 20 in the column direction Y is about 5 ⁇ m to 50 ⁇ m.
- the height L2 of the partition member 20 is about 0.5 ⁇ m to 5 ⁇ m.
- An interval L3 between the partition wall members 20 adjacent to each other in the column direction Y, that is, a width L3 of the recesses 18 in the column direction Y is about 10 ⁇ m to 200 ⁇ m.
- the widths of the first electrode 12 in the row direction X and the column direction Y are about 10 ⁇ m to 400 ⁇ m, respectively.
- an ink containing a material to be an organic EL layer is supplied to the recess 18 defined by the partition wall 17.
- ink containing a material that becomes the hole injection layer 13 corresponding to the organic EL layer is supplied to the recess 18 defined by the partition wall 17.
- any coating method that can selectively supply ink between adjacent partition members 20 may be used.
- Examples of such a method include a method of intermittently dropping ink, a method of flowing ink in a liquid column shape, and a method of printing ink attached to a printing plate.
- the method of intermittently dripping ink there may be a gap between droplets adhering at the ink adhesion point, and this interval may cause a decrease in film thickness uniformity.
- the method of flowing ink in the form of a liquid column is preferable as the above-described method of supplying ink.
- a method for supplying ink by flowing down ink in a liquid column shape a nozzle printing method in which ink is flowed down in a liquid column shape from a nozzle is preferable.
- Examples of the method for intermittently dropping the ink include an inkjet printing method, and examples of the method for printing the ink adhered to the printing plate include a relief printing method and an intaglio printing method.
- ink is supplied to each line (each recess 18) with a single stroke. That is, while the liquid columnar ink is ejected from the nozzles arranged above the support substrate 11, the support substrate 11 is moved in the column direction Y when the nozzles are reciprocated in the row direction X and the nozzles are turned back and forth. Ink is supplied to each recess 18 by moving it by a predetermined distance. For example, when the nozzles are turned back and forth, the support substrate 11 is moved by one row in the column direction Y, whereby ink can be supplied to all rows.
- Step of moving the nozzle from one end in the row direction X to the other end (2) Step of moving the support substrate 11 to one side in the column direction Y by one row (3) One end of the nozzle from the other end in the row direction X (4) The step of moving the support substrate by one row in one of the column directions Y
- the ink having a volume of 90% or more and 120% or less of the volume of the recess 18 which is an area defined by the partition wall 17 is supplied.
- the “volume of the concave portion 18” refers to the surface defined by the top surfaces or ridge lines corresponding to the maximum height in the section in the column direction Y of the adjacent partition wall members 20, and the side surfaces of the partition wall members 20 facing each other ( And the exposed surface of the insulating film 15), the surface connecting the end portions of the partition wall member 17 facing each other at both ends in the length direction of the partition wall member 20, and the exposed surface sandwiched between the side surfaces of the partition wall member 20 facing each other Means the volume of the region defined by (referred to as the volume defined by the partition wall 17).
- the cross-sectional shape of the partition wall member 20 in the column direction Y is shown as a trapezoid, but the cross-sectional shape of the partition wall member 20 is usually a dome shape formed of a curve.
- the volume of the concave portion 18 corresponds to the volume of the concave portion 18 with the plane connecting the ridge lines of the adjacent partition wall members 20 as the upper surface.
- the supply amount of ink is more preferably an amount corresponding to a volume of 90% to 118% of the volume of the concave portion 18.
- the supplied ink may not completely wet and spread on the bottom surface of the recess 18, resulting in the organic EL layer. Holes may be formed in
- the ink supplied to the predetermined recess 18 passes over the partition member 20 and enters the adjacent recess 18. May overflow.
- the ink when an ink having a volume of 90% or more and 120% or less of the volume of the recess 18 is supplied, the ink spreads on the bottom surface of the recess 18 and the organic EL layer without holes (in this embodiment, holes).
- the injection layer 13 As the injection layer 13) is formed, it is possible to prevent the ink from overflowing to the adjacent recesses 18, and the organic EL layer can be formed only in the recesses 18 supplied with the ink.
- the hole injection layer 13 corresponding to the organic EL layer is formed by solidification of the ink supplied to the recesses 18 between the adjacent partition members 20.
- the ink can be solidified, for example, by removing the solvent. The removal of the solvent can be performed by natural drying, heat drying, vacuum drying, or the like.
- the hole injection layer 13 may be solidified by applying energy such as light and heat after the ink is supplied.
- the light emitting layer 14 is formed.
- the material of the light emitting layer for each row.
- red ink containing a material that emits red light green ink containing a material that emits green light
- a material that emits blue light It is necessary to apply the blue ink containing the ink in the column direction Y with an interval of two rows.
- any coating method that can selectively supply ink to the recesses 18 between the partition members 20 may be used.
- the method may be used.
- the ink can be applied by a nozzle printing method, which is one of the methods for flowing the ink in a liquid column shape, in the same manner as the method for forming the hole injection layer described above.
- Step (1) Step of moving the nozzle in the row direction X from one end to the other end of the recess 18
- Step of moving the support substrate 11 in one of the column directions Y by three rows Step of moving the support substrate 11 in one of the column directions Y by three rows.
- Nozzle of the recess 18 A step of moving in the row direction X from the other end to the one end (4) a step of moving the support substrate in one of the column directions Y by three rows
- green ink and blue ink are respectively supplied between the partition wall members 20 (recesses 18) with an interval of two rows in the column direction Y. can do.
- an ink having a volume of 90% or more and 120% or less of the volume of the recess 18 defined by the partition wall 17 is supplied.
- the ink in this step corresponds to red ink, blue ink, and green ink.
- an organic EL layer (a light emitting layer 14 in the present embodiment) having no holes can be formed and adjacent to each other. It is possible to prevent the ink from overflowing to the concave portion 18 and to form the organic EL layer only in the concave portion 18 to which the ink has been supplied.
- the ink since one kind of ink is supplied to each row, that is, all the recesses 18, the ink overflows to the adjacent recesses 18 beyond the partition walls 17. However, the same kind of ink is only mixed. On the other hand, when different types of ink, such as red ink, blue ink, and green ink, are separately applied to a plurality of different recesses 18, the ink overflows to the adjacent recesses 18 beyond the partition wall 17, and different types of ink are mixed. When they are matched, the light emission characteristics such as emission color and light emission efficiency may be greatly affected. However, in the present embodiment, by adjusting the amount of ink to be supplied, it is possible to prevent different types of ink from being mixed in the concave portion 18, and as a result, it is possible to prevent a decrease in light emission characteristics.
- red ink red ink, blue ink, and green ink
- the light emitting layer is formed when the ink supplied between the partition members 20 is solidified.
- the ink can be solidified, for example, by removing the solvent. The removal of the solvent can be performed by natural drying, heat drying, vacuum drying, or the like.
- the ink to be used contains a material that is polymerized by applying energy such as light and heat
- the light emitting layer may be solidified by applying energy such as light and heat after the ink is supplied.
- a predetermined organic layer, an inorganic layer, or the like is formed by a predetermined method as necessary.
- the layers provided as necessary may be formed by a predetermined coating method such as a printing method, an ink jet method, a nozzle printing method, or a predetermined dry method.
- the second electrode 16 is formed. As described above, in the present embodiment, the second electrode 16 is formed on the entire surface of the support substrate 11. Thereby, a plurality of organic EL elements 22 can be formed on the support substrate 11.
- the ink used in the step of forming the above-described organic EL layer (in this embodiment, the hole injection layer 13 and the light emitting layer 14) preferably has a viscosity of 15 cP or more and 30 cP or less.
- the viscosity of the ink is too low, the ink supplied to the recesses 18 may exceed the partition member 20 and overflow into the adjacent recesses 18.
- the viscosity of the ink is too high, ink ejection failure from the nozzles may occur.
