JP2018147883A - Method for manufacturing organic el device and depositing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an organic EL device having a thin film sealing structure with improved mass productivity and moisture resistance reliability, and a depositing device used in the manufacturing method.SOLUTION: A method for manufacturing an organic EL device includes a step of preparing a substrate and an element substrate including a plurality of organic EL devices arranged on the substrate, and a step of forming a thin film sealing structure on the element substrate. The step of forming the thin film sealing structure further includes the steps of: forming a first inorganic barrier layer on the element substrate; condensing a photocurable resin on the first inorganic barrier layer; forming a photocurable resin layer by irradiating a plurality of regions in which the photocurable resin is selected with a laser beam and curing at least a part of the photocurable resin; removing an uncured portion of the photocurable resin; and forming a second inorganic barrier layer covering the photocurable resin layer on the first inorganic barrier layer.SELECTED DRAWING: Figure 1A

Description

  The present invention relates to an organic EL device, in particular, a method for manufacturing a flexible organic EL device and a film forming apparatus. Typical examples of the organic EL device are an organic EL display device and an organic EL lighting device.

  Organic EL (Electro Luminescence) display devices have been put into practical use. One of the characteristics of the organic EL display device is that a flexible display device can be obtained. The organic EL display device has at least one organic EL element (Organic Light Emitting Diode: OLED) for each pixel and at least one TFT (Thin Film Transistor) that controls a current supplied to each OLED. Hereinafter, the organic EL display device is referred to as an OLED display device. An OLED display device having a switching element such as a TFT for each OLED is called an active matrix OLED display device. A substrate on which TFTs and OLEDs are formed is referred to as an element substrate.

OLEDs (especially organic light-emitting layers and cathode electrode materials) are easily deteriorated by the influence of moisture, and display unevenness is likely to occur. As a technique for protecting the OLED from moisture and providing a sealing structure that does not impair flexibility, a thin film encapsulation (TFE) technique has been developed. In the thin film sealing technique, an inorganic barrier layer and an organic barrier layer are alternately laminated to obtain a sufficient water vapor barrier property with a thin film. From the viewpoint of moisture resistance reliability of the OLED display device, the WVTR (Water Vapor Transmission Rate: WVTR) of the thin film sealing structure is typically required to be 1 × 10 ⁻⁴ g / m ² / day or less.

  A thin film sealing structure used in an OLED display device currently on the market has an organic barrier layer (polymer barrier layer) having a thickness of about 5 μm to about 20 μm. Thus, the relatively thick organic barrier layer also plays a role of flattening the surface of the element substrate. However, when the organic barrier layer is thick, there is a problem that the flexibility of the OLED display device is limited.

  There is also a problem that mass productivity is low. The relatively thick organic barrier layer described above is formed using a printing technique such as an ink jet method or a micro jet method. On the other hand, the inorganic barrier layer is formed in a vacuum (for example, 1 Pa or less) atmosphere using a thin film deposition technique. The formation of the organic barrier layer using the printing technology is performed in the air or in a nitrogen atmosphere, and the formation of the inorganic barrier layer is performed in a vacuum. Therefore, in the process of forming the thin film sealing structure, the element substrate is removed from the vacuum chamber. The mass productivity is low because it is taken in and out.

  Accordingly, for example, as disclosed in Patent Document 1, a film forming apparatus capable of continuously manufacturing an inorganic barrier layer and an organic barrier layer has been developed.

  In Patent Document 2, when the first inorganic material layer, the first resin material, and the second inorganic material layer are formed in this order from the element substrate side, the first resin material is the first resin material. A thin film sealing structure is disclosed that is unevenly distributed around the convex portion of the inorganic material layer (the first inorganic material layer covering the convex portion). According to Patent Document 2, by allowing the first resin material to be unevenly distributed around the convex portion that may not be sufficiently covered with the first inorganic material layer, intrusion of moisture and oxygen from that portion is suppressed. In addition, since the first resin material functions as a base layer for the second inorganic material layer, the second inorganic material layer is appropriately formed, and the side surface of the first inorganic material layer is formed to have an intended film thickness. It becomes possible to coat appropriately. The first resin material is formed as follows. The heated and vaporized mist-like organic material is supplied onto an element substrate maintained at a temperature of room temperature or lower, and the organic material is condensed on the substrate to form droplets. The droplet-like organic material moves on the substrate due to capillary action or surface tension, and is unevenly distributed on the boundary portion between the side surface of the convex portion of the first inorganic material layer and the substrate surface. Thereafter, the first resin material is formed at the boundary by curing the organic material. Patent Document 3 also discloses an OLED display device having a similar thin-film sealing structure.

  Patent Document 4 discloses a film forming apparatus used for manufacturing an OLED display device.

JP 2013-186971 A International Publication No. 2014/196137 JP-A-2006-39120 JP2013-64187A

  Since the thin film sealing structure described in Patent Document 2 or 3 does not have a thick organic barrier layer, it is considered that the flexibility of the OLED display device is improved. In addition, since the inorganic barrier layer and the organic barrier layer can be continuously formed, mass productivity is also improved.

  However, according to the study of the present inventor, when the organic barrier layer is formed by the method described in Patent Document 2 or 3, there is a problem that sufficient moisture resistance reliability cannot be obtained.

  When an organic barrier layer is formed using a printing method such as an inkjet method, the organic barrier layer is formed only in an active region (also referred to as an “element formation region” or a “display region”) on an element substrate. It can be prevented from being formed in a region other than the active region. Therefore, in the periphery (outside) of the active region, there is a region where the first inorganic material layer and the second inorganic material layer are in direct contact, and the organic barrier layer includes the first inorganic material layer and the second inorganic material layer. Is completely surrounded and isolated from the surroundings.

  On the other hand, in the method for forming an organic barrier layer described in Patent Document 2 or 3, a resin (organic material) is supplied to the entire surface of the element substrate, and the surface tension of the liquid resin is utilized to utilize the surface tension of the liquid resin. Resin is unevenly distributed at the boundary between the side surface of the convex portion and the substrate surface. Therefore, the region outside the active region (also referred to as “peripheral region”), that is, the terminal region where a plurality of terminals are arranged, and the lead wiring region where the lead wiring from the active region to the terminal region is formed are also provided. An organic barrier layer may be formed. Specifically, for example, the ultraviolet curable resin is unevenly distributed at the boundary portion between the side surfaces of the lead wires and terminals and the substrate surface. If it does so, the edge part of the part of the organic barrier layer formed along the extraction | drawer wiring is not surrounded by the 1st inorganic barrier layer and the 2nd inorganic barrier layer, but is exposed to air | atmosphere (ambient atmosphere).

  Since the organic barrier layer has a lower water vapor barrier property than the inorganic barrier layer, the organic barrier layer formed along the lead-out wiring serves as a path for guiding water vapor in the atmosphere into the active region.

  The present invention provides an organic EL device manufacturing method and a film forming apparatus that can solve the above-described problems.

  In an exemplary embodiment, a method for manufacturing an organic EL device according to the present disclosure includes a substrate having an active region and a peripheral region located outside the active region, an electric circuit supported by the substrate, and the active region. A plurality of organic EL elements formed thereon and an electric circuit including a backplane circuit for driving the plurality of organic EL elements, the backplane circuit including a plurality of drawers each including a terminal on the peripheral region A step of preparing an element substrate having wiring, and a step of forming a thin film sealing structure on the plurality of organic EL elements in the element substrate and on the active region side portion of the plurality of lead-out wirings. Including. The step of forming the thin film sealing structure includes a step of forming a first inorganic barrier layer on the element substrate, a step of condensing a liquid photocurable resin on the first inorganic barrier layer, and a wavelength of 400 nm or less. Irradiating a selected region of the photo-curable resin with a laser beam, and curing at least a part of the photo-curable resin to form a photo-curable resin layer, each of the plurality of lead wirings Forming an opening in the photocurable resin layer, ashing a part of the surface of the photocurable resin layer to form an organic barrier layer, and a second inorganic barrier covering the organic barrier layer Forming a layer on the first inorganic barrier layer.

  In one embodiment, in the step of condensing the liquid photocurable resin, the thickness of the photocurable resin condensed on the flat portion of the first inorganic barrier is 100 nm or more and 500 nm or less.

  In one embodiment, the step of forming the organic barrier layer includes generating the laser beam from laser light emitted from at least one semiconductor laser element.

  In one embodiment, the substrate is a flexible substrate.

  In one embodiment, the photocurable resin includes an acrylic monomer.

  In an exemplary embodiment, a method for manufacturing an organic EL device according to the present disclosure includes a step of preparing an element substrate including a substrate and a plurality of organic EL devices arranged on the substrate, and a thin film seal on the element substrate. Forming a stop structure. The step of forming the thin film sealing structure includes a step of forming a first inorganic barrier layer on the element substrate, a step of condensing a photocurable resin on the first inorganic barrier layer, and the light by a laser beam. Irradiating a plurality of selected regions of the curable resin to cure at least a portion of the photocurable resin to form a photocurable resin layer, and removing the uncured portion of the photocurable resin And a step of forming a second inorganic barrier layer covering the photocurable resin layer remaining on the substrate on the first inorganic barrier layer.

  In one embodiment, the plurality of regions of the photo-curing resin are active in each organic EL device depending on a region where the first inorganic barrier layer and the second inorganic barrier layer are in contact with each other without passing through the organic barrier layer. The area is selected to be enclosed.

  In one embodiment, the plurality of regions of the photocurable resin each cover an active region of the plurality of organic EL devices and are separated from each other.

  In an exemplary embodiment, a film forming apparatus according to the present disclosure includes a chamber including a stage that supports a substrate, a raw material supply device that supplies a vapor or mist-like photocurable resin into the chamber, and a stage that is supported by the stage. And a light source device for irradiating a plurality of selected regions of the substrate with a laser beam. The light source device includes at least one semiconductor laser element that emits the laser beam, and an optical device that adjusts an intensity distribution of the laser beam emitted from the semiconductor laser element on the substrate.

  In one embodiment, the optical device has at least one movable mirror that scans the selected regions of the substrate with the laser beam.

  In one embodiment, the light source device includes a plurality of semiconductor laser elements including the at least one semiconductor laser element, and the substrate is selected by a plurality of laser beams emitted from the plurality of semiconductor laser elements. The plurality of regions are irradiated.

  In one embodiment, the light source device includes a drive device that moves the plurality of semiconductor laser elements relative to the substrate.

  In one embodiment, the optical device adjusts the intensity distribution so as not to cure at least a part of the photocurable resin condensed on the substrate.

  In one embodiment, the optical device includes a transmissive or reflective spatial light modulator that modulates the intensity distribution.

  According to the embodiment of the present invention, a method for manufacturing an organic EL device having a thin film sealing structure with improved mass productivity and moisture resistance reliability, and a film forming apparatus used in the manufacturing method are provided.

