JP2012129229A - Organic electronics panel manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electronics panel manufacturing method with which, even when an organic electronics panel is manufactured using a sheet-like base material, a belt-like resin film base material, and electrodes formed with a dry method or a wet method, occurrence of a short circuit or a leak current is suppressed and functional deterioration is reduced.SOLUTION: Provided is an organic electronics panel manufacturing method for manufacturing an organic electronics panel that has a first electrode, a second electrode, and a sealing layer on a base material and has at least one organic functional layer including an organic layer between the first electrode and the second electrode, the organic functional layer including a first organic functional layer. The organic electronics panel manufacturing method comprises: a first organic functional layer forming step for forming the first organic functional layer on a belt-like resin film; and a first electrode forming step for forming the first electrode on the first organic functional layer formed on the belt-like resin film.

Description

  The present invention relates to a method for manufacturing an organic electronics panel.

  In recent years, organic electroluminescence panels (hereinafter also referred to as organic EL panels), organic thin film transistor panels (hereinafter also referred to as organic TFT panels), organic solar cell panels (hereinafter also referred to as organic PV panels), organic photoelectric conversion panels, organic Development of various organic electronics panels including electrophotographic photoreceptors 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 panel is a device in which a light emitting layer made of an organic compound thin film is sandwiched between electrodes and emits light when a current is supplied between the electrodes. Therefore, when a thin-film organic EL panel is used as a light source, it is easy to reduce the size and weight, and the response speed of light emission is faster than that of a fluorescent lamp, and the amount of light immediately after lighting is relatively stable.

  An organic PV panel or an organic photoelectric conversion panel is an element that generates 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, if a thin-film organic photoelectric conversion panel 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-light or high-temperature environment as compared with existing inorganic semiconductor solar cells. The solar cell can be obtained.

  These organic electronics panels basically have an organic functional layer between an anode and a cathode and have a structure sealed with a sealing member. As a manufacturing method, a patterned anode or cathode is formed on a substrate, an organic functional layer is laminated on the anode or cathode, and then a cathode or anode is formed on the organic functional layer and sealed. It is manufactured by sealing with a member.

  The cathode or anode film is generally formed on the substrate by either a dry method or a wet method.

  Examples of the dry method include PVD (Physical Vapor Deposition: including physical vapor deposition; sputtering, ion plating, and vacuum deposition), and CVD (Chemical Vapor Deposition). These PVD and CVD methods are used to form metal oxide type transparent conductive films such as indium tin oxide (ITO), antimony tin oxide (ATO), fluorine-doped tin oxide (FTO), and aluminum-doped zinc oxide (FZO). Has been.

  The wet method is an extrusion method using an extrusion type coating coater, a coating method using a curtain type coating head, a coating method using a slide type coating coater, and a comma coating using a comma type coater. Examples thereof include an ink jet method using an ink jet head. These coating methods are used for forming a transparent conductive film by applying a conductive coating composition using conductive powder such as the above mixed oxide, metal nanowires and the like and a binder.

  As a specific method for manufacturing an organic electronics panel using a dry method of these electrodes, for example, indium tin oxide (hereinafter referred to as “ITO” for short) as an anode on a base material. Can be formed to a predetermined thickness on a transparent substrate using various methods such as sputtering deposition, electron beam deposition, and direct application and fusion by heating. However, the surface of the ITO formed is rough, and the value is the average roughness (Ra) of the surface roughness defined in the definition and indication (B0601) of the surface roughness defined by the Japanese Industrial Standard (JIS). About ten kilometers.

  For example, in the case of an organic EL panel, the thickness of the organic functional layer laminated on the anode is about 500 mm to 2000 mm. Therefore, if there is a convex portion on the ITO surface, the distance between the anode and the cathode is that much. When a voltage in the positive direction (direction in which the element emits light) is applied to the element, a phenomenon in which current flows intensively (leakage current) occurs in that portion. If a leak current is generated during light emission of the device, not only the brightness (current-luminance characteristics) with respect to the flowed current is reduced, but also the anode and cathode of that portion are short-circuited, and current flows only there. The element may not emit light. In some cases, the element where the current has flowed in a concentrated manner rapidly deteriorates and does not pass the current, and may appear as a non-light emitting portion (dark spot).

  Even in the organic PV panel, when a convex portion exists on the ITO surface, it causes a short circuit and a leakage current like the organic EL panel. The reduction of the parallel resistance due to the leakage current causes a problem that the open-circuit voltage is lowered in the voltage-current characteristic and the output characteristic of the solar cell is deteriorated such that a high maximum output point cannot be obtained.

  In response to these problems, Japanese Patent Application Laid-Open No. 9-245965 discloses a method of smoothing ITO on a glass substrate by a technique such as polishing, wrapping or tape wrapping, and forming an organic layer and subsequent layers thereon. Since these methods involve complicated steps, further studies have been made.

  For example, a method for polishing the surface of ITO with a polishing liquid containing water, colloidal silica having an average particle diameter of 5 nm to 50 nm dispersed in water, and a protective film forming agent and having a pH in the range of 2 to 3 is known. (For example, refer to Patent Document 1).

However, it has been found that the method described in Patent Document 1 has the following problems.
1) Polishing is easy for a single-wafer substrate such as a glass substrate, but is not suitable for a belt-shaped resin film.
2) Since the substrate after polishing needs to be thoroughly washed in running water and then dried, a long drying process is required to remove moisture that has permeated the long sheet film.

  In addition, a relatively simple apparatus can be used compared to the dry method, the productivity is high, and it can be easily applied to a continuous or large substrate, but the surface roughness of the electrode is the same as that of the electrode formed by the dry method. It is known that this is a potentially big problem when applied to photoelectric devices. Studies have been undertaken as a countermeasure for the surface roughness of electrodes formed by the dry method. For example, there is known a method of forming a network structure by applying a dispersion liquid in which metal nanowires having a wire diameter of 0.1 nm to 200 nm are dispersed in a binder, and then removing the solvent (for example, Patent Document 2). reference.).

