Method for manufacturing organic electroluminescent device
10950682 ยท 2021-03-16
Assignee
Inventors
Cpc classification
H10K71/00
ELECTRICITY
H10K50/8445
ELECTRICITY
H05B33/10
ELECTRICITY
H01L22/20
ELECTRICITY
International classification
H01L21/00
ELECTRICITY
Abstract
A method for manufacturing an organic EL device according to an embodiment of the present invention includes: a step for preparing an element substrate having a substrate and a plurality of organic electroluminescent elements (3) which are supported by the substrate; and a step for forming a thin film encapsulation structure (10) covering the organic electroluminescent elements. The step for forming a thin film encapsulation structure includes: a step A for forming a first inorganic barrier layer (12); after the step A, a step B for detecting particles (P) below or above the first inorganic barrier layer (12) and obtaining positional information on each particle; a step C in which microscopic liquid drops of a coating liquid containing a photocurable resin are applied for each particle by an inkjet, method on the basis of the positional information; after the step C, a step D for irradiating the photocurable resin with an ultraviolet ray and curing the photocurable resin to form an organic barrier layer (14); and after the step D, a step E for forming a second inorganic barrier layer (16) on the first inorganic barrier layer and the organic barrier layer.
Claims
1. A method for producing an organic electroluminescent device, comprising the steps of: preparing an element substrate including a substrate and a plurality of organic electroluminescent elements supported by the substrate; and forming a thin film encapsulation structure covering the plurality of organic electroluminescent elements, wherein the step of forming the thin film encapsulation structure includes: step A of forming a first inorganic barrier layer, step B of, after step A, detecting particles, which include a first particle having an equivalent spherical diameter of 0.2 m or longer and shorter than 0.3 m, below or above the first inorganic barrier layer and acquiring position information on each of the particles, step C0 of, after step A, ashing a surface of the first inorganic barrier layer, step C of, after step C0, supplying each of the particles with a microscopic liquid drop of a coating liquid containing a photocurable resin by an inkjet method based on the position information to form a concave surface of the photocurable resin surrounding each of the particles, step D of, after step C, irradiating the photocurable resin with ultraviolet rays and thus curing the photocurable resin to form an organic barrier layer, and step E of, after step D, forming a second inorganic barrier layer on the first inorganic barrier layer and the organic barrier layer, wherein the step C includes a step of supplying a first microscopic liquid drop having a volume of 0.1 fL or larger and smaller than 10 fL to the first particle.
2. The method of claim 1, wherein the step D further includes the step of partially ashing a photocured resin layer formed by curing the photocurable resin.
3. The method of claim 1, wherein the step B includes a step of detecting particles, which include the first particle and a second particle having an equivalent spherical diameter of 0.3 m or longer and 5 m or shorter, below or above the first inorganic barrier layer and acquiring size information on each of the particles, the step C includes a step of supplying a second microscopic liquid drop larger than the first microscopic liquid drop, and the step C including a step of selecting the first microscopic liquid drop to the first particle and selecting the second microscopic liquid drop to at least the second particle having an equivalent spherical diameter of 5 m, based on the size information on each of the particles.
4. The method of claim 3, wherein the first microscopic liquid drop does not contain a dye or a pigment and the second microscopic liquid drop contains a dye or a pigment.
5. The method of claim 3, wherein the second microscopic liquid drop has a volume of 10 fL or larger and 0.5 pL or smaller.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1)
(2)
(3)
(4)
(5)
(6)
(7)
DESCRIPTION OF EMBODIMENTS
(8) Hereinafter, a method for producing an organic EL device, and an organic EL device produced by the production method, according to an. embodiment. of the present invention will be described with reference to the drawings. Hereinafter, an OLED displays device will be described as an example of the organic EL device. The embodiments according the present invention are not limited to the embodiments described below as examples.
(9) First, with reference to
(10) The OLED display device 100 includes a plurality of pixels, and each of the pixels includes at least one organic EL element (OLED). Herein, a structure corresponding to one OLED will be described for the sake of simplicity.
