JP2014123441A - Method for manufacturing organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method capable of stably manufacturing organic EL display devices by protecting a light-emitting layer under a wet etching process environment.SOLUTION: A method for manufacturing an organic EL display device comprises the steps of: forming a patterning member having an opening in a region in which a lower electrode is provided on a substrate; forming an organic compound layer so as to cover at least the lower electrode; forming an etch stop layer so as to cover at least a part of the patterning member and the organic compound layer; forming a sacrificial layer so as to cover at least a part of the patterning member and the etch stop layer; removing the patterning member and a laminate composed of the organic compound layer formed on the patterning member, the etch stop layer, and the sacrificial layer; removing the sacrificial layer; forming a common organic compound layer; and forming an upper electrode on the common organic compound layer.

Description

  The present invention relates to a method for manufacturing an organic EL display device.

  An organic EL display device is a device having one or more organic EL elements. In general, an organic EL element is an electronic element having an anode and a cathode, and an organic compound layer provided between the anode and the cathode and having a hole transport layer, a light emitting layer, an electron transport layer, and the like. The hole injected from the anode side and the electron injected from the cathode side recombine in the light emitting layer via the charge transport layer (hole transport layer, electron transport layer), respectively, so that the organic EL element Get luminescence.

  As one of methods for manufacturing this organic EL display device, a vacuum deposition method is known. Specifically, an organic material is put into a crucible, and vapor of the vapor deposition material is generated by heating the vapor deposition material at a temperature equal to or higher than a vaporization temperature in a vacuum apparatus, and this vapor is deposited on a substrate that is a base of the organic EL display device. This is a manufacturing process for forming a thin film layer such as an organic compound layer.

  When manufacturing an organic EL display device using a vacuum deposition method, generally, a light emitting layer having a predetermined pattern shape is formed and formed using a metal mask having an opening in a predetermined region. Thereby, for example, an organic EL element that emits one of red, green, and blue is obtained. However, in a patterning method using a metal mask, if the opening width of the metal mask is narrowed, it becomes difficult to align the opening widths to the same width, so that there is a problem that the definition is limited.

  As a method for solving the problem of definition, a method disclosed in Patent Document 1 has been proposed. Specifically, a method using a photolithography method using a resist layer has been proposed. In the manufacturing process of Patent Document 1, an organic compound layer including a light emitting layer is formed on the resist layer during the process, but the entire resist layer is removed using lift-off.

Japanese Patent No. 4578026

  By the way, in the technique proposed in Patent Document 1, a solvent that dissolves the resist is used for the purpose of removing the resist layer. On the other hand, when the resist layer is removed, an end portion of the light emitting layer may be exposed in a part of the removed resist layer. In this case, the light emitting layer may be eroded by the solvent for removing the resist layer, which may hinder stable production of the organic EL display device.

  The present invention has been made to solve the above-described problems, and an object thereof is to protect an emission layer from a wet etching process environment and to provide an organic EL display device that enables stable production. It is to provide a manufacturing method.

The organic EL display device manufacturing method of the present invention includes a substrate,
A lower electrode provided on the substrate;
An organic compound layer formed on the lower electrode and including at least a light emitting layer;
An organic EL element including an upper electrode formed on the organic compound layer;
In the method of manufacturing an organic EL display device in which the organic compound layer has a predetermined pattern shape,
Forming a patterning member having an opening in a region where a lower electrode is provided on a substrate;
Forming an organic compound layer so as to cover at least a part of the patterning member and the lower electrode;
Forming an etch stop layer so as to cover at least a part of the patterning member and the organic compound layer;
Forming a sacrificial layer so as to cover at least a part of the patterning member and the etch stop layer;
Removing the patterning member, and a laminate including the organic compound layer, the etch stop layer, and the sacrificial layer formed on the patterning member;
Removing the sacrificial layer;
Forming a common organic compound layer;
Forming an upper electrode on the common organic compound layer,
The etch stop layer is a layer formed so as to include evaporation molecules having an incident angle component larger than an angle formed by a direction perpendicular to the substrate and a maximum incident angle of evaporation molecules of the organic compound layer,
The sacrificial layer is a layer formed so as to include evaporation molecules having an incident angle component larger than an angle formed by a direction perpendicular to the substrate and a maximum incident angle of the evaporation molecules of the etch stop layer,
The etch stop layer is slower in etching rate with respect to the solvent for dissolving the sacrificial layer than the sacrificial layer.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the organic electroluminescent display apparatus which protects a light emitting layer from the wet etching process environment, and enables stable manufacture can be provided.

It is a schematic diagram which shows the example of the organic electroluminescence display manufactured by the manufacturing method of this invention, (a) is a perspective view, (b) is AA 'sectional drawing of (a). It is a cross-sectional schematic diagram which shows 1st embodiment in the manufacturing method of the organic electroluminescence display of this invention. It is a cross-sectional schematic diagram which shows the mode of film-forming of each layer at the time of vapor-depositing an organic compound layer, an etch stop layer, and a sacrificial layer with a respectively different vapor deposition angle. It is a cross-sectional schematic diagram which shows the mode of film-forming of each layer at the time of vapor-depositing an organic compound layer, an etch stop layer, and a sacrificial layer with the same vapor deposition angle. It is a cross-sectional schematic diagram which shows 2nd embodiment in the manufacturing method of the organic electroluminescence display of this invention. It is a cross-sectional schematic diagram which shows 2nd embodiment in the manufacturing method of the organic electroluminescence display of this invention.

  The manufacturing method of the present invention includes a substrate, a lower electrode provided on the substrate, an organic compound layer formed on the lower electrode and including at least a light-emitting layer, and an upper electrode formed on the organic compound layer. This is a method of manufacturing an organic EL display device having an EL element. In the present invention, the organic compound layer has a predetermined pattern shape.

The production method of the present invention has at least the following steps (1) to (8).
(1) A step of forming a patterning member having an opening in a region where a lower electrode is provided on a substrate (patterning member forming step)
(2) Step of forming an organic compound layer so as to cover at least a part of the patterning member and the lower electrode (formation step of organic compound)
(3) Step of forming an etch stop layer so as to cover at least a part of the patterning member and the organic compound layer (etch stop layer formation step)
(4) A step of forming a sacrificial layer so as to cover at least a part of the patterning member and the etch stop layer (a sacrificial layer forming step)
(5) A step of removing the patterning member and the laminate formed on the patterning member and including the organic compound layer, the etch stop layer, and the sacrificial layer (lift-off step)
(6) Step of removing the sacrificial layer (Sacrificial layer removing step)
(7) Step of forming common organic compound layer (formation step of common organic compound layer)
(8) Step of forming the upper electrode on the common organic compound layer (upper electrode forming step)

  In the present invention, the etch stop layer is a layer formed so as to include evaporated molecules having an incident angle component larger than an angle formed by a direction perpendicular to the substrate and the maximum incident angle of the evaporated molecules of the organic compound layer. In the present invention, the sacrificial layer is a layer formed so as to include evaporated molecules having an incident angle component larger than an angle formed by a direction perpendicular to the substrate and the maximum incident angle of the evaporated molecules of the etch stop layer. In the present invention, the etch stop layer is a layer whose etching rate with respect to the solvent dissolving the sacrificial layer is slower than that of the sacrificial layer.

Moreover, if the manufacturing method of this invention is used, the organic electroluminescent display apparatus which has multiple types of organic electroluminescent element from which luminescent color differs can be manufactured. In the present invention, as a method of manufacturing an organic EL display device having a plurality of types of organic EL elements having different emission colors, there is a manufacturing method having steps shown in the following (i) to (viii).
(I) The process of forming the 1st laminated body on which a 1st organic compound layer, an etch stop layer, and a sacrificial layer are laminated | stacked in this order on a board | substrate (formation process of a 1st laminated body)
(Ii) A step of forming a patterning member having an opening in a region corresponding to a region where predetermined pixels are provided on the first stacked body (patterning member forming step)
(Iii) Process of processing the first organic compound layer to expose the lower electrode provided in the region where the predetermined pixel is provided (processing process of the first organic compound layer)
(Iv) A step of forming a second stacked body in which a second organic compound layer, an etch stop layer, and a sacrificial layer are stacked in this order on the exposed lower electrode (second stacked body) Formation process)
(V) Step of removing patterning member (patterning member removal step)
(Vi) Step of removing the sacrificial layer (Sacrificial layer removing step)
(Vii) A step of forming a common organic compound layer (a step of forming a common organic compound layer)
(Viii) Step of forming the upper electrode on the common organic compound layer (upper electrode forming step)

  In the present invention, among the steps shown in (i) to (viii) above, the steps shown in (ii) to (v) are repeated as appropriate according to the type of organic EL element included in the organic EL display device. Can be done. For example, when manufacturing an organic EL display device having three types of organic EL elements having different emission colors, the steps shown in (ii) to (v) may be repeated twice.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings as appropriate. However, the embodiments described below are merely specific examples, and the present invention is not limited to these embodiments.