- an ink having a viscosity of 15 cP or more and 30 cP or less By using an ink having a viscosity of 15 cP or more and 30 cP or less, it is possible to prevent the ink supplied to the recesses 18 from overflowing into the adjacent recesses 18 beyond the partition walls 17 and to prevent ink ejection failure.
- the concentration of the ink used in the step of forming the organic EL layer is preferably 10 mg / mL to 30 mg / mL. This is because if the ink concentration is too high, the ink may gel or the solid component of the ink may precipitate.
- the film thickness of the organic EL layer is mainly determined by the ink concentration and its supply amount. Usually, since the optimum value of the film thickness of the organic EL layer is determined in advance, the ink density and the ink supply amount are determined by calculating back from the optimum value of the film thickness of the organic EL layer. In this embodiment, since the ink having a volume of 90% or more and 120% or less of the volume of the recess 18 which is an area defined by the partition wall 17 is supplied, the amount of ink supplied is the height of the partition wall 17 (maximum height). ). Therefore, when the ink concentration is 10 mg / mL or more and 30 mg / mL or less, the height of the partition wall 17 is determined to be within a predetermined range.
- the ink concentration is low, it is necessary to increase the amount of ink supplied in order to obtain an organic EL layer having a predetermined film thickness. For this purpose, it is necessary to increase the height of the partition wall 17. For this reason, when an ink having a volume of 90% or more and 120% or less of the volume of the recess 18 defined by the partition wall 17 is supplied, an area where the surface of the partition wall 17 contacts with the ink increases. The ink is thinned while shrinking as the solvent is vaporized. At this time, the ink shrinks along the surface of the partition wall 17, and therefore, when the area where the ink contacts the surface of the partition wall 17 is large, In some cases, the organic EL layer having a uniform film thickness cannot be obtained due to the influence of the surface properties.
- the partition wall 17 having an appropriate height can be used. Therefore, the area where the ink and the partition wall 17 are in contact with each other can be made relatively small, and the influence of the properties of the surface of the partition wall 17 when the film is thinned is reduced. As a result, an organic EL layer having a uniform thickness is obtained. Can do.
- the partition wall 17 preferably has a contact angle with the supplied ink of 5 degrees or more and 50 degrees or less.
- the contact angle between the partition wall 17 and the ink is too small, the ink spreads along the surface of the partition wall 17, and the ink supplied to the recess 18 may overflow the adjacent recess 18 beyond the partition member 20. Because.
- the partition wall 17 in order to hold the ink supplied to the concave portion 18 in the predetermined concave portion 18, the partition wall 17 preferably exhibits liquid repellency.
- the partition wall 17 in order to increase the contact angle between the partition wall 17 and the ink, the partition wall 17 usually requires a liquid repellent treatment, and the number of processes increases.
- the contact angle between the partition wall 17 and the supplied ink it is necessary to perform plasma processing in CF 4 gas.
- the liquid repellent treatment when the liquid repellent treatment is performed, unintended impurities are mixed into the organic EL element, which may deteriorate the characteristics of the organic EL element. Therefore, by setting the contact angle between the partition wall 17 and the ink to 5 degrees or more and 50 degrees or less by selecting the ink concentration, the ink solvent, and the partition material, the ink can be prevented from overflowing and the number of processes can be reduced. An increase and a decrease in device characteristics can be suppressed.
- the ink used in the step of forming the organic EL layer (the hole injection layer 13 and the light emitting layer 14) preferably has a surface tension of 30 mN / m or more and 72 mN / m or less. If the surface tension of the ink is too low, the ink supplied to the recesses 18 may overflow to the adjacent recesses 18 beyond the partition member 20, but by using an ink having a high surface tension, the ink is separated from the partition members 20 It is possible to prevent overflowing into the adjacent recesses 18 beyond.
- the surface tension of the ink is preferably high, and it is not particularly necessary to define an upper limit value.
- the surface tension of the ink is usually 72 mN / m or less.
- the ink used in the step of forming the organic EL layer preferably includes a solvent having a boiling point of 190 ° C. or higher and 260 ° C. or lower.
- a solvent having a high boiling point is difficult to evaporate, and by using a solvent having a high boiling point exhibiting such characteristics, the drying speed of the ink supplied to the concave portion 18 can be reduced. As a result, it is possible to lengthen the time until the ink is solidified.
- the concentration of the ink and the height of the liquid surface in the recess 18 can be made uniform.
- the proportion of the solvent having a boiling point of 190 ° C. or more and 260 ° C. or less in the ink is preferably 10% by weight or more and 70% by weight or less, and more preferably 40% by weight or more and 60% by weight or less.
- the surface tension and viscosity of the ink described above can be adjusted by adjusting the concentration (solid content concentration) of the material to be the organic EL layer and the type of solvent.
- the composition and characteristics of the ink change with time when the ink is thinned.
- the above-described ink composition and its characteristics mean the ink composition and its characteristics when the ink is run down.
- a solvent having a predetermined boiling point may be used alone, or a plurality of types of solvents may be used in combination.
- the ink solvent examples include chloroform (boiling point 61 ° C.), methylene chloride (boiling point 40 ° C.), 1,1-dichloroethane (boiling point 57 ° C.), 1,2-dichloroethane (boiling point 83 ° C.), 1,1,1- Aliphatic chlorine solvents such as trichloroethane (boiling point 74 ° C), 1,1,2-trichloroethane (boiling point 113 ° C), chlorobenzene (boiling point 132 ° C), o-dichlorobenzene (boiling point 180 ° C), m-dichlorobenzene (boiling point 173) ° C), aromatic chlorine solvents such as p-dichlorobenzene (boiling point 174 ° C), aliphatic ether solvents such as tetrahydrofuran (boiling point 66 °
- a lyophilic treatment is performed on the concave portion 18 defined by the partition wall 17 after the step of preparing the support substrate 11 and before the step of supplying the ink.
- the lyophilic treatment can be performed by UV treatment or oxygen plasma treatment. Among these, oxygen plasma treatment is preferable. This is because oxygen plasma treatment is less likely to introduce unintended impurities into the organic EL element.
- the method of supplying ink by flowing it down in a liquid column shape is suitable as a method of easily supplying ink to the recesses 18 set in a stripe shape without defects. Furthermore, it is particularly suitable for a method of supplying ink that satisfies the above-described concentration, surface tension, contact angle with the partition wall 17, and viscosity.
- ink that satisfies the above-mentioned concentration, surface tension, and viscosity may cause clogging of the nozzle, so ink with low concentration is often used, and therefore ink with low surface tension and viscosity is used. Will do.
- the ink supplied to the recesses 18 may overflow to the adjacent recesses 18 beyond the partition member 20. Therefore, when ink with a low density is used, the partition 17 is often subjected to a liquid repellent treatment in order to increase the amount of ink supplied and prevent the ink from overflowing beyond the partition 17.
- applying the liquid repellent treatment to the partition wall 17 leads to unintended impurity contamination and an increase in the number of steps when performing the liquid repellent treatment as described above.
- the organic EL element 22 can have various layer configurations.
- the layer structure of the organic EL element 22, the configuration of each layer, and the method of forming each layer will be described in more detail.
- the organic EL element 22 includes a pair of electrodes including the anode and the cathode (the first electrode 12 and the second electrode 16), and one or more organic EL layers provided between the pair of electrodes. And having at least one light emitting layer 14 as one or more organic EL layers.
- the organic EL element 22 may include a layer containing an inorganic substance and an organic substance, an inorganic layer, and the like.
- the organic substance constituting the organic layer may be a low molecular compound or a high molecular compound, or a mixture of a low molecular compound and a high molecular compound.
- the organic layer preferably contains a polymer compound, and preferably contains a polymer compound having a polystyrene-equivalent number average molecular weight of 10 3 to 10 8 .
- Examples of the organic EL layer provided between the cathode and the light emitting layer 14 include an electron injection layer, an electron transport layer, and a hole blocking layer.
- an electron injection layer When both the electron injection layer and the electron transport layer are provided between the cathode and the light emitting layer 14, a layer close to the cathode is referred to as an electron injection layer, and a layer close to the light emitting layer is referred to as an electron transport layer.