  However, it was found that when an organic PV panel was produced using an electrode produced by the method described in Patent Document 2, a decrease in output due to leakage current and short-circuit was observed, and this was not sufficient.

  Under these circumstances, even when an organic electronics panel is produced using a dry-type or wet-type electrode using a sheet-like base material or a belt-like base material, functional deterioration due to short-circuit or leakage current occurs. It is desired to develop a method for manufacturing an organic electronics panel that does not have any.

JP 2007-154176 A JP 2009-129607 A

  The present invention has been made in view of the above circumstances, and the object thereof is to produce an organic electronics panel using a sheet-like substrate or a strip-like substrate, using an electrode formed by a dry method or a wet method. However, it is to provide a method for manufacturing an organic electronics panel that is less likely to cause functional degradation due to short or leakage current.

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

1. Organic electronics having a first electrode, a second electrode, a sealing layer, and at least one organic functional layer including an organic material layer between the first electrode and the second electrode on a substrate. In the panel manufacturing method,
The organic functional layer has a first organic functional layer,
A first organic functional layer forming step of forming the first organic functional layer on a belt-shaped resin film;
An organic electronics panel manufacturing method comprising: a first electrode forming step of forming the first electrode on the first organic functional layer formed on the belt-shaped resin film.

  2. 2. The method of manufacturing an organic electronics panel according to 1 above, wherein a surface of the belt-shaped resin film on which the first organic functional layer is formed has a fine structure.

  3. 3. The method for producing an organic electronic panel according to 1 or 2, wherein the base material has a gas barrier layer.

4). In the manufacturing method of the organic electronics panel of any one of said 1-3, the said organic functional layer has a said 1st organic functional layer and a 2nd organic functional layer,
And the manufacturing method of the organic electronics panel characterized by having each next process sequentially.

A) Said 1st organic functional layer formation process B) 1st electrode formation process C) Pattern formation process which forms a pattern in said 1st electrode D) Base material sticking which bonds the said base material on said 1st electrode Combined Step E) Peeling Step of Peeling the Strip-shaped Resin Film F) Second Organic Forming the Second Organic Functional Layer on the Surface of the First Organic Functional Layer from which the Strip-shaped Resin Film has been Stripped 4. Functional layer forming step G) Second electrode forming step of forming the second electrode on the second organic functional layer H) Sealing layer forming step of forming the sealing layer on the second electrode 4. The method of manufacturing an organic electronics panel according to any one of 1 to 3, wherein the organic functional layer includes the first organic functional layer and a second organic functional layer, and the first electrode forming step is a mask. Formed by vapor deposition using
And the manufacturing method of the organic electronics panel characterized by having each next process sequentially.

A) Said 1st organic functional layer formation process B) Said 1st electrode formation process C) Base material bonding process which bonds the said base material on the said 1st electrode D) Peeling which peels the said strip | belt-shaped resin film Step E) Second organic functional layer forming step of forming the second organic functional layer on the surface of the first organic functional layer from which the band-shaped resin film has been peeled. F) of the second organic functional layer 5. Second electrode forming step for forming the second electrode on top G) Sealing layer laminating step for forming the sealing layer on the second electrode 6. The method of manufacturing an organic electronics panel according to any one of 1 to 5, wherein the organic electronics panel is an organic photoelectric conversion element.

  7). 6. The method of manufacturing an organic electronics panel according to any one of 1 to 5, wherein the organic electronics panel is an organic electroluminescence panel.

  Organic electronics panels that do not cause functional degradation due to short-circuiting or leakage current, even when an organic electronics panel is manufactured using a dry-type or wet-type electrode using a sheet-like substrate or a strip-like substrate We were able to provide a manufacturing method.

It is the schematic which shows an example of an organic electronics panel. It is the schematic of the manufacturing process which manufactures the organic electronics panel of the structure shown in FIG. It is a schematic flowchart until an organic electronics panel continuous body is completed by the manufacturing process shown in FIG. It is the schematic of the manufacturing process which patterns and manufactures the 1st electrode by mask pattern shaping | molding of the organic electronics panel of the structure shown in FIG. FIG. 7 is a schematic flowchart until an organic electronics panel continuum is completed in the manufacturing process shown in FIG. 6. It is the schematic of the manufacturing process which manufactures the strip | belt-shaped resin film which has a fine structure on the surface.

  Hereinafter, 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 view showing an example of the configuration of an organic electronics panel manufactured by the method for manufacturing an organic electronics panel of the present invention. FIG. 1A is a schematic plan view of an organic electronics panel continuum having a plurality of organic electronics panels manufactured by the method for manufacturing an organic electronics panel of the present invention. FIG.1 (b) is a schematic sectional drawing in alignment with AA 'of Fig.1 (a).

  In the figure, 1 'represents an organic electronics panel continuum in which a plurality of individual organic electronics panels 1'a are continuously connected. The organic electronics panel continuous body 1 'is in a state in which a plurality of individual organic electronics panels 1'a are continuously formed on the substrate 101', and finally cut into individual organic electronics panels. 1'a is produced. This figure shows a state in which individual organic electronics panels 1'a are produced in two rows on the base material 101 'with an interval, but the number of rows of individual organic electronics panels 1'a is as follows. It can be changed according to the width of the substrate and the size of the organic electronics panel.

