JP2011040336A - Method for manufacturing organic electronics panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electronics panel having elements elongated in a life time and stable in performance quality by preventing generation of dust, and short-circuits and generation of dark spots accompanied with remainder of an organic functional layer at the time of removing unnecessary regions of the organic functional layer by a wiping method in forming the organic functional layer of the organic electronics panel by an application method. <P>SOLUTION: The organic electronics panel includes, on a base material, a first electrode, a second electrode, at least one organic functional layer including an organic layer between the first electrode and the second electrode, and a sealing layer. The method for manufacturing the organic electronics panel includes at least, a first electrode-forming step, an organic functional layer-forming step of forming the organic functional layer, a patterning step of the organic functional layer, and a cleaning step subsequently cleaning the whole surface of the base material including the patterned organic functional layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an organic electronics panel, and more particularly to a method for producing an organic electroluminescence panel, an organic TFT panel, an organic solar battery panel, an organic photoelectric conversion panel, and an organic electrophotographic photoreceptor.

  In recent years, including organic electroluminescence panels (hereinafter also referred to as organic EL panels), organic TFT panels, organic solar battery panels (hereinafter also referred to as organic PV panels), organic photoelectric conversion panels, organic electrophotographic photoreceptors, Development of various organic electronics panels is under consideration. Organic electronics panels are elements that perform electrical operations using organic materials, and are expected to exhibit features such as energy saving, low cost, and flexibility, and are attracting attention as a technology that replaces conventional inorganic semiconductors based on silicone. ing. These organic electronics panels are elements that emit light, generate power, charge, or control current and voltage by passing a current through an electrode through a very thin film of organic matter.

  An organic EL element is an element that emits light when a current is supplied between electrodes, in which a light emitting layer made of an organic compound thin film is sandwiched between electrodes. Therefore, when a thin-film organic EL element is used as a light source, it is easy to reduce the size and weight, and the illuminating device has a faster light emission response speed than a fluorescent lamp and a relatively stable light amount immediately after lighting.

  An organic PV element and an organic photoelectric conversion element are elements that generate electricity when irradiated with light in a configuration in which a power generation layer made of a thin film of an organic compound is sandwiched between electrodes. Therefore, when a thin-film organic photoelectric conversion element is used as a solar cell, it can be easily reduced in size and weight, and has a relatively stable output even in a low illuminance environment or a high temperature environment as compared with existing inorganic semiconductor solar cells. The solar cell can be obtained.

  Furthermore, these organic electronics panels can form a functional layer on a base material by applying a coating solution containing an organic solvent on the base material, which can potentially eliminate the need for a vacuum process. Cost reduction due to productivity can be expected. Organic electronics panels manufactured by these coating methods require pattern coating because it is necessary to make an electrode lead-out portion. Generally, the material solution used in organic electronics panels is from 0.5 mPa · s to 3 mPa · s. In the case where a low-viscosity and low-viscosity coating liquid is discharged from a coating die of an extrusion coating apparatus and coated on a substrate, even simple stripe coating is difficult.

  Until now, when manufacturing an organic electronics panel by a coating method, a method of making an electrode extraction portion instead of stripe coating has been studied.

  For example, the substrate has an anode, an organic functional layer including a light emitting layer made of at least an organic light emitting material, and a light emitting portion having a laminate formed by laminating a cathode, and a non-light emitting portion not having this laminate. When manufacturing an organic EL display device, after the organic functional layer is applied to the entire surface including the anode, the organic functional layer formed on the non-light emitting portion is wiped off with a solvent after the formation, and a method for making the electrode extraction portion is It is known (for example, refer to Patent Document 1).

  A method of providing a patterned electroluminescent layer by contacting and wiping a film formed on a substrate with a wiping head selectively moistened with a solvent is known (see, for example, Patent Document 2).

  A method is known in which a light-emitting layer laminated on one surface of an electrode is patterned by dry etching through a mask having a predetermined opening (see, for example, Patent Document 3).

However, it has been found that the methods described in Patent Document 1 and Patent Document 2 have the following drawbacks.
1) When the organic functional layer is wiped off, the generated dust adheres on the organic functional layer, causing a short circuit or a dark spot. The thickness of the organic functional layer to be laminated is 10 to 100 nm, and when the organic material is conductive, it causes a short circuit to the cathode. In addition, a non-functioning area called a dark spot occurs.
2) An unwiped portion is generated on the external electrode connecting electrode, resulting in poor contact with the external electrode. In addition, short-circuiting due to components dissolved in a trace amount of remaining solvent and adhesion of electrodes formed on the upper portion are lowered.
3) Dust adhering to the base material lowers the adhesion with the sealant in the subsequent sealing step, resulting in poor moisture resistance and shortening the device life.

Moreover, it turned out that the method of patent document 3 has the following faults.
1) When removing an organic functional layer, an unnecessary organic functional layer is removed at a time, and the generated dust adheres to the organic functional layer, thereby causing a short circuit or a dark spot. The thickness of the organic functional layer to be laminated is 10 to 100 nm, and when the organic material is conductive, it causes a short circuit to the cathode. In addition, a non-functioning area called a dark spot occurs.
2) The dust adhering to the base material lowers the adhesion with the sealant in the subsequent sealing step, resulting in poor moisture resistance and shortening the device life.
3) Complicated work and management are required to produce a precise mask.
4) In the roll-to-roll method, the organic functional layer can be removed continuously in the direction of transport of the base material, but removal in the direction perpendicular to the direction of transport of the base material cannot be performed simultaneously.

  In this situation, when the organic functional layer of the organic electronics panel is manufactured by the coating method, when the unnecessary organic functional layer is removed by the wiping method, the generation of dust and the occurrence of shorts and dark spots due to the remaining wiping are prevented. Therefore, it is desired to develop a method for manufacturing an organic electronics panel having a long lifetime.

JP 2004-152512 A JP-T-2007-515756 JP 2004-127726 A

  The present invention has been made in view of the above situation, and its purpose is to prevent the generation of dust when an unnecessary area of an organic functional layer is removed by a wiping method when an organic functional layer of an organic electronics panel is manufactured by a coating method. An object of the present invention is to provide a method of manufacturing an organic electronics panel that prevents occurrence of shorts and dark spots due to remaining wiping, prolongs the device life, and stabilizes the performance quality.

  The above object of the present invention has been achieved by the following constitution.

1. On the substrate, an organic substance is interposed between the first electrode, the first electrode external connection electrode, the second electrode, the second electrode external connection electrode, and the first electrode and the second electrode. In a method for producing an organic electronic panel having at least one organic functional layer including a layer and a sealing layer,
A first electrode forming step of forming a first electrode including at least a portion for forming the first electrode external connection electrode;
An organic functional layer forming step of forming at least one organic functional layer on the entire surface of the substrate including the first electrode;
A patterning process for removing and patterning unnecessary regions of the organic functional layer;
And a cleaning step of cleaning the entire surface of the base material having the patterned organic functional layer.

2. The solvent for removing unnecessary regions of the organic functional layer is Hansen's solubility parameter, and the plot of f _d , f _p , and f _h is within at least 45 points with respect to the plot of the solvent coated with the main organic functional layer. 2. The method for producing an organic electronic panel according to 1 above, wherein the organic electronics panel is at a distance of 20 points or more.

  3. 3. The method of manufacturing an organic electronic panel according to 1 or 2, wherein the patterning of the organic functional layer is performed by a wiping method in the patterning step.

  4). 4. The method of manufacturing an organic electronics panel according to any one of 1 to 3, wherein cleaning is performed by a dry etching method in the cleaning step.

  5. 5. The method of manufacturing an organic electronics panel according to any one of 1 to 4, further comprising the following steps.

A) A first electrode forming step in which the first electrode including at least a portion for forming the first electrode external connection electrode and a lead portion are patterned on the base material. B) The first electrode And an organic functional layer forming step of forming at least one organic functional layer on the entire surface of the substrate having the lead portion and C) a patterning step of patterning unnecessary regions of the organic functional layer. D) the patterned organic A cleaning step of cleaning the entire surface of the base material having the functional layer. E) The second electrode and the external connection electrode for the second electrode extending from the organic functional layer on the first electrode to the lead portion. Step of forming second electrode F) Sealing on and around the second electrode with a sealing member except for the first electrode external connection electrode and the second electrode external connection electrode with a sealing member Sealer 6. 5. The method of manufacturing an organic electronics panel according to any one of 1 to 4, further comprising the following steps.

A) A first electrode forming step in which the first electrode including at least a portion for forming the first electrode external connection electrode and a lead portion are patterned on the base material. B) The first electrode And an organic functional layer forming step of forming at least one organic functional layer on the entire surface of the substrate having the lead portion and C) a patterning step of patterning unnecessary regions of the organic functional layer. D) the patterned organic A cleaning step for cleaning the entire surface of the substrate having a functional layer. E) A second electrode forming step for forming the second electrode on the organic functional layer on the first electrode. F) The second electrode A conductive layer forming step of forming a conductive layer over the lead portion to form a second electrode external connection electrode; G) excluding the first electrode external connection electrode and the second electrode external connection electrode; Sealing member Sealing step 7 of sealing with a sealing member on and around the second electrode. 5. The method of manufacturing an organic electronics panel according to any one of 1 to 4, further comprising the following steps.

A) First electrode forming step of patterning and forming the first electrode including at least a portion for forming the first electrode external connection electrode on the base material. B) The base material having the first electrode. An organic functional layer forming step of forming at least one organic functional layer on the entire surface of the substrate C) A patterning step of patterning unnecessary regions of the organic functional layer D) The entire surface of the substrate having the patterned organic functional layer Cleaning step for cleaning E) A second electrode is formed on the organic functional layer on the first electrode, and at the same time, the organic functional layer removes the second electrode external connection electrode integrated with the second electrode. The second electrode forming step of forming on the base material that has been formed F) The second electrode external connection electrode and the second electrode external connection electrode, except for the second electrode external connection electrode, Sealing that seals the periphery with a sealing member Degree 8. 8. The method of manufacturing an organic electronics panel according to any one of 1 to 7, wherein the organic electronics panel is an organic electroluminescence panel.

  9. 8. The method for producing an organic electronics panel according to any one of 1 to 7, wherein the organic electronics panel is an organic photoelectric conversion element.

  When manufacturing the organic functional layer of organic electronics panel by coating method, when unnecessary areas of the organic functional layer are removed by wiping method, dust generation is prevented, short circuit and dark spot due to remaining wiping are prevented, element life is long We were able to provide a method for producing organic electronics panels that have a long life and stable performance quality.

It is a schematic sectional drawing which shows an example of an organic electronics panel. The organic electronics panel (a) shown in FIG. 1 is a process flow diagram from a substrate supply process to a cleaning process. The organic electronics panel (a) shown in FIG. 1 is a process flow diagram from the second electrode formation process to the recovery process. It is a process flow figure from the substrate supply process which produces the organic electronics panel (c) shown in Drawing 1 to a cleaning process. It is a process flow figure from the 2nd electrode formation process which produces the organic electronics panel (c) shown in Drawing 1 to a recovery process. It is a process flow figure from the substrate supply process which produces the organic electronics panel (b) shown in Drawing 1 to a cleaning process. It is a process flow figure from the 2nd electrode formation process which produces the organic electronics panel (b) shown in Drawing 1 to a collection process. It is the schematic of a patterning process. It is the schematic which shows an example of an atmospheric pressure plasma processing apparatus.

  Embodiments of the present invention will be described with reference to FIGS. 1 to 6, but the present invention is not limited thereto.

  FIG. 1 is a schematic sectional view showing an example of an organic electronics panel manufactured by the method for manufacturing an organic electronics panel of the present invention.

  This will be described with reference to (a).

  In the figure, reference numeral 1 denotes an organic electronics panel manufactured according to the manufacturing flow diagram shown in FIG. 101 shows a base material. Reference numeral 102 denotes a first electrode (anode), and reference numeral 102 a denotes a first electrode external connection electrode of the first electrode 102. Reference numeral 104a denotes a second electrode external connection electrode. When the first electrode 102 is formed, the second electrode external connection electrode 104 a is formed by joining the lead portion formed on the base material 101 at a position separated from the first electrode 102 and the second electrode (cathode) 104. Is formed. Reference numeral 103 denotes an organic functional layer including an organic material layer formed on and around the first electrode 102 except on the first electrode external connection electrode 102a. Reference numeral 104 denotes a second electrode (cathode) formed so as to cover the organic functional layer 103 and a part of the lead portion 102b. Reference numeral 105 denotes an adhesive layer provided on and around the second electrode (cathode) 104 except for a part of the first electrode external connection electrode 102a and the second electrode external connection electrode 104a. Reference numeral 106 denotes a sealing member attached via an adhesive layer 105.