[Organic EL display device]
FIG. 1 is a schematic view showing an example of an organic EL display device manufactured by the manufacturing method of the present invention, (a) is a perspective view, and (b) is an AA ′ cross-sectional view of (a). is there. In the organic EL display device 1 of FIG. 1, pixels 20 including a first sub-pixel 20 a, a second sub-pixel 20 b, and a third sub-pixel 20 c are provided in a matrix form on a support substrate 10. The first organic EL element 21a, the second organic EL element 21b, and the third organic EL element 21c are provided in regions where these three types of pixels (20a, 20b, and 20c) are provided. Here, when the light emission color of the three types of organic EL elements (21a, 21b, 21c) is one of the three primary colors (RGB) of light, the organic EL display device 1 of FIG. 1 is a display device capable of full color display. Become. However, in the present invention, the type of the organic EL element is not particularly limited.

  In the organic EL display device 1 of FIG. 1, the first organic EL element 21 a includes a lower electrode 22 a provided on the substrate 10, a first organic compound layer 23 a, a charge injection / transport layer 24 a, and a common organic compound layer 25. The upper electrode 26 is an element that is laminated in this order. In the organic EL display device 1 of FIG. 1, the second organic EL element 21 b includes a lower electrode 22 b provided on the substrate 10, a second organic compound layer 23 b, a charge injection / transport layer 24 b, and a common organic compound layer 25. The upper electrode 26 is an element that is laminated in this order. In the organic EL display device 1 of FIG. 1, the third organic EL element 21c includes a lower electrode 22c, a third organic compound layer 23c, a charge injection transport layer 24c, a common organic compound layer 25, and an upper electrode 26. The elements are stacked in this order. The common organic compound layer 25 and the upper electrode 26 are layers formed in common for all pixels (sub-pixels).

[Method for Manufacturing Organic EL Display Device]
(1) First Embodiment FIG. 2 is a schematic cross-sectional view showing a first embodiment in the method for manufacturing an organic EL display device of the present invention. Hereinafter, the manufacturing process included in the first embodiment of the present invention will be described with reference to FIG.

(1-1) Formation process of substrate with electrode (FIG. 2A)
First, the substrate 10 provided with the lower electrode 22 is manufactured (FIG. 2A).

  As the substrate 10, a base material (10a) itself made of glass, a film made of a polymer material, a Si wafer, or the like may be used. However, as shown in FIG. Also, a circuit board provided with a contact portion 12 can be suitably used. In addition, when providing the drive circuit 11 and the contact part 12 on a base material, it is desirable to provide the planarization layer 10b for filling up the unevenness | corrugation produced when providing the drive circuit 11 grade | etc.,.

  The constituent material of the contact portion 12 is preferably a metal that can make ohmic contact with the lower electrode 22. The contact portion 12 is electrically connected to a drive circuit 11 for driving an organic EL display device built in advance in the substrate 10. The shape of the contact portion 12 is not particularly limited as long as it is electrically connected to the lower electrode 22.

  The constituent material of the lower electrode 22 can be appropriately selected according to the light extraction direction. In the case of providing a top emission type organic EL element on the substrate 10, a material (Al, Ag, etc.) that efficiently reflects light emitted from the organic compound layer 23 without restricting the wavelength band is preferable. Not. In the case where a bottom emission type organic EL element is provided on the substrate 10, a material (ITO or the like) that efficiently transmits light emitted from the organic compound layer 23 without limiting the wavelength band is preferable, but is not limited thereto.

(1-2) Intermediate layer forming step (FIG. 2B)
Next, the intermediate layer 14 is formed on the substrate 10 (FIG. 2B). The intermediate layer 14 is intended to remove the protective layer 15 formed in a later step, and the organic compound layer 23, the etch stop layer 16 and the sacrificial layer 17 formed on the protective layer 15 by using lift-off. It is a layer formed as. The constituent material of the intermediate layer 14 is preferably a material that is dissolved in a solvent containing water, such as LiF, polyvinyl pyrrolidone, or polyvinyl alcohol. However, the material is not limited to the above-described materials as long as it can dissolve in a specific polar solvent and efficiently lift off the layer formed on the intermediate layer 14. The intermediate layer 14 can be selectively removed by immersing it in a solvent together with the substrate 10 in a lift-off process described later. Examples of the method for forming the intermediate layer 14 include, but are not limited to, a spin coating method, a slit coating method, and an ink jet method.

(1-3) Step of forming protective layer (FIG. 2 (c))
Next, the protective layer 15 is formed on the intermediate layer 14 (FIG. 2C). The protective layer 15 is a layer provided when the intermediate layer 14 can be damaged such as being dissolved by a solvent that dissolves the resist material that is a constituent material of the resist layer 30. That is, the protective layer 15 is formed for the purpose of preventing damage to the intermediate layer 14 in the resist layer forming process described later. The constituent material of the protective layer 15 is preferably an inorganic material (silicon nitride, silicon oxide, etc.) that has high moisture resistance and can be removed by dry etching so that a liquid such as a solvent does not penetrate. Examples of the method for forming the protective layer 15 include a plasma CVD method, but are not limited thereto.

(1-4) Step of forming a resist layer (FIG. 2 (d))
Next, a resist layer 30 is formed on the protective layer 15 (FIG. 2D). The resist layer 30 is preferably a positive photoresist in consideration of the influence on the lower layer during exposure, but is not limited thereto. As a method for forming the resist layer 30, a spin coating method, a slit coating method, an ink jet method, a printing method, or the like can be used, but the method is not limited thereto.

(1-5) Exposure / development process (FIG. 2 (e))
Next, the resist layer 30 provided in the lower electrode 22 and the surrounding area is irradiated (exposed) with light, and then development processing is performed. Thereby, the lower electrode 22 and the resist layer 30 provided in the surrounding area can be partially removed (FIG. 2E).

(1-6) Processing step of protective layer / intermediate layer (FIG. 2 (f))
Next, the protective layer 15 exposed by partially removing the resist layer 30 is processed by dry etching. When processing the protective layer 15 by dry etching, a reactive gas capable of efficiently etching the constituent material of the protective layer 15 may be selected in consideration of the constituent material of the protective layer 15. For example, when the constituent material of the protective layer 15 is SiN, a fluorine-based gas (fluorocarbon-based gas) such as CF ₄ gas or CHF ₃ may be used. For the purpose of removing the resist layer 30 remaining after the above-described exposure / development steps, oxygen may be mixed in the reaction gas at a constant concentration.

  In the present invention, when processing the protective layer 15, as shown in FIG. 2E, the taper shape in which the top surface side 15a of the protective layer is wider than the substrate side 15b of the protective layer, as shown in FIG. The protective layer 15 is processed so that is formed. This taper shape is important in determining the allowable range of the incident angle of the vapor deposition molecules in the organic compound layer forming step described later, and details thereof will be described later.

Next, the intermediate layer 14 exposed by processing the protective layer 15 is processed by dry etching. As a result, the surface layer of the lower electrode 22 is exposed, and the patterning member 16 having openings in the lower electrode 22 and its peripheral region is formed (FIG. 2F). When processing the intermediate layer 14 by dry etching, a reactive gas that can efficiently etch the constituent material of the intermediate layer 14 may be selected in consideration of the constituent material of the intermediate layer 14. For example, when an organic compound is used as the constituent material of the intermediate layer 14, O ₂ gas or the like may be used. Even if the resist layer 30 remains in the processing step of the protective layer 15, it is completely removed in this intermediate layer processing step.