  101 'shows a base material. Reference numeral 102 'denotes a first electrode (anode), and 102'a denotes an extraction electrode for external connection of the first electrode (anode) 102'. Reference numeral 103 ′ denotes an organic functional layer including an organic material layer formed on the first electrode 102 ′. The organic functional layer 103 'has a first organic functional layer 103'a and a second organic functional layer 103'b. Reference numeral 104 'denotes a second electrode (cathode) formed on the second organic functional layer 103'b, and 104'a denotes an extraction electrode for external connection of the second electrode (cathode) 104'. Reference numeral 105 ′ denotes a sealing layer provided on the second electrode (cathode) 104 ′ via an adhesive layer 106 ′.

  Although this figure shows a case where the organic functional layer is two layers, it may be a single layer or a multilayer as necessary, and can be set as necessary.

  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 block layer / photoelectric conversion layer / electron transport / hole block layer. The configuration of the organic EL panel and the organic PV panel will be described later.

  In the present invention, the organic electronics panel includes an organic EL panel, an organic TFT panel, an organic PV panel, an organic photoelectric conversion panel, and an organic electrophotographic photoreceptor.

  FIG. 2 is a schematic view of a manufacturing process for manufacturing the organic electronics panel having the configuration shown in FIG.

  In the figure, reference numeral 1 denotes a manufacturing process for manufacturing an organic electronics panel. The manufacturing process 1 includes a first organic functional layer forming process 1a, a first electrode forming process 1b, a pattern forming process 1c, a substrate bonding process 1d, a peeling process 1e, and a second organic functional layer forming process 1f. The second electrode forming step 1g and the sealing material bonding step 1h are included. Although this figure shows the case where each process is independently arranged, each process may be connected as necessary. For example, the first organic functional layer forming step 1a, the first electrode forming step 1b, the pattern forming step 1c, the substrate bonding step 1d, the peeling step 1e, and the second organic functional layer forming step 1f. It is also possible to connect them. Moreover, it is also possible to perform from the 1st organic functional layer formation process 1a to the 2nd organic functional layer formation process 1f continuously. The function of each process will be described.

  The 1st organic functional layer formation process 1a has the strip | belt-shaped resin film supply process 1a1, the application | coating process 1a2, the drying process 1a3, and the collection | recovery process 1a4.

  From the strip-shaped resin film supply step 1a1, the strip-shaped resin film 1a11 is fed out and supplied to the coating step 1a2.

  In the coating process 1a2, the coater 1a21 and the backup roll 1a22 are used, and the coating liquid for forming the first organic functional layer is coated on the belt-shaped resin film 1a11 held by the backup roll 1a22 by the coater 1a21. .

  The application method of the first organic functional layer forming coating solution is not particularly limited, and examples thereof include a post-metering type coating method and a pre-metering type coating method. Examples of the post-measuring type coating method include a post-metering type coating method such as a blade type coating method, an air knife type coating method, and a wire bar type coating method. The pre-weighing type coating method includes: an extrusion type coating method using an extrusion type coating coater, a coating type method using a curtain type coating head, a coating type method using a slide type coating coater, and a comma type coater. Examples thereof include a comma coating method used and an ink jet method using an ink jet head. This figure has shown the case of the application | coating system which uses the extrusion-type application | coating coater which is an extrusion system for the coater 1a21.

  In the drying step 1a3, the coating device applied on the belt-shaped resin film 1a11 in the coating step 1a2 is dried using the drying device 1a31 to form the first organic functional layer 103′a (see FIG. 3).

  In the collecting step 1a4, the belt-shaped resin film 1a11 on which the first organic functional layer 103′a (see FIG. 3) is formed is wound around a winding core in a roll shape by a winding device (not shown).

  The first electrode forming step 1b includes a supplying step 1b1, a coating step 1b2, a drying step 1b3, and a recovery step for supplying the belt-shaped resin film 1a11 on which the first organic functional layer 103′a (see FIG. 3) is formed. 1b4.

  From the supply step 1b1, the strip-shaped resin film 1a11 on which the first organic functional layer 103′a (see FIG. 3) is formed is fed out and supplied to the coating step 1b2.

  In the coating process 1b2, a coater 1b21 and a backup roll 1b22 are used, and the first resin layer 1a11 in the shape of a strip in which the first organic functional layer 103′a (see FIG. 3) held by the backup roll 1b22 is formed. A coating solution for forming a first electrode is applied to the entire surface of one organic functional layer 103′a (see FIG. 3) by a coater 1b21. The coating method of the first electrode forming coating solution is not particularly limited, and the same coating method as the first organic functional layer forming coating solution can be used. This figure has shown the case of the application | coating system which uses the extrusion-type application | coating coater which is an extrusion system for the coater 1b21.

  In the drying step 1b3, the coating device applied on the belt-shaped resin film 1a11 in the coating step 1b2 is dried using the drying device 1b31 to form the first electrode 102 ′ (see FIG. 3).

  In the collection step 1b4, the belt-shaped resin film 1a11 on which the first electrode is formed is wound and stored in a roll shape around a winding core by a winding device (not shown).

  In the pattern forming step 1c, a pattern that uses the pattern forming apparatus 1c1 and requires the first electrode 102 '(see FIG. 3) formed on the entire surface of the belt-shaped resin film 1a11 sent from the supplying step 1c2. The first electrodes 102'b and 102'c (see FIG. 3) are formed (for example, two rows in the width direction so as to form the continuous body 1 shown in FIG. 1).

  The pattern forming apparatus 1c1 is not particularly limited. For example, a reactive gas etching apparatus, an atmospheric pressure plasma reactive ion etching apparatus, a low pressure plasma reactive ion etching apparatus, a reactive ion beam etching apparatus, an ion beam etching apparatus, and a reactive laser are used. Examples thereof include a beam etching apparatus and a laser beam etching apparatus. These dry etching apparatuses can use commercially available dry etching apparatuses.

  In the collection step 1c3, the belt-shaped resin film 1a11 on which the first electrode 102 '(see FIG. 3) including the patterned extraction electrode is formed is wound around the winding core in a roll shape by a winding device (not shown). .