  This will be described with reference to (b).

  In the figure, reference numeral 1 ′ denotes an organic electronics panel manufactured according to the manufacturing flow diagram shown in FIG. 101 'shows a base material. Reference numeral 102 'denotes a first electrode (anode), and 102'a denotes an external connection electrode for the first electrode of the first electrode 102'. Reference numeral 104'a denotes a second electrode external connection electrode. The external connection electrode 104′a for the second electrode includes a lead portion and a second electrode (cathode) formed on the base material 101 ′ at a position separated from the first electrode 102 ′ when the first electrode 102 ′ is formed. ) 104 ′ and the conductive layer 105 ′. Reference numeral 103 ′ denotes an organic functional layer including an organic material layer formed on and around the first electrode (anode) 102 ′ except for the first electrode external connection electrode 102 ′. Reference numeral 104 ′ denotes a second electrode (cathode) formed in accordance with the size of the first electrode 102 ′ on the organic functional layer 103 ′. Reference numeral 105 'denotes a conductive layer, which is formed so as to join the second electrode 104' and the lead portion 102'b.

  Reference numeral 106 ′ denotes a part on the second electrode (cathode) 104 ′ and on and around the conductive layer 105 ′ except for a part of the first electrode external connection electrode 102 ′ a and the second electrode external connection electrode 104 ′ a. The adhesive layer provided in is shown. Reference numeral 107 'denotes a sealing member attached through an adhesive layer 106'.

  This will be described with reference to (c).

  In the figure, 1 ″ represents an organic electronics panel manufactured according to the manufacturing flow diagram shown in FIG. 1 (a). 101 ″ represents a substrate. 102 ″ represents the first electrode (anode), 102 ″ a represents the first electrode external connection electrode for the first electrode 102 ″, and 103 ″ represents the first electrode external connection electrode 102 ″ a. The organic functional layer including the organic material layer formed on and around the first electrode 102 ″ is shown. Reference numeral 104 ″ denotes a second electrode (cathode) formed on the organic functional layer and the base material 101 ″ in accordance with the size of the first electrode 102 ″. 104 ″ a indicates the second electrode (cathode) 104. ″ Denotes an external connection electrode for the second electrode of the second electrode (cathode) formed integrally with ″. 105 ″ denotes an external connection electrode for the first electrode 102 ″ a and an external connection electrode for the second electrode 104 ″. An adhesive layer provided on and around the second electrode (cathode) 104 "except a part of a is shown. 106" is a sealing member attached via an adhesive layer 105 ".

  The organic electronics panel shown in FIGS. 1A, 1B, and 1C is supplied with direct current from the first electrode external connection electrode and the second electrode external connection electrode as the organic EL element. As a result, light is emitted from the substrate. Further, in the organic PV element, a direct electromotive force is generated by irradiating light from the base material, and power is taken out from the first electrode external connection electrode and the second electrode external connection electrode.

  When producing the organic electronics panel shown in FIGS. 1A, 1B, and 1C, the present invention prevents the generation of dust when removing unnecessary areas of the organic functional layer by a wiping method. The present invention relates to a method for manufacturing an organic electronics panel that prevents the occurrence of short circuits and dark spots due to unwiping, extends the lifetime of the element, and stabilizes the performance quality.

  In the case of an organic EL panel, the organic functional layer refers to, for example, a hole injection / transport layer / light emitting layer / electron injection / transport layer. In the case of an organic PV panel, for example, it refers to a hole transport / electron blocking layer / photoelectric conversion layer / electron transport / hole blocking layer. The configuration of the organic EL panel and the organic PV panel will be described later.

  Next, the production of the organic electronics panels (a), (b), and (c) shown in FIG. 1 will be specifically described with reference to the manufacturing flowcharts shown in FIGS.

  FIG. 2 is a process flow diagram from the substrate supplying process to the cleaning process for producing the organic electronics panel (a) shown in FIG.

  FIG. 3 is a process flow diagram from the second electrode formation process to the recovery process for producing the organic electronics panel (a) shown in FIG.

  2 and 3, the right side is an enlarged schematic cross-sectional view along AA ′. The organic electronics panel (a) shown in FIG. 1 includes a substrate supply step, a first electrode formation step, an organic functional layer formation step, a patterning step, a cleaning step, as shown in the process flow diagrams shown in FIGS. It is produced according to the second electrode forming step, the sealing step, and the recovery step. Hereinafter, the production of the organic electronics panel (a) shown in FIG. 1 will be described with reference to FIGS.

  In the base material supply step, a strip-shaped or single-wafer-shaped base material is supplied as necessary. In the case of a strip-shaped base material, it is continuously supplied in a state of being fed out from a roll-shaped strip-shaped base material. This figure has shown the case where a strip | belt-shaped sheet-like base material is supplied.

  In the first electrode forming step, the first electrode 102 including a portion for forming the first electrode external connection electrode on the base material 101 supplied from the base material supplying step and the lead portion 102b are patterned. It is formed.

  In the organic functional layer forming step, the first electrode 102 including the portion for forming the first electrode external connection electrode supplied from the first electrode forming step, and the entire surface of the substrate 101 on which the lead portion 102b is formed. An organic functional layer 103 is formed.

  In the patterning step, an unnecessary region (non-functional expression region) of the organic functional layer 103 of the base material 101 in which the organic functional layer 103 is formed on the entire surface supplied from the organic functional layer forming step (for example, a non-light emitting portion in an organic EL panel, In the organic PV panel, a portion where no electromotive force is generated is wiped off by a wiping method. In this figure, the first electrode 102 is wiped and removed including the upper portion of the base material 103 so that the formation portion of the first electrode external connection electrode 102a and the lead portion 102b appear.

  In the cleaning process, with respect to the substrate having the patterned organic functional layer supplied from the patterning process, the remaining wiping in the patterning process and the cleaning of the adhered portion of the organic functional layer generated by the wiping are performed by a dry etching method. . Although there is no limitation in particular as a dry etching system, For example, atmospheric pressure plasma processing is mentioned.

  In the second electrode forming step, the lead portion 102b is adjusted to the size of the first electrode 102 on the organic functional layer 103 on the first electrode 102 formed on the cleaned substrate supplied from the cleaning step. The second electrode 104 is formed so as to be joined to each other, and the lead electrode 102b and the second electrode 104 are joined to form the second electrode external connection electrode 104.

  In the sealing step, the first electrode external connection formed on the substrate 101 on which the second electrode 104 and the second electrode external connection electrode 104a supplied from the second electrode forming step are formed. The sealing member 106 is attached and sealed with an adhesive provided on and around the second electrode 104 except for a part of the electrode for electrode 102a and the second electrode external connection electrode 104a. The electronics panel 1 (configuration shown in FIG. 1A) is manufactured.

  In the recovery process, the organic electronics panel supplied from the sealing process is recovered. The method of recovery varies depending on the substrate used. When the used base material is strip | belt shape, for example, after winding up and collect | recovering in roll shape, it cuts into the unit required by another process. Or it collects after cutting to the required size. When the used base material is sheet-like, for example, after being stacked and collected one by one, it is cut into a size required in another process. Or it collects after cutting to the required size.

  In this figure, the first electrode including a portion for forming the first electrode external connection electrodes in a row in the substrate transport direction in the first electrode forming step and the lead portion are formed in a pattern. Although the case is shown, a plurality of first electrodes may be formed between the first electrode and the lead portion in the transverse direction of the substrate.

  FIG. 4 is a process flow diagram from the substrate supplying process to the cleaning process for producing the organic electronics panel (c) shown in FIG.

  FIG. 5 is a process flow diagram from the second electrode formation process to the recovery process for producing the organic electronics panel (c) shown in FIG.

  4 and 5, the right side is an enlarged schematic cross-sectional view along BB '. The organic electronics panel (a) shown in FIG. 1 includes a base material supplying step, a first electrode forming step, an organic functional layer forming step, a patterning step, a cleaning step, as shown in the process flow charts shown in FIGS. It is produced according to the second electrode forming step, the sealing step, and the recovery step. Hereinafter, the production of the organic electronics panel (c) shown in FIG. 1 will be described with reference to FIGS.

  The base material supplying step is the same as the base material supplying step shown in FIG.

  In the first electrode forming step, the first electrode 102 ″ including a portion for forming the first electrode external connection electrode is formed on the base material 101 ″ supplied from the base material supplying step in a patterned state. The

  In the organic functional layer forming step, the organic functional layer 103 is formed on the entire surface of the base material 101 ″ on which the first electrode 102 ″ including the portion for forming the first electrode external connection electrode supplied from the first electrode forming step is formed. ″ Is formed.

  In the patterning step, an unnecessary region of the organic functional layer 103 ″ formed on the entire surface of the substrate 101 ″ formed with the organic functional layer 103 ″ on the entire surface supplied from the organic functional layer forming step (for example, non-light emission in the organic EL panel) The portion of the organic PV panel where no electromotive force is generated is wiped away. In this figure, the base material 103 ″ is formed so that the first electrode external connection electrode 102a ″ forming portion of the first electrode 102 ″ appears. Wipe off including the top.

  In the cleaning process, the substrate 103 ″ having the patterned organic functional layer supplied from the patterning process is left unwiped in the patterning process, and the organic functional layer generated by the wiping and the removal of the cleaning adhered to the wiped portion are removed. The dry etching method is used.

  In the second electrode forming step, the size of the first electrode 102 "is formed on the organic functional layer 103" on the first electrode 102 "formed on the cleaned substrate 103" supplied from the cleaning step. Accordingly, the second electrode 104 ″ and the second electrode external connection electrode 104 ″ a integrated with the second electrode 104 ″ are formed on the substrate.

  In the sealing step, the second electrode 104 ″ supplied from the second electrode forming step and the second electrode external connection electrode 104 ″ a are formed on the substrate on which the first electrode is formed. Except for a part of the external connection electrode 102 ″ a and the second electrode external connection electrode 104 ″ a, the sealing member 106 ″ is attached via an adhesive provided on and around the second electrode 104 ″. An organic electronics panel 1 ″ (the configuration shown in FIG. 1C) that is adhered and sealed is produced.

  Since the collection process is the same as the collection process shown in FIG.

  In addition, this figure has shown the case where it forms by patterning with the 1st electrode including the part which forms the electrode for 1st electrode external connection electrodes in the conveyance direction of a base material in the 1st electrode formation process. However, a plurality of first electrodes may be formed in the transverse direction of the substrate.

  FIG. 6 is a process flow diagram from the substrate supplying process to the cleaning process for producing the organic electronics panel (b) shown in FIG.

  FIG. 7 is a process flow diagram from the second electrode formation process to the recovery process for producing the organic electronics panel (b) shown in FIG.

  6 and 7, the right side is an enlarged schematic cross-sectional view along CC ′. The organic electronics panel (b) shown in FIG. 1 includes a substrate supply step, a first electrode formation step, an organic functional layer formation step, a patterning step, a cleaning step, as shown in the process flow diagrams shown in FIGS. It is produced according to the second electrode forming step, the sealing step, and the recovery step. Hereinafter, the production of the organic electronics panel (b) shown in FIG. 1 will be described with reference to FIGS.

  The base material supplying step is the same as the base material supplying step shown in FIG.

  In the first electrode forming step, the first electrode 102 ′ including a portion for forming the first electrode external connection electrode on the base material 101 ′ supplied from the base material supplying step, and the lead portion 102′b are patterned. Formed in the state.

  In the organic functional layer forming step, the base material 101 on which the first electrode 102 'including the portion for forming the first electrode external connection electrode supplied from the first electrode forming step and the lead portion 102'b is formed. An organic functional layer 103 ′ is formed on the entire surface of ′.

  In the patterning step, unnecessary regions of the organic functional layer 103 ′ of the base material 101 ′ in which the organic functional layer 103 ′ is formed on the entire surface supplied from the organic functional layer forming step (for example, a non-light emitting portion in an organic EL panel, an organic PV panel) Then, the portion where no electromotive force is generated is wiped away. In this drawing, the first electrode 102 'is wiped and removed so that the first electrode external connection electrode 102'a forming portion and the lead portion 102'b appear.

  In the cleaning process, the substrate 101 ′ having the patterned organic functional layer 103 ′ supplied from the patterning process is left uncleaned in the patterning process, and dust generated by wiping and adhering to the organic functional layer and the wiped portion. Removal is performed by a dry etching method.