  In the present invention, when the intermediate layer 14 is processed, the intermediate layer 14 is processed so that the processing region is wider than the protective layer 15. The processing mode of the intermediate layer 14 is important in determining the allowable range of the incident angle of the vapor deposition molecules in the organic compound layer forming step described later, as in the cross-sectional shape of the processed protective layer 15. Details thereof will be described later. In addition, by processing the intermediate layer 14 so that the processing region is wider than the protective layer 15, the patterned member 16 including the processed intermediate layer 14 and the protective layer 15 is compatible with the cross-sectional shape of the protective layer 15 described above. Thus, it has a bowl-like cross-sectional shape.

(1-7) Organic compound layer forming step (FIG. 2 (g))
Next, an organic compound layer 23 having a light emitting layer containing a light emitting material is formed on the lower electrode 22 (FIG. 2G). At this time, the organic compound layer 23 is selectively formed by using the patterning member 16 in a region where the lower electrode 22 is provided and a peripheral region thereof.

  In the present invention, the organic compound layer 23 is a single layer or a laminate composed of a plurality of layers having at least a light emitting layer. The organic compound layer 23 is preferably a laminate composed of a plurality of layers having a light emitting layer. When the organic compound layer 23 is a laminate composed of a plurality of layers, a hole injection layer, a hole transport layer, an electron block layer, a hole block layer, an electron transport are used as layers other than the light emitting layer of the organic compound layer 23. A layer, an electron injection layer, and the like. When the organic compound layer 23 has a layer other than the light emitting layer, the layer that the organic compound layer 23 has is appropriately selected in consideration of the characteristics of the lower electrode 22. Here, when the lower electrode 22 is an anode, examples of the layer of the organic compound layer 23 include a hole injection layer, a hole transport layer, an electron blocking layer, and the like, and are mainly provided between the lower electrode and the light emitting layer. Exists as a layer. On the other hand, when the lower electrode 22 is a cathode, examples of the layer of the organic compound layer 23 include an electron injection layer, an electron transport layer, and a hole blocking layer, and are mainly provided between the lower electrode and the light emitting layer. Present as a layer.

  As a constituent material of the light emitting layer included in the organic compound layer 23, a light emitting material such as a metal complex (aluminum complex, iridium complex) material or the like can be used. However, it is not limited to these materials.

  As a constituent material of a layer (hole injection layer, hole transport layer, electron block layer, etc.) for injecting and transporting holes contained in the organic compound layer 23, a phthalocyanine-based material, a triphenyldiamine-based material, or the like is used. Can do. However, it is not limited to these materials.

  As a constituent material of a layer (electron injection layer, electron transport layer, hole blocking layer, etc.) for injecting and transporting electrons contained in the organic compound layer 23, an oxazole derivative, a triazole derivative, or the like can be used. However, it is not limited to these materials.

  As a method for forming the organic compound layer 23, a vacuum vapor deposition method in which the straightness of the material during film formation is high is preferably used. When the straightness of the material is high, the amount of film deposited on the side wall portion of the patterning member 16 (particularly, the side wall portion of the protective layer 15) is reduced, so that the organic compound layer 23 and the like can be easily patterned.

(1-8) Etch stop layer forming step (FIG. 2 (h))
Next, an etch stop layer is formed on the organic compound layer 23 (FIG. 2H). Similar to the organic compound layer 23, the etch stop layer functions as a layer constituting an organic EL element included in the organic EL display device, specifically, the charge injection / transport layer 24 in the organic EL display device 1 of FIG. . Hereinafter, the etch stop layer will be described with the same reference numeral (reference numeral 24) as that of the charge injection / transport layer.

  By the way, the characteristics of the etch stop layer 24 functioning as a charge injection / transport layer depend on the characteristics of the upper electrode 26 manufactured in a later step. That is, when the upper electrode 26 is an anode, the etch stop layer 24 becomes a layer (hole transport layer, hole injection layer, electron block layer, etc.) that transports / injects holes into the light emitting layer. On the other hand, when the upper electrode 26 is a cathode, the etch stop layer 24 becomes a layer (electron transport layer, electron injection layer, hole blocking layer, etc.) that transports and injects electrons to the light emitting layer.

  In the present invention, the etch stop layer 24 is a layer made of a material insoluble in the solvent used when removing the sacrificial layer 31 formed in the next step. For this reason, the etch stop layer 24 functions as a layer that protects the organic compound layer 23 from the solvent used when the sacrificial layer 31 is removed.

(1-9) Sacrificial layer forming step (FIG. 2 (i))
Next, a sacrificial layer 31 is formed on the etch stop layer 24 (FIG. 2I). The constituent material of the sacrificial layer 31 is not particularly limited as long as the material is insoluble in the solvent used when removing the intermediate layer 14. For example, when a water-soluble material (water-soluble inorganic material or organic material) is used as the constituent material of the intermediate layer 14, a material insoluble in water may be used as the constituent material of the sacrificial layer 31.

(1-10) Various Conditions for Vapor Deposition Film Formation FIG. 3 shows the state of film formation of each layer when the organic compound layer 23, the etch stop layer 24, and the sacrificial layer 31 are vapor deposited at different vapor deposition angles. It is a cross-sectional schematic diagram shown.

By the way, when forming the organic compound layer 23, the incident angle (vapor deposition angle) of the evaporated molecules of the organic compound layer 23 is controlled within a certain range. This is because the organic compound layer 23 is efficiently formed while covering the upper surface and side surfaces of the lower electrode 22. Here the maximum value of the incident angle of evaporation molecules of the organic compound layer 23 with respect to the vertical direction to the substrate 10 and theta _alpha. In the present invention, when the etch stop layer 24 is formed on the organic compound layer 23, the maximum incident angle θ _β of the evaporated molecules of the etch stop layer 24 with respect to the direction perpendicular to the substrate 10 is determined from the above θ _α . Also set larger. When the etch stop layer 24 is formed under such conditions, the end portion of the organic compound layer 23 can be reliably covered with the etch stop layer 24. As a result, the end portion of the organic compound layer 23 can be protected from the solvent used when removing the sacrificial layer 31 formed in a later step. When the sacrificial layer 31 is formed, the maximum value θ _γ of the incident angle of the evaporated molecules of the sacrificial layer 31 with respect to the direction perpendicular to the substrate 10 is set larger than the above θ _β . When the sacrificial layer 31 is formed under such conditions, the end portion of the etch stop layer 24 can be reliably covered with the sacrificial layer 31. As a result, when performing the removal process of the sacrificial layer 31 in a later process, even if there is a variation in the wet etching rate, the sacrificial layer 31 is formed so as to cover the end of the etch stop layer 24. The etch stop layer 24 is not directly exposed to the solvent that dissolves the sacrificial layer 31. Thereby, in the removal process of the sacrificial layer 31, damage to the etch stop layer 24 due to the wet etching process is suppressed.

  FIG. 4 is a schematic cross-sectional view showing how each layer is formed when the organic compound layer, the etch stop layer, and the sacrificial layer are deposited at the same deposition angle. Temporarily, when the organic compound layer 23, the etch stop layer 24, and the sacrificial layer 31 are formed, the maximum value of the incident angle of the evaporated molecules with respect to the direction perpendicular to the substrate is set to the same angle (θ). Then, the film-forming aspect of each layer of the organic compound layer 23, the etch stop layer 24, and the sacrificial layer 31 is as shown in FIG. Here, when the maximum value of the incident angle of the evaporated molecules with respect to the direction perpendicular to the substrate is set at the same angle (θ), the film thicknesses of the etch stop layer 23 and the sacrificial layer 31 formed on the side surface of the organic compound layer 23 are as follows. Thin compared to the organic compound layer 23. For this reason, the organic compound layer 23 is easily damaged by the solvent that dissolves either the intermediate layer 14 or the sacrificial layer 31.

  In the present invention, when the organic compound layer 23, the etch stop layer 24, and the sacrificial layer 31 are formed, a vacuum deposition method is employed. However, the specific method of vacuum deposition is not particularly limited, and the film is formed by rotating the substrate while rotating the substrate, or by sequentially changing the relative position between the substrate and the evaporation source. Transport film formation or the like can be used.