- Examples of the organic EL layer provided between the anode and the light emitting layer 14 include a hole injection layer, a hole transport layer, and an electron block layer. When both the hole injection layer and the hole transport layer are provided, a layer close to the anode is referred to as a hole injection layer, and a layer close to the light emitting layer 14 is referred to as a hole transport layer.
- anode / light emitting layer / cathode b) anode / hole injection layer / light emitting layer / cathode c) anode / hole injection layer / light emitting layer / electron injection layer / cathode d) anode / hole injection layer / light emitting layer / Electron transport layer / cathode e) anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode f) anode / hole transport layer / light emitting layer / cathode g) anode / hole transport layer / light emitting layer / Electron injection layer / cathode h) anode / hole transport layer / light emitting layer / electron transport layer / cathode i) anode / hole transport layer / light emitting layer / electron transport
- the organic EL element 22 of the present embodiment may have two or more light emitting layers 14.
- structural unit A when the laminate sandwiched between the anode and the cathode is referred to as “structural unit A”, the configuration of the organic EL device having two light emitting layers is as follows. And the layer structure shown in the following q). Note that the two (structural unit A) layer structures may be the same or different. q) Anode / (structural unit A) / charge generating layer / (structural unit A) / cathode If “(structural unit A) / charge generating layer” is “structural unit B”, it has three or more light emitting layers.
- Examples of the structure of the organic EL element include the layer structure shown in the following r). r) anode / (structural unit B) x / (structural unit A) / cathode
- x represents an integer of 2 or more
- (structural unit B) x is a stack in which the structural unit B is stacked in x stages. Represents the body.
- a plurality of (structural units B) may have the same or different layer structure.
- the charge generation layer is a layer that generates holes and electrons by applying an electric field.
- Examples of the charge generation layer include a thin film made of vanadium oxide, indium tin oxide (abbreviated as ITO), molybdenum oxide, or the like.
- the organic EL element 22 may be provided on the support substrate 11 such that the anode of the pair of electrodes including the anode and the cathode is disposed closer to the support substrate 11 than the cathode, and the cathode is provided on the support substrate rather than the anode. You may arrange
- an electrode having optical transparency is used for the anode.
- an electrode exhibiting optical transparency thin films such as metal oxides, metal sulfides, and metals can be used.
- an electrode having high electrical conductivity and high light transmittance is preferably used.
- Specific examples of the electrode exhibiting optical transparency include a thin film made of indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (abbreviated as IZO), gold, platinum, silver, copper, and the like. Used.
- a thin film made of ITO, IZO, or tin oxide is preferably used.
- the method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
- an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used.
- the film thickness of the anode is appropriately set in consideration of the required characteristics, the simplicity of the film forming process, and the like.
- the film thickness of the anode is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, and more preferably 50 nm to 500 nm.
- a material for the cathode is preferably a material having a low work function, easy electron injection into the light emitting layer, and high electrical conductivity. Further, in the organic EL element configured to extract light from the anode side, a material having a high reflectivity with respect to visible light is preferable as the cathode material in order to reflect light emitted from the light emitting layer to the anode side by the cathode.
- a material having a high reflectivity with respect to visible light is preferable as the cathode material in order to reflect light emitted from the light emitting layer to the anode side by the cathode.
- an alkali metal, an alkaline earth metal, a transition metal, a Group 13 metal of the periodic table, or the like can be used.
- cathode materials include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, and ytterbium.
- An alloy, graphite, or a graphite intercalation compound is used.
- alloys include magnesium and silver alloys, magnesium and indium alloys, magnesium and aluminum alloys, indium and silver alloys, lithium and aluminum alloys, lithium and magnesium alloys, lithium and An alloy of indium, an alloy of calcium and aluminum, and the like can be given.
- a transparent conductive electrode made of a conductive metal oxide or a conductive organic material can be used as the cathode.
- the conductive metal oxide include indium oxide, zinc oxide, tin oxide, ITO, and IZO
- examples of the conductive organic substance include polyaniline or a derivative thereof, polythiophene or a derivative thereof, and the like.
- the cathode may be composed of a laminate in which two or more layers are laminated.
- the electron injection layer may be used as a cathode.
- the film thickness of the cathode is appropriately set in consideration of the required characteristics, the simplicity of the film forming process, and the like.
- the film thickness of the anode is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, and more preferably 50 nm to 500 nm.
- Examples of the method for producing the cathode include a vacuum deposition method, a sputtering method, and a lamination method in which a metal thin film is thermocompression bonded.
- the hole injection material constituting the hole injection layer examples include oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, phenylamine compounds, starburst type amine compounds, phthalocyanine compounds, amorphous carbon, polyaniline And polythiophene derivatives.
- the film thickness of the hole injection layer is appropriately set in consideration of the required characteristics and the simplicity of the film forming process.
- the thickness of the hole injection layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
- the hole transport material constituting the hole transport layer examples include polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene Derivative, triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylene vinylene) or derivative thereof, or poly (2,5-thienylene vinylene) ) Or a derivative thereof.
- the film thickness of the hole transport layer is set in consideration of the required characteristics and the simplicity of the film forming process.
- the thickness of the hole transport layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.
- the light emitting layer is usually formed of an organic substance that mainly emits fluorescence and / or phosphorescence, or an organic substance and a dopant that assists the organic substance.
- the dopant is added, for example, to improve luminous efficiency and change the emission wavelength.
- the organic substance which comprises a light emitting layer may be a low molecular compound or a high molecular compound, and when forming a light emitting layer by the apply
- the number average molecular weight in terms of polystyrene of the polymer compound constituting the light emitting layer is, for example, about 10 3 to 10 8 .
- the light emitting material constituting the light emitting layer include the following dye materials, metal complex materials, polymer materials, and dopant materials.
- dye material examples include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds, Examples thereof include a pyridine ring compound, a perinone derivative, a perylene derivative, an oligothiophene derivative, an oxadiazole dimer, a pyrazoline dimer, a quinacridone derivative, and a coumarin derivative.
- Metal complex materials examples include rare earth metals such as Tb, Eu, and Dy, or Al, Zn, Be, Ir, Pt, and the like as a central metal, and an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, and quinoline structure. And the like.
- metal complex materials include metal complexes that emit light from triplet excited states such as iridium complexes and platinum complexes, aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazolyl zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes. , Porphyrin zinc complex, phenanthroline europium complex, and the like.
- Polymer material examples include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, those obtained by polymerizing the above dye materials and metal complex materials, etc. Can be mentioned.
- the thickness of the light emitting layer is usually about 2 nm to 200 nm.
- electron transport material constituting the electron transport layer
- known materials can be used.
- electron transport materials include oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyl
- the film thickness of the electron transport layer is appropriately set in consideration of the required characteristics and the simplicity of the film forming process.
- the thickness of the electron transport layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
- ⁇ Electron injection layer> As a material constituting the electron injection layer, an optimum material is appropriately selected according to the type of the light emitting layer.
- the material for the electron injection layer include alkali metals, alkaline earth metals, alloys containing one or more of alkali metals and alkaline earth metals, oxides of alkali metals or alkaline earth metals, halides, carbonic acid A salt or a mixture of these substances can be used.
- alkali metals, alkali metal oxides, alkali metal halides, and alkali metal carbonates include lithium, sodium, potassium, rubidium, cesium, lithium oxide, lithium fluoride, sodium oxide, sodium fluoride, Examples include potassium oxide, potassium fluoride, rubidium oxide, rubidium fluoride, cesium oxide, cesium fluoride, and lithium carbonate.
- alkaline earth metals, alkaline earth metal oxides, alkaline earth metal halides, alkaline earth metal carbonates include magnesium, calcium, barium, strontium, magnesium oxide, magnesium fluoride, Examples thereof include calcium oxide, calcium fluoride, barium oxide, barium fluoride, strontium oxide, strontium fluoride, and magnesium carbonate.