  In the second electrode forming step, the size of the first electrode 102 'is formed on the organic functional layer 103' on the first electrode 102 'formed on the cleaned substrate 101' supplied from the cleaning step. Accordingly, the second electrode 104 'is formed.

  In the conductive layer forming step, a part of the second electrode 104 ′ of the base 101 ′ on which the second electrode 104 ′ supplied from the second electrode forming step is formed is connected to a part of the lead portion 102′b. Thus, a conductive layer 105 'is formed. The lead portion 102'b and the conductive layer 105 'are joined to form the second electrode external connection electrode 104'a.

  In the sealing step, the first electrode 104 ′ and the second electrode external connection electrode 104 ′ supplied from the second electrode formation step are formed on the base material 101 ′ on which the first electrode is formed. Except for a part of the electrode external connection electrode 102 ′ a and the second electrode external connection electrode 104 ′ a, the sealing member 107 is interposed via an adhesive provided on and around the second electrode 104 ′. An organic electronics panel 1 '(configuration shown in FIG. 1B) is prepared by sticking and sealing.

  Since the recovery process is the same as the recovery process shown in FIG.

  In this figure, the first electrode including a portion for forming the first electrode external connection electrodes in a row in the substrate transport direction in the first electrode forming step and the lead portion are formed in a pattern. Although the case is shown, a plurality of first electrodes may be formed between the first electrode and the lead portion in the transverse direction of the substrate.

FIGS. 2 to 4 show the case where the organic functional layer is one layer. However, when the organic functional layer is a multilayer, the processing methods in the patterning step and the cleaning step are as follows, and are appropriately selected as necessary. It is possible.
1) After performing the processing in the patterning step and the cleaning step for each layer, the organic functional layer is repeatedly laminated in the organic functional layer forming step.
2) After the organic functional layer is formed in a required multilayer, it is processed in a patterning step and a cleaning step.

  In addition, the process only in the patterning process is performed for each layer, the organic functional layer is stacked, and finally, the process in the cleaning process can remove dust generated in the patterning process performed for each layer and adhered to the organic functional layer. Since it disappears, it is not preferable. There is a possibility that dust adhering to the surface of the organic functional layer may cause a short circuit between the first electrode (anode) and the second electrode (cathode) or may become a dark spot.

  Dust adhering to the surface of the second electrode (cathode) or the surface of the base material does not cause a short circuit between the organic functional layer and the first electrode (anode), but the second electrode (cathode) and the conductive layer, lead This deteriorates the contact between the conductive layer and the conductive layer, or lowers the adhesion to the sealant in the subsequent sealing process, thereby deteriorating the moisture resistance of the organic electronics panel and shortening the life of the organic electronics panel.

  Next, the wiping device used in the patterning process will be described. The wiping device is not particularly limited as long as unnecessary portions of the organic functional layer formed on the substrate can be accurately and quickly removed and patterned. For example, a method in which an organic functional layer is dissolved or swollen with a solvent and sucked and removed, a method of wiping, or a soft head or tape-like member that has been “moistened” with a solvent is brought into contact with the organic functional layer continuously. A method of removing a part of the organic functional layer formed on the entire surface of the base material can be mentioned. A method for removing unnecessary portions of the organic functional layer by a wiping apparatus using a tape-like member “moistened” with a solvent will be described below.

  In the first electrode forming step shown in FIGS. 2 to 4, the first electrode including a portion for forming a row of first electrode external connection electrodes in the substrate transport direction and the lead portion are patterned. Although the case where it forms is shown, you may form a some 1st electrode between a 1st electrode and a lead part.

  FIG. 8 is a schematic view of the patterning process. FIG. 8A is a schematic perspective view of the patterning process. FIG. 8B is an enlarged schematic cross-sectional view along the line DD ′ in FIG.

  In the figure, 2 indicates a patterning step. The patterning step 2 uses a roller 4 that holds the substrate 3, a first wiping device 5, and a second wiping device 6. The roller 4 is rotatably held on both sides by holding members (not shown). The number of wiping devices depends on the number of the first electrodes 7 including the portion for forming the first electrode external connection electrode formed on the base material 3 and the position to be wiped depending on the presence or absence of the lead portion. It is possible to adjust appropriately according to the number. This figure shows the case where the 1st electrode 7 and the lead part 7a including the part which forms the electrode for 1st electrode external connection in a line in the conveyance direction (arrow direction in a figure) of the base material 3 are arrange | positioned. Yes.

  Reference numeral 8 denotes an organic functional layer formed on the entire surface of the substrate 3. In order to remove unnecessary regions of the organic functional layer 8 (portion indicated by hatching in the drawing) formed on the first electrode external connection electrode 701 forming portion of the first electrode and the lead portion 7a, Two units, a first wiping device 5 and a second wiping device 6 are arranged. Since the first wiping device 5 and the second wiping device 6 have the same structure, the structure of the first wiping device 5 will be described.

  The first wiping device 5 includes a feed roll 501, a take-up roll 502, a pressing roll 504, and a solvent tank 505 for the wiping member 503. In this figure, the case where the strip | belt-shaped member is used as the wiping member 503 is shown. Reference numeral 503a denotes a roll-shaped wiping member loaded on the delivery roll 501, and reference numeral 502a denotes a wiping member wound on the take-up roll 502 in a roll shape. In addition, the conveyance direction of the wiping member 503 may be opposite to the conveyance direction of the base material.

  The solvent in the solvent tank 505 is always impregnated in the wiping member 503 via the solvent supply pipe 505a.

  The pressing roll 504 is connected to the cylinder 504a so as to be movable up and down (in the direction of the arrow in the drawing), and can press the wiping member 503 against the organic functional layer 8 on the substrate 3 with a desired pressure. It is possible. The position where the wiping member 503 is pressed and contacted on the organic functional layer 8 by the pressing roll 504 is preferable because the position where the roller 504 and the base material 3 are contacted can be pressed with stable pressure. The first wiping device 5 and the second wiping device 6 have position adjusting means for adjusting the position of the pressing roll 504 to the position where the base material 3 is wiped.

  The wiping device shown in this figure is an unnecessary portion of the organic functional layer formed on the substrate that is continuously conveyed (in this figure, the first wiping device 5 is used for the first electrode of the first electrode 7. The organic functional layer 8 formed on and around the external connection electrode 701 forming portion and the second wiping device 6 are on the lead portion 7a and for external connection of the lead portion 7a and the first electrode 7 for the first electrode. The organic functional layer 8) formed in the periphery of the electrode 701 forming portion is continuously contacted by wiping and removing unnecessary portions of the organic functional layer by pressing and contacting the wiping member impregnated with the solvent while sending it out. In particular, it is possible to expose the formation portion of the first electrode external connection electrode 701 of the first electrode 7 and the surface of the lead portion 7a.

  In addition, this figure shows the case where two wiping devices are arranged in accordance with the location to be wiped in order to continuously remove unnecessary portions of the organic functional layer formed on the substrate that is continuously conveyed. However, when the equipment is a single sheet, the base material may be fixed and the wiping device may be moved.

  In the case of a strip-shaped wiping member as the wiping member 503, there is no particular limitation as long as it is a material that can withstand physical properties, impregnation with a solvent, solvent resistance, and a material that can absorb a dissolved organic functional layer, for example, porous, solvent resistance Moreover, fibrous woven fabric, nonwoven fabric, etc. are mentioned.

  The width of the wiping member 503 is preferably in the range of 100% to 80% with respect to the width of the organic functional layer to be wiped in consideration of the wettability of the solvent with respect to the base material and the permeability of the organic solvent into the organic functional layer. A range of 95% to 80% is particularly preferable.

  The thickness of the wiping member 503 is preferably 0.1 mm to 10 mm in consideration of the amount of impregnation of the solvent, the amount of absorption of the dissolved organic functional layer, and the like.

  The amount of the solvent supplied to the wiping member 503 is preferably 0.01 ml to 1 ml in consideration of the permeability of the organic solvent to the organic functional layer.

The pressing force of the wiping member 503 on the organic functional layer is 9.81 × 10 ³ Pa to 4.91 × 10 ⁵ Pa in consideration of wiping property of the organic functional layer, suppression of damage to the first electrode and the lead portion, and the like. The range of is preferable.

  The delivery speed of the wiping member 503 is a relative speed with respect to the base material 3, and the organic functional layer is dissolved and absorbed, the organic functional layer is dissolved by the lateral spreading of the solvent impregnated in the wiping member, and the organic functional layer is wiped off. In consideration of the patterning accuracy accompanying the disturbance of the thickness, the range of 1 cm / second to 50 cm / second is preferable.

  The wiping device shown in this figure shows a case where a belt-like wiping member is used as the wiping member, but instead of the belt-like wiping member, a blade made of a porous (for example, sponge-like) material having solvent absorption and elasticity is used. Alternatively, it may be pressed against the substrate and wiped off.

  The material used for the blade is composed of, for example, a material such as sponge, elastomer, thermoplastic resin, fiber mat, porous material, polyurethane rubber, synthetic rubber, natural rubber, silicone, or a solvent resistant material made of a combination thereof. May be.

  The shape of the blade is not particularly limited as long as it can be wiped off efficiently. For example, a trapezoidal cross-sectional shape can be preferably used. This shape may have a geometrical cross-sectional shape such as a pointed cross-sectional shape, a square cross-sectional shape, a rounded cross-sectional shape at the tip, etc., depending on the nature of the organic layer to be scraped or wiped off, the scraping speed, etc. You may design together. Further, since the tip has a predetermined thickness and the tip has elasticity, at the time of wiping, the organic functional layer can be wiped by bending and rubbing the substrate as a blade.

  The solvent to be impregnated in the wiping member 503 may be any solvent as long as it has a composition that facilitates wiping when the organic functional layer is removed. For example, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene , Halogen hydrocarbon solvents such as dichlorobenzene and chlorotoluene, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane and anisole, methanol, ethanol, isopropanol, butanol, cyclohexanol, 2-methoxyethanol, ethylene glycol, Alcohol solvents such as glycerin, aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene, paraffin solvents such as hexane, octane, decane and tetralin, Ester solvents such as ethyl acetate, butyl acetate and amyl acetate; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and isophorone Amine solvents such as pyridine, quinoline and aniline, nitrile solvents such as acetonitrile and valeronitrile, and sulfur solvents such as thiophene and carbon disulfide. These wiping solvents may be used alone or as a mixture of a plurality of solvents. Further, a plurality of solvents may be used by changing them sequentially.

As a more preferable wiping solvent, as a Hansen solubility parameter, considering the solubility of the organic material constituting the organic functional layer, a percentage calculated from ∂ _d , _{ｐ p} , ∂ _h , f _d (Dispersion force) ), F _p (Polar Force), and f _h (Hydrogen force) are at least 45 points closer to the plot of the solvent coated with the main organic functional layer, and 20 points or more. More preferably, they are separated. More preferably, the distance is within 40 points, more preferably 25 points or more.

The percentages calculated from _{ｄ d} , ∂ _p , ∂ _h , f _d , f _p , and f _h are obtained according to the following equations 1) to 3).

Formula 1) f _d = ∂ _d / (∂ _d + ∂ _p + ∂ _h )
Formula 2) f _p = ∂ _p / (∂ _d + ∂ _p + ∂ _h )
Equation _{3) f h = ∂ h /} (∂ d + ∂ p + ∂ h)
Moreover, the point difference Rf between the solubility parameter of the wiping solvent and the solvent for applying the organic functional layer can be obtained by the following equation 4).

Formula 4) (Rf) ² = (f _d2 −f _d1 ) ² + (f _p2 −f _p1 ) ² + (f _h2 −f _h1 ) ²
Here, the main organic functional layer corresponds to a light-emitting layer referred to as an organic EL element and a photoelectric conversion layer referred to as an organic PV element. Is a concern.

  The Hansen solubility parameters (hereinafter also referred to as SP values) are, for example, Hansen Solubility Parameters: A User's Handbook (by Charles M. Hansen 198), The Book and Paper Group ANNUAL, SolT SP values of various solvents can be obtained with reference to Application (by John Burke) and other known documents.

  In the present invention, the dry etching method is used in the cleaning process for removing dust remaining on the wiping residue and wiping in the patterning process and adhering to the organic functional layer and the wiped portion. Examples of the dry etching method include argon sputtering, electron beam irradiation, plasma treatment, and the like. As plasma processing, flame plasma processing, corona discharge processing, atmospheric pressure plasma processing, and plasma processing are targeted. Hereinafter, atmospheric pressure plasma that can be continuously processed under atmospheric pressure is an example of a dry etching method used in the cleaning process. The processing will be described as a representative of plasma processing.