  The base material bonding step 1d includes a supply step 1d1 of the strip-shaped resin film 1a11 on which the patterned first electrode 102 'is formed, an adhesive coating step 1d2, a base material supply step 1d3, and a bonding step. 1d4 and a recovery step 1d5.

  In the adhesive coating step 1d2, an adhesive is applied to the entire upper surface of the first electrode 102 '(102'b, 102'c) (see FIG. 3) patterned by the adhesive coating apparatus. 107 '(see FIG. 3) is formed.

  From the base material supply step 1d3, a belt-like base material 101 'serving as a substrate of the organic electronics panel is supplied by a feeding device (not shown).

  In the laminating step 1d4, the laminating device 1d41 is used, and the first electrode 102 ′ (102′b, 102′c) (see FIG. 3) formed with the pattern sent from the supplying step 1d1 is formed. A base material 101 'is stacked and bonded onto the resin film 1a11 via an adhesive layer 107' (see FIG. 3). Bonding may be performed separately in a reduced pressure environment or an atmospheric pressure environment, either one may be performed, or both may be disposed, and can be selected as necessary. .

  At this stage, a strip-shaped resin film 1a11 having a configuration configured in the order of the first organic functional layer / first electrode / adhesive layer / base material is completed on the strip-shaped resin film 1a11.

  In the peeling process 1e, the peeling device 1e1 is used, and the first organic functional layer / first electrode / adhesive layer / base is formed on the belt-like resin film 1a11 sent from the feeding process 1e2 of the belt-like resin film 1a11. The strip-shaped resin film 1a11 is peeled off from the first organic functional layer 103′a (see FIG. 3) of the strip-shaped resin film 1a11 in which the materials are laminated in this order, and is wound and collected in the collection step 1e4. 1e3 shows the strip-shaped resin film 1a11 which has been peeled off and wound up.

  In addition, after the strip-shaped resin film 1a11 is peeled off, the first organic functional layer 103'a (see FIG. 3) and the first organic functional layer 103'a (see FIG. 3) in the portion that becomes the lead electrode of the first electrode are unnecessary. The area portion is removed by a wiping method. The unnecessary region portion is, for example, a non-power generation region in the case of an organic PV panel, and a non-light emission region in the case of an organic EL panel.

  The second organic functional layer formation step 1f includes a supply step 1f1, a coating step 1f2, a drying step 1f3, and a recovery step 1f4.

  From the supply step 1f1, a strip-shaped base material 101 in which a first electrode 102 '(see FIG. 3) and a first organic functional layer 103'a (see FIG. 3) are laminated in this order on a base material 101'. 'Is fed out and supplied to the coating step 1f2.

  In the coating step 1f2, a coater 1f21 and a backup roll 1f22 are used, and a strip-like base material 101 ′ having a base material / adhesive layer / first electrode / first organic functional layer held by the backup roll 1f22. A coating solution for forming a second organic functional layer is applied on the first organic functional layer 103′a (see FIG. 3) by the coater 1f21. After the application, the coating film for forming the second organic functional layer in the portion that becomes the extraction electrode 102′a (see FIG. 3) of the first electrode and the unnecessary region portion is removed by the wiping method.

  The coating method for the second organic functional layer forming coating solution is not particularly limited, and the same coating method as that for the first organic functional layer forming coating solution can be used. This figure shows the case of a coating method using an extrusion type coating coater which is an extrusion method for the coater 1f21.

  In the drying step 1f3, the coating device for forming the second organic functional layer applied on the first organic functional layer 103′a (see FIG. 3) in the coating step 1f2 is dried using the drying device 1f31 and the second organic functional layer is dried. Layer 103′b (see FIG. 3) is formed.

  In the collection step 1f4, the belt-like base material 101 'on which the second organic functional layer 103'b (see FIG. 3) is formed is wound up in a roll shape around a winding core by a winding device (not shown).

  This figure shows the case where the organic functional layer 103 ′ (see FIG. 3) has two layers, ie, a first organic functional layer 103′a (see FIG. 3) and a second organic functional layer 103′b (see FIG. 3). As shown, in the case of multiple layers, it is possible to install the second organic functional layer forming step 1f in accordance with the number of required organic functional layers.

  The second electrode forming step 1g uses a second electrode forming device 1g2 and is a belt-like base material 101 ′ in which the layers up to the second organic functional layer 103′b (see FIG. 3) sent from the supplying step 1g1 are laminated. A second electrode 104 '(see FIG. 3) is formed on the second organic functional layer in accordance with the size of the first electrode 102' (see FIG. 3), and at the same time, a second electrode lead electrode 104'a (see FIG. 3) is formed. 3) is also formed on the adhesive layer 107 'from which the second organic functional layer 103'b (see FIG. 3) has been removed. Then, it is wound around the winding core in a roll shape by a winding device (not shown) in the collecting step 1g3. The second electrode forming apparatus 1g2 is not particularly limited, and examples thereof include a vapor deposition apparatus and a sputtering apparatus.

  The encapsulating material bonding step 1h includes a supplying step 1h1 of the band-shaped base material 101 ′ formed up to the second electrode, an adhesive coating step 1h2, an encapsulating material supplying step 1h3, and an adhering step 1h4. And a recovery step 1h5.

  In the adhesive coating process 1h2, the second electrode 104 ′ (see FIG. 3), the second electrode lead electrode 104′a (see FIG. 3), and the first electrode lead electrode 102 formed by the adhesive coating apparatus. Adhesive is applied to the entire surface including the top of 'a (see FIG. 3) to form an adhesive layer 107'.

  From the sealing material supply step 1h3, a strip-shaped sealing material 105 ′ for sealing the organic electronics panel is supplied by a feeding device (not shown).