(11) As shown in
(12) The substrate 1 is, for example, a polyimide film having a thickness of 15 m. The circuit 2 including the TFT has a thickness for example, 4 m. The OLED 3 has a thickness of, for example, 1 m. The TFE structure 10 has a thickness of, for example, less than, or equal to, 1.5 m.
(13)
(14) As described below, the organic barrier layer 14 is formed only in a discontinuous portion of a portion, of the first inorganic barrier layer 12, that is formed on a particle (microscopic dust particle) (see, for example,
(15) The first inorganic barrier layer 12 and the second inorganic barrier layer 16 are each, for example, an SiN layer having a thickness of, for example, 400 nm. The first inorganic barrier layer 12 and the second inorganic barrier layer 16 each have a thickness of 200 nm or greater and 1000 nm or less independently. The thickness of the TFE structure 10 is preferably 400 nm or greater and less than 2 m, and more preferably 400 nm or greater and less than 1.5 m. The thickness of the organic barrier layer 14, which depends on the size the particle, is generally 50 nm or greater and less than 200 nm.
(16) The TFE structure 10 is formed so as to protect the active region (see the active region R1 in
(17) With reference to
(18)
(19) The OLED display device 100 includes the flexible substrate 1, the circuit (backplane) 2 formed on the flexible substrate 1, a plurality of the OLEDs 3 formed on the circuit 2, and the TFE structure 10 formed on the OLEDs 3. A layer including the plurality of OLEDs 3 may be referred to as an OLED layer 3. The circuit 2 and the OLED layer 3 may share a part of components. The optional polarizing plate (see reference sign 4 in
(20) The circuit 2 includes plurality of TFTs (not shown), and a plurality of gate bus lines (not shown) and a plurality of source bus lines (not shown) each connected with either one of the plurality of TFTs (not shown). The circuit 2 may be known circuit that drives the plurality of OLEDs 3. The plurality of LEDs 3 are each connected with either one of the plurality of TFTs included in the circuit 2. The OLEDs 3 may be known OLEDs.
(21) The OLED display device 100 further includes a plurality of terminal portions 38 located in a peripheral region R2 outer to the active region R1 (region enclosed by the dashed line in
(22) Hereinafter, an example in which the lead wires 30 and the terminal portions 38 are integrally formed in the same conductive layer will be described. Alternatively, the lead wires 30 and the terminal portions 38 may be formed in different conductive layers (encompassing stack structures).
(23) Now, with reference to
(24) As shown in
(25)
(26) As shown in, for example,
(27) A substrate of G4.5 (730 mm920 mm) may include, for example, several tens to about 100 particles each having a size of approximately 0.3 m or longer and 5 m or shorter. One OLED display device (active region) may include approximately several particles. Needless to say, there, are OLED display devices with no particle P. The organic barrier layer 14 is formed of, for example, a photocured resin formed by curing photocurable resin. A portion where the photocured resin is actually present is referred to as a solid portion. The organic barrier layer 14 includes at least one solid portion, and may include two or more solid portions.
(28) Now, with reference to
(29) In the TFE structure 10 of the OLED display device 100, as shown in
(30) The organic barrier layer (solid portion) 14 having the concave surface couples the surface of the first inorganic barrier layer 12a on the particle P and the surface of the first inorganic barrier layer 12b on the flat portion to each other continuously and smoothly. Therefore, the second inorganic barrier layer 16 formed thereon is a fine film with no defect. As can be seen, even if the particle P is present, the organic barrier layer 14 keeps high the level of barrier property of the TFE structure 10.
(31) As shown in
(32) In this example, the organic barrier layer 14 is formed only in a discontinuous portion of a portion, of the first inorganic barrier layer 12, that is farmed on the particle P, and the particle P is already present before the first inorganic barrier layer 12 is formed on the OLED 3. Alternatively, the particle P may be present on the first inorganic barrier layer 12. In this case, the organic barrier layer 14 is formed only at the border, namely, in a discontinuous portion, between the first inorganic barrier layer 12 and the particle P present on the first inorganic barrier layer 12, and thus maintains the barrier property of the TFE structure 10 like the, above-described case. organic barrier layer 14 may also be formed with a small thickness on the surface of the first inorganic barrier layer 12a on the, particle P, or on the surface of the particle P. In this specification, the expression that the organic barrier layer (solid portion) 14 is present in the vicinity of the particle P encompasses all these forms.