  The atmospheric pressure plasma treatment relating to the method for producing an organic electronics panel of the present invention is preferably performed at or near atmospheric pressure. However, the atmospheric pressure plasma treatment that is possible at atmospheric pressure is followed by coating. Is preferable from the viewpoint of productivity, such as being able to perform application quickly. The specific pressure is preferably from 70 kPa to 130 kPa, and most preferably atmospheric pressure with no pressure reduction or pressurization.

  In order to generate plasma, it is necessary to discharge in an atmosphere of an inert gas as a carrier gas. Here, the inert gas refers to a group 18 element of the periodic table, so-called rare gas, helium, neon , Argon, krypton, xenon, radon or the like, and further in a nitrogen gas atmosphere, argon or helium is particularly preferably used from the viewpoint of processability. However, from the viewpoint of manufacturing cost, it is most preferable to use nitrogen gas by optimizing the discharge conditions.

  As a preferred embodiment in the present invention, it is preferable to contain 0.01% to 30% (volume ratio) of a reactive gas together with an inert gas, more preferably 0.1% to 20%, and most preferably 1%. To 15% of reactive gas is more preferable.

  A plurality of reactive gases used in the present invention can be used, but at least one kind is preferably one that contains a component that is in a plasma state in the discharge space and can treat the surface of the object.

  As a preferable example of the reactive gas, a gas such as oxygen, carbon dioxide, nitrogen (except in the case of a nitrogen atmosphere), hydrogen, or the like may be included. In addition, in order to positively modify the surface, it is also a preferred embodiment in the present invention to use methane, ammonia, various organometallic compounds, fluorine compounds and the like as reactive gases. In the present invention, it is most preferable to use an appropriate amount of hydrogen gas mixed with an inert gas, particularly from the viewpoint of preventing deterioration of the substrate and the electrode surface simultaneously with the removal of organic substances.

  When plasma treatment is performed under atmospheric pressure, the starting voltage increases. To suppress this, a dielectric is sandwiched between the discharge electrode surfaces, the atmospheric gas is helium, argon, or nitrogen. It is preferable to use it.

The frequency is preferably 1 kHz to 1 GHz. The power to be applied varies depending on the composition of the target sample, surface characteristics, and the like, and it is necessary to optimize the conditions. However, in consideration of surface smoothness, scattered substance contamination due to discharge, etc., 0.01 W / cm ² The discharge treatment is preferably performed in the range from 0.1 seconds to several tens of seconds using power in the range of 10 to 10 W / cm ² . An example of an atmospheric pressure plasma processing apparatus used in the cleaning process will be described with reference to FIG.

  FIG. 9 is a schematic view showing an example of an atmospheric pressure plasma processing apparatus. This figure is an example of a so-called roll-to-roll plasma processing apparatus that can be applied to a flexible film substrate transport process.

  In the figure, 9 indicates an atmospheric pressure plasma processing apparatus. The atmospheric pressure plasma processing apparatus 9 is an apparatus having at least a plasma discharge processing apparatus 9a, an electric field applying means 9b having two power supplies, a gas supply means 9c, and an electrode temperature adjusting means 9d.

  The atmospheric pressure plasma processing apparatus 9 includes gas supply means between the counter electrodes (discharge space) 9a3 between the roll rotating electrode (first electrode) 9a1 and the plurality of rectangular tube electrodes (second electrodes) 9a2 of the plasma discharge processing apparatus 9a. A mixture G of an organometallic compound gas and / or oxygen gas supplied from 9c and a discharge gas such as nitrogen is supplied, activated here, and introduced onto the substrate F. Plasma discharge treatment is performed.

  A discharge space (between the opposing electrodes) 9a3 between the roll rotating electrode (first electrode) 9a1 and the rectangular tube electrode (second electrode) 9a2 is connected to the roll rotating electrode (first electrode) 9a1 from the first power supply 9b1. A first high-frequency electric field having a frequency ω1, an electric field strength V1, and a current I1, and a second high-frequency electric field having a frequency ω2, an electric field strength V2, and a current I2 from a second power source 9b2 to a rectangular tube electrode (second electrode) 9a2. It is supposed to multiply.

  A first filter 9b3 is installed between the roll rotation electrode (first electrode) 9a1 and the first power supply 9b1, and the first filter 9b3 is transferred from the first power supply 9b1 to the roll rotation electrode (first electrode) 9a1. Is designed so that the current from the second power source 9b2 is grounded and the current from the second power source 9b2 to the first power source 9b1 is difficult to pass. A second filter 9b4 is installed between the square tube electrode (second electrode) 9a2 and the second power source 9b2, and the second filter 9b4 receives a square tube electrode (second electrode) from the second power source 9b2. (Two electrodes) 9a2 is designed to make it easy to pass current, ground current from the first power supply 9b1, and make it difficult to pass current from the first power supply 9b1 to the second power supply 9b2.

  The roll rotating electrode (first electrode) 9a1 may be the second electrode, and the square tube fixed electrode 9a2 group may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power source preferably applies a higher high-frequency electric field strength (V1> V2) than the second power source. Further, the frequency has the ability to satisfy ω1 <ω2.

The current is preferably I1 <I2. The current I1 of the first high-frequency electric field is preferably 0.3 mA / cm ² to 20 mA / cm ² , more preferably 1.0 mA / cm ² to 20 mA / cm ² . The current I2 of the second high-frequency electric field is preferably 10 mA / cm ² to 100 mA / cm ² , more preferably 20 mA / cm ² to 100 mA / cm ² .

  In the gas supply means 9c, the reactive gas G generated by the gas generator 9c1 is introduced into the atmospheric pressure plasma processing vessel 9a4 through the air supply port 9c2 while controlling the flow rate.

  The base material F is unwound from the original winding (not shown) or is transported, or transported from the previous process, and the air entrained by the base material F is blocked by the nip roll 9f via the guide roll 9e. Then, while being wound while being in contact with the roll rotating electrode (first electrode) 9a1, it is transported between the rectangular tube electrode (second electrode) 9a2, and the roll rotating electrode (first electrode) 9a1 and the rectangular tube electrode ( An electric field is applied from both the second electrode 9a2 and discharge plasma is generated between the opposing electrodes (discharge space) 9a3.

  The substrate F is treated with a plasma state gas while being wound while being in contact with the roll rotating electrode (first electrode) 9a1. The base material F is transferred to the next process through the nip roll 9g and the guide roll 9h. The treated exhaust G ′ after the discharge treatment is discharged from the exhaust port 9a5.

  In order to heat or cool the roll rotating electrode (first electrode) 9a1 and the rectangular tube type electrode (second electrode) 9a2 during the plasma treatment, a medium whose temperature is adjusted by the electrode temperature adjusting means 9d is supplied by the liquid feed pump P. It sends to both electrodes through the pipe 9d1, and the temperature is adjusted from the inside of the electrode.

  Reference numerals 9a6 and 9a7 denote partition plates that partition the atmospheric pressure plasma processing vessel 9a4 from the outside.

  Each square tube electrode 9a2 is preferably used in the present invention because it has an effect of expanding the discharge range (discharge area) as compared with the cylindrical electrode. Furthermore, it is preferable to cover the surface of the metallic base material with a dielectric to form a rectangular tube electrode in order to discharge under atmospheric pressure.

  The distance between the opposing roll rotating electrode (first electrode) 9a1 and rectangular tube electrode (second electrode) 9a2 is that when a dielectric is provided on one of the electrodes, the surface of the dielectric and the other electrode It means the shortest distance from the surface of the conductive metallic base material, and when a dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces.

  The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metal base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of performing, it is preferably 0.1 mm to 20 mm, particularly preferably 0.5 mm to 2 mm.

  As the atmospheric pressure plasma processing container 9a4, a processing container made of Pyrex (registered trademark) glass or the like is preferably used, but it is also possible to use a metal as long as it can be insulated from the electrode. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation. Hereinafter, a high frequency power source applicable to the atmospheric pressure plasma processing apparatus according to the present invention will be exemplified.

As the first power source (high frequency power source) installed in the atmospheric pressure plasma discharge processing apparatus of the present invention,
Manufacturer Frequency Product name Shinko Electric 3kHz SPG3-4500
Shinko Electric 5kHz SPG5-4500
Kasuga Electric 15kHz AGI-023
Shinko Electric 50kHz SPG50-4500
HEIDEN Laboratory 100kHz * PHF-6k
Pearl industry 200kHz CF-2000-200k
Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second power source (high frequency power source),
Manufacturer Frequency Product name Pearl Industry 800kHz CF-2000-800k
Pearl industry 2MHz CF-2000-2M
Pearl Industry 13.56MHz CF-5000-13M
Pearl industry 27MHz CF-2000-27M
Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high frequency power source that can apply only a continuous sine wave.

  In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma processing apparatus.

In the present invention, the electric power applied between the opposing electrodes supplies electric power (power density) of 1 W / cm ² or more to the rectangular tube electrode (second electrode) (second high frequency electric field) to excite the discharge gas. Then, plasma is generated, and the target sample surface is processed.

The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

Further, by supplying power (power density) of 1 W / cm ² or more to the roll rotating electrode (first electrode) (first high frequency electric field), the uniformity of the second high frequency electric field is maintained, The power density can be improved. More preferably, it is 5 W / cm ² or more. The upper limit value of the power supplied to the roll rotating electrode (first electrode) is preferably 50 W / cm ² .

  Thereby, the further uniform high-density plasma can be produced | generated, and the improvement of the further process speed and processability can be compatible.

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted. On the electrode side (second high frequency electric field), a continuous sine wave is more preferable.

  The plasma discharge treatment according to the method for producing an organic electronics panel of the present invention is preferably performed at a temperature as high as possible from the viewpoint of reactivity, and at least the temperature of the roll rotating electrode (first electrode) using the electrode temperature adjusting means 9d. It is preferable to process while adjusting.

  The temperature of the roll rotating electrode (first electrode) is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and most preferably 90 ° C. or higher.

  The plasma irradiation time can be controlled by the conveyance speed of the base material F, and is appropriately adjusted according to the irradiation time. A preferred irradiation time is 1 second to 30 minutes, more preferably 5 seconds to 10 minutes, and most preferably 10 seconds to 2 minutes. Although the effect of the present invention is easily exhibited as the irradiation is continued for a long time, the treatment is preferably performed in a shorter time in consideration of productivity, damage to the organic functional layer, and the substrate.

  The atmospheric pressure plasma discharge treatment apparatus applicable to the present invention is described in, for example, JP-A-2004-68143, 2003-49272, WO 02/48428, etc., in addition to the above description. And an atmospheric pressure plasma discharge treatment apparatus.

On the substrate, an organic substance is interposed between the first electrode, the first electrode external connection electrode, the second electrode, the second electrode connection electrode, and the first electrode and the second electrode. An organic electronic panel having at least one organic functional layer including a layer is patterned by removing unnecessary portions of the organic functional layer by a wiping method, and then the entire surface of the substrate having the patterned organic functional layer is dry-etched. The following effects were obtained by the method of manufacturing an organic electronics panel that was cleaned and formed the second electrode and the second electrode portion connecting electrode.
1. When unnecessary parts of the organic functional layer are removed by the wiping method, the occurrence of shorts and dark spots due to the remaining wiping is eliminated, and it becomes possible to manufacture organic electronic panels with stable performance.
2. When unnecessary parts of the organic functional layer are removed by the wiping method, it is possible to produce organic electronic panels with stable performance by eliminating the occurrence of shorts and dark spots due to the dust generated on the organic functional layer.
3. When unnecessary parts of the organic functional layer are removed by the wiping method, the generated dust will not adhere to the base material, the adhesion between the sealing member and the base material will be improved, and the moisture resistance of the sealed organic electronics panel will be improved As a result, it has become possible to manufacture organic electronics panels with extended life.

  Next, the structure of the organic EL panel and the organic PV panel in the organic electronics panel according to the method for producing the organic electronics panel of the present invention will be described.

(Organic EL panel configuration)
An organic EL panel has a structure in which one or a plurality of organic functional layers are laminated between electrodes. In general, a hole injection / transport layer / light emitting layer is formed as an organic layer on the first electrode (anode). / An electron injecting / transporting layer is laminated, and a second electrode (cathode) is laminated thereon. Other typical layer configurations between the first electrode (anode) and the second electrode (cathode) include the following configurations.