  In the bonding process 1h4, the bonding apparatus 1h41 is used, and the second electrode 104 ′ (see FIG. 3) of the band-shaped base material 101 ′ formed up to the second electrode 104 ′ (see FIG. 3) sent from the supply process 1h1. 3), the sealing material 105 'is stacked and bonded via the adhesive layer 107'. Bonding may be performed separately in a reduced pressure environment or an atmospheric pressure environment, either one may be performed, or both may be disposed, and can be selected as necessary. .

  At this stage, individual organic electronic panels having the structure of substrate / adhesive layer / first electrode / first organic functional layer / second organic functional layer / adhesive layer / sealing layer are continuously formed on the substrate. The continuum of organic electronics panel formed as shown in FIG. 1 is completed. Thereafter, individual organic electronics panels are manufactured by cutting.

  FIG. 3 is a schematic flow chart until the organic electronics panel having the configuration shown in FIG. 1 is completed in the manufacturing process shown in FIG.

  In the first organic functional layer forming step 1a, the first organic functional layer 103′a is formed on the belt-shaped resin film 1a11.

  In the first electrode forming step 1b, the first electrode 102 'is formed on the first organic functional layer 103'a formed in the first organic functional layer forming step 1a.

  In the pattern forming step 1c, the first electrode 102 'formed in the first electrode forming step 1b is formed into a required pattern. This figure shows a case where the first electrode 102'b and the first electrode 102'c are patterned in two rows as shown in FIG.

  In the substrate bonding step 1d, the first electrode 102 '(first electrode 102'b, first electrode 102'c) and the first organic functional layer 103'a on which the pattern is formed in the pattern forming step 1c are formed. An adhesive is applied to form an adhesive layer 107 ′, and the substrate 101 ′ is bonded through the adhesive layer 107 ′. Since the convex portion generated on the surface of the first electrode 102 ′ when the first electrode 102 ′ is formed by bonding the base material 101 ′ onto the first electrode layer 102 ′, The distance between the two electrodes 104 ′ and the first electrode 102 ′ is constant. For this reason, for example, in the case of an organic EL panel, when a voltage is applied, a decrease in luminance, a partial light emission failure, a dark spot, which occurs when the distance between the second electrode 104 ′ and the first electrode 102 ′ is shortened. Such failures are suppressed.

  In the case of an organic PV panel, a decrease in output due to leakage current can be suppressed, and a stable and highly efficient product can be obtained.

  In the peeling process 1e, the strip-shaped resin film 1a11 is peeled from the first organic functional layer 103′a. Thereafter, the formation portion of the extraction electrode 102′a of the first electrode 102 ′ and the first organic functional layer 103′a in the unnecessary region are removed by a wiping method.

  In the second organic functional layer forming step 1f, the second organic functional layer 103'a is removed from the surface of the first organic functional layer 103'a from which the strip-shaped resin film 1a11 has been peeled off in the peeling step 1e and the second organic functional layer 103'a is removed. An organic functional layer 103′b (a portion indicated by oblique lines in the figure) is formed. Thereafter, the formation portion of the extraction electrode 102'a of the first electrode 102 'and the second organic functional layer 103'b in the unnecessary region are removed by a wiping method.

  In the second electrode forming step 1g, the second electrode 104 ′ is formed on the second organic functional layer 103′b formed in the second organic functional layer forming step 1f. In addition, a lead electrode 104′a for the second electrode is formed on the base material 101 ′ from which the second organic functional layer 103′b has been removed.

  In the sealing material bonding step 1h, the sealing material 105 ′ is bonded to the second electrode 104 ′ formed in the second electrode forming step 1g via the adhesive 106 ′. At this stage, an organic electronics panel continuum as shown in FIG. 1 in which individual organic electronics panels are continuously formed on a substrate is completed. Thereafter, individual organic electronics panels are manufactured by cutting.

  FIG. 4 is a schematic view of a manufacturing process for manufacturing the organic electronics panel having the configuration shown in FIG. 1 by patterning the first electrode by forming a mask pattern.

  In the figure, reference numeral 3 denotes a manufacturing process for manufacturing an organic electronics panel. The manufacturing process 3 includes a first organic functional layer forming process 3a, a first electrode forming process 3b, a substrate bonding process 3c, a peeling process 3d, a second organic functional layer forming process 3e, and a second electrode forming process. 3f and the sealing material bonding process 3g. The difference between the manufacturing process 3 shown in this figure and the manufacturing process 1 shown in FIG. 2 is the same except that the method of patterning the first electrode is different.

  Although this figure shows the case where each process is independently arranged, each process may be connected as necessary. For example, the base material bonding step 3c, the peeling step 3d, and the second organic functional layer forming step 3f can be connected and performed. Moreover, it is also possible to perform continuously from the 1st organic functional layer formation process 3b to the 2nd organic functional layer formation process 3e.

  The difference between the manufacturing process 3 shown in FIG. 4 and the manufacturing process 1 shown in FIG. 2 is the same except that the method of patterning the first electrode is different. The function of each process will be described.

  The 1st organic functional layer formation process 3a has the supply process 3a1, application | coating process 3a2, drying process 3a3, and collection | recovery process 3a4 of the strip | belt-shaped resin film 3a11. The coating process 3a2 uses a coater 3a21 and a backup roll 3a22. The drying step 3a3 uses a drying device 3a31. In the first organic functional layer forming step 3a, the first organic functional layer 103′a (see FIG. 5) is formed on the belt-shaped resin film 3a11. Since the function of each process is the same as the 1st organic functional layer formation process 1a shown in FIG. 2, it abbreviate | omits.

  In the first electrode forming step 3b, the first organic functional layer 103′a (see FIG. 5) formed in the first organic functional layer forming step 3a sent from the supplying step 3b1 using the first electrode forming device 3b2 is used. A patterned film is formed on the first organic functional layer 103′a (see FIG. 5) of the belt-shaped resin film 3a11 having a mask to form a patterned first electrode 102 ′ (see FIG. 5). The Then, it is wound around the winding core in a roll shape by a winding device (not shown) in the collecting step 3b3. The first electrode forming device 3b2 is not particularly limited, and examples thereof include a vapor deposition device and a sputtering device.