(1-11) Lift-off process (FIGS. 2 (j) to (k))
Next, the substrate 10 is immersed in a solvent to dissolve the intermediate layer 14 provided on the substrate 10. When the intermediate layer 14 is dissolved and removed from the substrate 10, the film provided on the intermediate layer 14 is also removed together with the intermediate layer 14 (FIGS. 2 (j) to (k)). However, since the sacrificial layer 31 itself is insoluble in the solvent that dissolves the intermediate layer 14, the sacrificial layer 31 formed on the lower electrode 22 is not removed. In this step, since the sacrificial layer 31 formed on the lower electrode 22 is not removed, the etch stop layer 24 covered by the sacrificial layer 31 and the organic compound layer 23 covered by the etch stop layer 24 are not removed. Remains. Therefore, the sacrificial layer 31 functions as a layer that protects the etch stop layer 24 and the organic compound layer 23.

(1-12) Sacrificial layer removal step (FIG. 2 (l))
Next, the sacrificial layer 31 provided on the substrate 10 is dissolved and removed by immersing the substrate 10 in a solvent different from the solvent used in the previous process (lift-off process) (FIG. 2 (l)). . At this time, since the etch stop layer 24 is insoluble in the solvent that dissolves the sacrificial layer 31, it remains without being removed in this step. Therefore, the etch stop layer 24 functions as a layer that protects the organic compound layer 23. In the present invention, the etch stop layer 24 covers the end portion and the side wall surface of the organic compound layer 23 as shown in FIG. For this reason, the edge part and side wall surface of the organic compound layer 23 are not damaged by the solvent used in this step (sacrificial layer removing step), and the film is reduced by the solvent used in this step, film peeling, etc. Will not occur.

(1-13) Common organic compound layer formation step (FIG. 2 (m))
Next, a common organic compound layer 25 is formed on the etch stop layer 24 (FIG. 2 (m)). The common organic compound layer 25 is not particularly limited as long as it is a layer made of an organic compound that can efficiently inject carriers into the organic compound layer 23. Specifically, the light extraction method (top emission method, bottom emission method), the nature of the carriers injected into or transported into the organic compound layer 23 (hole injection transport property, electron injection transport property), etc. The material can be selected as appropriate. When the common organic compound layer 24 is formed, a vacuum deposition method can be used, but is not limited thereto.

(1-14) Upper electrode forming step (FIG. 2 (n))
Next, the upper electrode 26 is formed on the common organic compound layer 25, whereby the organic EL display device is completed (FIG. 2 (n)). The upper electrode 26 can be appropriately selected in consideration of the light extraction direction. In the case of producing a top emission type organic EL element, the constituent material of the upper electrode 26 is not particularly limited as long as it does not inhibit light emission emitted from the organic compound layer 23. For example, transparent oxide materials (ITO, indium zinc oxide, IWZO, etc.) are mentioned. In the case of producing a bottom emission type organic EL element, the constituent material of the upper electrode 26 is not particularly limited as long as it is a material that reflects light emitted from the organic compound layer 23. For example, metal materials (Al, Ag, etc.) are mentioned. As a method for forming the upper electrode 26, a sputtering method, a vacuum evaporation method, or the like can be used, but the method is not limited thereto.

  As described above, in the manufacturing method of the present invention, a plurality of layers (etch stop layer 24 and sacrificial layer 31) having different solvent resistance performances are formed on the organic compound layer 23 on the surface and end portions of the organic compound layer 23. Protect. For this reason, the organic compound layer 23 can be protected from the wet etching process.

(Second embodiment)
FIG. 5 is a schematic cross-sectional view showing a second embodiment in the method for manufacturing an organic EL display device of the present invention. The manufacturing process shown in FIG. 5 is also a manufacturing process for manufacturing the organic EL display device of FIG. Hereinafter, the present embodiment will be described focusing on differences from the first embodiment.

(2-1) Formation process of substrate with electrode (FIG. 5A)
In the present embodiment, it is necessary to form at least three (22a, 22b, and 22c) lower electrodes 22 provided on the substrate 10 according to the types (three types) of subpixels. Hereinafter, the substrate with electrodes in which the lower electrode 22a is provided in the first subpixel 20a, the lower electrode 22b is provided in the second subpixel 20b, and the lower electrode 22c is provided in the third subpixel 20c will be described. Further, as shown in FIG. 5A, when a circuit board with a drive circuit 11 and a contact portion 12 provided on a base material 10a is manufactured, one set of drive circuit 11 and one set for one pixel. Contact portions 12 are formed respectively.

(2-2) First organic compound layer forming step (FIG. 5B)
Next, the first organic compound layer 23a is formed on the entire surface of the substrate 10 (FIG. 5B). The first organic compound layer 23a is included in the first organic EL element 21a included in the first sub-pixel 20a, and is a single layer or a laminate including a plurality of layers having a light emitting layer that outputs light having a predetermined wavelength. . The first organic compound layer 23a is preferably a stacked body including a plurality of layers. When the first organic compound layer 23a is a laminate composed of a plurality of layers, a hole injection layer, a hole transport layer, an electron block layer, a hole block are provided as layers other than the light emitting layer of the first organic compound layer 23a. A layer, an electron transport layer, an electron injection layer, and the like. In addition, when the 1st organic compound layer 23a has layers other than a light emitting layer, the layer which the 1st organic compound layer 23a has is suitably selected in consideration of the characteristics of the lower electrodes (22a, 22b, 22c). Here, when the lower electrode (22a, 22b, 22c) is an anode, examples of the layer of the first organic compound layer 23a include a hole injection layer, a hole transport layer, an electron blocking layer, and the like. It exists as a layer provided between (22a, 22b, 22c) and the light emitting layer. On the other hand, when the lower electrode (22a, 22b, 22c) is a cathode, examples of the layer of the first organic compound layer 23a include an electron injection layer, an electron transport layer, a hole blocking layer, and the like. 22a, 22b, 22c) and the light emitting layer.

(2-3) Etch stop layer forming step (FIG. 5C)
Next, an etch stop layer 24a is formed on the first organic compound layer 23a (FIG. 5C). Here, the etch stop layer 24a formed on the first organic compound layer 23a is a layer included in the first organic EL element 21a of the first subpixel 20a.

(2-4) Sacrificial layer forming step (FIG. 5D)
Next, a sacrificial layer 31a is formed on the etch stop layer 24a (FIG. 5D). The sacrificial layer 31a is not limited in its constituent material as long as it is insoluble in the solvent used when removing the intermediate layer 14 formed in a later step. For example, when a material (water-soluble inorganic material or organic material) that can be removed by washing with water is used as the constituent material of the intermediate layer 14, a material that is insoluble in water is used as the sacrificial layer 31a.

(2-5) Incident Angle of Vapor Deposition Molecule When the first organic compound layer 23a is formed, the incident angle (vapor deposition angle) of the evaporated molecules of the first organic compound layer 23a is controlled within a certain range. Specifically, as shown in FIG. 3, the maximum value of the incident angle of the evaporated molecules of the first organic compound layer 23a with respect to the direction perpendicular to the substrate 10 is controlled to be a predetermined value (θ _α ). Next, when the etch stop layer 24a is formed on the first organic compound layer 23a, the maximum value θ _β of the incident angle of the evaporated molecules of the etch stop layer 24a with respect to the direction perpendicular to the substrate 10 is set to the above θ _α. Set larger than. When forming the sacrificial layer 31a, the maximum value θ _γ of the incident angle of the evaporated molecules of the sacrificial layer 31a with respect to the direction perpendicular to the substrate 10 is set to be larger than the above θ _β . By forming the first organic compound layer 23a, the etch stop layer 24a, and the sacrificial layer 31a under such conditions, wet etching on the etch stop layer (24a) is performed in the sacrificial layer (31a) removal process. Damage from the process is suppressed.

(2-6) Intermediate layer forming step (FIG. 5E)
Next, the intermediate layer 14 is formed on the sacrificial layer 31 (FIG. 5E). As the constituent material and forming method of the intermediate layer 14 formed in this step, the same materials and methods as in the first embodiment can be employed.

(2-7) Step of forming protective layer (FIG. 5 (f))
Next, the protective layer 15 is formed on the intermediate layer 14 (FIG. 5F). As a constituent material and a forming method of the protective layer 15 formed in this step, the same materials and methods as in the first embodiment can be adopted.