(1) First electrode (anode) / light emitting layer / second electrode (cathode)
(2) First electrode (anode) / light emitting layer / electron transport layer / second electrode (cathode)
(3) First electrode (anode) / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / second electrode (cathode)
(4) First electrode (anode) / anode buffer layer (hole injection layer) / hole transport layer / light emitting layer // electron transport layer / cathode buffer layer (electron injection layer) / second electrode (cathode)
(5) First electrode (anode) / anode buffer layer (hole injection layer) / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / second electrode ( cathode)
The main organic material layer constituting the organic EL panel will be described below.

(Light emitting layer)
Organic light-emitting materials contained in the light-emitting layer include aromatic heterocyclic compounds such as carbazole, carboline, diazacarbazole, triarylamine derivatives, stilbene derivatives, polyarylenes, aromatic condensed polycyclic compounds, aromatic heterocondensed compounds. Examples thereof include a ring compound, a metal complex compound, and the like, and a single oligo body or a composite oligo body thereof. However, the present invention is not limited to this, and widely known materials can be used.

  In the light emitting layer (film forming material), a dopant of preferably about 0.1% by mass to 20% by mass may be included in the light emitting material. Examples of the dopant include known fluorescent dyes such as perylene derivatives and pyrene derivatives, and in the case of phosphorescent light emitting layers, for example, tris (2-phenylpyridine) iridium, bis (2-phenylpyridine) (acetylacetonate). A complex compound such as an orthometalated iridium complex represented by iridium, bis (2,4-difluorophenylpyridine) (picolinato) iridium, and the like is similarly contained in an amount of about 0.1 to 20% by mass.

  The phosphorescent light emitting method is a preferable embodiment in the present invention in which uneven light emission hardly occurs due to the fact that the light emitting layer has a light emitting region. The thickness of the light emitting layer is preferably in the range of 1 nm to several hundred nm.

(Configuration of organic PV panel)
The organic PV panel of the present invention has a layer containing a p-type semiconductor material and an n-type semiconductor material as a photoelectric conversion layer sandwiched between the first electrode and the second electrode, and is excited by light irradiation. In this panel, an electromotive force is generated when a child moves to a p / n interface and charges are separated into carriers.

  In order to increase the p / n interface between the p-type semiconductor material and the n-type semiconductor material, the photoelectric conversion layer preferably forms a so-called bulk heterojunction structure in which both semiconductor materials are mixed (hereinafter referred to as a bulk heterojunction layer or BHJ). Layer and i layer).

  A general organic PV panel has a structure in which a hole transport / electron blocking layer / photoelectric conversion layer / electron transport / hole blocking layer is laminated as an organic material layer on a first electrode (anode), However, the present invention is not limited to this, and the photoelectric conversion layer is a layer made of a p-type semiconductor material and an n-type semiconductor material, and the above-described bulk heterojunction layer is sandwiched between them. A so-called p-i-n configuration may be applied. As a result, the rectification of holes and electrons as generated carriers becomes higher, loss due to recombination of charge-separated holes and electrons is reduced, and higher photoelectric conversion efficiency can be obtained.

(P-type semiconductor material)
Examples of the p-type semiconductor material used for the photoelectric conversion layer (bulk heterojunction layer) include various condensed polycyclic aromatic low molecular compounds and conjugated polymers / oligomers.

  Examples of the condensed polycyclic aromatic low-molecular compound include pentacene and derivatives thereof, porphyrin and phthalocyanine, copper phthalocyanine and derivatives thereof.

  Examples of the conjugated polymer include polythiophene such as poly-3-hexylthiophene (P3HT) and oligomers thereof, polythiophene-thienothiophene copolymer, polythiophene-diketopyrrolopyrrole copolymer, polythiophene-thiazolothiazole copolymer, Nature Mat. vol. 6 (2007), p497 described in PCPDTBT, etc., polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, Examples thereof include polymer materials such as σ-conjugated polymers such as polysilane and polygermane.

(N-type semiconductor material)
The n-type semiconductor material used for the photoelectric conversion layer (bulk heterojunction layer) is not particularly limited. For example, fullerene, octaazaporphyrin, and other p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), Examples thereof include aromatic carboxylic acid anhydrides such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, and perylenetetracarboxylic acid diimide, and polymer compounds containing an imidized product thereof as a skeleton. .

  A common material used for the configuration of the organic EL panel and the organic PV panel will be described.

(Hole injection / transport layer, electron block layer)
Materials used for the hole injection / transport layer and the electron blocking layer include phthalocyanine derivatives, heterocyclic azoles, aromatic tertiary amines, polyvinylcarbazole, polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT: PSS), etc. Represented polymer materials such as conductive polymers are also used in the light-emitting layer. For example, carbazole-based light-emitting materials such as 4,4′-dicarbazolylbiphenyl and 1,3-dicarbazolylbenzene , (Di) azacarbazoles, low molecular light emitting materials typified by pyrene-based luminescent materials such as 1,3,5-tripyrenylbenzene, polyphenylene vinylenes, polyfluorenes, polyvinyl carbazoles Examples thereof include molecular light emitting materials.

  In the present invention, a hole injection layer and a hole transport layer may be laminated according to the purpose, and an optimum material may be selected for the hole transport property and the bonding between the electrodes.

  In the present invention, a material that has a function of blocking electrons as reverse carriers and improves the selectivity of charges may be selected.

  A preferable film thickness range of each of the hole injection / transport layer and the electron blocking layer is preferably 0.1 nm to 100 nm, more preferably 5 nm to 70 nm, and most preferably 10 nm to 50 nm.

(Electron injection / transport layer, hole blocking layer)
Various n-type materials can be used as the electron injection / transport layer material. Examples of materials that can be preferably used in the organic electronics panel of the present invention include metal complex compounds such as 8-hydroxyquinolinate lithium and bis (8-hydroxyquinolinate) zinc, or nitrogen-containing five-membered rings listed below. There are derivatives. That is, oxazole, thiazole, oxadiazole, thiadiazole or triazole derivatives are preferred. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1 -Phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5-bis ( 1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1 , 3,4-thiadiazole, 1,4-bis [2- (5-phenyl) Asiazolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4 -Triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like.

  In addition to the above-mentioned compounds, fullerenes, carbon nanotubes, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), and n-type inorganic oxides such as titanium oxide, zinc oxide, gallium oxide, etc. It is also preferable in the present invention to use.

  In the present invention, an electron injection layer and an electron transport layer may be laminated according to the purpose, and an optimal material may be selected in connection with electron transport properties and electrodes.

  In the present invention, a material that has a function of blocking electrons as reverse carriers and improves the selectivity of charges may be selected.

  A preferable film thickness range of each of the electron injection / transport layer and the hole blocking layer is preferably 0.1 nm to 100 nm, more preferably 5 nm to 80 nm, and most preferably 10 nm to 60 nm.

  The electron injection layer (buffer layer) has a structure in which halides containing ions such as lithium, potassium, sodium, and cesium, for example, lithium fluoride, potassium fluoride, and the like are stacked to improve the bonding with the electrode. Particularly preferred in the invention.

  When using these electron-injecting materials made of inorganic materials, it is preferable to form a film by patterning mainly by vapor deposition through a shadow mask, but if it can be formed as a solution, it should be formed by coating from the viewpoint of productivity. Is more preferable.

  In the case of a vapor deposition method, the manufacturing method which forms a vapor deposition film after performing the wiping patterning mentioned above is especially preferable in this invention.

(Formation method of organic functional layer)
As a method for forming each organic functional layer, it can be formed by vapor deposition or the like, but coating and printing are preferable from the viewpoint of film forming speed. Although there is no restriction | limiting in the coating method to be used, For example, die coating method, spin coating, transfer coating, extrusion coating, blade coating method, wire bar coating method, gravure coating method, spray coating method etc. are mentioned. Moreover, screen printing, offset printing, inkjet printing, etc. can be used for printing. After coating, it is preferable to perform heat drying annealing in order to remove residual solvent and moisture, gas, and improve the mobility of the semiconductor material.

(Solvent used for coating liquid for organic functional layer formation)
Each organic material has solubility characteristics (solubility parameters, ionization potential, polarity), and there are limitations on the solvents that can be dissolved. In this case, since the solubility is different, the concentration cannot be generally determined. However, the type of the solvent used in the present invention is suitable for the above conditions depending on the organic material to be deposited. May be selected from known solvents, for example, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, dibutyl ether, tetrahydrofuran, Ether solvents such as dioxane and anisole, methanol, alcohol solvents such as ethanol, isopropanol, butanol, cyclohexanol, 2-methoxyethanol, ethylene glycol, glycerin, benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbon solvents, paraffin solvents such as hexane, octane, decane and tetralin, ester solvents such as ethyl acetate, butyl acetate and amyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N- Amide solvents such as methylpyrrolidone, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, amine solvents such as pyridine, quinoline and aniline, nitrile solvents such as acetonitrile and valeronitrile, sulfur such as thiophene and carbon disulfide And system solvents. In addition, the solvent which can be used is not restricted to these, You may mix and use 2 or more types of these as a solvent.

  Of these, preferable examples of the good solvent for the material used in the organic electronics panel include, for example, aromatic solvents, halogen solvents, ether solvents, and preferably aromatic solvents, ether solvents. It is. Examples of the poor solvent include alcohol solvents, ketone solvents, paraffin solvents, and the like. Among them, alcohol solvents and paraffin solvents are used.

  In addition, when laminating | stacking these organic substance layers by application | coating etc., it is necessary to select a material and a solvent so that the lower layer may not be dissolved.

  For this reason, a structure in which the material of the organic layer is insolubilized by positively crosslinking it can be preferably used. For example, a polymer having a polymerizable group such as a vinyl group or a cross-linking group and forming a polymer or a cross-linked structure having the above-described structural units by heating or light irradiation can be used. As a result, dissolution of the film due to the multilayer, disturbance of the interface, and the like can be suppressed.

(First electrode)
The first electrode is not particularly limited to a cathode and an anode, and can be selected depending on the element structure, but preferably a transparent electrode is used as the anode. For example, when used as an anode, it is preferably an electrode that transmits light from 380 nm to 800 nm. A material having a work function larger (deep) than 4 eV is suitable as a material, for example, a transparent conductive metal oxide such as indium tin oxide (ITO), SnO ₂ , or ZnO, or a metal such as gold, silver, or platinum. Thin films, metal nanowires, carbon nanotubes, and the like can be used.

(Second electrode)
The second electrode is not particularly limited to a cathode and an anode, and can be selected depending on the element configuration, but preferably a transparent electrode is used as the anode. For example, when used as a cathode, it is preferable to use a metal, an alloy, an electrically conductive compound having a work function of 4 eV or less (shallow), and a mixture thereof as an electrode material. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electrical bonding with the organic functional layer and durability against oxidation, etc., these metals and the second metal, which is a stable metal having a larger (deep) work function value than this, Mixtures such as magnesium / silver mixtures, magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum alone and the like are suitable.

  The second electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm.

  If a highly reflective metal material is used as the second electrode, for example, in an organic EL element, a part of the emitted light can be reflected and taken out to the outside, and the organic PV element passes through a photoelectric conversion layer. The effect of increasing the optical path length can be obtained by reflecting the reflected light and returning it to the photoelectric conversion layer again, and in any case, improvement of the external quantum efficiency can be expected.

  Furthermore, it may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.) or a nanoparticle, nanowire, or nanostructure made of carbon. A highly dispersible paste is preferable because a transparent and highly conductive counter electrode can be formed by a coating method or a printing method.

  Further, when the counter electrode side is made light transmissive, for example, a conductive material suitable for the counter electrode such as aluminum and aluminum alloy, silver and silver compound is formed with a thin film thickness of about 1 nm to 20 nm, and then the above-mentioned By providing a film of the conductive light-transmitting material mentioned in the description of the transparent electrode, a light-transmitting electrode can be obtained.

(Base material)
The base material is preferably a member capable of transmitting emitted light or light for generating electromotive force, that is, a member transparent to the wavelength of these lights. Preferred examples of the substrate that can be used in the present invention include a glass substrate and a resin substrate, but it is desirable to use a transparent resin film from the viewpoint of lightness and flexibility.