(33) Now, with reference to
(34) The lead wires 30 are patterned by the same process as that of, for example, the gate bus liner or the source bus lines. Thus, in this example, the gate bus lines and the source bus lines formed in the active region R1 also have the same cross-sectional structure as that of the portion 34, of each of the lead wires 30, closer to the active region R1 shown in
(35) The active region R1 of the OLED display device 100 substantially covered with the inorganic barrier layer joint portion, where the first inorganic barrier layer 12 and the second inorganic barrier layer 16 are in direct contact with each other, except for the portion in the vicinity of the particle P, namely, the portion where the organic barrier layer 14 is selectively formed. Therefore, it does not occur that the organic barrier layer 14 acts as an entrance route for moisture and allows the moisture to reach the active region R1 of the OLED display device.
(36) In the case where the lead wire 30 includes the forward tapering side surface portion TSF, formation of defects in the first inorganic barrier layer 12 and the second inorganic barrier layer 16 formed on the lead wire 30 is prevented. Namely, the moisture-resistance reliability of the TFE structure 10 is improved. The tapering angle of the forward tapering side surface portion TSF is preferably smaller than, or equal to, 70 degrees.
(37) The OLED display device 100 according to an embodiment of the present invention is preferably usable for, for example, medium- to small-sized high-definition smartphones and tablet terminals. In a medium- to small-sized g., 5.7-inch) high-definition (e.g., 500 ppi) OLED display device, it is preferred that lines (encompassing the gate bus lines and the source bus lines) in the active region R1 have a cross-sectional shape, taken in a direction parallel to a line width direction, close to a rectangle (side surfaces of the lines have a tapering angle of about 90 degrees) in order to allow the lines to have a sufficiently low resistance with a limited line, width. In order to form the lines having a low resistance, the tapering angle of the forward tapering side surface portion TSF may be larger than 70 degrees and smaller than 90 degrees, or the tapering angle may be about 90 degrees in the entire length of the lines with no forward tapering side surface portion TSF being provided as long as no defect is formed in the, first inorganic barrier layer 12 or the second inorganic barrier layer 16.
(38) Now,
(39) The organic barrier layer (solid portion) 14 included in the OLED display device 100 according to an embodiment of the present invention is formed only in the vicinity of the particle P by an inkjet method. Therefore, no resin is present locally, more specifically, at a border between the side surfaces of the lead wires or the side surfaces of the terminal portions and the surface of the substrate. For this reason, even if the tapering angle is about 90 degrees, the organic barrier layer (solid portion) is not formed along the lead wires, and the moisture-resistance reliability is not declined by the formation of the organic barrier layer (solid portion) 14.
(40) Now, with reference to
(41) A method for producing an OLED display device according to an embodiment of the present invention includes a step of preparing an element substrate including a substrate and a plurality of organic EL elements supported the substrate, and a step of forming a thin film encapsulation structure covering the plurality of organic EL elements. The step of forming the thin film encapsulation structure includes step A of forming a first inorganic barrier layer; step B of, after step A, detecting particles below or above the first inorganic barrier layer and acquiring position information on each of the particles; step C of supplying each of the particles with a microscopic liquid drop of a coating liquid containing a photocurable resin by an inkjet method based on the acquired position information; step D of, after step C, irradiating the photocurable resin with ultraviolet rays and thus curing the photocurable resin to form an organic barrier layer; and step E of, after step D, forming a second inorganic barrier layer on the first inorganic, barrier layer and the organic barrier layer.
(42) The method for producing an OLED display device according to an embodiment includes a foreign object detection step (step B) and an inkjet step (step C). This allows the OLED display device having the above-described structure to be produced.
(43)
(44) The foreign object detection device 40 shown in
(45) The controller 42 includes a memory and a processor (neither is shown), and controls the detection head 44 and/or the stage 70 to operate in accordance with information stored on the memory, so that the detection head 44 scans on the substrate 100M. A signal that controls the detection head 44 and/or the stage 70 to operate is generated by the processor and supplied to the detection head 44 and/or the stage 70 via an interface (represented by the arrow in the figure).