(2-8) Resist layer forming step (FIG. 5G)
Next, a resist layer 30 is formed on the protective layer 15 (FIG. 5G). As a constituent material and a forming method of the resist layer 30 formed in this step, the same materials and methods as in the first embodiment can be employed. In the following description, a case where a resist layer is formed using a positive resist will be described.

(2-9) Exposure / development process (FIG. 5 (h))
Next, development is performed after selectively irradiating (exposing) light to the region where the second subpixel 20b is provided and the surrounding region, and the resist layer 30 provided in the region where the second subpixel 20b is provided is formed. Selectively remove. As a result, the protective layer 15 provided in the region where the second sub-pixel 20b is provided is exposed (FIG. 5H). As a specific method of exposing and developing the resist layer 30 performed in this step, the same method as in the first embodiment can be employed.

(2-10) Processing steps such as protective layer (FIG. 5 (i))
Next, the protective layer 15 exposed by partially removing the resist layer 30 is processed by dry etching. Next, the intermediate layer 14 exposed by processing the protective layer 15 is processed by dry etching. Subsequently to the intermediate layer 14, the sacrificial layer 31, the etch stop layer 24, and the first organic compound layer 23a are sequentially processed. As a result, the surface layer of the lower electrode 22b, which is a constituent member of the second organic EL element 21b of the second subpixel 20b, is exposed, and a patterning member having openings in the lower electrode 22b and the surrounding area is formed. (FIG. 2 (i)). As a specific processing method of the protective layer 15 and the intermediate layer 14 performed in this step, the same method as in the first embodiment can be employed. In this step, as the processing method of the sacrificial layer 31, the etch stop layer 24, and the first organic compound layer 23a, the method employed when processing the intermediate layer 14 can be employed as it is. By this step, the cross-sectional shape of the protective layer 15 becomes a tapered shape in which the top surface side 15a of the protective layer is wider than the substrate side 15b of the protective layer, as shown in FIG. On the other hand, the intermediate layer 14 is processed over a wider area than the protective layer 15 by this step. By processing the member such as the protective layer 15 as described above, the patterning member 16 made of the processed members (14, 15, 31, 24, 23a) is combined with the cross-sectional shape of the protective layer 15 described above. And has a bowl-like cross-sectional shape. Note that the resist layer 30 remaining in the development process is simultaneously removed when the protective layer 15 or the intermediate layer 14 is processed.

(2-11) Step of forming second organic compound layer, etch stop layer, sacrificial layer (FIGS. 5 (j) (l))
Next, the second organic compound layer 23b, the etch stop layer 24b, and the sacrificial layer 31b are sequentially formed on the lower electrode 22b (FIGS. 5J to 5L). Here, the second organic compound layer 23b outputs light of a different type from the light output from the first organic compound layer 23a.

By the way, when forming the 2nd organic compound layer 23b, the incident angle (vapor deposition angle) of the evaporation molecule of the 2nd organic compound layer 23b is controlled to a fixed range. Specifically, as shown in FIG. 3, the maximum value of the incident angle of the evaporated molecules of the second organic compound layer 23b with respect to the direction perpendicular to the substrate 10 is controlled to be a predetermined value (θ _α ). Next, when the etch stop layer 24b is formed on the second organic compound layer 23b, the maximum incident angle θ _β of the evaporated molecules of the etch stop layer 24b with respect to the direction perpendicular to the substrate 10 is set to the above θ _α. Set larger than. In forming the sacrificial layer 31b is the maximum value theta _gamma angle of incidence of the evaporation molecules of the sacrificial layer 31b with respect to the vertical direction to the substrate 10 is set larger than the theta _beta. Under such conditions, the first organic compound layer 23b, the etch stop layer 24b, and the sacrificial layer 31b are formed, so that the etch stop layer (24b) is wet etched in the sacrificial layer (31b) removal process. Damage from the process is suppressed.

  In the present embodiment, the constituent materials and forming methods of the second organic compound layer 23b, the etch stop layer 24b, and the sacrificial layer 31b can be the same as those in the first embodiment.

(2-12) Lift-off process (FIG. 5 (m))
Next, the substrate 10 is immersed in a solvent to dissolve the intermediate layer 14 provided on the substrate 10. When the intermediate layer 14 is dissolved and removed from the substrate 10, the film provided on the intermediate layer 14 is also removed together with the intermediate layer 14 (FIG. 5 (m)).

(2-13) Step of forming third organic compound layer, etc. (FIGS. 5 (n) to (w))
Through the above manufacturing process, the first organic compound layer 23a is formed in the region where the first subpixel 20a is provided, and the second organic compound layer 23b is formed in the region where the second subpixel 20b is provided. Here, in the present invention, by repeating the processes (2-6) to (2-12), a predetermined subpixel is provided among a plurality of types (specifically, three or more types) of subpixels. An organic compound layer that outputs a desired color can be selectively formed in the region. In the present embodiment, by repeating the processes (2-6) to (2-12) once more, the third organic compound layer 23c is formed in the region where the third subpixel 20c is provided (FIG. 5 (n)-(v)).

(2-14) Sacrificial layer removal step (FIG. 5 (x))
Next, the sacrificial layers (31a, 31b, 31c) formed on the entire surface of the substrate 10 are removed (FIG. 5 (x)). As a specific method for removing the sacrificial layers (31a, 31b, 31c), the same method as in the first embodiment can be used.

(2-15) Common organic compound layer and upper electrode forming step (FIGS. 5 (y) to (z))
Next, a common organic compound layer 25 provided in common to all pixels is formed on the etch stop layer (24a, 24b, 24c) (FIG. 5 (y)), and further on the common organic compound layer 25. The upper electrode 26 is formed (FIG. 5 (z)). Through the above process, the organic EL display device 1 having the three types of pixels (20a, 20b, 20c) shown in FIG. 1 is obtained.

  As described above, in the present invention, the step of forming the patterning member 16 when forming the organic compound layer in the region where the predetermined pixel is provided, and removing the patterning member 16 after forming the organic compound layer is repeated. . Thereby, the organic compound layer (23a, 23b, 23c) including the light emitting layer material that emits light with a desired emission color can be formed in a desired region (desired pixel region).

  In the manufacturing process described above, the organic compound layer 23 and the etch stop layer are more preferably protected so that the end portions of the organic compound layer 23 respectively included in the subpixels adjacent to each other are protected by the etch stop layer 24. 24 is formed. For example, as shown in FIG. 5K, the etch stop layer 24b is formed so that the end portion of the second organic compound layer 23b is protected by the etch stop layer 24b. Further, as shown in FIG. 2T, the etch stop layer 24c is formed so that the end portion of the third organic compound layer 23c is protected by the etch stop layer 24c.

  Particularly preferably, each organic compound layer is formed so as not to contact the organic compound layers provided in the pixels adjacent to each other. When formed in this manner, the organic compound layers (23a, 23b, 23c) provided in each subpixel are formed as a stacked body separated in units of subpixels. For this reason, so-called crosstalk light emission, in which other adjacent subpixels emit light due to carrier movement that can occur between organic compound layers provided in adjacent pixels, respectively, does not occur.

  An organic EL display device was manufactured according to the manufacturing process shown in FIG.

(1-1) Manufacturing process of substrate with electrode (FIG. 2A)
First, a substrate 10 having a drive circuit 11 provided on the base material 10a and a contact portion 12 was prepared (FIG. 2A). A lower electrode 22 is formed on the substrate 10 by laminating an Ag film and an ITO film in this order, and the drive circuit 11 and the lower electrode 22 are electrically connected by the contact portion 12. It was.

(1-2) Intermediate layer forming step (FIG. 2B)
Next, polyvinylpyrrolidone and water were mixed to prepare a coating solution. Next, this coating solution was dropped on the substrate 10, and then a polyvinyl pyrrolidone film was formed on the entire surface of the substrate 10 by spin coating to form an intermediate layer 14 (FIG. 2B). At this time, the film thickness of the intermediate layer 14 was 500 nm.

(1-3) Step of forming protective layer (FIG. 2 (c))
Next, a protective layer 15 was formed by forming a SiN film on the intermediate layer 14 by plasma CVD (FIG. 2C). At this time, the film thickness of the protective layer 15 was 1000 nm.