  There is no restriction | limiting in particular in a transparent resin film, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known things. For example, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, polyolefin resins such as cyclic olefin resin Film, vinyl resin film such as polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film, A polyamide resin film, a polyimide resin film, an acrylic resin film, a triacetyl cellulose (TAC) resin film, and the like can be given. If the resin film transmittance of 80% or more at ~800nm), can be preferably applied to a transparent resin film according to the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.

  The transparent substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesiveness of the coating solution. A conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. Examples of the easy-adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer.

  In order to suppress the permeation of oxygen and water vapor, a barrier coat layer may be formed in advance on the transparent substrate, or a hard coat layer is formed in advance on the side where the transparent conductive layer is formed or on the opposite side. May be.

(Sealing)
In order to prevent the produced organic photoelectric conversion element from being deteriorated by oxygen, moisture, etc. in the atmosphere, it is preferable to seal the organic EL element and the organic PV element by a known method. For example, a method of sealing and bonding a plastic film on which a gas barrier layer such as a thin film of aluminum, silicon oxide, or aluminum oxide is formed and an organic electronics panel with an adhesive, UV curable / thermosetting resin, etc., gas barrier properties Spin coating of organic polymer materials (polyvinyl alcohol, etc.) with high viscosity, sputtering methods and CVD methods for inorganic thin films (silicon oxide, aluminum oxide, etc.) or organic films (parylene, etc.) with high gas barrier properties under vacuum or air The method of depositing by these, the method of laminating | stacking these compositely, etc. can be mentioned.

  Furthermore, in the present invention, from the viewpoint of improving the lifetime of the element, the entire organic electronics panel including the base material may be laminated and sealed with two base materials with a barrier, and preferably a configuration in which a moisture getter or the like is enclosed. It doesn't matter.

  Hereinafter, although an example is given and the concrete effect of the present invention is shown, the mode of the present invention is not limited to this.

Example 1
When producing an organic EL element as the organic electronics panel having the configuration shown in FIG. 1A according to the process flow chart for producing the organic electronics panel shown in FIGS. 2 and 3, and the organic electronics panel shown in FIGS. In accordance with the process flow chart for manufacturing the organic EL panel as the organic electronics panel having the structure shown in FIG. 1B, a patterning process and a cleaning process for removing unnecessary regions of the organic functional layer as shown in Table 1 The organic EL panel was manufactured by changing the conditions of Sample No. 101 to 110.

  Note that the wiping device shown in FIG. 5 was used in the patterning step, and the atmospheric pressure plasma processing device shown in FIG. 6 was used in the cleaning step. The layer structure of the organic EL panel is as follows: substrate / first electrode (anode) / organic functional layer (hole injection layer / hole transport layer / light emitting layer / electron transport layer) / electron injection layer / second electrode (cathode) / It was set as the sealing layer.

A light emitting layer which is a main organic functional layer was used, and toluene was used as a solvent in the light emitting layer forming coating solution. The percentages (f _d , f _p , f _h ) calculated from Hansen solubility parameters _{ｄ d} , ∂ _p , ∂ _{h of} the solvent (toluene) used in the light emitting layer forming coating solution are f _d 80, f _p 7 and f _h 13. The percentages (f _d , f _p , f _h ) shown above represent values obtained according to the following formulas 1) to 3).

Formula 1) f _d = ∂ _d / (∂ _d + ∂ _p + ∂ _h )
Formula 2) f _p = ∂ _p / (∂ _d + ∂ _p + ∂ _h )
Equation _{3) f h = ∂ h /} (∂ d + ∂ p + ∂ h)

Plots of percentages (f _d1 , f _p1 , f _h1 ) calculated from Hansen solubility parameters _{ｄ d1} , _{ｐ p1} , ∂ _h1 , used for the wiping device in the patterning step, and used for the light emitting layer forming coating solution The point difference Rf with respect to the percentage (f _d2 , f _p2 , f _h2 ) plot calculated from Hansen solubility parameters _{ｄ d2} , _{ｐ p2} , ∂ _h2 , of the solvent (toluene) obtained was determined according to the following formula 4) It is shown in 2.

Formula 4) (Rf) ² = (f _d2 −f _d1 ) ² + (f _p2 −f _p1 ) ² + (f _h2 −f _h1 ) ²

f _d *, f _p *, and f _h * are quoted from The Book and Paper Group ANNUAL, Volume Three 1984, Solubility Parameters: Theory and Application (shown by John Burke).

<Sample No. 101 Production>
(Preparation of base material)
A barrier film having a thickness of 60 nm is prepared by sputtering under a vacuum environment condition in which a polyethylene terephthalate (PET) film (manufactured by Teijin DuPont) having a thickness of 100 μm and a width of 180 mm is prepared as a base material and reduced in pressure to 5 × 10 ⁻² Pa A layer (a layer mainly made of SiO ₂ ) was formed.

(Formation of the first electrode (anode))
On the prepared PET film, ITO (Indium Tin Oxide) with a thickness of 120 nm is formed by sputtering under vacuum environment conditions, and a mask pattern is formed, and a first electrode having a size of 10 mm × 100 mm having a lead portion on the right end is formed. Twelve rows were formed at intervals of 3 mm.

(Preparation of hole injection layer forming coating solution)
Polyethylenedioxythiophene / polystyrenesulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) is diluted with 40% by mass with 30% by mass of pure water and 30% by mass of isopropanol to prepare a coating solution for forming a hole injection layer. did.

(Formation of hole injection layer)
Subsequently, the prepared coating solution for forming the hole injection layer is applied to the entire surface including the first electrode of the PET film formed up to the first electrode using a slit coater, and subsequently dried and heated at 150 ° C. for 15 minutes. A hole injection layer having a thickness of 30 nm was formed by treatment. The coating speed was 5 m / min. The film thickness is a value measured using a spectroscopic ellipsometer manufactured by Joban Yvon.

(Preparation of coating solution for hole transport layer formation)
A toluene solution containing 0.5% by mass of hole transport material 1 was prepared as a coating solution for forming a hole transport layer.

(Formation of hole transport layer)
Subsequently, the PET film formed up to the hole injection layer is transported into a nitrogen chamber (N 2 gas environment at 25 ° C., dew point temperature −20 ° C. or lower, atmospheric pressure, and cleanliness class 5 or lower (JIS B 9920)). Then, the prepared coating liquid for forming a hole transport layer was applied to the entire upper surface of the hole transport layer using a slit coater similar to the above. After the solvent was dried, the region of the lead part composed of the first electrode was wiped off using the method described in the patterning of the organic functional layer described later. Furthermore, UV irradiation was performed with a 100 W high-pressure mercury lamp for 180 seconds in a nitrogen atmosphere, photopolymerization and crosslinking were performed, and a hole transport layer having a thickness of about 20 nm was formed. The coating speed was 5 m / min. A film thickness shows the value measured by the same method as the measurement of the film thickness of a positive hole injection layer.

(Preparation of light emitting layer forming coating solution)
A toluene solution containing 1% by mass of PVK and 0.1% by mass of dopant 4 was prepared as a light emitting layer forming coating solution.

(Formation of light emitting layer)
Subsequently, the prepared light emitting layer forming coating solution was applied to the entire upper surface of the hole transport layer on the PET film formed up to the hole transport layer using a slit coater and dried at 120 ° C. A light emitting layer was formed. The coating speed was 5 m / min. A film thickness shows the value measured by the same method as the measurement of the film thickness of a positive hole injection layer.

(Preparation of coating solution for electron transport layer formation)
An n-butanol solution containing 0.5% by mass of the electron transport material 1 was prepared and used as a coating solution for forming an electron transport layer.

(Formation of electron transport layer)
Subsequently, the prepared coating solution for forming an electron transport layer was applied to the entire surface of the light emitting layer on the PET film formed up to the light emitting layer using a slit coater, dried at 60 ° C., and transported with a thickness of 15 nm. A layer was formed. The coating speed was 5 m / min. A film thickness shows the value measured by the same method as the measurement of the film thickness of a positive hole injection layer.

(Patterning of organic functional layer)
(Preparation of wiping device)
The wiping device shown in FIG. 5 was aligned with the positions of the 12 rows of first electrodes patterned on the PET film, and 13 units were arranged in the width direction of the base material so as to be orthogonal to the transport direction of the base material.

(Removal of unnecessary area of organic functional layer)
Subsequently, the organic functional layer is unnecessary by using 13 wiping devices prepared in the patterning process for the PET film laminated with each organic functional layer (hole injection layer / hole transport layer / light emitting layer / electron transport layer). The region (the region for forming the first electrode external connection electrode and the upper portion of the lead portion) was continuously wiped and removed under the conditions shown below.

Wiping conditions of the wiping device Wiping member width: 95% of the width of the organic functional layer to be wiped Wiping member thickness: 8 mm
Material of wiping member: Non-woven tape Solvent used: o-xylene Supply amount of solvent used: 20 ml / sec. Pressing force of wiping member to organic functional layer by pressing roll: 1.96 × 10 ⁵ Pa
Feeding speed of wiping member (relative speed with the base material): 5 cm / second (formation of electron injection layer)
Subsequently, the PET film patterned by removing unnecessary regions from the organic functional layer in the patterning process is transported to a vacuum deposition chamber without being processed in the cleaning process, and lithium fluoride (LiF) is used as a deposition material. Under vacuum conditions where the pressure was reduced to 10 ⁻⁴ Pa, vapor deposition was performed so as to overlap with the patterned light emitting region, thereby forming an electron injection layer having a thickness of 0.6 nm.

(Formation of second electrode)
Subsequently, under the vacuum condition in which the PET film formed up to the electron injection layer was depressurized to 5 × 10 ⁻⁴ Pa, the electron injection layer (the upper part of the first electrode (light emission) was removed except for the external connection electrode part of the first electrode. 1) and a region reaching the lead portion, a mask pattern is formed by vapor deposition using aluminum to form a second electrode (cathode) made of aluminum having a thickness of 100 nm, and the structure shown in FIG. An organic EL element was prepared.

[Pasting of sealing member]
(Formation of adhesive layer)
Subsequently, in the produced organic EL element, the leftmost first electrode external connection electrode (region where the organic functional layer is removed by patterning) connected in series in 12 columns is excluded, and the rightmost second electrode external connection electrode is excluded. Then, an ultraviolet curable liquid adhesive (epoxy resin) was dropped from a plurality of nozzles onto the inner region. A sealing film (letter printing GX film: thickness 100 μm) was bonded to the adhesive coating surface by a roll laminator method, and after pressure-bonding at a pressure of 0.1 MPa in an atmospheric pressure environment, a 100 W high-pressure mercury lamp was attached. A band-shaped organic EL panel having 12 rows of light emitting regions in the horizontal direction was prepared by applying an irradiation intensity of 5 mW / cm ² to 20 mW / cm ² and a distance of 5 mm to 15 mm for 1 minute. . 101.

<Sample No. Production of 102>
(Preparation of base material)
Sample No. The same PET film as 101 was prepared.

(Formation of the first electrode (anode))
On the prepared PET film, Sample No. The first electrode having a size of 10 mm × 100 mm having a lead portion at the right end was formed in 12 rows at intervals of 3 mm under the same conditions and the same method as 101.

(Formation of light emitting layer from hole transport layer)
Subsequently, on the entire surface including the first electrode of the PET film formed up to the first electrode, the sample No. Organic functional layers up to a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer were sequentially laminated under the same conditions and the same method as 101.

(Patterning of organic functional layer)
Subsequently, sample no. Unnecessary regions of the organic functional layer were wiped and removed under the same conditions and the same method as 101.

(Formation of electron injection layer)
Subsequently, sample no. An electron injection layer was formed under the same conditions and the same method as 101.

(Formation of second electrode)
Subsequently, under the vacuum condition in which the PET film formed up to the electron injection layer was depressurized to 5 × 10 ⁻⁴ Pa, except for the first electrode external connection electrode part, on the upper part (light emitting region) of the first electrode, A mask pattern was formed by vapor deposition using aluminum to form a second electrode (cathode) made of aluminum having a thickness of 100 nm.

(Formation of conductive layer)
Subsequently, in a vacuum condition in which the PET film formed up to the second electrode is depressurized to 5 × 10 ⁻⁴ Pa, aluminum is used for the region where the end portion of the second electrode and the lead portion are connected by vapor deposition. A mask pattern was formed, a conductive layer made of aluminum having a thickness of 100 nm was formed, and an organic EL element having a configuration shown in FIG.

[Pasting of sealing member]
Subsequently, sample no. A sealing member was bonded under the same conditions and in the same manner as in 101, and an organic EL panel was prepared. 102.