2 is a schematic diagram showing a configuration of a film forming apparatus 200 used for forming an organic barrier layer 14. FIG. 6 is a schematic diagram showing a state where a laser beam 232 is emitted from a light source device 230 included in the film forming apparatus 200. FIG. 4 is a perspective view showing an arrangement example of a plurality of regions (irradiation regions) 20S on the element substrate 20 irradiated with a laser beam emitted from the light source device 230. FIG. It is a figure which shows typically an example of arrangement | positioning relationship between the one OLED display device 100 currently formed in the element substrate 20, and the irradiation area | region 20S corresponding to this OLED display device 100. FIG. It is a figure which shows typically a mode that the some irradiation area | region 20S is irradiated with the laser beam 232. FIG. 10 is a perspective view showing an example in which a plurality of irradiation regions 20S are irradiated with a plurality of laser beams 232; FIG. 6 is a perspective view showing an example in which a plurality of irradiation regions 20S are irradiated with a line-shaped laser beam 232; FIG. It is a perspective view which shows typically the basic composition of a typical semiconductor laser element. It is a figure which shows the structural example which converts the intensity distribution of the laser beam 232 into a top hat type | mold using the refractive optical apparatus 260. FIG. 6 is a diagram showing an example in which a plurality of laser beams emitted from an array of a plurality of semiconductor laser elements 25 are combined to form one laser beam 232 having a top hat type intensity distribution. FIG. FIG. 6 is a diagram schematically showing an example in which one light source device 230 irradiates one irradiation region 20S with a laser beam 232; It is a figure which shows the example of a structure which reflects the laser beam 232 radiate | emitted from the fixed light source (for example, one or several semiconductor laser element 25) by the movable mirror 23, and irradiates each irradiation area | region 20S sequentially. . It is a perspective view which shows typically the different state of the micromirror array. It is a perspective view which shows typically the different state of the micromirror array. (A) is a typical fragmentary sectional view of the active area | region of the OLED display apparatus 100 by embodiment of this invention, (b) is a fragmentary sectional view of the TFE structure 10 formed on OLED3. It is a top view which shows typically the structure of 100 A of OLED display apparatuses by Embodiment 1 of this invention. (A)-(d) is typical sectional drawing of 100 A of OLED display apparatuses, (a) is sectional drawing along the 3A-3A 'line in FIG. 13, (b) is in FIG. It is sectional drawing along 3B-3B 'line, (c) is sectional drawing along 3C-3C' line in FIG. 13, (d) is along 3D-3D 'line in FIG. It is sectional drawing. 14A is an enlarged view of a portion including the particle P in FIG. 14A, and FIG. 14B is a schematic cross-sectional view of a first inorganic barrier layer (SiN layer) covering the particle P. FIG. It is a figure which shows the example of the "non-exposure area | region S" for forming the inorganic barrier layer junction part which crosses the extraction wiring 30A. It is a figure which shows the other example of the "non-exposure area | region S" for forming the inorganic barrier layer junction part which crosses the extraction wiring 30A. It is a figure which shows the further another example of the "non-exposure area | region S" for forming the inorganic barrier layer junction part which crosses the extraction wiring 30A. (A) And (b) is typical sectional drawing which shows the example of TFT which the OLED display apparatus by Embodiment 1 can have, respectively. It is a typical fragmentary sectional view of TFE structure 10D in the OLED display device by Embodiment 2 of this invention, (a) is sectional drawing of the part containing particle P, (b) is the foundation | substrate of organic barrier layer 14D It is sectional drawing of the part containing inorganic barrier layer junction part 3DB which substantially surrounds the active area | region formed in the surface (for example, surface of OLED3). It is a cross-sectional SEM image of the 1st inorganic barrier layer (SiN layer) which covers particle | grains (spherical silica with a diameter of 1 micrometer), and also shows the plane SEM image (lower left). It is a cross-sectional SEM image of a TFE structure that covers particles (spherical silica having a diameter of 2.15 μm), and also shows a planar SEM image (lower left). (A)-(c) is a typical cross section for demonstrating the process of forming organic barrier layer 14D. (A)-(c) is a typical cross section for demonstrating the process of forming 2nd inorganic barrier layer 16D. It is typical sectional drawing which shows organic barrier layer 14Dd ashed excessively. It is typical sectional drawing which shows 2nd inorganic barrier layer 16D formed on organic barrier layer 14Dd ashed excessively.

  In the exemplary embodiment, the “element substrate” in the present disclosure includes a substrate (base) having an active region and a peripheral region located outside the active region, and an electric circuit supported by the substrate. A typical example of this electric circuit includes a plurality of organic EL elements formed on the active region and a backplane circuit that drives the plurality of organic EL elements, and each of the backplane circuits includes a terminal on the peripheral region. A plurality of lead wires are provided.

  In order to form the organic barrier layer disclosed in Patent Document 2, conventionally, after the photocurable resin is condensed on the element substrate on which the first inorganic barrier layer is formed, the entire surface of the element substrate is irradiated with ultraviolet rays. Then, the entire photocurable resin has been cured. According to a conventional film forming apparatus, ultraviolet rays are emitted from a high-pressure UV lamp.

  On the other hand, in the embodiment of the present invention, a plurality of selected regions of the element substrate in which a relatively thin liquid photocurable resin having a thickness of, for example, 500 nm or less in the flat portion is formed on the surface. Irradiate with laser beam. As a result, the photocurable resin condensed in a region (non-exposed region) other than the plurality of selected regions (exposed regions) is not cured, and these unnecessary photocurable resins are selectively selected from the element substrate. It becomes possible to remove. For this reason, the subject that a part of organic barrier layer forms the path | route which guides the water vapor | steam in air | atmosphere in an active area | region can be solved.

  According to the embodiment of the present invention, the presence of the organic barrier layer (solid portion) is limited to a selected region between the first inorganic barrier layer and the second inorganic barrier layer constituting the thin film sealing structure. Has been. The entire thin film sealing structure is substantially defined by the shapes of the first inorganic barrier layer and the second inorganic barrier layer. When the thin film sealing structure is viewed from the normal direction of the substrate, the organic barrier The region where the layer exists is located inside the outer shape (contour) of the thin film sealing structure.

  According to the embodiment of the present invention, for example, since a coherent laser beam emitted from a semiconductor laser element is used, the light beam has high straightness, and selective exposure can be realized without bringing a mask into close contact with the element substrate. For this reason, even in an element substrate placed in a state where a liquid photocurable resin is formed on the surface in the film forming apparatus, selective exposure to a desired region is realized as it is. If the element substrate on which the liquid photo-curing resin is formed (wet) is moved or vibrated before exposure and curing, the photo-curing resin moves from the agglomeration position, and is moved to a desired position. Although there is a problem that the organic barrier layer cannot be formed, according to the embodiment of the present invention, such a problem can be avoided.

  FIG. 1A is a diagram schematically showing an example of a basic configuration of a film forming apparatus 200 suitably used in the method for manufacturing an organic EL device according to the present invention. This film forming apparatus 200 is used for forming an organic barrier layer constituting a thin film sealing structure.

  The illustrated film forming apparatus 200 includes a chamber 210 and a partition wall 234 that divides the inside of the chamber 210 into two spaces. A stage 212 and a shower plate 220 are arranged in one space of the inside of the chamber 210 that is partitioned by the partition wall 234. In the other space partitioned by the partition wall 234, a light source device (ultraviolet irradiation device) 230 is disposed. The chamber 210 is controlled to have a predetermined pressure (degree of vacuum) and temperature in the internal space.

  The stage 212 has an upper surface that supports the element substrate 20, and can cool the upper surface to, for example, −20 ° C. As will be described in detail later, the element substrate 20 includes, for example, a flexible substrate and a plurality of organic EL devices arranged on the flexible substrate. The element substrate 20 is placed on the stage 212 in a state where a first inorganic barrier layer (not shown in FIG. 1) constituting the thin film sealing structure is formed on the element substrate 20. The first inorganic barrier layer is a base layer for the organic barrier layer.

  A gap 224 is formed between the shower plate 220 and the partition wall 234. The vertical size of the gap 224 can be, for example, 100 mm or more and 1000 mm or less. The shower plate 220 has a plurality of through holes 222. The plurality of through holes 222 function as a raw material supply nozzle, and supply a photocurable resin (liquid) supplied to the gap portion 224 at a predetermined flow rate in the form of vapor or mist to the element substrate 20 in the chamber 210. . The photocurable resin is heated as necessary. A typical example of the photocurable resin is an acrylic monomer. In the illustrated example, the vapor or mist of acrylic monomer 26p adheres to or contacts the first inorganic barrier layer of the element substrate 20. The acrylic monomer 26 is supplied from the container 202 into the chamber 210 at a predetermined flow rate. The acrylic monomer 26 is supplied to the container 202 through the pipe 206 and nitrogen gas is supplied from the pipe 204. The flow rate of the acrylic monomer to the container 202 is controlled by the mass flow controller 208. The raw material supply apparatus is configured by the shower plate 222, the piping 204, the mass flow controller 208, and the like.

  The light source device 230 is configured to irradiate a selected plurality of regions of the element substrate 20 supported by the stage 212 with a laser beam 232. FIG. 1B is a schematic diagram showing a state in which a laser beam 232 is emitted from the light source device 230. As described above, in the chamber 210 of the film forming apparatus 200, the space in which the light source device 230 is disposed is partitioned from the space to which the source gas is supplied by the partition wall 234. The partition wall 234 and the shower plate 220 are made of a material that transmits the laser beam 232 (for example, quartz). The configuration of the film forming apparatus according to the present disclosure is not limited to the illustrated example.

  Hereinafter, a configuration example of the light source device 230 will be described in detail with reference to FIGS. 2 to 11B.

  FIG. 2 is a perspective view illustrating an arrangement example of a plurality of regions (irradiation regions) 20 </ b> S in the element substrate 20 that is irradiated with the laser beam emitted from the light source device 230. The rectangular areas surrounded by the broken lines are the individual irradiation areas 20S, which are arranged apart from each other. FIG. 2 shows, as an example, 24 irradiation regions 20S arranged in 4 rows and 6 columns, but the number and arrangement of the irradiation regions 20S are not limited to the illustrated example. Further, the shape and size of each irradiation region 20S are not limited to the illustrated example.

  FIG. 3 is a diagram schematically illustrating an example of an arrangement relationship between one OLED display device 100 formed on the element substrate 20 and an irradiation region 20 </ b> S corresponding to the OLED display device 100. The upper part of FIG. 3 shows a planar layout, and the lower part of FIG. 3 shows a cross-sectional configuration.