  The base material bonding step 3c includes a supply step 3c1 of the strip-shaped resin film 3a11 on which the patterned first electrode 102 '(see FIG. 5) is formed, an adhesive coating step 3c2, and a base material supply step 3c3. And a bonding step 3c4 and a recovery step 3c5.

  In the base material bonding step 3c, a strip-shaped base material 101 '(see FIG. 5) is bonded onto the first electrode 102' (see FIG. 5) via an adhesive layer 107 '(see FIG. 5). Since the function of each process is the same as the base material bonding process 1d shown in FIG.

  At this stage, a belt-like resin film 3a11 having a structure in the order of the first organic functional layer / first electrode / adhesive layer / base material is formed on the belt-like resin film 3a11.

  In the peeling step 3d, the first organic functional layer of the strip-shaped resin film 3a11 in which the stripping device 3d1 is used and the base material 101 ′ (see FIG. 5) sent from the supply step 3d2 of the strip-shaped resin film 3a11 is laminated. The strip-shaped resin film 3a11 is peeled off from 103′a (see FIG. 5), and taken up and collected in a collecting step 3d4. 3d3 shows the strip-shaped resin film 3a11 which is peeled off and wound up. After the strip-shaped resin film 3a11 is peeled off, the portion of the first organic functional layer 103'a (see FIG. 5) that becomes the lead electrode 102'a (see FIG. 5) of the first electrode 102 '(see FIG. 5). And the unnecessary area | region part is removed by the wiping method. The unnecessary region portion is, for example, a non-power generation region in the case of an organic PV panel, and a non-light emission region in the case of an organic EL panel.

  The second organic functional layer formation step 3e includes a supply step 3e1, a coating step 3e2, a drying step 3e3, and a recovery step 3e4. The first resin layer 3a11 is peeled off in the peeling step 3d. A second organic functional layer 103′b (see FIG. 5) is formed on the surface of the organic functional layer 103′a (see FIG. 5). The coating process 3e2 uses a coater 3e21 and a backup roll 3e22. After applying the coating solution for forming the second organic functional layer in the applying step 3e2, the part of the first electrode 102 '(see FIG. 5) that becomes the extraction electrode 102'a (see FIG. 5) and the unnecessary organic part of the second organic layer The functional layer 103′b is removed by a wiping method.

  The drying process 3e3 uses a drying device 3e31. Since the function of each step is the same as the second organic functional layer forming step 1f shown in FIG.

  This figure shows the case where the organic functional layer 103 ′ (see FIG. 5) has two layers, ie, a first organic functional layer 103′a (see FIG. 5) and a second organic functional layer 103′b (see FIG. 5). As shown, in the case of multiple layers, the second organic functional layer forming step 3e can be installed according to the number of required organic functional layers.

  The second electrode forming step 3f uses a second electrode forming device 3f2, and a band-shaped base material 101 ′ in which the layers up to the second organic functional layer 103′b (see FIG. 5) sent from the supplying step 3f1 are laminated. A second electrode 104 ′ (see FIG. 5) is formed on the second organic functional layer 103′b (see FIG. 5) in accordance with the size of the first electrode, and at the same time, a second electrode lead electrode 104′a (see FIG. 5). 5) is also formed on the adhesive layer 107 ′ (see FIG. 5) from which the second organic functional layer has been removed. Then, it is wound around the winding core in a roll shape by a winding device (not shown) in the collecting step 3f3. The second electrode forming device 3f2 is not particularly limited, and examples thereof include a vapor deposition device and a sputtering device.

  The sealing material bonding process 3g includes a supply process 3g1, a adhesive coating process 3g2, and a sealing material supply process 3g3 for the band-shaped substrate 101 ′ (see FIG. 5) on which the second electrodes 104 ′ are formed. And a bonding step 3g4 and a recovery step 3g5. In the adhesive coating process 3g2, the second electrode 104 ′ (see FIG. 5), the second electrode lead electrode 104′a (see FIG. 5) and the first electrode 102 ′ (see FIG. 5) formed by the adhesive coating apparatus. 5)), an adhesive is applied over the entire surface including the top of the extraction electrode 102'a (see FIG. 5) to form an adhesive layer 106 '. The bonding process 3g4 uses the bonding apparatus 3g41. Since the function of each process is the same as the sealing material bonding process 1h shown in FIG.

  At this stage, individual organic electronics panels having the structure of substrate / adhesive layer / first electrode layer / first resin layer / second resin layer / adhesive layer / sealing layer are continuously formed on the substrate. The organic electronics panel continuum shown in FIG. Thereafter, individual organic electronics panels are manufactured by cutting.

  FIG. 5 is a schematic flow chart until the organic electronics panel continuous body shown in FIG. 1 is completed in the manufacturing process shown in FIG.

  In the first organic functional layer forming step 3a, the first organic functional layer 103a is formed on the belt-shaped resin film 3a11.

  In the first electrode forming step 3b, the first electrode 102 'patterned in two rows of the first electrode 102'b and the first electrode 102'c is formed on the first organic functional layer 103'a.

  In the base material bonding step 3c, the base material 101 'is bonded to the patterned first electrode layer 102' via an adhesive layer 107 '(part indicated by hatching in the figure). . By laminating the substrate 101 ′ on the first electrode layer 102 ′, the same effect as that obtained in the substrate laminating step 1d shown in FIG. 3 is obtained.

  In the peeling step 3d, the strip-shaped resin film 3a11 is peeled off from the first organic functional layer 103′a. Thereafter, the formation portion of the extraction electrode 102'a of the first electrode 102 'and the unnecessary first organic functional layer 103'a are removed by a wiping method.