(1-4) Step of forming a resist layer (FIG. 2 (d))
Next, AZ1500 made by AZ Electronic Materials, which is a positive photoresist, was formed on the protective layer 15 by spin coating to form a resist layer 30 (FIG. 2D). At this time, the film thickness of the resist layer 30 was 1000 nm.

(1-5) Exposure / development process (FIG. 2 (e))
Next, exposure was performed on the lower electrode 22 and its surrounding area using an exposure apparatus. The exposure time at this time was 40 seconds. Next, a developer (concentration: 50%) was prepared by diluting 312MIF manufactured by AZ Electronic Materials with water. Next, the exposed resist layer 30 was removed using this developer. At this time, the development time was 60 seconds. By this development process, the resist layer provided in the lower electrode 22 and the surrounding area is removed, while the resist layer 30a provided in the area other than this area remains (FIG. 2E). )).

(1-6) Processing step of protective layer / intermediate layer (FIG. 2 (f))
Next, the protective layer 15 was processed by partially removing the protective layer 15 provided in a region not covered with the resist layer 30 by dry etching using a fluorine-based gas. At this time, the etching speed and range are set so that the cross-sectional shape of the processed protective layer 15 is tapered so that the opening on the top surface 15a side of the protective layer 15 is larger than the opening on the substrate side 15b of the protective layer 15. Controlled.

Next, by processing the exposed intermediate layer 14 by dry etching using O ₂ gas, the lower electrode 22 is exposed, and the patterning member 16 is formed on the substrate 10 (FIG. 2 ( f)). At this time, the flow rate of the etching gas (O ₂ gas) was 20 sccm, the pressure in the etching apparatus was 8 Pa, the output of the etching apparatus was 150 W, and the etching time was 300 seconds. In the etching of the intermediate layer 14, the etching conditions were optimized so that the processed region of the intermediate layer 14 was wider than the opening on the substrate side 15b of the protective layer 15. Moreover, the resist layer 30 was completely removed at the stage where this step was completed.

(1-7) Organic compound layer forming step (FIG. 2 (g))
Next, a hole transport layer was formed on the entire surface of the substrate 10 having the exposed lower electrode 22 by vacuum deposition using the patterning member 16. At this time, the thickness of the hole transport layer was 120 nm. Next, a blue light emitting layer was formed on the hole transport layer by a vacuum deposition method. At this time, the thickness of the blue light emitting layer was set to 20 nm. In addition, the laminated body which consists of a positive hole transport layer and a blue light emitting layer functions as the organic compound layer 23 (FIG.2 (g)). Further, when forming the hole transport layer and the blue light emitting layer, the maximum incident angle of the evaporated molecules of each layer with respect to the direction perpendicular to the substrate 10 was set to 10 °.

(1-8) Etch stop layer forming step (FIG. 2 (h))
Next, an etch stop layer 24 (hole blocking layer) was formed on the organic compound layer 23 by vacuum deposition (FIG. 2H). At this time, the thickness of the etch stop layer 24 was set to 10 nm, and the maximum incident angle of the evaporated molecules of the etch stop layer 24 with respect to the direction perpendicular to the substrate was set to 15 °.

(1-9) Sacrificial layer forming step (FIG. 2 (i))
Next, a sacrificial layer 31 was formed on the etch stop layer 24 by vacuum deposition (FIG. 2I). At this time, the thickness of the sacrificial layer 31 was set to 40 nm, and the maximum incident angle of the evaporated molecules of the sacrificial layer 31 with respect to the direction perpendicular to the substrate was set to 20 °.

(1-10) Lift-off process (FIGS. 2 (j) to (k))
Next, the substrate 10 was immersed in water. At this time, since the intermediate layer 14 is a layer formed of water-soluble polyvinyl pyrrolidone, the intermediate layer 14 is dissolved, and the layer formed on the intermediate layer 14 is lifted off from the substrate 10 in the process of dissolving the intermediate layer 14. (FIGS. 2 (j) to (k)).

(1-11) Sacrificial layer removal step (FIG. 2 (k))
Next, the sacrificial layer 31 was removed by immersing the substrate 10 in a solvent (polar solvent other than water) (FIG. 2 (k)).

(1-12) Step of forming a common organic compound layer (FIG. 2 (m))
Next, a common organic compound layer 25 (electron injection layer) was formed on the etch stop layer 24 by vacuum deposition (FIG. 2 (m)). At this time, the film thickness of the common organic compound layer 25 was 20 nm.

(1-13) Upper electrode formation step (FIG. 2 (n))
Next, Ag was formed on the common organic compound layer 25 by a sputtering method to form the upper electrode 26 (FIG. 2 (n)). At this time, the film thickness of the upper electrode 26 was 16 nm.

(1-14) Sealing Step Next, the substrate 10 is moved to a nitrogen atmosphere, and an ultraviolet curable resin is used to bond the substrate 10 and a sealing glass plate (not shown) to form a nitrogen sealing structure. The organic EL display device was protected from being exposed to the outside air. Thus, an organic EL display device was obtained.

(1-15) Evaluation of Device Regarding the obtained organic EL display device, the characteristics of the organic EL element provided in the device are the organic included in the organic EL display device manufactured using a metal mask vapor deposition method in a consistent vacuum environment. Evaluation was performed while comparing EL elements. Each characteristic (light emission chromaticity, current efficiency, luminance degradation during long-term driving) of the organic EL element (blue light emitting element) produced in this example is an organic EL element produced by patterning using a metal mask vapor deposition method. Was found to be equivalent. Moreover, the light emitting state of the organic EL display device produced by the method of the present invention was good, and no light emission unevenness or the like occurred at the edge of the light emitting layer. As described above, according to the manufacturing method of the present invention, it was found that the organic compound layer can be formed in a predetermined pattern shape in a predetermined region, there is no damage in the wet etching process, and there is no problem in device characteristics. .

  According to the manufacturing process shown in FIG. 5, the organic EL display device of FIG. 1 was produced.

(2-1) Manufacturing process of substrate with electrode (FIG. 5A)
First, a substrate 10 having a plurality of drive circuits 11 and contact portions 12 provided on the base material 10a was prepared (FIG. 5A). The substrate 10 is provided with at least three separated lower electrodes (22a, 22b, 22c) as shown in FIG. Each lower electrode (22a, 22b, 22c) is a laminated electrode layer formed by laminating an Ag film and an ITO film in this order on the substrate 10, and each lower electrode (22a, 22b, 22c) Each of them is electrically connected to a set of driving circuits (11a, 11b, 11c) through a contact portion 12.

(2-2) First organic compound layer forming step (FIG. 5B)
Next, a hole transport layer was formed on the entire surface of the substrate 10 by vacuum deposition. At this time, the thickness of the hole transport layer was 120 nm. Next, a blue light emitting layer was formed by a vacuum evaporation method. At this time, the thickness of the blue light emitting layer was set to 20 nm. In addition, the laminated body which consists of a positive hole transport layer and a blue light emitting layer functions as the 1st organic compound layer 23a (FIG.5 (b)). Further, the maximum incident angle of the evaporated molecules of the hole transport layer and the blue light emitting layer with respect to the direction perpendicular to the substrate 10 was set to 10 °.

(2-3) Etch stop layer forming step (FIG. 5C)
Next, an etch stop layer 24a (hole block layer) was formed on the first organic compound layer 23a by vacuum vapor deposition (FIG. 5C). At this time, the film thickness of the etch stop layer 24a was 10 nm, and the maximum value of the incident angle of the evaporated molecules of the etch stop layer 24a with respect to the direction perpendicular to the substrate 10 was set to 15 °.

(2-4) Sacrificial layer forming step (FIG. 5D)
Next, a sacrificial layer 31 was formed by depositing an electron transporting material on the etch stop layer 24a by a vacuum deposition method (FIG. 5D). At this time, the thickness of the sacrificial layer 31 was set to 20 nm, and the maximum value of the incident angle of the evaporated molecules of the sacrificial layer 31 with respect to the direction perpendicular to the substrate 10 was set to 20 °.