  In the example shown in FIG. 3, the OLED display device 100 includes a substrate 1, a circuit (backplane circuit) 2 supported by the substrate 1, and an OLED 3 formed on the circuit 2. The element substrate 20 shown in FIG. 2 is in a stage before the substrate 1 of FIG. 3 is divided for each OLED display device 100, and the substrates 1 of the plurality of OLED display devices 100 continuously serve as the base of the element substrate 20. It is composed.

  The entire circuit 2 and OLED 3 shown in FIG. 3 are covered and sealed by a thin film sealing structure (TFE structure) 10. As shown in FIG. 3, one irradiation region 20S is wider than the region where the circuit 2 and the OLED 3 are formed, but is narrower than the region where the TFE structure 10 is formed. For this reason, in the intermediate region (included in the non-exposed region) from the outer edge of the irradiation region 20S to the outer edge of the region where the TFE structure 10 is formed, even if the photocurable resin such as the acrylic monomer 26 is condensed, It is not cured and no organic barrier layer is formed. For this reason, in the “intermediate region”, the first inorganic barrier layer and the second inorganic barrier layer constituting the TFE structure 10 are in direct contact with each other. As will be described later, a portion where the first inorganic barrier layer and the second inorganic barrier layer are in direct contact may be referred to as an “inorganic barrier layer bonding portion” in this specification. In the example of FIG. 3, the “inorganic barrier layer bonding portion” includes a portion having a width Gx extending in the vertical direction and a portion having a width Gy extending in the horizontal direction, and surrounds the circuit 2 and the OLED 3.

  The OLED display device 100 shown in FIG. 3 includes a plurality of lead lines 30 for connecting the circuit 2 to, for example, a driver integrated circuit (IC). In the present disclosure, the circuit 2 and the plurality of lead wires are collectively referred to as “electrical circuitry”. In the example of FIG. 3, four lead wires 30 are illustrated for simplicity, but the actual number of lead wires 30 is not limited to this example. The lead wiring 30 does not need to extend linearly, and may include a bent portion and / or a branch.

  The lead-out wiring 30 extends from the circuit 2 to the outside of the “intermediate region” described above. That is, a part of the lead wiring 30 is covered with the TFE structure 10, but the other part of the lead wiring 30 (at least an end functioning as a pad portion, that is, a terminal) is not covered with the TFE structure 10. A portion of the lead wiring 30 that is not covered by the TFE structure 10 can be connected in electrical contact with, for example, a terminal of a driver integrated circuit (IC).

FIG. 4 is a diagram schematically showing a state (maskless projection exposure) in which a plurality of irradiation regions 20S are irradiated with a laser beam 232. As shown in FIG. 3, each of the plurality of irradiation areas 20 </ b> S covers an area where an organic barrier layer needs to be formed in each OLED display device 100. In other words, a region where the organic barrier layer is not required to be formed in each OLED display device 100 is not irradiated with the laser beam 232. It is not required that the laser beam 232 is not irradiated at all in the region outside the irradiation region 20S (non-exposure region). If the irradiation amount of the laser beam 232 in a certain region is lower than the level necessary for curing the photocurable resin, the region is a “non-exposure region” and is not a region (irradiation region) selected for exposure. . In order to cure an acrylic monomer having a thickness of, for example, 100 to 500 nm with ultraviolet rays (wavelength of, for example, 370 to 390 nm), an irradiation dose of, for example, 100 to 200 mJ / cm ² is required. In this case, in the region other than the selected region (irradiation region 20S), the irradiation amount of the laser beam 232 may be suppressed to, for example, 50 mJ / cm ² or less.

  In FIG. 4, it is described that the plurality of irradiation regions 20 are simultaneously irradiated with the laser beam 232, but irradiation with the plurality of laser beams 232 is not necessarily performed simultaneously. Each of the plurality of irradiation regions 20 may be sequentially irradiated with the laser beam 232. Further, although the laser beam 232 shown in FIG. 4 is a bundle of parallel rays, the actual laser beam 232 may be converged or expanded. The incident angle of the laser beam 232 with respect to the element substrate 20 is not limited to be vertical. In the case of incidence from an oblique direction, the cross-sectional shape of the laser beam 232 can be appropriately corrected according to the incident angle so as to realize the shape of the irradiation region 20S shown in FIG.

  FIG. 5A is a perspective view schematically showing an example in which a plurality of irradiation regions 20S arranged in a straight line are irradiated with a plurality of laser beams 232. In the drawing, for reference, coordinate axes composed of an X axis, a Y axis, and a Z axis that are orthogonal to each other are described. The light source device 230 in this example is configured to emit a laser beam 232 from each of a plurality of light emitting units arranged in a line along the X-axis direction. Each light emitting section may be one semiconductor laser element or an array of a plurality of semiconductor laser elements. In the example of FIG. 5, the light source device 230 is supported so as to be movable at least in the Y-axis direction, and is driven by, for example, a motor (not shown). The position of the light source device 230 is changed by such a driving device such as a motor, and different portions of the plurality of irradiation regions 20S can be sequentially irradiated with the laser beam 232 from a plurality of different positions.

  A plurality of light source devices 230 each having the configuration shown in FIG. 5A may be arranged in the Y-axis direction.

  FIG. 5B is an example in which one irradiation region 20 </ b> S by the laser beam 232 has a shape extending in the X-axis direction so as to straddle a plurality of OLED display devices 100. A non-exposure region sandwiched between adjacent irradiation regions 20S extends in a slit shape along the X-axis direction. The arrangement pattern of the plurality of irradiation regions 20 </ b> S is set so that the non-exposure region completely crosses the lead wiring 30. When the photocurable resin is not formed on the flat portion, or when the organic barrier layer formed on the flat portion is removed by ashing, the flat portion where the lead-out wiring 30 does not exist may be irradiated with a laser beam. This is because the organic barrier layer can be finally removed from such a flat portion. In such a case, as shown in FIG. 5B, even if one irradiation region 20 </ b> S straddles a plurality of OLED display devices 100, there is an unnecessary organic barrier layer around the active region of each OLED display device 100. do not do.

  FIG. 6 is a perspective view schematically showing a basic configuration of a typical semiconductor laser element. The semiconductor laser element 25 shown in FIG. 6 has an end face (facet) 254 including a light emitting region (emitter) 256 that emits a laser beam 232. A striped electrode 252 is provided on the upper surface of the semiconductor laser element 25, and a back electrode (not shown) is provided on the rear surface of the semiconductor laser element 25. When a current exceeding the oscillation threshold value flows between the striped electrode 252 and the back electrode, laser oscillation occurs, and the laser beam 232 is emitted from the light emitting region 256.

  The configuration shown in FIG. 6 is merely a typical example of the configuration of the semiconductor laser element 25, and is simplified for the sake of simplicity. In the example of FIG. 6, since the end face 254 of the semiconductor laser element 25 is parallel to the XY plane, the laser beam 232 is emitted from the light emitting region 256 in the Z-axis direction. The optical axis of the laser beam 232 is parallel to the Z-axis direction. The spread of the laser beam 232 in the Y-axis direction is defined by an angle θf, and the spread in the X-axis direction is defined by an angle θs. Due to the diffraction effect, the angle θf is usually larger than the angle θs, and the cross section of the laser beam 232 (the portion where the intensity is greater than or equal to a predetermined value) has an elliptical shape. Therefore, in this embodiment, the intensity distribution of the laser beam 232 is adjusted by an optical device such as a lens or an optical fiber, instead of using the laser beam 232 emitted from the semiconductor laser element 25 as it is for the exposure of the photocurable resin. To do.

  FIG. 7 is a diagram illustrating a configuration example in which the intensity distribution of the laser beam 232 is converted into a top-hat type using the refractive optical device 260. In the optical device 260, the refraction in the XZ plane and the refraction in the YZ plane are different from each other, and the laser beam 232 can be shaped so as to have an intensity distribution matched to the irradiation region 20S shown in FIG. it can. FIG. 7 schematically shows an example of the intensity distribution L in a cross section (cross section parallel to the XY plane) perpendicular to the optical axis (parallel to the Z axis) of the laser beam 232. The intensity distribution L has a portion (flat portion) having a substantially uniform intensity regardless of the position, and the shape of such a distribution can be referred to as a “top hat type”. If the cross-sectional shape of the laser beam having the “top hat type” intensity distribution matches the shape of the active area of the circuit 2 and the OLED 3 as shown in FIG. 3, selective exposure can be performed efficiently.

As a semiconductor laser element that emits a laser beam having a wavelength in the ultraviolet region (400 nm or less), for example, a laser diode having a product number NDU7216 manufactured by Nichia Corporation can be used. According to this laser diode, a laser beam having a continuous wave (CW) output of 200 milliwatts (mW) and a wavelength of 370 to 390 nm can be obtained. In addition, according to the laser diode module of product number NUU102E manufactured by Nichia Corporation, a continuous wave laser beam having an output of 3 watts (W) and a wavelength of 370 to 390 nm can be obtained. A laser beam with a CW output of 3 watts (W) even when irradiated in the enlarged area of 100 cm ^2, to achieve a dose of 300 mJ / cm ² by irradiation of 10 seconds. For this reason, even in a short time required for mass production, an irradiation dose sufficient for curing a relatively thin photo-curing resin (thickness on the flat portion of the first inorganic barrier layer is 100 to 500 nm). Can be obtained.

  It is not necessary to irradiate each irradiation region 20S with the laser beam 232 emitted from one semiconductor laser element 25. FIG. 8 shows an example in which a plurality of laser beams emitted from an array of a plurality of semiconductor laser elements 25 are combined to form one laser beam 232 having a top hat type intensity distribution. Each of the plurality of semiconductor laser elements 25 need not emit a laser beam with the same light output. Further, the arrangement of the semiconductor laser elements 25 need not be evenly spaced. The position, direction, output, wavelength, and the like of each semiconductor laser element 25 can be appropriately adjusted so as to optimize the intensity distribution of the laser beam 232 on the element substrate. In FIG. 8, the description of an optical device such as a lens or a mirror is omitted for simplicity. In order to achieve a desired intensity distribution, known optical devices can be used as appropriate. The optical device may include a light shielding mask having a slit or an opening that transmits part of the laser beam 232. The laser beam is highly coherent and can form a precise light irradiation pattern defined by a narrow slit or opening.

  FIG. 9 schematically illustrates an example in which one light source device 230 irradiates one irradiation region 20 </ b> S with a laser beam 232. Actually, a plurality of light source devices 230 may be arranged so as to face all the irradiation regions 20S. Alternatively, all the irradiation regions 20S may be sequentially irradiated with the laser beam 232 while one or several light source devices 230 move.