(46) The detection head 44 includes, for example, a laser light source (e.g., semiconductor laser element), an image-forming optical system, and an image-capturing element (none of these components is shown). Laser light is directed toward a predetermined position on the substrate 100M, and the light scattered by the substrate, 100M is caused, by the image-forming optical system, to form an image on a light receiving surface of the image-capturing element. Regarding the result of image-capturing performed by the image-capturing element, the processor finds whether or not there is a particle, the size of the particle, and the like in accordance with a predetermined algorithm, and stores the obtained results on the memory. Such a foreign object detection device is described in, for example, Japanese Laid-Open Patent. Publication No. 2016-105052. The entirety of the disclosure of Japanese Laid-Open Patent Publication No. 2016-105052 is incorporated herein by reference. As the foreign object detection device 40, for example, HS-930 produced by Toray Engineering Co., Ltd. is preferably usable. HS-930 is capable of detecting a foreign object, having a size of 0.3 m (evaluation performed by scattering standard particles). HS-930 is capable of inspecting, for example, a G4.5 substrate in a time period shorter than 60 seconds.
(47) The standard particle is a true sphere polystyrene latex particle. The actual particle P is a microscopic piece of broken glass, a metal particle or an organic particle (organic EL material), and is covered with an SiN layer (refractive index: about 1.8; second inorganic barrier layer). Therefore, the actual particle P is mote easily detectable than the standard particle. With the above-described foreign object detection device using scattered laser light, a foreign object having an equivalent spherical diameter of 0.2 m or longer is detected.
(48) The inkjet device 50 shown in
(49) The controller 52 includes a memory and a processor (neither is shown), and controls the inkjet head 54, the UV irradiation head 56 and/or the stage 70 to operate in accordance with information stored on the memory, so that the inkjet head 54 and the UV irradiation head 56 move to a desired position on the substrate 100M.
(50) A signal that controls the inkjet head 54, the UV irradiation head 56 and/or the stage 70 to operate is generated by the processor and supplied to the inkjet head 54, the UV irradiation head 56 and/or the stage 70 via interfaces (represented by the arrows in the figure) For example, position information (e.g., xy coordinates), on the position at which the particle is present, stored on the memory of the controller 42 of the foreign object detection device 40 is received by the, controller 52. Based on the position information, microscopic liquid drops of the coating liquid containing the photocurable resin are supplied from the inkjet head 54. The amount of the coating liquid (the number of the microscopic liquid drops, namely, the, number of shots) supplied from the, inkjet head 54 is, for example, found by the processor based on size information on the particle stored on the memory of the controller 42 of the foreign object detection device 40 and received by the controller 52.
(51) Then, the UV irradiation head 56 irradiates the supplied photocurable resin with ultraviolet rays and thus cures the photocurable resin to form the organic barrier layer. The above-described operation is performed on each of the particles.
(52)
(53) Alternatively, for example, a plurality of inkjet heads may be prepared. For example, two or more inkjet heads generating different sizes of microscopic liquid drops may be prep red, so that different inkjet heads are used for particles of different sizes.
(54) For example, the inkjet head 54 preferably usable may generate microscopic liquid drops each having a volume of the order of 1 fL (1 fL or larger and smaller than 10 fL) or may generate microscopic liquid drops each having a volume smaller than 1 fL. 1 fL corresponds to a volume of a sphere having a diameter of about 1.2 m, and 0.1 fL corresponds to a volume of a sphere having a diameter of about 0.6 m. For example, the inkjet device, produced by SIJ Technology Inc., tint is capable of injecting 0.1 fL microscopic liquid drops (specifically, Super Inkjet (registered trademark)) is preferably usable.