- the electron injection layer may be composed of a laminate in which two or more layers are laminated. As an electron injection layer, the laminated body of a LiF film
- the thickness of the electron injection layer is preferably about 1 nm to 1 ⁇ m.
- the coating method When there are a plurality of organic EL layers that can be formed by the coating method among the organic EL layers, it is preferable to form all the organic EL layers by using the coating method. It is also possible to form at least one of a plurality of organic EL layers that can be applied by using a coating method and to form another organic EL layer by a method different from the coating method. Further, even when a plurality of organic EL layers are formed by a coating method, the plurality of organic EL layers may be formed by a coating method in which a specific method of the coating method is different. For example, in the present embodiment, the example in which the hole injection layer 13 and the light emitting layer 14 are formed by the nozzle coating method has been described.
- the hole injection layer 13 may be formed by spin coating, and the light emitting layer 14 may be formed by nozzle coating.
- the organic EL layer may be formed by a vacuum deposition method, a sputtering method, a laminating method, a spray coating method, or the like.
- a light-emitting device having substantially the same configuration as the light-emitting device schematically shown in FIGS. 1 and 2 was produced.
- the organic EL device produced in this example further includes an intermediate layer between the hole injection layer and the light emitting layer.
- a support substrate having an anode and an insulating film formed thereon was prepared.
- the support substrate is made of a glass plate
- the anode is made of an ITO thin film
- the insulating film is made of a SiO 2 film.
- the thickness of the anode and the insulating film is 200 nm.
- a rectangular opening is formed in the insulating film so that a part of the ITO thin film is exposed. The size of the opening is 200 ⁇ m in the row direction X and 70 ⁇ m in the column direction Y.
- a stripe-shaped partition wall member was formed.
- OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd.
- a photomask designed so that the width of the partition wall member in the column direction Y is 20 ⁇ m, and the distance (cycle) between the partition wall member and the partition wall member is 100 ⁇ m, and further, an alkali developer (NMD- 3: developed by Tokyo Ohka Co., Ltd.
- NMD- 3 developed by Tokyo Ohka Co., Ltd.
- a heat curing treatment was performed at 230 ° C. for 30 minutes to completely insolubilize the partition wall member.
- the volume of the recess defined by the partition wall member was 1.63 ⁇ 10 ⁇ 10 m 3 per unit length in the row direction X.
- the supporting substrate on which the anode, the insulating film, and the partition walls were formed was subjected to oxygen plasma treatment.
- oxygen plasma treatment was performed for 30 seconds under conditions of 5 Pa, 40 SCCM, and 30 W.
- a PEDOT film was formed as a hole injection layer.
- H. C. The ink was prepared by mixing CLEVIOS P VP CH8000 manufactured by Starck and pure water so that the volume ratio was 40:60.
- the surface tension of the ink was 70 mN / m and the viscosity was 6.3 cP.
- the contact angle of the ink with respect to the partition wall was 40 degrees.
- a hole injection layer was formed by heating at 200 ° C. for 20 minutes in an air atmosphere using a clean oven (DT610, manufactured by Yamato Chemical Co., Ltd.).
- an intermediate layer was formed.
- a polymer material as an intermediate layer is added at a concentration of 10 mg / mL to a solvent obtained by mixing 1: 1 grade (volume ratio) of special grade anisole and special grade phenylcyclohexane manufactured by Wako Pure Chemical Industries, Ltd.
- An ink for forming an intermediate layer was prepared by heating and stirring at 10 ° C. for 10 hours.
- the surface tension of the ink was 34 mN / m, and the viscosity of the ink was 4.5 cP.
- the contact angle of the ink with respect to the partition wall was 15 degrees. Apply the prepared ink to each recess using a nozzle printing device (NP-300G, manufactured by Dainippon Screen Mfg.
- a light emitting layer was formed.
- polymer blue light-emitting material, polymer green light-emitting material, and polymer red light-emitting material were respectively mixed in a solvent in which special grade anisole and special grade phenylcyclohexane manufactured by Wako Pure Chemical Industries, Ltd. were mixed at 1: 1 (volume ratio).
- the ink was added at a concentration of 20 mg / mL, and stirred at 50 ° C. for 10 hours to prepare an ink for forming a light emitting layer.
- the surface tensions of blue ink, green ink and red ink were all 34 mN / m, the viscosity of blue ink was 26 cP, the viscosity of green ink was 20 cP, and the viscosity of red ink was 24 cP.
- the contact angles of the blue ink, green ink, and red ink with respect to the partition walls were all 15 degrees.
- the red ink, blue ink, and green ink prepared above were supplied to the recess every two rows.
- a nozzle printing apparatus manufactured by Dainippon Screen Mfg. Co., Ltd., NP-300G was used for ink supply, and blue ink, green ink, and red ink were applied in this order.
- the blue ink application conditions were a flow rate of 26 ⁇ L / min and a nozzle scanning speed of 2.6 m / s.
- the conditions for applying the green ink were a flow rate of 30 ⁇ L / min and a nozzle scanning speed of 2.6 m / s.
- the conditions for applying the red ink were a flow rate of 36 ⁇ L / min and a nozzle scanning speed of 3.0 m / s. Thereafter, a light emitting layer was formed by heating at 130 ° C. for 15 minutes in a nitrogen atmosphere using a hot plate (manufactured by ASONE Co., Ltd., HP-1LA). Next, vapor deposition was performed so that the film thickness of Ba was 5 nm, and further, vapor deposition was performed so that the film thickness of Al was 100 nm, thereby forming a cathode.
- a plurality of the above-described light emitting devices were produced by changing supply amounts of red ink, green ink, and blue ink.
- the ink supply amount was adjusted by controlling the ink discharge amount per unit time and / or the nozzle scanning speed.
- FIG. 3 is a diagram showing the evaluation results.
- the horizontal axis represents the amount of ink supplied and represents the ratio of the volume of ink supplied to the volume of the recess.
- the vertical axis represents the evaluation result.
- the evaluation results are represented such that samples with the same degree of evaluation are shown at higher positions as the samples with higher evaluation are shown at higher positions.
- a sample on which the intended organic EL layer can be formed is represented by a symbol “ ⁇ ”, and the ink is not completely wetted and spread on the bottom surface of the concave portion, and a hole is partially formed in the organic EL layer. Is represented by the symbol “ ⁇ ”, and the ink does not overflow to the adjacent concave portion, but the sample in which the organic EL layer is formed on the partition is represented by the symbol “ ⁇ ”, and the ink straddles the partition.
- a sample overflowing to an adjacent concave portion is represented by a symbol “x”.