  FIG. 10 shows an example of a configuration in which a laser beam 232 emitted from a fixed light source (for example, one or a plurality of semiconductor laser elements 25) is reflected by the movable mirror 23 to sequentially irradiate each irradiation region 20S. Show. The movable mirror 23 can be, for example, a polygon mirror or a galvanometer mirror. The movable mirror 23 may have a non-reflective region 23B that absorbs or scatters part of the laser beam 232. The cross-sectional shape and intensity distribution of the laser beam 232 on the element substrate 20 can be adjusted by such a non-reflective region 23B. The direction of the movable mirror 23 can be changed by a biaxial actuator (not shown), for example, and can reflect the laser beam 232 in an arbitrary direction. As described above, in order to realize the shape of the irradiation region 20S shown in FIG. 3 while changing the direction of the movable mirror 23, the cross-sectional shape of the laser beam 232 is appropriately corrected according to the incident angle (trapezoid). Correction) is preferred. Such correction can be realized by arranging an optical element (not shown) on the optical path and performing beam shaping. The number of movable mirrors 23 and the number of light sources is not limited to one, but may be plural.

  The movable mirror 23 may be a reflective spatial light modulator (for example, a liquid crystal display panel). If it is a spatial light modulator, the cross-sectional shape and intensity distribution of the laser beam 232 on the element substrate 20 can be dynamically changed.

  Instead of the movable mirror 23, a laser beam emitted from the semiconductor laser element 25 may be converted into a laser beam 232 having an arbitrary intensity distribution by using a reflective or transmissive spatial light modulator. By adopting such a configuration, it becomes possible to irradiate the whole or a part of the element substrate 20 with a laser beam 232 having an arbitrary intensity distribution, and trapezoidal correction can be easily realized. In addition, the shape, size, and arrangement of the irradiation region 20S can be easily changed according to the type of the element substrate 20. When a transmissive spatial light modulation element is used, the spatial light modulation element may be disposed between the laser light source of the light source device 230 and the element substrate 20 as shown in FIGS. 5A, 5B, and 9, for example. Such a light source device 230 functions as a projector including an ultraviolet laser light source.

  The movable mirror 23 may be a micro mirror array. 11A and 11B are perspective views schematically showing different states of the same micromirror array 28, respectively. The micromirror array 28 includes a plurality of micromirrors 28M arranged two-dimensionally, an actuator that changes the direction of each micromirror 28M, and a circuit that drives the actuator. By adjusting the direction of each micromirror 28M, the laser beam incident on the micromirror array 28 can be spatially modulated to irradiate an arbitrary region of the element substrate 20 with the laser beam. It is also possible to scan the upper surface of the element substrate 20 with the laser beam 232 by changing the direction of the minute mirror 28M. By using the micromirror array 28, the shape, size, and arrangement of the irradiation region 20S can be easily changed according to the type of the element substrate 20.

  By adopting the film forming apparatus 200 including the light source device 230 described above, a step of condensing the photocurable resin on the first inorganic barrier layer of the element substrate 20, and a plurality of photocurable resins selected by the laser beam are selected. It is possible to perform the step of irradiating the region and curing the at least part of the photocurable resin to form the photocurable resin layer. In addition, the structure of the light source device which can be used for the film-forming apparatus by this invention is not limited to said example. Any projection-type or scanning-type light source device that emits a laser beam in a wavelength region capable of curing the photo-curable resin can be used in the film forming apparatus of the present invention.

  In an embodiment to be described later, the second inorganic barrier layer covering the photocurable resin layer remaining on the substrate after the step of removing the uncured portion of the photocurable resin that has not been exposed and cured is used as the first inorganic barrier layer. A thin film sealing structure can be completed by performing a process of forming on the barrier layer.

(Configuration example of display device)
Hereinafter, a configuration example of a display device that can be manufactured according to an embodiment of the present invention will be described. In addition, embodiment of this invention is not limited to embodiment illustrated below.

  First, with reference to FIGS. 12A and 12B, a basic configuration of an OLED display device 100 will be described as an example of a display device manufactured according to an embodiment of the present invention. 12A is a schematic partial cross-sectional view of an active region of the OLED display device 100 according to the embodiment of the present invention, and FIG. 12B is a partial cross-sectional view of the TFE structure 10 formed on the OLED 3. It is. The OLED display devices according to Embodiments 1 and 2 to be described later have basically the same configuration, and in particular, the structure other than the TFE structure may be the same as that of the OLED display device 100.

  The OLED display device 100 has a plurality of pixels, and has at least one organic EL element (OLED) for each pixel. Here, for simplicity, a structure corresponding to one OLED will be described.

  As shown in FIG. 12A, an OLED display device 100 includes a flexible substrate (hereinafter, simply referred to as “substrate”) 1 and a circuit (backplane circuit) including TFTs formed on the substrate 1. 2, an OLED 3 formed on the circuit 2, and a TFE structure 10 formed on the OLED 3. The OLED 3 is, for example, a top emission type. The uppermost part of the OLED 3 is, for example, an upper electrode or a cap layer (refractive index adjusting layer). An optional polarizing plate 4 is disposed on the TFE structure 10.

  The substrate 1 is, for example, a polyimide film having a thickness of 15 μm. The thickness of the circuit 2 including the TFT is, for example, 4 μm, the thickness of the OLED 3 is, for example, 1 μm, and the thickness of the TFE structure 10 is, for example, 1.5 μm or less.

  FIG. 12B is a partial cross-sectional view of the TFE 10 formed on the OLED 3. A first inorganic barrier layer (for example, SiN layer) 12 is formed immediately above the OLED 3, an organic barrier layer (for example, acrylic resin layer) 14 is formed on the first inorganic barrier layer 12, and the organic barrier layer 14 A second inorganic barrier layer (for example, a SiN layer) 16 is formed thereon.

  For example, the first inorganic barrier layer 12 and the second inorganic barrier layer 16 are SiN layers having a thickness of 400 nm, for example, and the organic barrier layer 14 is an acrylic resin layer having a thickness of less than 100 nm. The thicknesses of the first inorganic barrier layer 12 and the second inorganic barrier layer 16 are independently 200 nm or more and 1000 nm or less, and the thickness of the organic barrier layer 14 is 50 nm or more and less than 200 nm. When particles as described later are present on the first inorganic barrier layer 12, the thickness of the organic barrier layer 14 locally increases around the particles, and is approximately the same as the thickness of the second inorganic barrier layer. obtain. The thickness of the TFE structure 10 is preferably 400 nm or more and less than 2 μm, and more preferably 400 nm or more and less than 1.5 μm.

  The TFE structure 10 is formed so as to protect the active area of the OLED display device 100 (see the active area R1 in FIG. 13). At least in the active area, as described above, in order from the side closer to the OLED 3, The first inorganic barrier layer 12, the organic barrier layer 14, and the second inorganic barrier layer 16 are included. Note that the organic barrier layer 14 does not exist as a film covering the entire surface of the active region, but has an opening. A portion of the organic barrier layer 14 excluding the opening and where the organic film actually exists is referred to as a “solid portion”. Further, the “opening” (sometimes referred to as “non-solid portion”) does not need to be surrounded by the solid portion and includes a notch or the like, and the first inorganic barrier layer 12 is formed in the opening. And the second inorganic barrier layer 16 are in direct contact. The opening of the organic barrier layer 14 includes at least an opening formed so as to surround the active region, and the active region is in direct contact between the first inorganic barrier layer 12 and the second inorganic barrier layer 16. Part ("inorganic barrier layer joint") is completely surrounded. The planar shape of the organic barrier layer 14 is defined by a portion where an area where the photocurable resin is condensed and an area (irradiation area) selectively exposed by a laser beam overlap. That is, even when a region where the photocurable resin does not exist is irradiated with a laser beam, the organic barrier layer 14 is not generated in the region. Further, even in a region where the photocurable resin exists, the organic barrier layer 14 is not generated in a region where the laser beam is not irradiated with a necessary irradiation amount. Furthermore, the planar shape of the organic barrier layer 14 can be reduced by ashing the organic barrier layer 14 as necessary.

(Embodiment 1)
A manufacturing method of the OLED display device according to the first embodiment of the present invention will be described with reference to FIGS.

  FIG. 13 shows a schematic plan view of an OLED display device 100A according to Embodiment 1 of the present invention. The OLED display device 100A includes a flexible substrate 1, a circuit (backplane circuit) 2 formed on the flexible substrate 1, a plurality of OLEDs 3 formed on the circuit 2, and a TFE structure 10A formed on the OLED 3. have. A layer in which a plurality of OLEDs 3 are arranged may be referred to as an OLED layer 3. Note that the circuit 2 and the OLED 3 may share some components. An optional polarizing plate (see reference numeral 4 in FIG. 12) may be further disposed on the TFE structure 10A. In addition, for example, a layer having a touch panel function may be disposed between the TFE structure 10A and the polarizing plate. That is, the OLED display device 100A can be modified to an on-cell display device with a touch panel.

  The circuit 2 includes a plurality of TFTs (not shown), a plurality of gate bus lines (not shown) and a plurality of source bus lines (not shown) each connected to one of the plurality of TFTs (not shown). Have. The circuit 2 may be a known circuit for driving the plurality of OLEDs 3. The plurality of OLEDs 3 are connected to any of the plurality of TFTs included in the circuit 2. The OLED 3 may also be a known OLED.

  The OLED display device 100A further includes a plurality of terminals 38A disposed in a peripheral region R2 outside the active region (region surrounded by a broken line in FIG. 13) R1 in which a plurality of OLEDs 3 are disposed, and a plurality of terminals 38A and a plurality of lead lines 30A for connecting a plurality of gate bus lines or a plurality of source bus lines, and the TFE structure 10A has an active region R1 on the plurality of OLEDs 3 and on the plurality of lead lines 30A. It is formed on the side part. That is, the TFE structure 10A covers the entire active region R1 and is selectively formed on the active region R1 side portion of the plurality of lead wirings 30A. The terminal 38A side and the terminal 38A of the lead wiring 30A are It is not covered with the TFE structure 10A.

  Hereinafter, an example in which the lead wiring 30A and the terminal 38A are integrally formed using the same conductive layer will be described, but they may be formed using different conductive layers (including a laminated structure).

  Next, a TFE structure 10A of the OLED display device 100A will be described with reference to FIGS. 14A shows a cross-sectional view taken along line 3A-3A ′ in FIG. 13, FIG. 14B shows a cross-sectional view taken along line 3B-3B ′ in FIG. 13, and FIG. ) Shows a cross-sectional view taken along the line 3C-3C ′ in FIG. 13, and FIG. 14D shows a cross-sectional view taken along the line 3D-3D ′ in FIG. FIG. 14D is a cross-sectional view of a region where the TFE structure 10A is not formed.

  As shown in FIG. 14A, the TFE structure 10A includes a first inorganic barrier layer 12A formed on the OLED 3, an organic barrier layer 14A in contact with the first inorganic barrier layer 12A, and a first inorganic barrier layer 14A in contact with the organic barrier layer 14A. 2 inorganic barrier layers 16A. The first inorganic barrier layer 12A and the second inorganic barrier layer 16A are, for example, SiN layers, and are selectively formed only in a predetermined region so as to cover the active region R1 by a plasma CVD method using a mask.