(55) Now, with reference to
(56) Now, is assumed that the particle P or the first inorganic barrier layer 12a formed so as to cover the particle P (the particle P and the first inorganic barrier layer 12a formed so as to cover the particle P may be collectively referred to as a protruding portion by the particle P) is spherical. An organic barrier layer 14v in the vicinity of the particle P may be formed to cover the particle P and/or the inorganic barrier layer 12a on the particle P. However, if the organic barrier layer 14 is too thick, there is, an undesirable possibility that the protruding portion by the particle P is visually recognized by a refraction function (lens effect) of the organic barrier layer 14. Therefore, it is preferred that as shown in
(57) Assuming that a concave surface of the organic barrier layer 14v is a curved surface having a radius of curvature that is the same as the radius R of the protruding portion by the particle P, the volume V.sub.0 of the organic barrier layer 14v shown in
V.sub.0=(4)R.sup.3(1)
(58) When the radius R of the protruding portion by the particle P is 0.15 m, V.sub.0 is about 0.009 fL. When the radius R is 0.25 m, V.sub.0 is about 0.04 fL. When the radius R is 2.5 m, V.sub.0 is about 42 fL.
(59) It is preferred that the volume of the organic barrier layer 14v is larger than, or equal to, about of Vo. If the volume of the organic barrier layer 14v is smaller than this range, there is an undesirable possibility that the effect of the formation of the organic barrier layer 14v is not provided, namely, the second inorganic barrier layer 16 with a fine film with no defect is not formed. The upper limit of the volume of the organic barrier layer 14v may be a level at which the protruding portion by the particle P is not visually recognized by the refraction function (lens effect). The upper limit preferably does not exceed five times of V.sub.0, and more preferably does not exceed twice of V.sub.0. In the case where the radius R of the protruding portion by the particle P is shorter than 2.5 m (in the case where V.sub.0 is smaller than about 42 fL), the volume of the organic barrier layer 14v is not limited to the above-described range. The volume of the organic barrier layer 14v is merely required not to exceed about 200 fL, and is preferably smaller than, or equal to, about 100 fL.
(60) It is preferred that the size of the microscopic liquid drops is appropriately set in accordance with the radius R of the protruding portion by the particle P. It is preferred that, for example, the size of the microscopic liquid drops is set such that one to three drops satisfy V.sub.0. A solvent may be incorporated into the coating liquid, so that the microscopic liquid drops are made large (to a size range from a size larger than the final size to 10 times the original size) with respect to the solid content in the coating liquid (amount left as the organic barrier layer 14v in a final state).
(61) A protruding portion, the particle P, having diameter shorter than 0.2 m (having a radius R shorter than 0.1 m) is considered to have substantially no influence on the moisture-resistance reliability even if the organic barrier layer 14v is not provided. Therefore, it is merely needed to detect protruding portions, by the particle P, having a diameter of 0.2 m or longer (having a radius R of 0.1 m or longer) and form the organic barrier layer 14v in corresponding portions.
(62) It is not efficient to supply a microscopic drop of 0.1 fL, a great number of times for a particle P having a diameter of 5 m (having a radius R of 2.5 m). Therefore, for example, an inkjet head generating microscopic liquid drops smaller than 1 fL (e.g., 0.1 fL) and an inkjet head generating microscopic liquid drops of 10 fL or larger and smaller than 0.5 pL (e.g., 50 fL) may be prepared, so that one of the infect heads is selected in accordance with the size of the particle P. The UV irradiation head 56 is commonly usable. Needless to say, three or more inkjet heads generating microscopic liquid drops of different sizes may be prepared.
(63) A coating liquid containing a photocurable resin (monomer) contains a photoinitiator (radical polymerization initiator or cationic polymerization initiator) and also a small amount of additive such as a surfactant or the like. The photocurable resin is contained in the coating liquid at a content of about 80% by mass to about 90% by mass, and the photoinitiator is contained at a content of about 5% by mass to about 10% by mass. A pigment or a dye may be incorporated into the coating liquid the case where a pigment is incorporated, dispersant may also be incorporated. A preferred viscosity is, for example, about 0.5 mPa.Math.s or higher and 10 Pa.Math.s or less. In the case where a dye or a pigment is incorporated, it is easily checked whether or not the organic barrier layer (solid portion) has been formed at a desired position. The pigment needs to be put into microscopic pieces, which raises the viscosity. Therefore, it is preferred to use a dye. In the case where, for example, microscopic liquid drops of 0.1 fL are generated, it is preferred that the coating liquid does not contain a pigment or a dye. In order to adjust the viscosity or the size. (volume) of the microscopic liquid drops, a solvent (e.g., an organic solvent such as alcohol or the like) may be incorporated.