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Abstract
Description
図4Aに示されるように、まず有機EL層となる材料を含むインキを、支持基板11上で隣り合う隔壁1同士によって画成された領域である凹部2に供給する。供給されたインキは乾燥しつつ収縮する。
図4Bに示されるように、結果として、凹部2に有機EL層3が形成される(たとえば特許文献1参照。)。
図5および図6を参照して塗布法により形成された有機EL層の形状について説明する。図5および図6は、意図した形状とは異なる有機EL層が形成された表示装置を模式的に示す図である。
有機EL層3の膜厚は、当該有機EL層3の全てに亘って均一であることが好ましい。しかしながら、たとえば図5に示されるように隔壁1と有機EL層3との境界近傍の膜厚が極めて薄い有機EL層3が形成されることがある。このような有機EL層3が形成されると、有機EL層3の膜厚の極めて薄い部分の電気抵抗が極めて小さくなり、リーク電流が発生するという問題がある。
[1] 支持基板と、該支持基板上に設けられ、前記支持基板上に設定される凹部を画成する隔壁と、前記凹部に設けられ、第1の電極と、第2の電極と、第1の電極および第2の電極間に設けられる有機エレクトロルミネッセンス層とを含む複数の有機エレクトロルミネッセンス素子とを備える発光装置の製造方法であって、
前記第1の電極と前記隔壁とが設けられた前記支持基板を用意する工程と、
有機エレクトロルミネッセンス層となる材料を含むインキを、前記凹部の容積の90%以上120%以下の体積として、前記凹部に供給する工程と、
供給されたインキを固化することにより前記有機エレクトロルミネッセンス層を形成する工程と、
前記第2の電極を形成する工程と
を含む、発光装置の製造方法。
[2] 前記隔壁は、前記支持基板上において所定の行方向にそれぞれ延在する複数本の隔壁部材から構成され、
複数本の隔壁部材は、前記行方向とは方向が異なる列方向に所定の間隔をあけて配置されている、[1]記載の発光装置の製造方法。
[3] 前記インキの粘度が15cP以上30cP以下である、[1]または[2]記載の発光装置の製造方法。
[4] 前記インキの濃度が10mg/mL以上30mg/mL以下である、[1]~[3]のいずれか1つに記載の発光装置の製造方法。
[5] 前記隔壁と前記インキとの接触角が5度以上50度以下である、[1]~[4]のいずれか1つに記載の発光装置の製造方法。
[6] 前記支持基板を用意する工程の後、かつ前記インキを供給する工程の前に、酸素プラズマ処理を施す、[5]記載の発光装置の製造方法。
[7] 前記インキの表面張力が30mN/m以上72mN/m以下である、[1]~[6]のいずれか1つに記載の発光装置の製造方法。
[8] 前記インキは、沸点が190℃以上260℃以下の溶媒を含む、[1]~[7]のいずれか1つに記載の発光装置の製造方法。
[9] 前記インキを供給する工程では、液柱状にインキを流下する、[1]~[8]のいずれか1つに記載の発光装置の製造方法。
[10] 前記インキを供給する工程では、ノズルプリンティング法によってインキを供給する、[1]~[9]のいずれか1つに記載の発光装置の製造方法。
本発明の発光装置の製造方法は、支持基板と、該支持基板上に設けられ、前記支持基板上に設定される凹部を画成する隔壁と、凹部に設けられ、第1の電極と、第2の電極と、第1の電極および第2の電極間に設けられる有機EL層とを含む複数の有機EL素子とを備える発光装置の製造方法であって、前記第1の電極と前記隔壁とがその上に設けられた前記支持基板を用意する工程と、有機EL層となる材料を含むインキを、前記凹部の容積の90%以上120%以下の体積として、凹部に供給する工程と、供給されたインキを固化することにより前記有機EL層を形成する工程と、前記第2の電極を形成する工程とを含む。
まず図1および図2を参照して発光装置の構成について説明する。図1は本実施形態の発光装置を模式的に示す平面図である。図2は発光装置を模式的に示す断面図である。
発光装置21は主に支持基板11と、支持基板11上に設けられ、支持基板11上に設定される区画である凹部18を画成する隔壁17と、凹部18に設けられた複数の有機EL素子22(22R、22G、22B)とを備え、該有機EL素子22が、第1の電極12と、第2の電極16と、第1の電極12および第2の電極16間に設けられる有機EL層である正孔注入層13と発光層14(14R、14G、14B)とを含んで構成される。
本実施形態では支持基板11にストライプ状の隔壁17が設けられる形態の発光装置について説明する。すなわち本実施形態では隔壁17は、支持基板11上において所定の行方向Xに、それぞれ略平行に延在する複数本の隔壁部材20から構成されている。複数本の隔壁部材20は、行方向Xとは方向が異なる列方向Yに所定の間隔をあけて配置されている。なお本実施形態おける行方向Xおよび列方向Yは、互いに直交する方向であって、かつ行方向Xおよび列方向Yが支持基板11の厚み方向Zに直交する方向である。支持基板11上には複数本の隔壁部材20同士の間隙に対応する複数本の凹部18が設定される。
絶縁膜15の開口15aは、支持基板の厚み方向の一方から見て(以下、「平面視で」ということがある。)有機EL素子22と重なる位置に形成される。絶縁膜15の開口15aは平面視で、後述する第1の電極12とほぼ一致するように形成され、たとえば略矩形、小判形、略円形および略楕円形などに形成される。格子状の絶縁膜15は平面視で、第1の電極12の一部を露出させるように形成され、絶縁膜15の一部が第1の電極12の周縁を覆うように形成されている。また前述した複数本の隔壁部材20は、絶縁膜15の複数本の帯状の部分上に設けられる。
(II)緑色の光を放つ複数の有機EL素子22Gが行方向Xに所定の間隔をあけて配置される行
(III)青色の光を放つ複数の有機EL素子22Bが行方向Xに所定の間隔をあけて配置される行
(ii)緑色の光を放つ発光層14Gが設けられる行
(iii)青色の光を放つ発光層14Bが設けられる行
次に発光装置の製造方法について説明する。
本工程では第1の電極12と隔壁17とがその上に設けられた支持基板11を用意する。アクティブマトリクス駆動型の表示装置の場合、複数の有機EL素子22を個別に駆動するための回路が予め形成された基板を支持基板11として用いることができる。たとえばTFT(Thin Film Transistor)およびキャパシタなどが予め形成された基板を支持基板11として用いることができる。なお第1の電極12と隔壁17とを以下のように本工程で形成することによって、第1の電極12と隔壁17とが設けられた基板を支持基板11として用意してもよい。また第1の電極12と隔壁17とが予め設けられた基板を市場から入手することにより支持基板11として用意してもよい。
本実施形態では、格子状の絶縁膜15と隔壁17とを一体の構成として説明する場合がある。以下の説明において、「隔壁17によって画成される凹部18」は、絶縁膜15および隔壁17、並びに支持基板11または隣り合う隔壁17同士の間の露出面(底面)により画成された(囲まれた)領域をいう場合がある。
本工程ではまず有機EL層となる材料を含むインキを、隔壁17によって画成される凹部18に供給する。本実施形態では有機EL層に相当する正孔注入層13となる材料を含むインキを、隔壁17によって画成される凹部18に供給する。
(1)ノズルを行方向Xの一端から他端に移動する工程
(2)支持基板11を列方向Yの一方に1行分だけ移動する工程
(3)ノズルを行方向Xの他端から一端に移動する工程
(4)支持基板を列方向Yの一方に1行分だけ移動する工程
インキの供給量は、前記凹部18の容積の90%以上118%以下の体積に相当する量とすることがさらに好ましい。
次に発光層14を形成する。前述したようにカラー表示装置を作製する場合、3種類の有機EL素子22を作製する必要がある。そのため発光層の材料を行ごとに塗りわける必要がある。たとえば3種類の発光層14(14R、14G、14B)を行ごとに形成する場合、赤色の光を放つ材料を含む赤インキ、緑色の光を放つ材料を含む緑インキ、青色の光を放つ材料を含む青インキを、それぞれ列方向Yに2行の間隔をあけて塗布する必要がある。これら赤インキ、緑インキ、青インキを所定の行に順次塗布することによって、3種類の発光層14を塗布成膜することができる。赤インキ、緑インキ、青インキを所定の行に順次塗布する方法としては、隔壁部材20同士の間である凹部18にインキを選択的に供給することが可能な塗布法であればどのような方法でもよい。このような方法としては、インキを断続的に滴下する方法、液柱状にインキを流下する方法、および印刷版に付着させたインキを印刷する方法などがあるが、上述したように本実施形態では液柱状にインキを流下する方法が好ましい。たとえば液柱状にインキを流下する方法の1つであるノズルプリンティング法によって、前述した正孔注入層を形成する方法と同様にしてインキを塗布することができる。