  The organic barrier layer 14A can be formed, for example, by the method described in Patent Document 2. For example, vapor or a mist-like photocurable resin (for example, an organic material such as an acrylic monomer) is supplied onto an element substrate maintained at a temperature of room temperature or lower in a chamber. The photocurable resin is unevenly distributed at the boundary portion between the side surface of the convex portion of the first inorganic barrier layer 12A and the flat portion by capillary action or surface tension of the photocurable resin condensed on the element substrate and turned into a liquid state. Can do. Thereafter, the selected region of the photocurable resin is irradiated with, for example, an ultraviolet laser beam to partially cure the photocurable resin, and an organic barrier layer is formed at the boundary portion around the convex portion in the selected region. A solid part (for example, an acrylic resin layer) 14A is formed. The organic barrier layer 14 formed by this method has substantially no solid part in the flat part. Regarding the method for forming the organic barrier layer, the disclosure of Patent Document 2 is incorporated herein by reference.

  FIG. 14A is a cross-sectional view taken along line 3A-3A ′ in FIG. 13 and shows a portion including particles P. FIG. The particles P are fine dust generated during the manufacturing process of the OLED display device, and are, for example, fine glass fragments, metal particles, and organic particles. When the mask vapor deposition method is used, particles are particularly likely to be generated.

  As shown in FIG. 14A, the organic barrier layer (solid portion) 14A can be formed only around the particle P. This is because the acrylic monomer applied after forming the first inorganic barrier layer 12A is condensed and unevenly distributed around the surface of the first inorganic barrier layer 12Aa on the particles P. On the flat part of the first inorganic barrier layer 12A, an opening (non-solid part) of the organic barrier layer 14A is formed.

  Here, with reference to FIGS. 15A and 15B, the structure of the portion including the particles P will be described. FIG. 15A is an enlarged view of a portion including the particle P in FIG. 14A, and FIG. 15B is a schematic cross-sectional view of a first inorganic barrier layer (for example, SiN layer) covering the particle P. is there.

  As shown in FIG. 15B, when particles P (for example, a diameter of about 1 μm or more) P are present, cracks (defects) 12Ac may be formed in the first inorganic barrier layer. As will be described later, this is considered to have occurred because the SiN layer 12Aa growing from the surface of the particle P and the SiN layer 12Ab growing from the flat portion of the surface of the OLED 3 collide (impinge). When such a crack 12Ac exists, the barrier property of the TFE structure 10A is lowered.

  In the TFE structure 10A of the OLED display device 100A, as shown in FIG. 15A, the organic barrier layer 14A is formed so as to fill the cracks 12Ac of the first inorganic barrier layer 12A, and the organic barrier layer 14A The surface continuously and smoothly connects the surface of the first inorganic barrier layer 12Aa on the particle P and the surface of the first inorganic barrier layer 12Ab on the flat portion of the OLED 3. Therefore, a dense film is formed without forming defects in the first inorganic barrier layer 12A on the particles P and the second inorganic barrier layer 16A formed on the organic barrier layer 14A. Thus, the organic barrier layer 14A can maintain the barrier property of the TFE structure 10A even if particles are present.

  Next, referring to FIGS. 14B and 14C, a specific example of the TFE structure 10A on the lead wiring 30A will be described. FIG. 14B is a cross-sectional view taken along line 3B-3B 'in FIG. 13, and shows a cross section of the portion 32A of the lead wiring 30A. The portion 32A of the lead wiring 30A is located in the laser beam irradiation region. On the other hand, FIG. 14C is a cross-sectional view taken along line 3C-3C 'in FIG. 13, and shows a cross section of the portion 34A of the lead wiring 30A. The portion 34A of the lead wiring 30A is located outside (non-exposure region) the laser beam irradiation region.

  The lead wiring 30A is patterned by the same process as, for example, the gate bus line or the source bus line. Here, the gate bus line and the source bus line formed in the active region R1 are also the portions 32A, 32A of the lead wiring 30A. An example having the same cross-sectional structure as the portion 34B will be described. Note that the cross-sectional shape of the lead-out wiring 30A is not limited to the example shown in FIG.

  The OLED display device 100A according to the embodiment of the present invention is suitably used for, for example, high-definition small and medium smartphones and tablet terminals. In a high-definition (for example, 500 ppi) small and medium-sized (for example, 5.7 type) OLED display device, a sufficiently low resistance wiring (including a gate bus line and a source bus line) is formed with a limited line width. In addition, the cross-sectional shape parallel to the line width direction of the wiring in the active region R1 is preferably close to a rectangle. On the other hand, since the active region R1 of the OLED display device 100A is substantially surrounded by the inorganic barrier layer bonding portion in which the first inorganic barrier layer 12A and the second inorganic barrier layer 16A are in direct contact, the organic barrier layer 14A is Moisture does not reach the active region R1 of the OLED display device as a moisture intrusion route.

  The organic barrier layer (solid portion) 14 exists between the first inorganic barrier layer 12A and the second inorganic barrier layer 16A on the side surface portion of the portion 32A of the lead wiring 30A shown in FIG. 14B. Yes.

  On the other hand, the organic barrier layer (solid portion) 14 does not exist on the side surface of the portion 34A of the lead wiring 30A shown in FIG. 14C, and the first inorganic barrier layer 12A and the second inorganic barrier layer 16A Are in direct contact (that is, an inorganic barrier layer bonding portion is formed). Further, since the organic barrier layer 14 (solid portion) A is not formed in the flat portion, the lead-out wiring 30A has a first inorganic barrier layer 12A in the cross section taken along the line 3C-3C ′ in FIG. And the second inorganic barrier layer 16 </ b> A are covered with an inorganic barrier layer bonding portion in direct contact.

  Therefore, as described above, the organic barrier layer formed along the lead-out wiring does not become a path for guiding water vapor in the atmosphere into the active region. From the viewpoint of moisture resistance reliability, the length of the portion 34A of the lead wiring 30A, that is, the size (width) of the inorganic barrier layer joint portion measured along the direction in which the lead wiring 30A extends is at least 0.01 mm. It is preferable. There is no particular upper limit to the width of the inorganic barrier layer joint, but even if it exceeds 0.1 mm, the effect of improving moisture resistance reliability is almost saturated, and even if it is made longer, it will only increase the frame width. 0.1 mm or less, for example, 0.05 mm or less. In the conventional TFE structure in which the organic barrier layer is formed by the inkjet method, an inorganic barrier layer bonding portion having a width of about 0.5 mm to 1.0 mm is provided in consideration of variation in the position where the end portion of the organic barrier layer is formed. It has been. On the other hand, according to the embodiment of the present invention, since the width of the inorganic barrier layer bonding portion may be 0.1 mm or less, the organic EL display device can be narrowed.

  Next, refer to FIG. FIG. 14D is a cross-sectional view of a region where the TFE structure 10A is not formed. Since the portion 36A of the lead-out wiring 30A shown in FIG. 14D is located outside the laser beam irradiation region (non-exposure region), the organic barrier layer 14A is not formed at the bottom of the side surface. Therefore, the organic barrier layer (solid portion) 14A does not exist on the side surfaces of the portion 34A of the lead wiring 30A and the terminal 38A. Further, the organic barrier layer (solid portion) 14A does not exist on the flat portion.

  As described above, the formation of the organic barrier layer 14A includes a step of supplying a vapor or mist-like photocurable resin (for example, an acrylic monomer), so that the first inorganic barrier layer 12A and the second inorganic barrier layer 16A are formed. Thus, the photocurable resin cannot be selectively condensed only in a predetermined region. Therefore, in the conventional method of exposing the entire surface of the substrate with ultraviolet rays, the organic barrier layer (solid portion) 14A can be formed at an unnecessary position. However, according to this embodiment, since a plurality of selected regions are irradiated with a laser beam, it is possible to suppress the formation of the organic barrier layer (solid portion) 14A at the stepped portion formed by the lead-out wiring. .

  16A, 16B, and 16C are diagrams showing examples of the “non-exposure region S” for forming an inorganic barrier layer junction that crosses the lead wiring 30A. In these drawings, the white portions are “non-exposed areas S”. The non-exposure region S extending in a slit shape only needs to completely traverse the lead wiring 30A, and does not need to cover the whole lead wiring 30A. The shape and size of the non-exposure area S are not limited to the illustrated example. The non-exposure region S may have various shapes and sizes that block a moisture intrusion path by the organic barrier layer 14A that can be formed along the lead wiring 30A.

  Next, with reference to FIG. 17, an example of a TFT used in the OLED display device 100A and an example of an extraction wiring and a terminal formed using a gate metal layer and a source metal layer when the TFT is manufactured will be described.

  For high-definition small and medium OLED display devices, high mobility low temperature polysilicon (abbreviated as “LTPS”) TFT or oxide TFT (for example, In (indium), Ga (gallium), Zn (zinc) And quaternary (In—Ga—Zn—O) oxide TFT) containing O (oxygen). Since the structure and manufacturing method of the LTPS-TFT and the In—Ga—Zn—O-based TFT are well known, only a brief description will be given below.

17 (a) is a schematic sectional view of the _{LTPS-TFT2 P T, TFT2 P} T may be included in the circuit 2 of the OLED display device 100A. LTPS-TFT2 _P T is a top-gate type TFT.

The TFT 2 _P T is formed on the base coat 2 _P p on the substrate (for example, polyimide film) 1. Although omitted in the above description, it is preferable to form a base coat made of an inorganic insulator on the substrate 1.

TFT 2 _P T is formed with the base coat 2 _P p on the formed polysilicon layer 2 _P se, a gate insulating layer 2 _P gi formed on the polysilicon layer 2 _P se, the gate insulating layer 2 _P gi a gate electrode 2 _P g which is, and the interlayer insulating layer 2 _P i formed on the gate electrode 2 _P g, the source electrode 2 _P ss and drain electrodes 2 _P sd formed in the interlayer insulating layer 2 _P i have. The source electrode 2 _P ss and the drain electrode 2 _P sd are connected to the source region and the drain region of the polysilicon layer 2 _P se in the contact holes formed in the interlayer insulating layer 2 _P i and the gate insulating layer 2 _P gi, respectively. Has been.

The gate electrode 2 _P g is included in the same gate metal layer and the gate bus line, a source electrode 2 _P ss and drain electrodes 2 _P sd is included in the same source metal layer and the source bus line. Lead wires and terminals are formed using the gate metal layer and the source metal layer.

TFT 2 _P T, for example, be produced as follows.

  For example, a polyimide film having a thickness of 15 μm is prepared as the substrate 1.

Base coat 2 _P p (SiO ₂ film: 250 nm / SiN _x film: 50 nm / SiO ₂ film: 500 nm (upper layer / intermediate layer / lower layer)) and a-Si film (40 nm) are formed by plasma CVD.