<Sample No. 103 production>
(Preparation of base material)
Sample No. The same PET film as 101 was prepared.

(Formation of the first electrode (anode))
On the prepared PET film, Sample No. The first electrode having a size of 10 mm × 100 mm having a lead portion at the right end was formed in 12 rows at intervals of 3 mm under the same conditions and the same method as 101.

(Formation of light emitting layer from hole transport layer)
Subsequently, on the entire surface including the first electrode of PET formed up to the first electrode, the sample No. Organic functional layers up to a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer were sequentially laminated under the same conditions and the same method as 101.

(Patterning of organic functional layer)
Subsequently, sample no. Unnecessary regions of the organic functional layer were wiped and removed under the same conditions and the same method as 101.

(Cleaning of PET film with a patterned organic functional layer)
Subsequently, the entire surface of the PET film formed up to the patterned organic functional layer was cleaned with the atmospheric pressure plasma processing apparatus shown in FIG. 6 under the following conditions.

Atmospheric pressure plasma treatment conditions Carrier gas: Nitrogen (under atmospheric pressure)
Reactive gas: Hydrogen (4% by volume with respect to nitrogen)
First power supply: HEIDEN lab PHF-6k (100kHz)
Second power supply: Pearl Industrial CF-5000-13M (13.56 MHz)
Applied output: 1.0 W / cm ²
Electrode temperature control: 80 ° C
Processing time: 20 seconds (formation of electron injection layer)
Subsequently, sample No. 1 was formed on the electron transport layer of the PET film formed up to the electron transport layer. An electron injection layer was formed under the same conditions and the same method as 101.

(Formation of second electrode)
Subsequently, the upper part of the first electrode (light emitting region) and the lead except for the external connection electrode part of the first electrode under a vacuum condition in which the PET film formed up to the electron injection layer was decompressed to 5 × 10 ⁻⁴ Pa. An organic EL element having a structure shown in FIG. 1A is formed by forming a mask pattern by vapor deposition using aluminum and forming a second electrode (cathode) made of aluminum having a thickness of 100 nm up to a region reaching the portion. Was made.

[Pasting of sealing member]
Subsequently, sample no. A sealing member was bonded under the same conditions and in the same manner as in 101, and an organic EL panel was prepared. 103.

<Sample No. Production of 104>
(Preparation of base material)
Sample No. The same PET film as 101 was prepared.

(Formation of the first electrode (anode))
On the prepared PET film, Sample No. The first electrode having a size of 10 mm × 100 mm having a lead portion at the right end was formed in 12 rows at intervals of 3 mm under the same conditions and the same method as 101.

(Formation of light emitting layer from hole transport layer)
Subsequently, on the entire surface including the first electrode of PET formed up to the first electrode, the sample No. Organic functional layers up to a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer were sequentially laminated under the same conditions and the same method as 101.

(Patterning of organic functional layer)
Subsequently, sample no. Unnecessary regions of the organic functional layer were wiped and removed under the same conditions and the same method as 101.

(Cleaning of PET film formed up to organic functional layer)
Subsequently, sample no. The entire surface of the PET film on which the organic functional layer was formed under the same conditions and the same method as 103 was cleaned.

(Formation of electron injection layer)
Subsequently, sample no. An electron injection layer was formed under the same conditions and the same method as 101.

(Formation of second electrode)
Subsequently, the sample No. 1 was formed under a vacuum condition in which the PET film formed up to the electron injection layer was decompressed to 5 × 10 ⁻⁴ Pa. A second electrode (cathode) was formed under the same conditions and method as in 102.

(Formation of conductive layer)
Subsequently, in a vacuum condition in which the PET film formed up to the second electrode was depressurized to 5 × 10 ⁻⁴ Pa, sample no. A conductive layer was formed under the same conditions and in the same manner as in 102, and an organic EL device having the configuration shown in FIG.

[Pasting of sealing member]
Subsequently, sample no. A sealing member was bonded under the same conditions and in the same manner as in 101, and an organic EL panel was prepared. 104.

<Sample No. Production of 105>
Sample No. The atmospheric pressure plasma treatment used for cleaning the entire surface of the PET film formed up to the organic functional layer in the production of 103 was performed using an RF magnetron sputtering apparatus (an apparatus modified from Anelva Co., Ltd.) under a reduced pressure of 100 Pa or less. The sample No. was changed to the substrate cleaning (etching) mode except that the cleaning process was performed under the following conditions. An organic EL panel was prepared under the same conditions and in the same manner as in sample No. 103, and sample no. 105.

RF magnetron sputtering apparatus RF sputtering cleaning (etching) mode processing conditions Ion source: Argon (99.998%)
Acceleration voltage: 5 kV
Ion current: 10 μA / cm ²
<Sample No. Production of 106>
Sample No. In the preparation of No. 103, all samples except for the solvent used for removing unnecessary regions of the organic functional layer were changed from o-xylene to chloroform. An organic EL panel was prepared under the same conditions and in the same manner as in sample No. 103, and sample no. 106.

<Sample No. Preparation of 107>
Sample No. In the production of the sample No. 103, all the samples except for the solvent used for removing the unnecessary area of the organic functional layer were changed from o-xylene to butyl acetate. An organic EL panel was prepared under the same conditions and in the same manner as in sample No. 103, and sample no. 107.

<Sample No. 108 Production>
Sample No. In the preparation of the sample No. 103, all the samples except for the solvent used for removing the unnecessary area of the organic functional layer were changed from o-xylene to ethyl acetate. An organic EL panel was prepared under the same conditions and in the same manner as in sample No. 103, and sample no. 108.

<Sample No. 109 production>
Sample No. In the preparation of the sample No. 103, all samples except for the solvent used for removing the unnecessary area of the organic functional layer were changed from o-xylene to acetone. An organic EL panel was prepared under the same conditions and in the same manner as in sample No. 103, and sample no. 109.

<Sample No. 110 Production>
Sample No. In the preparation of the sample No. 103, all the samples except for the solvent used for removing the unnecessary area of the organic functional layer were changed from o-xylene to n-butanol. An organic EL panel was prepared under the same conditions and in the same manner as in sample No. 103, and sample no. 110.

Evaluation Sample No. of a strip-shaped organic EL panel having 12 rows of light emitting regions on the side. About 101 to 110, the number of dark spots (spot-like non-light emitting parts), the emission luminance half-life, and the storage stability were tested by the test methods shown below, and the results evaluated according to the evaluation rank shown below are shown in Table 3. Show.

(Measurement method for the number of dark spots)
Each sample was cut into a horizontal row, a DC voltage of 5 V was applied to the organic EL panel using a constant voltage power source, and the presence or absence of dark spots was visually counted using a microscope. Observation was made in all areas of the panel where 12 rows were connected.

(Evaluation rank of the number of dark spots)
◎: No dark spots are generated ○: Dark spots 1 or more, less than 5 △: Dark spots 5 or more, less than 10 ×: Dark spots 10 or more (Measurement method of light emission luminance half-life)
Cut from each sample in a horizontal row, using a DC voltage / current source R6243 made by ADC Co., Ltd., a DC constant current of 25 A / m ² was passed through the element, and a spectral radiance meter CS1000 made by Konica Minolta Sensing Co., Ltd. Measure the 2 ° viewing angle front luminance as the emission luminance. Evaluation was made with relative values when the light emission luminance half-life of 101 was taken as 100.

Preservation test method The organic EL panels cut in a horizontal row from each sample were exposed to the conditions of an environmental temperature of 65 ° C. and a relative humidity of 85% RH for 500 hours, and then applied to the organic EL panel using a constant voltage power source. DC 5V was applied, and the presence or absence of dark spots was visually observed from a place 1 m away and visually observed using a microscope, and a storability test was performed.

(Evaluation rank for preservation)
(Double-circle): A conspicuous dark spot is not seen by visual evaluation. And even when observed with a microscope, there are less than 10 dark spots.

  ○: Conspicuous dark spots are not seen in visual evaluation. When observed with a microscope, the number of dark spots is 10 or more and less than 20.

  Δ: A dark spot can be seen by visual evaluation, but is an allowable size because it is 1 mm or less.

  X: A large dark spot is clearly seen by visual evaluation, and is an unacceptable size because the size is 1 mm or more.

  XX: Many large dark spots appear by visual evaluation

  When an organic EL panel having a first electrode / a hole injection layer / a hole transport layer / a light emitting layer / an electron injection layer / a second electrode (cathode) / a sealing layer on a substrate is formed, the organic function After removing unnecessary regions of the layer (hole injection layer / hole transport layer / light emitting layer) by a wiping method, cleaning is subsequently performed by a dry etching method, and then an electron injection layer / second electrode (cathode) / sealing layer is formed. The formed organic EL panel sample No. From 103 to 110, it was confirmed that excellent performance was obtained in terms of the number of dark spots (spot-like non-light-emitting portions), emission luminance half-life, and storage stability. Alternatively, when unnecessary regions of the organic functional layer (hole injection layer / hole transport layer / light emitting layer) are removed by a wiping method, the solvent to be used may be selected for the solvent SP value region of a specific Hansen solubility parameter. It was confirmed that excellent performance was obtained in terms of the number of dark spots (spot-like non-light-emitting portions), emission luminance half-life, and storage stability.

  After removing unnecessary areas of the organic functional layer (hole injection layer / hole transport layer / light emitting layer) by the wiping method, the electron injection layer / second electrode (cathode) / sealing layer is formed without cleaning. The organic EL panel sample No. Reference numerals 101 and 102 indicate the number of dark spots (spot-like non-light-emitting portions), emission luminance half-life, and storage stability. Compared with 103 to 110, the number of dark spots (spot-like non-light emitting portions), the emission luminance half-life, and the storage stability were all inferior. The effectiveness of the present invention was confirmed.

Example 2
When an organic PV panel is manufactured as an organic electronics panel having the configuration shown in FIG. 1A according to a process flow diagram for manufacturing the organic electronics panel shown in FIG. 2, a patterning process after removing an unnecessary region of the organic functional layer is performed. An organic PV panel was prepared with or without a cleaning process. 201 and 202.

  Note that the wiping device shown in FIG. 5 was used in the patterning step, and the atmospheric pressure plasma processing device shown in FIG. 6 was used in the cleaning step. The layer structure of the organic PV panel is: base material / first electrode (anode) / organic functional layer (hole injection layer / hole transport layer / photoelectric conversion layer / electron injection layer) / second electrode (cathode) / sealing. Layered.

<Sample No. Production of 201>
(Preparation of base material)
Sample No. 1 prepared in Example 1 was used. The same PET film as 101 was prepared as a substrate.

(Formation of the first electrode (anode))
Sample No. produced in Example 1 on the prepared PET film. Twelve rows of first electrodes were formed under the same conditions and method as in 101.

(Formation of hole injection layer)
Subsequently, the sample No. 1 prepared in Example 1 was formed on the entire surface including the first electrode of the PET film formed up to the first electrode. A hole injection layer was formed under the same conditions and method as in 101.

(Formation of hole transport layer)
Subsequently, the sample No. 1 prepared in Example 1 was formed on the entire upper surface of the hole injection layer of the PET film formed up to the hole injection layer. A hole transport layer was formed under the same conditions and method as in 101.

(Preparation of coating liquid for photoelectric conversion layer formation)
Chlorobenzene P3HT (plectrovirus Toro Nix Co., Ltd. regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon Corporation: 6,6-phenyl _{-C 61} - butyric acid methyl ester) to a of 3.0 wt% Was mixed at 1: 0.8 to prepare a coating solution for forming a photoelectric conversion layer.

The percentages (f _d , f _p , f _h ) calculated from Hansen solubility parameters _{ｄ d} , _{ｐ p} , ∂ _{h of} chlorobenzene are f _d 65, f _p 17, f _h 8. Percentages (f _d , f _p , f _h ) indicate values quoted from the same literature as the literature described in Example 1.

(Formation of photoelectric conversion layer)
Subsequently, the PET film formed up to the hole transport layer was heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere, and then the prepared photoelectric conversion layer forming coating solution was filtered on the hole transport layer using a slit coater. The solution was applied while filtering, and allowed to stand at room temperature for drying, followed by heat treatment at 150 ° C. for 15 minutes to form a photoelectric conversion layer having a film thickness of 100 nm.

(Patterning of organic functional layer)
(Preparation of wiping device)
The wiping device shown in FIG. 5 was aligned with the positions of the 12 rows of first electrodes patterned on the PET film, and 13 units were arranged in the width direction of the base material so as to be orthogonal to the agent transport direction.