(1)ノズルを凹部18の一端から他端に亘って行方向Xに移動する工程
(2)支持基板11を列方向Yの一方に3行分だけ移動する工程
(3)ノズルを凹部18の他端から一端に亘って行方向Xに移動する工程
(4)支持基板を列方向Yの一方に3行分だけ移動する工程
次に第2の電極16を形成する。前述したように本実施形態では第2の電極16を支持基板11上の全面に形成する。これによって複数の有機EL素子22を支持基板11上に形成することができる。
インキの濃度が低い場合、所定の膜厚の有機EL層を得るためにはインキの供給量を多くする必要があるが、そのためには隔壁17の高さを高くする必要がある。そのため、隔壁17によって画成される凹部18の容積の90%以上120%以下の体積のインキを供給すると、隔壁17の表面とインキとが接触する面積が大きくなる。インキはその溶媒が気化することによって収縮しつつ薄膜化するが、その際に、隔壁17の表面を伝いつつ収縮するので、インキと隔壁17の表面とが接触する面積が大きい場合、隔壁17の表面の性状の影響を大きく受け、結果として均一な膜厚の有機EL層を得ることができないことがある。これに対して、濃度が10mg/mL以上30mg/mL以下のインキを使用した場合には、適度な高さの隔壁17を使用することができる。そのためインキと隔壁17とが接触する面積を比較的小さくすることができ、薄膜化する際の、隔壁17の表面の性状の影響を小さくし、結果として均一な膜厚の有機EL層を得ることができる。
インキの溶媒としては、たとえばクロロホルム(沸点61℃)、塩化メチレン(沸点40℃)、1,1-ジクロロエタン(沸点57℃)、1,2-ジクロロエタン(沸点83℃)、1,1,1-トリクロロエタン(沸点74℃)、1,1,2-トリクロロエタン(沸点113℃)等の脂肪族塩素溶媒、クロロベンゼン(沸点132℃)、o-ジクロロベンゼン(沸点180℃)、m-ジクロロベンゼン(沸点173℃)、p-ジクロロベンゼン(沸点174℃)等の芳香族塩素溶媒、テトラヒドロフラン(沸点66℃)、1,4-ジオキサン(沸点101℃)等の脂肪族エーテル溶媒、アニソール(沸点154℃)、エトキシベンゼン(沸点170℃)等の芳香族エーテル溶媒、トルエン(沸点111℃)、o-キシレン(沸点144℃)、m-キシレン(沸点139℃)、p-キシレン(沸点138℃)、エチルベンゼン(沸点136℃)、p-ジエチルベンゼン(沸点184℃)、メシチレン(沸点211℃)、n-プロピルベンゼン(沸点159℃)、イソプロピルベンゼン(沸点152℃)、n-ブチルベンゼン(沸点183℃)、イソブチルベンゼン(沸点173℃)、sec-ブチルベンゼン(沸点173℃)、テトラリン(沸点208℃)、シクロヘキシルベンゼン(沸点235℃:737mmHgで測定)等の芳香族炭化水素溶媒、シクロヘキサン(沸点81℃)、メチルシクロヘキサン(沸点101℃)、n-ペンタン(沸点36℃)、n-ヘキサン(沸点69℃)、n-へプタン(沸点98℃)、n-オクタン(沸点126℃)、n-ノナン(沸点151℃)、n-デカン(沸点174℃)、デカリン(cis体は沸点196℃、trans体は沸点187℃)、ビシクロヘキシル(沸点217℃~233℃)等の脂肪族炭化水素溶媒、アセトン(沸点56℃)、メチルエチルケトン(沸点80℃)、メチルイソブチルケトン(沸点117℃)、シクロヘキサノン(沸点156℃)、2-ヘプタノン(沸点150℃)、3-ヘプタノン(沸点147℃:765mmHgで測定)、4-ヘプタノン(沸点144℃)、2-オクタノン(沸点174℃)、2-ノナノン(沸点195℃)、2-デカノン(沸点209℃)等の脂肪族ケトン溶媒、アセトフェノン(沸点202℃)等の芳香族ケトン溶媒、酢酸エチル(沸点77℃)、酢酸ブチル(沸点120℃~125℃)等の脂肪族エステル溶媒、安息香酸メチル(沸点200℃)、安息香酸ブチル(沸点213℃)、酢酸フェニル(沸点196℃)等の芳香族エステル溶媒、エチレングリコール(沸点198℃)、エチレングリコールモノブチルエーテル(沸点171℃)、エチレングリコールモノエチルエーテル(沸点135℃)、エチレングリコールモノメチルエーテル(沸点125℃)、1,2-ジメトキシエタン(沸点85℃)、プロピレングリコール(沸点188℃)、1,2-ジエトキシメタン(沸点124℃)、トリエチレングリコールジエチルエーテル(沸点222℃)、2,5-ヘキサンジオール(沸点218℃)等の脂肪族多価アルコール溶媒及び脂肪族多価アルコールの誘導体からなる溶媒、メタノール(沸点65℃)、エタノール(沸点78℃)、プロパノール(沸点97℃)、イソプロパノール(沸点82℃)、シクロヘキサノール(沸点161℃)等の脂肪族アルコール溶媒、ジメチルスルホキシド(沸点37℃)等の脂肪族スルホキシド溶媒、N-メチル-2-ピロリドン(沸点202℃)、N,N-ジメチルホルムアミド(沸点153℃)等の脂肪族アミド溶媒があげられる。
前述したように有機EL素子22は種々の層構成をとりうるが、以下では有機EL素子22の層構造、各層の構成、および各層の形成方法についてさらに詳しく説明する。
a)陽極/発光層/陰極
b)陽極/正孔注入層/発光層/陰極
c)陽極/正孔注入層/発光層/電子注入層/陰極
d)陽極/正孔注入層/発光層/電子輸送層/陰極
e)陽極/正孔注入層/発光層/電子輸送層/電子注入層/陰極
f)陽極/正孔輸送層/発光層/陰極
g)陽極/正孔輸送層/発光層/電子注入層/陰極
h)陽極/正孔輸送層/発光層/電子輸送層/陰極
i)陽極/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
j)陽極/正孔注入層/正孔輸送層/発光層/陰極
k)陽極/正孔注入層/正孔輸送層/発光層/電子注入層/陰極
l)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/陰極
m)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
n)陽極/発光層/電子注入層/陰極
o)陽極/発光層/電子輸送層/陰極
p)陽極/発光層/電子輸送層/電子注入層/陰極
ここで、記号「/」は、記号「/」を挟む各層が隣接して積層されていることを示す。
以下同じ。
q)陽極/(構造単位A)/電荷発生層/(構造単位A)/陰極
また「(構造単位A)/電荷発生層」を「構造単位B」とすると、3層以上の発光層を有する有機EL素子の構成として、下記r)に示す層構成を挙げることができる。
r)陽極/(構造単位B)x/(構造単位A)/陰極
なお記号「x」は、2以上の整数を表し、(構造単位B)xは、構造単位Bがx段積層された積層体を表す。また複数ある(構造単位B)の層構成は同じでも、異なっていてもよい。
発光層から放たれる光が陽極を通って有機EL素子外に出射する構成の場合、陽極には光透過性を示す電極が用いられる。光透過性を示す電極としては、金属酸化物、金属硫化物および金属などの薄膜を用いることができる。光透過性を示す電極としては、電気伝導度および光透過率の高いものが好適に用いられる。光透過性を示す電極としては、具体的には酸化インジウム、酸化亜鉛、酸化スズ、ITO、インジウム亜鉛酸化物(Indium Zinc Oxide:略称IZO)、金、白金、銀、および銅などから成る薄膜が用いられる。これらの中でもITO、IZO、または酸化スズから成る薄膜が好適に用いられる。
陽極の作製方法の例としては、真空蒸着法、スパッタリング法、イオンプレーティング法、メッキ法などを挙げることができる。また陽極として、ポリアニリンもしくはその誘導体、ポリチオフェンもしくはその誘導体などの有機の透明導電膜を用いてもよい。
陰極の材料としては、仕事関数が小さく、発光層への電子注入が容易で、電気伝導度の高い材料が好ましい。また陽極側から光を取出す構成の有機EL素子では、発光層から放たれる光を陰極で陽極側に反射するために、陰極の材料としては可視光に対する反射率の高い材料が好ましい。陰極には、たとえばアルカリ金属、アルカリ土類金属、遷移金属および周期表の第13族金属などを用いることができる。陰極の材料としては、たとえばリチウム、ナトリウム、カリウム、ルビジウム、セシウム、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、アルミニウム、スカンジウム、バナジウム、亜鉛、イットリウム、インジウム、セリウム、サマリウム、ユーロピウム、テルビウム、イッテルビウムなどの金属、前記金属のうちの2種以上の合金、前記金属のうちの1種以上と、金、銀、白金、銅、マンガン、チタン、コバルト、ニッケル、タングステン、錫のうちの1種以上との合金、またはグラファイト若しくはグラファイト層間化合物などが用いられる。合金の例としては、マグネシウムと銀との合金、マグネシウムとインジウムとの合金、マグネシウムとアルミニウムとの合金、インジウムと銀との合金、リチウムとアルミニウムとの合金、リチウムとマグネシウムとの合金、リチウムとインジウムとの合金、カルシウムとアルミニウムとの合金などを挙げることができる。また陰極としては導電性金属酸化物および導電性有機物などから成る透明導電性電極を用いることができる。具体的には、導電性金属酸化物として酸化インジウム、酸化亜鉛、酸化スズ、ITO、およびIZOを挙げることができ、導電性有機物としてポリアニリンもしくはその誘導体、ポリチオフェンもしくはその誘導体などを挙げることができる。なお陰極は、2層以上を積層した積層体で構成されていてもよい。なお電子注入層が陰極として用いられることもある。