  Dehydrogenation treatment (for example, annealing at 450 ° C. for 180 minutes) of the a-Si film is performed.

  The a-Si film is made into polysilicon by excimer laser annealing (ELA).

  An active layer (semiconductor island) is formed by patterning the a-Si film in a photolithography process.

A gate insulating film (SiO ₂ film: 50 nm) is formed by plasma CVD.

Doping (B ⁺ ) is performed on the channel region of the active layer.

Gate metal: a (Mo 250 nm) was deposited by sputtering, (to form the gate electrode 2 _P g and the gate bus lines, etc.) that a photolithography process for patterning (including a dry etching process).

Doping (P ⁺ ) is performed on the source region and drain region of the active layer.

Activation annealing (for example, annealing at 450 ° C. for 45 minutes) is performed. In this way, the polysilicon layer 2 _P se is obtained.

An interlayer insulating film (for example, SiO ₂ film: 300 nm / SiN _x film: 300 nm (upper layer / lower layer)) is formed by plasma CVD.

Contact holes are formed in the gate insulating film and the interlayer insulating film by dry etching. Thus, the interlayer insulating layer 2 _P i and the gate insulating layer 2 _P gi are obtained.

Source metal (Ti film: 100 nm / Al film: 300 nm / Ti film: 30 nm) is formed by sputtering and patterned by a photolithography process (including a dry etching process) (source electrode 2 _P ss and drain electrode 2 _P sd and source bus lines are formed).

FIG. 17B is a schematic cross-sectional view of an In—Ga—Zn—O-based TFT 2 _O T, and the TFT 2 _O T can be included in the circuit 2 of the OLED display device 100A. TFT2 _O T is a bottom-gate type TFT.

The TFT 2 _O T is formed on the base coat 2 _O p on the substrate (for example, polyimide film) 1. The TFT 2 _O T is formed on the gate electrode 2 _O g formed on the base coat 2 _O p, the gate insulating layer 2 _O gi formed on the gate electrode 2 _O g, and the gate insulating layer 2 _O gi. The oxide semiconductor layer 2 _O se has a source electrode 2 _O ss and a drain electrode 2 _O sd connected to the source region and the drain region of the oxide semiconductor layer 2 _O se, respectively. The source electrode 2 _O ss and the drain electrode 2 _O sd are covered with an interlayer insulating layer 2Oi.

The gate electrode 2 _O g is included in the same gate metal layer as the gate bus line, and the source electrode 2 _O ss and the drain electrode 2 _O sd are included in the same source metal layer as the source bus line. Lead wires and terminals can be formed using the gate metal layer and the source metal layer.

TFT 2 _O T, for example, be produced as follows.

  For example, a polyimide film having a thickness of 15 μm is prepared as the substrate 1.

Base coat 2 _O p (SiO ₂ film: 250 nm / SiN _x film: 50 nm / SiO ₂ film: 500 nm (upper layer / intermediate layer / lower layer)) is formed by plasma CVD.

  Gate metal (Cu film: 300 nm / Ti film: 30 nm (upper layer / lower layer)) is formed by sputtering, and patterned by a photolithography process (including a dry etching process) (a gate electrode 2Og, a gate bus line, etc. are formed) To do).

A gate insulating film (SiO ₂ film: 30 nm / SiN _x film: 350 nm (upper layer / lower layer)) is formed by plasma CVD.

  An oxide semiconductor film (In—Ga—Zn—O-based semiconductor film: 100 nm) is formed by sputtering, and patterned by a photolithography process (including a wet etching process) to form an active layer (semiconductor island). To do.

Source metal (Ti film: 100 nm / Al film: 300 nm / Ti film: 30 nm (upper layer / intermediate layer / lower layer)) is formed by sputtering, and patterned by a photolithography process (including a dry etching process) (source electrode) 2 _O ss, drain electrode 2 _O sd, source bus line and the like are formed).

Activation annealing (for example, annealing at 300 ° C. for 120 minutes) is performed. In this way, the oxide semiconductor layer 2 _O se is obtained.

Thereafter, an interlayer insulating layer 2Oi (for example, SiN _x film: 300 nm / SiO ₂ film: 300 nm / (upper layer / lower layer)) is formed as a protective film by a plasma CVD method.

(Embodiment 2)
In the formation of the organic barrier layer 14A described in the first embodiment, a photocurable resin such as an acrylic monomer is unevenly distributed in the step portion. In the manufacturing method of the OLED display device according to Embodiment 2 described below, an organic barrier layer is formed by forming a resin layer (for example, an acrylic resin layer) on at least a part of the flat portion and partially ashing the resin layer. Is included. Various forms can be achieved by adjusting the thickness of the resin layer to be formed first (for example, less than 100 nm), selecting the irradiation region of the laser beam, and / or adjusting the ashing conditions (including time). The organic barrier layer can be formed. That is, the organic barrier layer 14A included in the OLED display device 100A described in the first embodiment can be formed, or an organic barrier layer (solid portion) that substantially covers part or all of the flat portion is formed. You can also. In addition, when the area of an organic barrier layer is large, the effect which improves a bending resistance will be acquired. In the following, an OLED display device having a TFE structure having an organic barrier layer (solid portion) covering part or all of the flat portion and a manufacturing method thereof will be mainly described. Note that the structure of the element substrate before forming the TFE structure, in particular, the structure of the lead wiring and the terminal and the structure of the TFT may be any of those described in the first embodiment.

  FIG. 18A is a schematic partial cross-sectional view of the TFE structure 10D in the OLED display device according to the second embodiment of the present invention, and shows a portion including particles P. FIG. As described with reference to FIG. 15B, when the particles P are present, cracks (defects) 12Dc may be formed in the first inorganic barrier layer 12D. It can be considered from the cross-sectional SEM image shown in FIG. 19 that the SiN layer 12Da growing from the surface of the particle P and the SiN layer 12Db growing from the flat portion of the surface of the OLED 3 collide (impinge). When such a crack 12Dc exists, the barrier property of the TFE structure 10D is lowered. Note that the SEM image in FIG. 19 is a cross-sectional SEM image of a sample in which a SiN film is formed by a plasma CVD method in a state where spherical silica having a diameter of 1 μm is arranged as particles P on a glass substrate. The cross section does not pass through the center of the particle P. The outermost surface is a carbon layer (C-depo) for protection during cross-section processing. Thus, cracks (defects) 12Dc are formed in the SiN layer 12D only by the presence of a relatively small spherical silica having a diameter of 1 μm.

  In the TFE structure 10D in the OLED display device of the second embodiment, as shown in FIG. 18A, the organic barrier layer 14Dc is filled with the crack 12Dc of the first inorganic barrier layer 12D and the overhang portion of the particles P. Since it is formed, the barrier property can be maintained by the second inorganic barrier layer 16D. This can be confirmed by a cross-sectional SEM image shown in FIG. In FIG. 20, the interface is not observed at the place where the second inorganic barrier layer 16D is directly formed on the first inorganic barrier layer 12D, but the first inorganic barrier layer is easy to understand in the schematic diagram. 12D and the second inorganic barrier layer 16D are indicated by different hatching.

  The cross-sectional SEM image shown in FIG. 20 is a cross-sectional SEM image of a sample in which the TFE structure 10D is formed in a state where spherical silica having a diameter of 2.15 μm is arranged on a glass substrate, similarly to the cross-sectional SEM image of FIG. It is. As can be seen by comparing FIG. 20 with FIG. 19, even if the particle P has a diameter of about twice that shown in FIG. 20, the SiN film formed on the acrylic resin layer is a dense film without defects. I understand that. Similarly to the case of FIG. 19, after forming a SiN film by plasma CVD so as to cover the particles P (spherical silica having diameters of 2.15 μm and 4.6 μm), an acrylic resin layer is formed as the organic barrier layer 14D. After that, it was confirmed by SEM observation that a dense SiN film having no defect was formed on the acrylic resin layer even in the sample in which the SiN film was formed again by the plasma CVD method.

  The organic barrier layer 14 shown in FIG. 18A is formed of, for example, an acrylic resin, as will be described later. In particular, those formed by photocuring (for example, ultraviolet curing) an acrylic monomer (acrylate) having a viscosity of about 1 to 100 mPa · s at room temperature (for example, 25 ° C.) are preferable. Thus, the low-viscosity acrylic monomer can easily penetrate into the overhang portions of the cracks 12Dc and the particles P. In addition, acrylic resin has high visible light transmittance, and is suitably used for top emission type OLED display devices. A photoinitiator can be mixed with the acrylic monomer as needed. The photosensitive wavelength can be adjusted according to the type of the photopolymerization initiator. Instead of the acrylic monomer, other photocurable resins can also be used. As the photocurable resin, an ultraviolet curable resin is preferable from the viewpoint of reactivity and the like. The laser beam to be irradiated is preferably a UV-A region having a wavelength of 315 nm or more and 400 nm or less among near ultraviolet rays (200 nm or more and 400 nm or less), but a laser beam having a wavelength of 300 nm or more and less than 315 nm may be used. Alternatively, a photocurable resin that is cured by irradiation with a visible light laser beam from 400 nm to 450 nm in blue-violet to blue color can be used.

  The surface of the organic barrier layer 14Dc filled in the crack 12Dc and the overhanging portion of the particle P is the surface of the first inorganic barrier layer 12Da on the particle P and the organic barrier layer 14Db formed on the flat portion of the surface of the OLED 3. And smoothly connect the surface with. Therefore, a dense film is formed without forming defects in the first inorganic barrier layer 12D on the particle P and the second inorganic barrier layer (SiN layer) 16D formed on the organic barrier layer 14D.

  Further, the surface 14Ds of the organic barrier layer 14D is oxidized by the ashing process, has hydrophilicity, and has high adhesion with the second inorganic barrier layer 16D.

  In order to improve the bending resistance, the organic barrier layer 14D is formed so that the organic barrier layer 14D remains on almost the entire surface except for the convex portion of the first inorganic barrier layer 12Da formed on the particle P. It is preferable to ash. The thickness of the organic barrier layer 14Db present on the flat portion is preferably 10 nm or more.

  Patent Documents 2 and 3 describe configurations in which the organic barrier layer is unevenly distributed. However, when the inventor conducted various experiments, the organic barrier layer 14D is almost the entire surface of the flat portion, that is, the first inorganic barrier layer. It may be formed on almost the entire surface excluding the 12 Da convex portion, and its thickness is preferably 10 nm or more from the viewpoint of bending resistance.

  When the organic barrier layer 14D is interposed between the first inorganic barrier layer 12D and the second inorganic barrier layer 16D, the adhesion between the layers within the TFE structure 10D is enhanced. In particular, since the surface of the organic barrier layer 14D is oxidized, the adhesiveness with the second inorganic barrier layer 16D is high.