(64) Usable as the photocurable resin may be a radical polymerizable monomer containing a vinyl group such as an acrylic resin (acrylate monomer) or the like, or a cationic polymerizable monomer containing an epoxy group. An appropriate photoinitiator is selected in accordance with the type of the resin to be used and the wavelength range of the DV light to be, directed. Instead of the UV irradiation head 56, an ultraviolet irradiation device such as a high pressure mercury lamp, a super-high pressure mercury lamp or the like may be, used to, for example, irradiate the entirety of the photocurable resin on the substrate 100M with ultraviolet rays at the same time.
(65) The production method may further include a step of partially ashing the photocured resin layer formed by curing the photocurable resin. Ashing may be performed by use, of a known plasma aching device, a known aching device using corona discharge, a known photo-excited aching device, a known UV ozone asking device or the like. Ashing may be performed, for example, by plasma aching using at least one type of gas among N.sub.2O, O.sub.2 and O.sub.3, or by a combination of plasma ashing and ultraviolet irradiation. In the case where an SiN film is formed by CVD as each of the first inorganic barrier layer 12 and the second inorganic barrier layer 16, N.sub.2O is used as material gas. Therefore, use of N.sub.2O for ashing provides an advantage of simplifying the ashing device.
(66) Ashing results in oxidizing the surface the organic barrier layer 14 to modify the surface the organic barrier layer 14 to hydrophilic. In addition, ashing results in shaving the surface the organic barrier layer 14 substantially uniformly and forming extremely tiny concaved and convexed portions to increase the surface area size of the organic barrier layer 14. The effect of aching of increasing the surface area size is greater for the surface of the organic barrier layer 14 than for the surface of the first inorganic barrier layer 12 formed of an inorganic material. Since the surface of the organic barrier layer 14 is modified to be hydrophilic and the surface area size thereof is increased, the adhesiveness between the organic barrier layer 14 and the second inorganic barrier layer 16 is improved.
(67) In order to improve the adhesiveness between the first inorganic barrier layer 12 and the organic barrier layer 14, the surface, of the first inorganic barrier layer 12 may be ached before the organic barrier layer 14 is formed.
(68) Ashing results in, for example, removing the photocured resin layer formed on the protruding portion by the particle P to adjust the location and; or the volume of tree organic barrier layer 14 left in final state, and also results in improving the adhesiveness between the organic barrier layer 14 and the second inorganic barrier layer 16.
(69) Embodiments of a method for producing an OLED display device including a flexible substrate, and such an OLED display device, according to an embodiment of the present invention are described above. The embodiments of the present invention are not limited to the embodiment described above as examples, and the present invention is widely applicable to an organic EL device including an organic EL element formed on a non-flexible substrate (e.g., glass substrate) and a thin film encapsulation structure formed on organic EL element (applicable to, for example, an organic EL illumination device).
INDUSTRIAL APPLICABILITY
(70) Embodiments of the pre Sent invention are applicable to a method for producing an organic EL device and to an organic EL device. The embodiments of the present invention are especially preferably applicable to a method for producing a flexible organic EL display device and to an organic EL display device.
REFERENCE SIGNS LIST
(71) 1 flexible substrate 2 circuit (backplane) 3 OLED layer (OLED) 4 polarizing plate 10 TFE structure 12, 12a, 12b first inorganic barrier layer (SiN layer) 12c crack 14 organic barrier layer 16 second inorganic barrier layer 30 lead wire 34 portion of the lead wire 36 portion of the lead wire 38 terminal portion 40 foreign object detection device 42 controller 44 detection head 50 inkjet device 52 controller 54 inkjet head 56 UV irradiation head 100 OLED display device P particle R1 active region R2 peripheral region TSF forward tapering side sur ace portion