正孔注入層を構成する正孔注入材料の例としては、酸化バナジウム、酸化モリブデン、酸化ルテニウム、および酸化アルミニウムなどの酸化物、フェニルアミン化合物、スターバースト型アミン化合物、フタロシアニン化合物、アモルファスカーボン、ポリアニリン、およびポリチオフェン誘導体などを挙げることができる。
正孔輸送層を構成する正孔輸送材料の例としては、ポリビニルカルバゾール若しくはその誘導体、ポリシラン若しくはその誘導体、側鎖若しくは主鎖に芳香族アミンを有するポリシロキサン誘導体、ピラゾリン誘導体、アリールアミン誘導体、スチルベン誘導体、トリフェニルジアミン誘導体、ポリアニリン若しくはその誘導体、ポリチオフェン若しくはその誘導体、ポリアリールアミン若しくはその誘導体、ポリピロール若しくはその誘導体、ポリ(p-フェニレンビニレン)若しくはその誘導体、又はポリ(2,5-チエニレンビニレン)若しくはその誘導体などを挙げることができる。
発光層は、通常、主として蛍光及び/又はりん光を発光する有機物、または該有機物とこれを補助するドーパントとから形成される。ドーパントは、たとえば発光効率の向上、発光波長を変化させるために加えられる。なお発光層を構成する有機物は、低分子化合物でも高分子化合物でもよく、塗布法によって発光層を形成する場合には、発光層は高分子化合物を含むことが好ましい。発光層を構成する高分子化合物のポリスチレン換算の数平均分子量はたとえば103~108程度である。発光層を構成する発光材料としては、たとえば以下の色素系材料、金属錯体系材料、高分子系材料、ドーパント材料を挙げることができる。
色素材料としては、たとえば、シクロペンダミン誘導体、テトラフェニルブタジエン誘導体化合物、トリフェニルアミン誘導体、オキサジアゾール誘導体、ピラゾロキノリン誘導体、ジスチリルベンゼン誘導体、ジスチリルアリーレン誘導体、ピロール誘導体、チオフェン環化合物、ピリジン環化合物、ペリノン誘導体、ペリレン誘導体、オリゴチオフェン誘導体、オキサジアゾールダイマー、ピラゾリンダイマー、キナクリドン誘導体、クマリン誘導体などを挙げることができる。
金属錯体材料としては、たとえばTb、Eu、Dyなどの希土類金属、またはAl、Zn、Be、Ir、Ptなどを中心金属に有し、オキサジアゾール、チアジアゾール、フェニルピリジン、フェニルベンゾイミダゾール、キノリン構造などを配位子に有する金属錯体を挙げることができる。金属錯体材料としては、たとえばイリジウム錯体、白金錯体などの三重項励起状態からの発光を有する金属錯体、アルミニウムキノリノール錯体、ベンゾキノリノールベリリウム錯体、ベンゾオキサゾリル亜鉛錯体、ベンゾチアゾール亜鉛錯体、アゾメチル亜鉛錯体、ポルフィリン亜鉛錯体、フェナントロリンユーロピウム錯体などを挙げることができる。
高分子材料の例としては、ポリパラフェニレンビニレン誘導体、ポリチオフェン誘導体、ポリパラフェニレン誘導体、ポリシラン誘導体、ポリアセチレン誘導体、ポリフルオレン誘導体、ポリビニルカルバゾール誘導体、上記色素材料、金属錯体材料を高分子化したものなどを挙げることができる。
電子輸送層を構成する電子輸送材料としては、公知のものを使用できる。電子輸送材料の例としては、オキサジアゾール誘導体、アントラキノジメタン若しくはその誘導体、ベンゾキノン若しくはその誘導体、ナフトキノン若しくはその誘導体、アントラキノン若しくはその誘導体、テトラシアノアントラキノジメタン若しくはその誘導体、フルオレノン誘導体、ジフェニルジシアノエチレン若しくはその誘導体、ジフェノキノン誘導体、又は8-ヒドロキシキノリン若しくはその誘導体の金属錯体、ポリキノリン若しくはその誘導体、ポリキノキサリン若しくはその誘導体、ポリフルオレン若しくはその誘導体などを挙げることができる。
電子注入層を構成する材料としては、発光層の種類に応じて最適な材料が適宜選択される。電子注入層の材料の例としては、アルカリ金属、アルカリ土類金属、アルカリ金属およびアルカリ土類金属のうちの1種類以上を含む合金、アルカリ金属若しくはアルカリ土類金属の酸化物、ハロゲン化物、炭酸塩、またはこれらの物質の混合物などを挙げることができる。アルカリ金属、アルカリ金属の酸化物、アルカリ金属のハロゲン化物、およびアルカリ金属の炭酸塩の例としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、酸化リチウム、フッ化リチウム、酸化ナトリウム、フッ化ナトリウム、酸化カリウム、フッ化カリウム、酸化ルビジウム、フッ化ルビジウム、酸化セシウム、フッ化セシウム、炭酸リチウムなどを挙げることができる。また、アルカリ土類金属、アルカリ土類金属の酸化物、アルカリ土類金属のハロゲン化物、アルカリ土類金属の炭酸塩の例としては、マグネシウム、カルシウム、バリウム、ストロンチウム、酸化マグネシウム、フッ化マグネシウム、酸化カルシウム、フッ化カルシウム、酸化バリウム、フッ化バリウム、酸化ストロンチウム、フッ化ストロンチウム、炭酸マグネシウムなどを挙げることができる。電子注入層は、2層以上を積層した積層体で構成されてもよい。電子注入層としては、たとえばLiF膜とCa膜との積層体などを挙げることができる。
次にBaの膜厚が5nmとなるように蒸着し、さらにAlの膜厚が100nmとなるよう蒸着して、陰極を形成した。
図3は、評価結果を示す図である。横軸は、インキの供給量であって、凹部の容積に対する供給されたインキの体積の割合を表している。縦軸は評価結果を表している。評価結果は、評価の高いサンプルほど高い位置に示されるように、同程度の評価結果のサンプルが同程度の高さの位置に示されるように表している。図3中、意図した有機EL層が成膜できたサンプルを記号「○」で表し、インキが凹部の底面で完全には濡れ拡がらず、部分的に有機EL層に穴が形成されたサンプルを記号「□」で表し、インキが隣り合う凹部にまで溢れ出るまでには至らないが、隔壁上にまで有機EL層が形成されたサンプルを記号「△」で表し、インキが隔壁をまたいで隣り合う凹部にまで溢れ出したサンプルを記号「×」で表している。
2、18 凹部
3 有機EL層
11 支持基板
12 第1の電極(陽極)
13 正孔注入層
14 発光層
15 絶縁膜
15a 開口
16 第2の電極(陰極)
20 隔壁部材
21 発光装置
22 有機EL素子
Claims (10)
- 支持基板と、該支持基板上に設けられ、前記支持基板上に設定される凹部を画成する隔壁と、前記凹部に設けられ、第1の電極と、第2の電極と、第1の電極および第2の電極間に設けられる有機エレクトロルミネッセンス層とを含む複数の有機エレクトロルミネッセンス素子とを備える発光装置の製造方法であって、
前記第1の電極と前記隔壁とが設けられた前記支持基板を用意する工程と、
有機エレクトロルミネッセンス層となる材料を含むインキを、前記凹部の容積の90%以上120%以下の体積として、前記凹部に供給する工程と、
供給されたインキを固化することにより前記有機エレクトロルミネッセンス層を形成する工程と、
前記第2の電極を形成する工程と
を含む、発光装置の製造方法。 - 前記隔壁は、前記支持基板上において所定の行方向にそれぞれ延在する複数本の隔壁部材から構成され、
複数本の隔壁部材は、前記行方向とは方向が異なる列方向に所定の間隔をあけて配置されている、請求項1記載の発光装置の製造方法。 - 前記インキの粘度が15cP以上30cP以下である、請求項1記載の発光装置の製造方法。
- 前記インキの濃度が10mg/mL以上30mg/mL以下である、請求項1記載の発光装置の製造方法。
- 前記隔壁と前記インキとの接触角が5度以上50度以下である、請求項1記載の発光装置の製造方法。
- 前記支持基板を用意する工程の後、かつ前記インキを供給する工程の前に、酸素プラズマ処理を施す、請求項5記載の発光装置の製造方法。
- 前記インキの表面張力が30mN/m以上72mN/m以下である、請求項1記載の発光装置の製造方法。
- 前記インキは、沸点が190℃以上260℃以下の溶媒を含む、請求項1記載の発光装置の製造方法。
- 前記インキを供給する工程では、液柱状にインキを流下する、請求項1記載の発光装置の製造方法。