  In addition, when the organic barrier layer 14Db on the flat portion is formed on the entire surface (the organic barrier layer 14D does not have the opening 14Da), it occurs in the TFE structure 10D when an external force is applied to the OLED display device. As a result of uniform distribution of stress (or strain), destruction (particularly, destruction of the first inorganic barrier layer 12D and / or the second inorganic barrier layer 16D) is suppressed. The organic barrier layer 14D, which is in close contact with the first inorganic barrier layer 12D and the second inorganic barrier layer 16D, is considered to act so as to disperse and relieve stress. Thus, the organic barrier layer 14D also has an effect of improving the bending resistance of the OLED display device.

  However, if the thickness of the organic barrier layer 14D is 200 nm or more, the bending resistance may be lowered, and therefore the thickness of the organic barrier layer 14D is preferably less than 200 nm.

  The organic barrier layer 14D is formed through an ashing process. Since the ashing process may vary in the plane, a part of the organic barrier layer 14Db formed on the flat portion may be completely removed, and the surface of the first inorganic barrier layer 12D may be exposed. At this time, the organic barrier layer (solid portion) 14Db formed on the flat portion of the OLED 3 in the organic barrier layer 14D is controlled so as to have a larger area than the opening 14Da. That is, the area of the solid portion 14Db is controlled to be more than 50% of the area of the organic barrier layer (including the opening) 14D on the flat portion. The area of the solid part 14Db is preferably 80% or more of the area of the organic barrier layer 14D on the flat part. However, the area of the solid portion 14Db preferably does not exceed about 90% of the area of the organic barrier layer on the flat portion. In other words, the organic barrier layer 14D on the flat portion preferably has the opening portion 14Da having an area of about 10% in total. The opening 14Da has an effect of suppressing peeling at the interface between the first inorganic barrier layer 12D and the organic barrier layer 14D and at the interface between the organic barrier layer 14D and the second inorganic barrier layer 16D. When the opening 14Da has an area of 80% or more and 90% or less of the area of the organic barrier layer 14D on the flat part, particularly excellent bending resistance can be obtained.

  Further, when the organic barrier layer 14D is formed on the entire surface of the flat portion, the organic barrier layer 14D in the flat portion becomes a moisture intrusion path, and the moisture resistance reliability of the OLED display device is lowered. In order to prevent this, the OLED display device according to the second embodiment has an inorganic barrier layer bonding portion 3DB that substantially surrounds the active region, as shown in FIG. Is defined by the unexposed area of the laser beam.

  In the inorganic barrier layer bonding portion 3DB, the photocurable resin that existed before the exposure is not irradiated with the laser beam and is selectively removed without being cured. For this reason, the opening 14Da of the organic barrier layer 14D is located in the inorganic barrier layer bonding portion 3DB, and the solid portion 14Db does not exist. That is, in the inorganic barrier layer bonding portion 3DB, the first inorganic barrier layer 12D and the second inorganic barrier layer 16D are in direct contact. Although the OLED display device of Embodiment 2 has the organic barrier layer 14D in the flat portion, the active region is completely surrounded by the inorganic barrier layer bonding portion 3DB, and thus has high moisture resistance reliability.

  With reference to FIG. 21 and FIG. 22, the formation process of the organic barrier layer 14D and the second inorganic barrier layer 16D, particularly the ashing process will be described. FIG. 21 shows a process for forming the organic barrier layer 14D, and FIG. 22 shows a process for forming the second inorganic barrier layer 16D.

  As schematically shown in FIG. 21A, after forming the first inorganic barrier layer 12D covering the particles P on the surface of the OLED 3, the organic barrier layer 14D is formed on the first inorganic barrier layer 12D. The organic barrier layer 14D is obtained, for example, by condensing vapor or mist of acrylic monomer on a cooled element substrate, and then curing the acrylic monomer by irradiating light (for example, ultraviolet rays). By using a low-viscosity acrylic monomer, the acrylic monomer can be penetrated into the crack 12Dc formed in the first inorganic barrier layer 12D.

  FIG. 21A shows an example in which the organic barrier layer 14Dd is formed on the first inorganic barrier layer 12Da on the particle P, but the size and shape of the particle P and the type of acrylic monomer are shown. Depending on the case, the acrylic monomer may not be deposited (or adhered) on the first inorganic barrier layer 12Da on the particle P, or may be deposited (or adhered) only in a very small amount. The organic barrier layer 14D can be formed using, for example, a film forming apparatus 200 shown in FIG. The initial thickness of the organic barrier layer 14D is adjusted to be 100 nm to 500 nm on the flat portion. The surface 14Dsa of the initial organic barrier layer 14D thus formed is smoothly continuous and is hydrophobic. For the sake of simplicity, the same reference numerals are also given to the organic barrier layer before ashing.

Next, as shown in FIG. 21B, the organic barrier layer 14D is ashed. Ashing can be performed using a known plasma ashing device, photoexcited ashing device, or UV ozone ashing device. For example, plasma ashing using at least one of N ₂ O, O _2, and O ₃ , or further combined with ultraviolet irradiation may be performed. When forming the SiN film by the CVD method as a first inorganic barrier layer 12D and the second inorganic barrier layer 16D, as a material gas, so using N ₂ O, that the N ₂ O of the apparatus can be simplified and used in ashing Benefits are gained.

  When ashing is performed, the surface 14Ds of the organic barrier layer 14D is oxidized and modified to be hydrophilic. In addition, the surface 14Ds is scraped almost uniformly, extremely fine irregularities are formed, and the surface area is increased. The effect of increasing the surface area when ashing is performed is greater on the surface of the organic barrier layer 14D than on the first inorganic barrier layer 12D, which is an inorganic material. Therefore, the surface 14Ds of the organic barrier layer 14D is modified to be hydrophilic, and the surface area of the surface 14Ds is increased, so that the adhesion with the second inorganic barrier layer 16D is improved.

  When the ashing is further advanced, an opening 14Da is formed in a part of the organic barrier layer 14D as shown in FIG.

  Further, when the ashing is advanced, the organic barrier layer 14Dc is left only in the vicinity of the crack 12Dc of the first inorganic barrier layer 12D and the overhang portion of the particle P as in the organic barrier layer 14A shown in FIG. Can do. At this time, the surface of the organic barrier layer 14Dc continuously and smoothly connects the surface of the first inorganic barrier layer 12Da on the particle P and the surface of the flat portion of the surface of the OLED 3.

  In order to improve the adhesion between the first inorganic barrier layer 12D and the organic barrier layer 14D, the surface of the first inorganic barrier layer 12D may be subjected to an ashing treatment before the organic barrier layer 14D is formed. Good.

  Next, the structure after the second inorganic barrier layer 16D is formed on the organic barrier layer 14D will be described with reference to FIG.

  In FIG. 22A, the surface 14Dsa of the organic barrier layer 14D shown in FIG. 21A is oxidized by ashing to be modified to a hydrophilic surface 14Ds, and then the second inorganic barrier layer 16D is formed. The structure is shown schematically. Here, a case where the surface 14Dsa of the organic barrier layer 14D is slightly ashed is shown, and an example in which the organic barrier layer 14Dd formed on the first inorganic barrier layer 12Da on the particle P also remains is shown. However, the organic barrier layer 14D may not be formed (or remain) on the first inorganic barrier layer 12Da on the particle P.

  As shown in FIG. 22A, the second inorganic barrier layer 16D formed on the organic barrier layer 14D has no defect and is excellent in adhesion with the organic barrier layer 14D.

  As shown in FIGS. 22B to 22C, when the second inorganic barrier layer 16D is formed on the organic barrier layer 14D shown in FIGS. 21B to 21C, there is no defect, and the organic barrier layer A second inorganic barrier layer 16D having excellent adhesion with 14D is obtained. Even if the organic barrier layer 14D on the flat part of the OLED 3 is completely removed, the surface of the organic barrier layer 14Dc is the surface of the first inorganic barrier layer 12Da on the particle P and the surface of the flat part of the surface of the OLED 3 If it is continuously and smoothly connected, the second inorganic barrier layer 16D having no defects and excellent adhesion to the organic barrier layer 14D can be obtained.

  As shown in FIG. 22B, the organic barrier layer 14D is ashed so that the organic barrier layer 14D remains thin on the entire surface except for the convex portions of the first inorganic barrier layer 12Da formed on the particles P. May be. From the viewpoint of bending resistance, as described above, the thickness of the organic barrier layer 14Db on the flat portion is preferably 10 nm or more and less than 200 nm.

  Since the ashing treatment varies in the plane, a part of the organic barrier layer 14D formed on the flat portion may be completely removed, and the surface of the first inorganic barrier layer 12D may be exposed. Further, since the material and size of the particle P also vary, there may be a portion having the structure shown in FIG. 22C or the structure shown in FIG. Even when part of the organic barrier layer 14D formed on the flat portion is completely removed, the organic barrier layer (solid portion) 14Db formed on the flat portion of the OLED 3 in the organic barrier layer 14D is: It is preferable to control the area to be larger than the opening 14Da. As described above, the area of the solid part 14Db is preferably 80% or more of the area of the organic barrier layer 14D on the flat part, and preferably does not exceed about 90%.

  If the organic barrier layer 14D is over-ashed, as shown in FIG. 23, the organic barrier layer 14Db formed on the flat portion of the OLED 3 is not only completely removed, but is also filled in the crack 12Dc formed by the particles P. In addition, the organic barrier layer 14Dd becomes smaller, and the surface of the base on which the second inorganic barrier layer 16D is formed does not have the function of making the surface continuous smoothly. As a result, as shown in FIG. 24, defects 16Dc are formed in the second inorganic barrier layer 16D, and the barrier characteristics of the TFE structure are deteriorated. Even if the defect 16Dc is not formed, if the acute concave portion 16Dd is formed on the surface of the second inorganic barrier layer 16D, stress is likely to concentrate on the portion, and cracks are likely to be generated due to external force.

  Further, for example, in an experiment using convex lens-like silica (diameter: 4.6 μm) as the particle P, the film thickness of the second inorganic barrier layer is partially increased as a result of excessive etching of the organic barrier layer at the end of the convex lens-like silica. In some cases, it became extremely thin. In such a case, even if no defect occurs in the second inorganic barrier layer, a crack is generated in the second inorganic barrier layer when an external force is applied to the TFE structure in the manufacturing process of the OLED display device or after the manufacturing. There is a fear.

  Examples of cases where an external force is applied to the TFE structure 10 include the following cases. For example, when the flexible substrate 1 of the OLED display device is peeled from the glass substrate which is the support substrate, bending stress acts on the OLED display device including the TFE structure 10. Further, in the process of manufacturing a curved display, bending stress acts on the TFE structure 10 when the OLED display device is bent along a predetermined curved shape. Of course, when the final usage form of the OLED display device is a form using the flexibility of the OLED display device (for example, folding, bending, or rounding), various stresses may be generated during use by the user. The structure 10 will be hung.