(Removal of unnecessary area of organic functional layer)
Subsequently, the PET film laminated up to each organic functional layer (hole injection layer / hole transport layer / photoelectric conversion layer) was used as an unnecessary area (first layer) using 13 wiping devices prepared in the patterning step. Sample No. 1 of Example 1 except that acetone was used as the solvent for wiping off the region for forming the external electrode connection electrode of one electrode and the lead portion). It was continuously wiped and removed under the same conditions and the same method as the method for removing unnecessary regions of the organic functional layer when producing 101.

The percentage (f _d 47, f _p 32, f _h 21) calculated from Hansen solubility parameters 、 _d , _{ｐ p} , ∂ _h , of acetone *, and the solvent (chlorobenzene) used in the coating solution for forming the photoelectric conversion layer The point difference Rf with respect to the plot with the percentages (f _d 75, f _p 17, f _h 8) calculated from the Hansen solubility parameters ∂ _d , _{ｐ p} , ∂ _h is Rf = 34.

The percentages calculated from Hansen solubility parameters ∂ _d , _{ｐ p} , ∂ _h , of acetone * are values quoted from the same literature as in Example 1. The points indicate values obtained by the same method as in the first embodiment.

(Formation of electron injection layer)
Subsequently, the PET film patterned by removing unnecessary regions from the organic functional layer in the patterning process is transported to a vacuum deposition chamber without being processed in the cleaning process, and lithium fluoride (LiF) is used as a deposition material. Under vacuum conditions where the pressure was reduced to 10 ⁻⁴ Pa, vapor deposition was performed so as to overlap with the patterned power generation region, thereby forming an electron injection layer having a thickness of 0.6 nm.

(Formation of second electrode)
Subsequently, under the vacuum condition in which the PET film formed up to the electron injection layer was decompressed to 5 × 10 ⁻⁴ Pa, the electron injection layer (the upper part of the first electrode (power generation) 1) and a region reaching the lead portion, a mask pattern is formed by vapor deposition using aluminum to form a second electrode (cathode) made of aluminum having a thickness of 100 nm, and the structure shown in FIG. An organic PV element was prepared.

[Pasting of sealing member]
(Formation of adhesive layer)
Subsequently, in the produced organic PV element, the sample No. 1 produced in Example 1 was used. After forming the adhesive layer under the same conditions and the same conditions as in 101, the sample No. 1 prepared in Example 1 was used. A strip-shaped organic PV panel was prepared by sealing with a sealing film under the same conditions and in the same manner as in 101, and having twelve rows of photoelectric conversion regions in the lateral direction. 201.

<Sample No. 202 Production>
(Preparation of base material)
Sample No. The same PET film as 201 was prepared.

(Formation of the first electrode (anode))
On the prepared PET film, Sample No. Twelve rows of first electrodes having a size of 10 mm × 100 mm having a lead portion at the right end were formed at intervals of 3 mm under the same conditions and the same method as 201.

(Formation of photoelectric conversion layer from hole transport layer)
Subsequently, on the entire surface including the first electrode of the PET film formed up to the first electrode, the sample No. Organic functional layers up to a hole injection layer, a hole transport layer, and a photoelectric conversion layer were sequentially laminated under the same conditions and the same method as 201.

(Patterning of organic functional layer)
Subsequently, sample no. The unnecessary area | region of the organic functional layer was wiped away by the same conditions and the same method as 201. FIG.

(Cleaning of PET film with a patterned organic functional layer)
Subsequently, the entire surface of the PET film formed up to the patterned organic functional layer was cleaned with the atmospheric pressure plasma processing apparatus shown in FIG. 6 under the following conditions.

(Atmospheric pressure plasma treatment conditions)
Carrier gas: Nitrogen (under atmospheric pressure)
Reactive gas: Hydrogen (4% by volume with respect to nitrogen)
First power supply: HEIDEN lab PHF-6k (100kHz)
Second power supply: Pearl Industrial CF-5000-13M (13.56 MHz)
Applied output: 1.0 W / cm ²
Electrode temperature control: 80 ° C
Processing time: 20 seconds (formation of electron injection layer)
Subsequently, sample No. 1 was formed on the photoelectric conversion layer of the PET film formed up to the photoelectric conversion layer. An electron injection layer was formed under the same conditions and the same method as in 201.

(Formation of second electrode)
Subsequently, the sample No. 1 was formed under a vacuum condition in which the PET film formed up to the electron injection layer was decompressed to 5 × 10 ⁻⁴ Pa. A second electrode (cathode) was formed under the same conditions and in the same manner as in 201 to produce an organic PV element having the configuration shown in FIG.

[Pasting of sealing member]
Subsequently, sample no. The sealing member was bonded by the same method and the same method as 201, an organic PV panel was prepared, and sample No. 202.

(Evaluation)
Sample No. of a strip-shaped organic PV panel having twelve rows of photoelectric conversion regions formed on the side. Table 4 shows the results of testing 201 and 202 for the defect rate, light durability, and storage stability according to the test methods shown below and evaluated according to the evaluation rank shown below.

Defect rate measurement method Cut from each sample in a horizontal row, and by the LBIC (laser beam electromotive force) measurement method, the amount of power generation in the organic PV element plane in the effective area contributing to power generation of the panel connected to 12 rows The area where the drop is measured was measured, and the defect rate was determined according to the following formula.

Defect rate (%) = [area of the area where the power generation amount is reduced by 20% or more relative to the average value of the power generation area] / [area of the power generation area of the panel] × 100
Evaluation rank of defect rate ◎: Defect rate is less than 3% ○: Defect rate is 3% or more and less than 5% △: Defect rate is 5% or more and less than 8% ×: Defect rate is 8% or more Evaluation of light durability Each sample was cut in a horizontal row, and the organic PV solar cell panel was exposed to light (pseudo sunlight) of a 100 mW / cm ² metal halogen lamp for 1000 hours, and the short-circuit current density before and after the exposure. And the retention rate (%) was calculated according to the following formula to evaluate the light durability. In addition, the short circuit current density was calculated | required from IV characteristic evaluation using a source meter (Caseley 2400).

Retention rate (%) = short-circuit current density after exposure / short-circuit current density before exposure × 100
Preservation test method: Expose for 500 hours under conditions of an ambient temperature of 65 ° C and a relative humidity of 85% RH, measure the short-circuit current density before and after the exposure in the same manner as above, and determine the retention rate (%) according to the following formula. Asked. The results are shown in Table 4.

      Retention rate (%) = short-circuit current density after exposure / short-circuit current density before exposure × 100

  When producing an organic PV panel having a first electrode / hole injection layer / hole transport layer / photoelectric conversion layer / electron injection layer / second electrode (cathode) / sealing layer on the substrate, organic When the unnecessary region of the functional layer (hole injection layer / hole transport layer / photoelectric conversion layer) is removed by the wiping method, the solvent used is selected and removed for the solvent SP value region of the solubility parameter of the specific Hansen, Subsequently, cleaning was performed by a dry etching method, and then an electron injection layer / second electrode (cathode) / sealing layer was formed. It was confirmed that 202 has excellent performance in terms of defect rate, light durability, and storage stability.

  After removing unnecessary areas of the organic functional layer (hole injection layer / hole transport layer / photoelectric conversion layer) by the wiping method, the solvent to be used is selected and removed for the solvent SP value area of the solubility parameter of the specific Hansen. The organic PV panel sample No. 1 was prepared by forming the electron injection layer / second electrode (cathode) / sealing layer without cleaning. 201 is a defect rate, light durability, and storage stability. Compared to 202, the defect rate, light durability, and storage stability were all inferior. The effectiveness of the present invention was confirmed.

1, 1 ′, 1 ″ organic electronics panel 101, 101 ′, 101 ″, 3, F base material 102, 102 ′, 102 ″, 7 First electrode (anode)
102a, 102′a, 102 ″ a, 701 External connection electrodes for first electrodes 102b, 102′b, 7a Lead portions 103, 103 ′, 103 ″, 8 Organic functional layers 104, 104 ′, 104 ″ Second electrodes (cathode)
104a, 104′a, 104 ″ a External connection electrode for second electrode 105 ′ Conductive layer 105, 106 ′, 105 ″ Adhesive layer 106, 106 ″, 107 ′ Sealing member 2 Patterning process 4 Roller 5 First wiping Device 503 Wiping member 504 Press roll 505 Solvent tank 6 Second wiping device 9 Atmospheric pressure plasma processing device 9a Plasma discharge processing device 9a1 Roll electrode (first electrode)
9a2 Square tube electrode (second electrode)
9a3 Between counter electrodes (discharge space)
9b Electric field application means 9c Gas supply means

Claims (9)

On the substrate, an organic substance is interposed between the first electrode, the first electrode external connection electrode, the second electrode, the second electrode external connection electrode, and the first electrode and the second electrode. In a method for producing an organic electronic panel having at least one organic functional layer including a layer and a sealing layer,
A first electrode forming step of forming a first electrode including at least a portion for forming the first electrode external connection electrode;
An organic functional layer forming step of forming at least one organic functional layer on the entire surface of the substrate including the first electrode;
A patterning process for removing and patterning unnecessary regions of the organic functional layer;
And a cleaning step of cleaning the entire surface of the base material having the patterned organic functional layer. The solvent for removing unnecessary regions of the organic functional layer is Hansen's solubility parameter, and the plot of f _d , f _p , and f _h is within at least 45 points with respect to the plot of the solvent coated with the main organic functional layer. The method for producing an organic electronic panel according to claim 1, wherein the organic electronics panel is at a distance of 20 points or more.   3. The method of manufacturing an organic electronics panel according to claim 1, wherein the patterning of the organic functional layer is performed by a wiping method in the patterning step.   4. The method of manufacturing an organic electronics panel according to claim 1, wherein cleaning is performed by a dry etching method in the cleaning step. The method for manufacturing an organic electronics panel according to any one of claims 1 to 4, further comprising the following steps in order.
A) A first electrode forming step in which the first electrode including at least a portion for forming the first electrode external connection electrode and a lead portion are patterned on the base material. B) The first electrode And an organic functional layer forming step of forming at least one organic functional layer on the entire surface of the substrate having the lead portion and C) a patterning step of patterning unnecessary regions of the organic functional layer. D) the patterned organic A cleaning step of cleaning the entire surface of the base material having the functional layer. E) The second electrode and the external connection electrode for the second electrode extending from the organic functional layer on the first electrode to the lead portion. Step of forming second electrode F) Sealing on and around the second electrode with a sealing member except for the first electrode external connection electrode and the second electrode external connection electrode with a sealing member Sealer The method for manufacturing an organic electronics panel according to any one of claims 1 to 4, further comprising the following steps in order.
A) A first electrode forming step in which the first electrode including at least a portion for forming the first electrode external connection electrode and a lead portion are patterned on the base material. B) The first electrode And an organic functional layer forming step of forming at least one organic functional layer on the entire surface of the substrate having the lead portion and C) a patterning step of patterning unnecessary regions of the organic functional layer. D) the patterned organic A cleaning step for cleaning the entire surface of the substrate having a functional layer. E) A second electrode forming step for forming the second electrode on the organic functional layer on the first electrode. F) The second electrode A conductive layer forming step of forming a conductive layer over the lead portion to form a second electrode external connection electrode; G) excluding the first electrode external connection electrode and the second electrode external connection electrode; Sealing member Sealing step of sealing with a sealing member on and around the second electrode The method for manufacturing an organic electronics panel according to any one of claims 1 to 4, further comprising the following steps in order.
A) First electrode forming step of patterning and forming the first electrode including at least a portion for forming the first electrode external connection electrode on the base material. B) The base material having the first electrode. An organic functional layer forming step of forming at least one organic functional layer on the entire surface of the substrate C) A patterning step of patterning unnecessary regions of the organic functional layer D) The entire surface of the substrate having the patterned organic functional layer Cleaning step for cleaning E) A second electrode is formed on the organic functional layer on the first electrode, and at the same time, the organic functional layer removes the second electrode external connection electrode integrated with the second electrode. The second electrode forming step of forming on the base material that has been formed F) The second electrode external connection electrode and the second electrode external connection electrode, except for the second electrode external connection electrode, Sealing that seals the periphery with a sealing member Degree   The method of manufacturing an organic electronics panel according to any one of claims 1 to 7, wherein the organic electronics panel is an organic electroluminescence panel.   The said organic electronics panel is an organic photoelectric conversion element, The manufacturing method of the organic electronics panel of any one of Claim 1 to 7 characterized by the above-mentioned.

Images