- 前記インキを供給する工程では、ノズルプリンティング法によってインキを供給する、請求項1記載の発光装置の製造方法。
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EP11759459A EP2555591A1 (en) | 2010-03-26 | 2011-03-23 | Method for manufacturing light-emitting device |
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KR101941178B1 (ko) | 2012-09-28 | 2019-01-23 | 삼성디스플레이 주식회사 | 유기 발광 표시 장치 및 유기 발광 표시 장치의 제조 방법 |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000323276A (ja) * | 1999-05-14 | 2000-11-24 | Seiko Epson Corp | 有機el素子の製造方法、有機el素子およびインク組成物 |
JP2002075640A (ja) | 2000-08-30 | 2002-03-15 | Dainippon Screen Mfg Co Ltd | 有機el表示装置の製造方法およびその製造装置 |
JP2006175307A (ja) * | 2004-12-21 | 2006-07-06 | Seiko Epson Corp | 成膜方法、色要素膜付き基板、電気光学装置、および電子機器 |
JP2007242272A (ja) * | 2006-03-06 | 2007-09-20 | Dainippon Printing Co Ltd | エレクトロルミネッセント素子の製造方法 |
JP2008192311A (ja) * | 2005-05-16 | 2008-08-21 | Sharp Corp | 有機エレクトロルミネッセンス素子の製造方法 |
JP2009164236A (ja) * | 2007-12-28 | 2009-07-23 | Casio Comput Co Ltd | 表示装置及びその製造方法 |
JP2009267299A (ja) * | 2008-04-30 | 2009-11-12 | Nippon Hoso Kyokai <Nhk> | インク組成物、有機el素子の作製方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4627617B2 (ja) * | 2003-05-23 | 2011-02-09 | 東洋インキ製造株式会社 | 着色組成物、カラーフィルタの製造方法およびブラックマトリックス基板の製造方法 |
US20060022174A1 (en) * | 2004-07-27 | 2006-02-02 | General Electric Company | Electroactive chemical composition and method of coating |
JP4984433B2 (ja) * | 2005-05-16 | 2012-07-25 | 大日本印刷株式会社 | 発光層の形成方法およびそれを用いた有機発光デバイスの製造方法 |
US20090064885A1 (en) * | 2007-09-11 | 2009-03-12 | Toppan Printing Co., Ltd. | Printed material and manufacturing method thereof |
JP4497185B2 (ja) * | 2007-09-18 | 2010-07-07 | カシオ計算機株式会社 | 表示装置の製造方法 |
US8349392B2 (en) * | 2007-10-09 | 2013-01-08 | Toppan Printing Co., Ltd. | Printed material and manufacturing method thereof |
EP2216380A1 (en) * | 2007-11-16 | 2010-08-11 | Sumitomo Chemical Company, Limited | Coating liquid used in coating method for discharging coating liquid through slit-shaped discharge outlet |
JP2010067543A (ja) * | 2008-09-12 | 2010-03-25 | Sumitomo Chemical Co Ltd | 印刷用のインキ |
WO2010092931A1 (ja) * | 2009-02-16 | 2010-08-19 | 凸版印刷株式会社 | 有機エレクトロルミネッセンスディスプレイ及びその製造方法 |
-
2010
- 2010-03-26 JP JP2010071816A patent/JP2011204524A/ja active Pending
-
2011
- 2011-03-23 WO PCT/JP2011/057033 patent/WO2011118654A1/ja active Application Filing
- 2011-03-23 KR KR1020127025039A patent/KR20130018249A/ko not_active Application Discontinuation
- 2011-03-23 US US13/636,929 patent/US20130059405A1/en not_active Abandoned
- 2011-03-23 EP EP11759459A patent/EP2555591A1/en not_active Withdrawn
- 2011-03-23 CN CN2011800154818A patent/CN102845133A/zh active Pending
- 2011-03-25 TW TW100110276A patent/TW201214835A/zh unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000323276A (ja) * | 1999-05-14 | 2000-11-24 | Seiko Epson Corp | 有機el素子の製造方法、有機el素子およびインク組成物 |
JP2002075640A (ja) | 2000-08-30 | 2002-03-15 | Dainippon Screen Mfg Co Ltd | 有機el表示装置の製造方法およびその製造装置 |
JP2006175307A (ja) * | 2004-12-21 | 2006-07-06 | Seiko Epson Corp | 成膜方法、色要素膜付き基板、電気光学装置、および電子機器 |
JP2008192311A (ja) * | 2005-05-16 | 2008-08-21 | Sharp Corp | 有機エレクトロルミネッセンス素子の製造方法 |
JP2007242272A (ja) * | 2006-03-06 | 2007-09-20 | Dainippon Printing Co Ltd | エレクトロルミネッセント素子の製造方法 |
JP2009164236A (ja) * | 2007-12-28 | 2009-07-23 | Casio Comput Co Ltd | 表示装置及びその製造方法 |
JP2009267299A (ja) * | 2008-04-30 | 2009-11-12 | Nippon Hoso Kyokai <Nhk> | インク組成物、有機el素子の作製方法 |
Non-Patent Citations (3)
Title |
---|
"DT610", YAMATO SCIENTIFIC CO., LTD. |
"First, 'CLEVIOS 'P VP CH8000", H. C. STARCK LTD. |
"NP-30OG", DAINIPPON SCREEN MFG. CO., LTD. |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021077783A (ja) * | 2019-11-11 | 2021-05-20 | 株式会社Joled | 機能層形成用インクおよび自発光素子の製造方法 |
JP7523213B2 (ja) | 2019-11-11 | 2024-07-26 | JDI Design and Development 合同会社 | 機能層形成用インクおよび自発光素子の製造方法 |
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