  In order to prevent this, the organic barrier layer (solid portion) 14Db has a larger area than the opening 14Da so that more than 50% of the organic barrier layer formed on the flat portion of the OLED 3 remains. Thus, it is preferable to adjust the ashing conditions. The organic barrier layer (solid portion) 14Db remaining on the flat portion of the OLED 3 is more preferably 80% or more, and more preferably about 90%. However, about 10% of the openings 14Da are present to suppress peeling at the interface between the first inorganic barrier layer 12D and the organic barrier layer 14D and at the interface between the organic barrier layer 14D and the second inorganic barrier layer 16D. Since an effect is acquired, it is more preferable. As shown in FIGS. 22A to 22C, the surface of the second inorganic barrier layer 16D formed on the moderately remaining organic barrier layer 14D has an angle of 90 ° or less (recessed in FIG. 24). 16Dd), there is no stress concentration even if an external force is applied.

  A method for manufacturing an OLED display device according to Embodiment 2 of the present invention includes a step of preparing an OLED 3 having a first inorganic barrier layer 12D formed in a chamber, and a vapor or mist photocurable resin (for example, acrylic resin) in the chamber. Monomer), a step of condensing the photocurable resin on the first inorganic barrier layer 12D to form a liquid film, and a light irradiation of the liquid film of the photocurable resin with light. It includes a step of forming a cured resin layer (cured resin layer) and a step of forming the organic barrier layer 14D by partially ashing the photocurable resin layer.

  Since an ultraviolet curable resin is suitably used as the photocurable resin, an example using an ultraviolet curable resin will be described below. However, a light source that emits light of a predetermined wavelength that can cure the photocurable resin. Can be applied to a visible light curable resin.

  Using the film forming apparatus 200 shown in FIGS. 1A and 1B, for example, the organic barrier layer 14 can be formed as follows. The following example is one of typical examples of conditions used for trial manufacture of the TFE structure 10 and preparation of the sample shown in the SEM photograph.

  The acrylic monomer 26p is supplied into the chamber 210. After the acrylic monomer 26p is introduced into the gap portion 224, the acrylic monomer 26p is supplied to the element substrate 20 on the stage 212 through the through hole 222 of the shower plate 220. The element substrate 20 is cooled to, for example, −15 ° C. on the stage 212. The acrylic monomer 26p is condensed on the first inorganic barrier layer 12 of the element substrate to become a liquid film. The deposition rate of the acrylic monomer (liquid) can be adjusted by controlling the supply amount of the acrylic monomer 26p and the temperature and pressure (vacuum degree) in the chamber 210. For example, the acrylic monomer can be deposited at 500 nm / min. Therefore, a layer of acrylic monomer having a thickness of about 200 nm can be formed in about 24 seconds.

  By controlling the conditions at this time, the acrylic monomer can be unevenly distributed only around the convex portion as in the method of forming the organic barrier layer in the first embodiment.

  Various known acrylic monomers can be used as the acrylic monomer. A plurality of acrylic monomers may be mixed. For example, a bifunctional monomer and a trifunctional or higher polyfunctional monomer may be mixed. Moreover, you may mix an oligomer. However, it is preferable to adjust the viscosity at room temperature (for example, 25 ° C.) to about 1 to 100 mPa · s. A photoinitiator can be mixed with the acrylic monomer as needed.

  Thereafter, the inside of the chamber 210 is evacuated to remove the vapor or mist-like acrylic monomer 26p, and then, as shown in FIG. 1B, selective exposure with the laser beam 232 is performed to thereby form the first inorganic barrier layer 12D. The acrylic monomer is cured. By using the high-power laser diode module described above, selective exposure can be completed in an irradiation time of about 10 seconds.

  Thus, the tact time of the formation process of the organic barrier layer 14D is about 34 seconds, and the mass productivity is very high.

The first inorganic barrier layer 12D is formed as follows, for example. With a plasma CVD method using SiH ₄ and N ₂ O gas, for example, in a state where the temperature of the substrate to be deposited (OLED 3) is controlled to 80 ° C. or less, the deposition rate is 400 nm / min, and the thickness is The first inorganic barrier layer 12D can be formed. The refractive index of the first inorganic barrier layer 12D thus obtained is 1.84, and the visible light transmittance at 400 nm is 90% (thickness 400 nm). The absolute value of the film stress is 50 MPa.

The ashing of the organic barrier layer 14D is performed by, for example, a plasma ashing method using N ₂ O gas. Ashing is performed in an ashing chamber. The ashing rate is, for example, 500 nm / min. As described above, when the organic barrier layer 14D having a thickness of 200 nm is formed, the thickness (maximum value) of the organic barrier layer (solid portion) 14Db on the flat portion is about 20 nm for about 22 seconds. Ashing.

  By adjusting the conditions at this time, the organic barrier layer 14A shown in FIGS. 14A and 14B can be formed. Further, since the thickness of the organic barrier layer 14D on the lead-out wiring is smaller than that of the other portions, the organic barrier layer 14D on the lead-out wiring is removed, and more than 50% of the area of the organic barrier layer 14D on the flat portion is removed. You can leave it.

After ashing, the N ₂ O gas is exhausted and transferred to a CVD chamber for forming the second inorganic barrier layer 16D. For example, the second inorganic barrier layer 16D is formed under the same conditions as the first inorganic barrier layer 12D. To do.

  In this manner, an OLED display device including the TFE structure 10D and the TFE structure 10D can be manufactured. In the method for manufacturing an OLED display device according to the second embodiment of the present invention, an organic barrier layer having a sufficient thickness is once formed and ashed to obtain an organic barrier layer having a desired thickness. Therefore, unlike the manufacturing methods described in Patent Documents 2 and 3, there is no need to unevenly distribute the resin material, so that the process margin is wide and the mass productivity is excellent.

Further, as described above, since the surface of the organic barrier layer 14D is oxidized, the adhesion with the first inorganic barrier layer 12D and the second inorganic barrier layer 16D is high, and the moisture resistance reliability is excellent. For example, when the WVTR of the TFE structure 10D specifically exemplified above (a polyimide film having a thickness of 15 μm instead of the OLED 3 in FIG. 8) is evaluated, it is 1 × 10 ⁻⁴ g / m which is the lower limit of measurement in terms of room temperature. It was less than ² · day.

  Further, the structure in which the organic barrier layer 14D is present on almost the entire surface between the first inorganic barrier layer 12D and the second inorganic barrier layer 16D on the flat portion is excellent in bending resistance.

In addition to the SiN layer, a SiO layer, a SiON layer, a SiNO layer, an Al ₂ O ₃ layer, or the like can be used as the inorganic barrier layer. As the resin for forming the organic barrier layer, a photocurable resin such as a vinyl group-containing monomer can be used in addition to the acrylic resin. An ultraviolet curable silicone resin can also be used as the photocurable resin. Silicone resins (including silicone rubber) are excellent in visible light transmittance and weather resistance, and are characterized by being hardly yellowed even after long-term use. A photocurable resin that is cured by irradiation with visible light can also be used. It is preferable that the viscosity at room temperature (for example, 25 ° C.) before curing of the photocurable resin used in the embodiment of the present invention does not exceed 10 Pa · s, and particularly 1 to 100 mPa · s as described above. preferable.

  In each of the above embodiments, a display device is manufactured as an example of an organic EL device, but the present invention is also applicable to manufacturing an organic EL device other than the display device, for example, an organic EL lighting device. Further, the substrate is not limited to a flexible substrate, and may be formed from a highly rigid material. The size of the display device is not limited to the medium and small size, and may be a large size for a large screen television.

  The embodiment of the present invention can be applied to an organic EL display device, particularly a flexible organic EL display device and a manufacturing method thereof.

1: Board 2: Backplane circuit 3: OLED
4: Polarizing plates 10, 10A, 10B, 10C, 10D: Thin film sealing structure (TFE structure)
12, 12A, 12B, 12C, 12D: first inorganic barrier layer (SiN layer)
14, 14A, 14B, 14D: Organic barrier layer (acrylic resin layer)
14Da: Opening part 14Db of the organic barrier layer: Solid part 14Ds of the organic barrier layer: Surface of the organic barrier layer (after ashing)
14Dsa: surface of organic barrier layer (before ashing)
16A, 16B, 16C, 16D: second inorganic barrier layer (SiN layer)
16Dc: Defect 16Dd: Recess 20: Element substrate 26: Acrylic monomer 26p: Acrylic monomer vapor or mist-like acrylic monomer 100, 100A: Organic EL display device 210: Chamber 212: Stage 220: Shower plate 222: Through hole 224: Gap 230: Light source device 232: Laser beam 234: Partition

Claims (7)

Preparing an element substrate comprising a substrate and a plurality of organic EL devices arranged on the substrate;
Forming a thin film sealing structure on the element substrate;
Including
The step of forming the thin film sealing structure includes:
Forming a first inorganic barrier layer on the element substrate;
Condensing a photocurable resin on the first inorganic barrier layer;
Irradiating a selected region of the photocurable resin with a laser beam to cure at least a portion of the photocurable resin to form a photocurable resin layer;
Removing the uncured portion of the photocurable resin;
Forming a second inorganic barrier layer on the first inorganic barrier layer covering the photocurable resin layer remaining on the substrate;
Including
A method of manufacturing an organic EL device, wherein a region where the first inorganic barrier layer and the second inorganic barrier layer are in contact with each other without passing through the organic barrier layer is formed in a part around the active region of each organic EL device. . The element substrate is
A substrate having an active region and a peripheral region located outside the active region;
An electric circuit supported by the substrate and including a plurality of organic EL elements formed on the active region and a backplane circuit for driving the plurality of organic EL elements;
The backplane circuit has a plurality of lead wires each including a terminal on the peripheral region,
2. The manufacturing method according to claim 1, wherein the region where the first inorganic barrier layer and the second inorganic barrier layer are in contact with each other without the organic barrier layer crossing the plurality of lead wirings.   The manufacturing method according to claim 1, wherein the region where the first inorganic barrier layer and the second inorganic barrier layer are in contact with each other without the organic barrier layer extending in a slit shape.   The thickness of the said photocurable resin condensed on the flat part of a said 1st inorganic barrier layer in the process of condensing the said liquid photocurable resin is 100 nm or more and 500 nm or less in any one of Claim 1 to 3 The manufacturing method as described in.   5. The manufacturing method according to claim 1, wherein the step of forming the organic barrier layer includes generating the laser beam from laser light emitted from at least one semiconductor laser element.   The manufacturing method according to claim 1, wherein the substrate is a flexible substrate.   The said photocurable resin is a manufacturing method in any one of Claim 1 to 6 containing an acrylic monomer.

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