(2-5) Intermediate layer forming step (FIG. 5E)
Next, polyvinylpyrrolidone and water were mixed to prepare a coating solution. Next, after dripping the said coating liquid on the sacrificial layer 31, the polyvinyl pyrrolidone was formed into a film by the spin coat method, and the intermediate | middle layer 14 was formed (FIG.5 (e)). At this time, the film thickness of the intermediate layer 14 was 500 nm.

(2-6) Step of forming protective layer (FIG. 5 (f))
Next, a protective layer 15 was formed by forming a SiN film on the intermediate layer 14 by plasma CVD (FIG. 5F). At this time, the film thickness of the protective layer 15 was 1000 nm.

(2-7) Resist layer forming step (FIG. 5G)
Next, after applying a positive photoresist (AZ 1500, manufactured by AZ Electronic Materials) on the protective layer 15, a thin film was formed by spin coating to form a resist layer 30 (FIG. 5G). ). At this time, the film thickness of the resist layer 30 was 1000 nm.

(2-8) Exposure / development process (FIG. 5 (h))
Next, exposure was performed using an exposure apparatus using a photomask having an opening in a region where the second subpixel 20b is provided. The exposure time at this time was 40 seconds. Next, development processing is performed using a developer (manufactured by AZ Electronic Materials, 312 MIF diluted with water to have a concentration of 50%), so that the second sub-pixel 20b is provided in the region. The resist layer 30 was removed (FIG. 5 (h)). The development time at this time was 60 seconds.

(2-9) Processing step for first organic compound layer and the like (FIG. 5 (i))
Next, the protective layer 15 was processed by removing the protective layer 15 not covered with the resist layer 30 by a dry etching method using CF ₄ gas. At this time, the flow rate of CF ₄ gas was 30 sccm, the pressure in the etching apparatus was 10 Pa, the output of the etching apparatus was 150 W, and the etching time was 420 seconds. Further, the etching speed and range were controlled so that the processed protective layer 15 had a cross-sectional shape in which the opening on the top surface 15a side of the protective layer 15 had a tapered shape larger than the opening on the substrate side 15b of the protective layer 15. .

Next, the intermediate layer 14, the sacrificial layer 31, the etch stop layer 24a, and the first organic compound layer 23a not covered with the protective layer 15 were sequentially removed by a dry etching method using O ₂ gas. Thereby, the intermediate layer 14, the sacrificial layer 31, the etch stop layer 24a, and the first organic compound layer 23a were processed. At this time, the flow rate of O ₂ gas was 20 sccm, the pressure in the etching apparatus was 8 Pa, the output of the etching apparatus was 150 W, and the etching time was 300 seconds. When the intermediate layer 14, the sacrificial layer 31, the etch stop layer 24a, and the first organic compound layer 23a are etched, the processed region of the member to be etched (14, 31, 24a, 23a) is on the substrate side of the protective layer 15. The etching conditions were optimized so as to be wider than the opening of 15b. By processing the intermediate layer 14, the sacrificial layer 31, the etch stop layer 24a, and the first organic compound layer 23a as described above, the patterning member 16 is formed and the lower electrode 22b included in the second subpixel 20b is formed. Appeared (FIG. 5 (i)).

(2-10) Step of forming second organic compound layer (FIG. 5 (j))
Next, a hole transport layer was formed on the entire surface of the substrate 10 including the exposed lower electrode 22b by vacuum deposition. At this time, the thickness of the hole transport layer was 160 nm. Next, a green light emitting layer was formed on the hole transport layer by vacuum deposition. At this time, the thickness of the green light emitting layer was set to 30 nm. In addition, the laminated body which consists of a positive hole transport layer and a green light emitting layer functions as the 2nd organic compound layer 23b (FIG.5 (j)). Further, the maximum incident angle of the evaporated molecules of the hole transport layer and the green light emitting layer with respect to the direction perpendicular to the substrate 10 was set to 10 °.

(2-11) Etch stop layer forming step (FIG. 5 (k))
Next, an etch stop layer 24b (hole block layer) was formed on the second organic compound layer 23b by vacuum vapor deposition (FIG. 5 (k)). At this time, the film thickness of the etch stop layer 24b was set to 10 nm, and the maximum value of the incident angle of the evaporated molecules of the etch stop layer 24b with respect to the direction perpendicular to the substrate 10 was set to 15 °.

(2-12) Sacrificial layer forming step (FIG. 5L)
Next, a sacrificial layer 31 was formed by depositing an electron transporting material on the etch stop layer 24b by vacuum deposition (FIG. 5L). At this time, the thickness of the sacrificial layer 31 was set to 20 nm, and the maximum value of the incident angle of the evaporated molecules of the sacrificial layer 31 with respect to the direction perpendicular to the substrate 10 was set to 20 °.

(2-13) Lift-off process (FIG. 5 (m))
Next, the substrate 10 was immersed in water. At this time, since the intermediate layer 14 is a layer formed of water-soluble polyvinyl pyrrolidone, the intermediate layer 14 is dissolved, and the layer formed on the intermediate layer 14 is lifted off from the substrate 10 in the process of dissolving the intermediate layer 14. (FIG. 5 (m)).

(2-14) Intermediate layer forming step (FIG. 5 (n))
Next, polyvinylpyrrolidone and water were mixed to prepare a coating solution. Next, after dripping the said coating liquid on the sacrificial layer 31, the polyvinyl pyrrolidone was formed into a film by the spin coat method, and the intermediate | middle layer 14 was formed (FIG.5 (n)). At this time, the film thickness of the intermediate layer 14 was 500 nm.

(2-15) Step of forming protective layer (FIG. 5 (o))
Next, a protective layer 15 was formed by forming a SiN film on the intermediate layer 14 by plasma CVD (FIG. 5 (o)). At this time, the film thickness of the protective layer 15 was 1000 nm.

(2-16) Resist layer forming step (FIG. 5 (p))
Next, after applying a positive type photoresist (AZ 1500, manufactured by AZ Electronic Materials) on the protective layer 15, a thin film was formed by spin coating to form a resist layer 30 (FIG. 5 (p)). ). At this time, the film thickness of the resist layer 30 was 1000 nm.

(2-17) Exposure / development process (FIG. 5 (q))
Next, using an exposure apparatus, exposure was performed using a photomask having an opening in a region where the third subpixel 20c is provided. The exposure time at this time was 40 seconds. Next, development processing is performed using a developer (manufactured by AZ Electronic Materials, 312 MIF diluted with water to have a concentration of 50%), so that the third subpixel 20c is provided in the region. The resist layer 30 was removed (FIG. 5 (q)). The development time at this time was 60 seconds.

(2-18) Processing step for first organic compound layer and the like (FIG. 5 (r))
Next, the protective layer 15 was processed by removing the protective layer 15 not covered with the resist layer 30 by a dry etching method using CF ₄ gas. At this time, the flow rate of CF ₄ gas was 30 sccm, the pressure in the etching apparatus was 10 Pa, the output of the etching apparatus was 150 W, and the etching time was 420 seconds. Further, the etching speed and range were controlled so that the processed protective layer 15 had a cross-sectional shape in which the opening on the top surface 15a side of the protective layer 15 had a tapered shape larger than the opening on the substrate side 15b of the protective layer 15. .

Next, the intermediate layer 14, the sacrificial layer 31, the etch stop layer 24a, and the first organic compound layer 23a not covered with the protective layer 15 were sequentially removed by a dry etching method using O ₂ gas. Thereby, the intermediate layer 14, the sacrificial layer 31, the etch stop layer 24a, and the first organic compound layer 23a were processed. At this time, the flow rate of O ₂ gas was 20 sccm, the pressure in the etching apparatus was 8 Pa, the output of the etching apparatus was 150 W, and the etching time was 300 seconds. When the intermediate layer 14, the sacrificial layer 31, the etch stop layer 24a, and the first organic compound layer 23a are etched, the processed region of the member to be etched (14, 31, 24a, 23a) is on the substrate side of the protective layer 15. The etching conditions were optimized so as to be wider than the opening of 15b. By processing the intermediate layer 14, the sacrificial layer 31, the etch stop layer 24a, and the first organic compound layer 23a as described above, the patterning member 16 is formed and the lower electrode 22c included in the third subpixel 20c is formed. Appeared (FIG. 5 (r)).