  In the second organic functional layer forming step 3e, the second organic functional layer 103′a is removed from the surface of the first organic functional layer 103′a from which the belt-shaped resin film 3a11 has been peeled off in the peeling step 3d and the second organic functional layer 103′a is removed. An organic functional layer 103'b (a portion indicated by cross diagonal lines in the figure) is formed. Thereafter, the formation portion of the extraction electrode 102 ′ a of the first electrode 102 ′ and the second organic functional layer 103 ′ b in the unnecessary region are removed by a wiping method.

  In the second electrode forming step 3f, the second electrode 104 'and the second organic functional layer 103'b are removed from the second organic functional layer 103'b formed in the second organic functional layer forming step 3e. A lead electrode 104′a of the second electrode is formed on the agent layer 107 ′.

  In the sealing material bonding step 3g, the sealing material 105 is disposed on the second electrode 104 ′ and the extraction electrode 104′a of the second electrode 104 ′ formed in the second electrode formation step 3f via the adhesive layer 106 ′. 'Is pasted. At this stage, an organic electronics panel continuum as shown in FIG. 1 in which individual organic electronics panels are continuously formed on a substrate is completed. Thereafter, individual organic electronics panels are manufactured by cutting.

  The base material used in each base material bonding step of the manufacturing process shown in FIG. 2 and FIG. 4 is a barrier coat layer (in order to suppress the permeation of oxygen and water vapor and improve the storage stability of the organic electronics panel on at least one side. For example, it is preferable to have an inorganic thin film (such as silicon oxide or aluminum oxide) having a high gas barrier property.

  The characteristic of this invention is that a base material is bonded to the surface of a 1st electrode through an adhesive bond layer in each base material bonding process of the manufacturing process shown in FIG. 2, FIG. Although the convex part has generate | occur | produced on the surface of the 1st electrode when forming a 1st electrode, this convex part turns into a base material side by bonding a base material. For this reason, the distance between the second electrode and the first electrode is constant. For this reason, for example, in the case of an organic EL panel, when a voltage is applied, the brightness decreases when the distance between the second electrode and the first electrode is shortened, a partial light emission failure, a failure such as a dark spot, etc. Disappears. In the case of an organic PV panel, a decrease in output due to leakage current can be suppressed, and a stable and highly efficient product can be obtained.

  FIG. 6 is a schematic view of a production process for producing a strip-shaped resin film having a fine structure on the surface. FIG. 6A is a schematic view of a manufacturing process for manufacturing a strip-shaped resin film having a fine structure on the surface used in the manufacturing process shown in FIGS. FIG. 6B is a schematic cross-sectional view of a strip-shaped resin film having a fine structure on the surface.

  In the figure, 4 indicates a manufacturing process. The manufacturing process 4 includes a supply process 4a1, a coating process 4a2, a drying process 4a3, a surface processing process 4a4, and a recovery process 4a5.

  From the supply step 4a1, a band-shaped base film 401 serving as a base of the band-shaped film is supplied. The coating process 4a2 uses the coater 4a21 and the backup roll 4a22, and the surface layer forming coating solution is applied to the surface of the belt-like substrate film 401 supplied from the supply process 4a1.

  In the drying step 4a3, the drying device 4a31 is used to remove the solvent from the surface layer forming coating film formed by coating in the coating step 4a2, thereby forming the surface layer 402.

  The surface processing step 4a4 uses a roll imprint apparatus 4a41, and a resin to be used after a microstructure having a concave portion 402a and a convex portion 402b is embossed on the entire surface of the surface layer 402 by the roll die 4a42. A strip-shaped resin film 403 having a fine structure fixed to the surface and having a fine structure on the surface is prepared. For example, when the resin to be used is an ultraviolet curable resin, the resin layer is cured by irradiating with ultraviolet rays to fix the fine structure. T represents the distance from the center of the recess to the center of the next recess. In the present invention, the distance T is referred to as a pitch.

  The fine structure means an uneven structure having a pitch of 1 nm to 1000 nm and an aspect ratio of 1 or more. There is no limitation in particular as a cross-sectional shape of a convex part, For example, a rectangle, a triangle, a semicircle, a trapezoid, etc. are mentioned. This figure shows a rectangular case.

  Examples of the resin used for the surface layer include an active energy ray curable resin. The active energy ray curable resin will be described later.

  The band-shaped resin film 403 having a fine structure on the produced surface is formed by the first organic functional layer forming step 1a in the manufacturing step shown in FIG. 2 and the first organic functional layer forming step 3a in the manufacturing step shown in FIG. It is possible to use.

  A band-shaped resin film having a fine structure on the surface as shown in this figure is used in the first organic functional layer forming step of the manufacturing step shown in FIGS. By peeling the strip-shaped resin film 403 after sequentially laminating the electrodes and the base material, the fine structure of the surface of the strip-shaped resin film 403 is transferred to the surface of the first organic functional layer. By forming a 2nd organic functional layer on this, the contact area of a 1st organic functional layer and a 2nd organic functional layer increases. For this reason, for example, in the case of an organic PV panel, the charge and the charge separation amount are increased, and the charge recombination is suppressed because the structure is regular. As a result, the series resistance is lowered, and high energy conversion efficiency can be obtained. Furthermore, it can be expected to contribute to the energy conversion efficiency by improving the optical characteristics such as suppressing the sudden change in refractive index at the contact interface and suppressing internal reflection.