(2-19) Step of forming the third organic compound layer (FIG. 5 (s))
Next, a hole transport layer was formed on the entire surface of the substrate 10 including the exposed lower electrode 22c by vacuum deposition. At this time, the thickness of the hole transport layer was set to 200 nm. Next, a red light emitting layer was formed on the hole transport layer by vacuum deposition. At this time, the thickness of the red light emitting layer was set to 30 nm. In addition, the laminated body which consists of a positive hole transport layer and a red light emitting layer functions as the 3rd organic compound layer 23c (FIG.5 (s)). Further, the maximum incident angle of the evaporated molecules of the hole transport layer and the red light emitting layer with respect to the direction perpendicular to the substrate 10 was set to 10 °.

(2-20) Etch stop layer forming step (FIG. 5 (t))
Next, an etch stop layer 24c (hole block layer) was formed on the third organic compound layer 23c by vacuum deposition (FIG. 5 (t)). At this time, the film thickness of the etch stop layer 24c was 10 nm, and the maximum value of the incident angle of the evaporated molecules of the etch stop layer 24c with respect to the direction perpendicular to the substrate 10 was set to 15 °.

(2-21) Sacrificial layer forming step (FIG. 5 (u))
Next, a sacrificial layer 31 was formed by depositing an electron transporting material on the etch stop layer 24b by a vacuum deposition method (FIG. 5 (u)). At this time, the thickness of the sacrificial layer 31 was set to 20 nm, and the maximum value of the incident angle of the evaporated molecules of the sacrificial layer 31 with respect to the direction perpendicular to the substrate 10 was set to 20 °.

(2-22) Lift-off process (FIGS. 5 (v) to (w))
Next, the substrate 10 was immersed in water. At this time, since the intermediate layer 14 is a layer formed of water-soluble polyvinyl pyrrolidone, the intermediate layer 14 is dissolved, and the layer formed on the intermediate layer 14 is lifted off from the substrate 10 in the process of dissolving the intermediate layer 14. (FIGS. 5 (v) to (w)).

(2-23) Sacrificial layer removal step (FIG. 5 (w))
Next, the sacrificial layer 31 was removed by immersing the substrate 10 in a solvent (polar solvent other than water) (FIG. 5 (w)).

(2-24) Common organic compound layer forming step (FIG. 5 (y))
Next, a common organic compound layer 25 (electron injection layer) provided in common to each sub-pixel (20a, 20b, 20c) was formed on the etch stop layer 24 by vacuum deposition (FIG. 5 (y)). ). At this time, the film thickness of the common organic compound layer 25 was 20 nm.

(2-25) Upper electrode formation process (FIG. 5 (z))
Next, Ag was formed on the common organic compound layer 25 by a sputtering method to form the upper electrode 26 provided in common to each subpixel (20a, 20b, 20c) (FIG. 5 (n)). . At this time, the film thickness of the upper electrode 26 was 16 nm.

(2-27) Sealing Step Next, the substrate 10 is moved under a nitrogen atmosphere, and the substrate 10 and a sealing glass plate (not shown) are bonded together using an ultraviolet curable resin to form a nitrogen sealing structure. The organic EL display device was protected from being exposed to the outside air. Thus, an organic EL display device was obtained.

(2-28) Evaluation of device About the obtained organic EL display device, the element characteristic with the organic EL display device which patterned the organic compound layer of red, green, and blue using the metal mask vapor deposition method in a vacuum consistent environment Compared. In each color, it has been found that the characteristics of light emission chromaticity, current efficiency, and luminance deterioration during long-term driving are equivalent to an element patterned using a metal mask vapor deposition method. Moreover, the light emitting state of the organic EL display device produced by the method of the present invention was good, and no light emission unevenness or the like occurred at the edge of the light emitting layer. As described above, it has been found that the organic compound layer can be patterned by the method of the present invention, there is no damage in the wet etching process, and there is no problem in device characteristics.

  1: organic EL display device, 10: substrate, 11 (11a, 11b, 11c): drive circuit, 12 (12a, 12b, 12c): contact hole, 14: intermediate layer, 15: protective layer, 16: patterning member, 20: Pixel, 20a: First subpixel, 20b: Second subpixel, 20c: Third subpixel, 21a: First organic EL element, 21b: Second organic EL element, 21c: Third organic EL element, 22 (22a, 22b, 22c): lower electrode, 23: organic compound layer, 23a: first organic compound layer, 23b: second organic compound layer, 23c: third organic compound layer, 24 (24a, 24b, 24c): Charge injection transport layer (etch stop layer), 25: common organic compound layer, 26: upper electrode, 30: resist layer, 31: sacrificial layer

Claims (6)

A substrate,
A lower electrode provided on the substrate;
An organic compound layer formed on the lower electrode and including at least a light emitting layer;
An organic EL element including an upper electrode formed on the organic compound layer;
In the method of manufacturing an organic EL display device in which the organic compound layer has a predetermined pattern shape,
Forming a patterning member having an opening in a region where a lower electrode is provided on a substrate;
Forming an organic compound layer so as to cover at least a part of the patterning member and the lower electrode;
Forming an etch stop layer so as to cover at least a part of the patterning member and the organic compound layer;
Forming a sacrificial layer so as to cover at least a part of the patterning member and the etch stop layer;
Removing the patterning member, and a laminate including the organic compound layer, the etch stop layer, and the sacrificial layer formed on the patterning member;
Removing the sacrificial layer;
Forming a common organic compound layer;
Forming an upper electrode on the common organic compound layer,
The etch stop layer is a layer formed so as to include evaporation molecules having an incident angle component larger than an angle formed by a direction perpendicular to the substrate and a maximum incident angle of evaporation molecules of the organic compound layer,
The sacrificial layer is a layer formed so as to include evaporation molecules having an incident angle component larger than an angle formed by a direction perpendicular to the substrate and a maximum incident angle of the evaporation molecules of the etch stop layer,
The method of manufacturing an organic EL display device, wherein the etch stop layer has an etching rate with respect to a solvent that dissolves the sacrificial layer slower than that of the sacrificial layer. A substrate,
A plurality of types of pixels provided on the substrate;
An organic EL element in which the pixel includes a lower electrode provided on the substrate, an organic compound layer having a predetermined pattern shape provided on the lower electrode, and an upper electrode provided on the organic compound layer In an organic EL display device having
Forming a first stacked body in which a first organic compound layer, an etch stop layer, and a sacrificial layer are stacked in this order on the substrate;
Forming a patterning member having an opening in a region corresponding to a region where predetermined pixels are provided on the first stacked body;
Processing the first organic compound layer to expose a lower electrode provided in a region where the predetermined pixel is provided;
A step of forming a second stacked body in which a second organic compound layer, an etch stop layer, and a sacrificial layer are stacked in this order on the exposed lower electrode;
Removing the patterning member;
Removing the sacrificial layer;
Forming a common organic compound layer;
Forming an upper electrode on the common organic compound layer,
The etch stop layer is a layer formed so as to include evaporation molecules having an incident angle component larger than an angle formed by a direction perpendicular to the substrate and a maximum incident angle of evaporation molecules of the organic compound layer,
The sacrificial layer is a layer formed so as to include evaporation molecules having an incident angle component larger than an angle formed by a direction perpendicular to the substrate and a maximum incident angle of the evaporation molecules of the etch stop layer,
The method of manufacturing an organic EL display device, wherein the etch stop layer has an etching rate with respect to a solvent that dissolves the sacrificial layer slower than that of the sacrificial layer.   The method of manufacturing an organic EL display device according to claim 1, wherein the patterning member contains an organic compound. The patterning member has an intermediate layer that dissolves in a predetermined solvent,
The method for manufacturing an organic EL display device according to claim 1, wherein the patterning member is removed by dissolving the intermediate layer. The patterning member has a protective layer;
The method for manufacturing an organic EL display device according to claim 1, wherein the protective layer is formed on the intermediate layer. Forming the patterning member includes forming an intermediate layer;
Forming a protective layer on the intermediate layer;
Forming a resist layer on the protective layer;
Exposing and developing the resist layer; and
Processing the protective layer provided in a region not covered with the resist layer in a tapered shape in which the substrate side is narrowed; and
The method for manufacturing an organic EL display device according to claim 1, further comprising a step of processing the intermediate layer in a region wider than a processing region of the protective layer.

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