The following effects can be given as the effects of the method for manufacturing the organic electronics panel of the present invention shown in FIGS.
1. By sticking the base material to the surface of the first electrode, the convex portion generated on the surface of the first electrode at the time of forming the first electrode becomes the base material side, so the distance between the second electrode and the first electrode is constant. Thus, when a voltage is applied, a failure due to an unstable distance between the second electrode and the first electrode is eliminated, and a stable organic electronics panel can be manufactured.
2. Since there is a fine structure between the first organic functional layer and the second organic functional layer, the contact area between the first organic functional layer and the second organic functional layer is increased, and an organic electronics panel with high energy conversion efficiency is manufactured. Became possible.

  Next, the configuration and materials 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.

(Strip-shaped resin film)
There is no restriction | limiting in particular as a strip | belt-shaped resin film, It can select suitably from well-known thermoplastic dendritic films. 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 800 nm) from nm, 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.

(Active energy ray curable resin)
The active energy ray-curable resin used in the present invention is a resin that is cured through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays and electron beams. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin curable by irradiation with actinic rays other than ultraviolet rays and electron beams may be used. It is also possible to use an antioxidant or an ultraviolet absorber in combination with the active energy ray curable resin.

  The active energy ray-curable resin is a resin obtained by curing a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule upon irradiation with energy rays.

  There is no restriction | limiting in particular as an ultraviolet-ray and an electron beam curable resin, It can use suitably selecting from what is used conventionally. This ultraviolet curable resin contains a photopolymerizable prepolymer, a photopolymerizable monomer, a photopolymerization initiator or a photosensitizer. The electron beam curable resin contains a photopolymerizable prepolymer or a photopolymerizable monomer.

  Examples of the photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, and polyol acrylate. These photopolymerizable prepolymers may be used alone or in combination of two or more. Examples of the photopolymerizable monomer include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate.

  Specific examples of the ultraviolet curable resin include, for example, acrylic resin PAK02 (manufactured by Toyo Gosei Co., Ltd.), Adekaoptomer KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (manufactured by Asahi Denka Kogyo Co., Ltd.), Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M- 101, M-102, T-102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), Seika Beam PHC2210 (S), PHCX-9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, 1500, P1600, SCR900 (above, manufactured by Dainichi Seika Kogyo Co., Ltd.), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB Ltd.), RC-5015, RC-5016, RC -5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (above, manufactured by Dainippon Ink & Chemicals, Inc.) ), Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), Sun Rad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (above, Sanyo Chemical Industries, Ltd.) , SP-1509, SP-1507 (above, manufactured by Showa Polymer Co., Ltd.), RCC-15C (produced by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (above, Toagosei Co., Ltd.) (Made by Co., Ltd.), or other commercially available products.

(Polymerization initiator)
The polymerization initiator may be a radical reaction type or an ion reaction type, and examples thereof include acetophenones, butylphenones, benzophenones, α-amyloxime esters, tetramethylchuram monosulfide, thioxanthones, and oxetane compounds. Moreover, n-butylamine, triethylamine, poly-n-butylphosphine, etc. can be mixed and used as a photosensitizer.

(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, 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 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.

  Further, for the purpose of suppressing the permeation of oxygen and water vapor, a barrier coat layer (for example, an inorganic thin film having high gas barrier properties (silicon oxide, aluminum oxide, etc.)) may be formed on the transparent substrate in advance, or transparent A hard coat layer may be formed in advance on the side on which the conductive layer is formed or on the opposite side.

(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.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
When manufacturing the organic PV panel as the organic electronics panel having the structure shown in FIG. 1 using the manufacturing process for manufacturing the organic electronics panel shown in FIG. 2, the resin film as shown in Table 1, Organic PV panels were produced by changing the type of substrate.

  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.

<Preparation of resin film A>
A polyethylene terephthalate film (Teijin-DuPont film, hereinafter abbreviated as PET film) having a thickness of 100 μm, a width of 180 mm, and a length of 10 m was prepared as a resin film A.

<Preparation of resin film B>
A belt-shaped resin film composed of a resin layer having a fine structure as shown in FIG. 6B on the surface and a base film is manufactured using the manufacturing process shown in FIG. did.

(Preparation of base film)
As a base film of the resin film B, a PET film having a thickness of 100 μm, a width of 180 mm, and a length of 10 m was prepared as a base film.

(Preparation of active energy ray-curable resin for resin layer formation)
As an active energy ray curable resin, an acrylic resin PAK02 (manufactured by Toyo Gosei Co., Ltd.), which is an ultraviolet curable resin, was prepared.

(Formation of fine structure)
After forming a 50 μm thick resin layer using an extrusion coater, the following microstructure was formed on the entire surface of the resin layer by the roll nanoimprint method.

Microstructure Pitch: 70nm
Aspect ratio: 1
Cross-sectional shape of convex portion: cylindrical shape <Preparation of base material 1>
A polyethylene terephthalate (PET) film (manufactured by Teijin / DuPont) having a thickness of 100 μm and a width of 180 mm was prepared as the substrate 1.

<Preparation of base material 2>
Using the same base material as the prepared base material 1, a barrier layer (mainly SiO ₂ layer) having a thickness of 60 nm is formed on both surfaces by a sputtering method under vacuum environment conditions reduced to 5 × 10 ⁻² Pa. The base material 2 was prepared.

<Sample No. 101 Production>
(Formation of hole injection layer (formation of first organic functional layer))
(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.

(Application of hole injection layer forming coating solution)
The hole injection layer forming coating solution prepared on the prepared resin film A is applied using a slit coater, followed by drying and heat treatment at 150 ° C. for 15 minutes to form a hole injection layer having a thickness of 30 nm. After forming, it was wound up and stored in a roll. The coating speed was 5 m / min. The film thickness is a value measured using a spectroscopic ellipsometer manufactured by Joban Yvon.

(Formation of the first electrode (anode))
(Preparation of coating solution for forming the first electrode (anode))
Y. Sun, B.D. Gates, B.B. Mayers, Y.M. Xia, Nanoletters, Vol. 2, p. Based on the polyol method described in 165 and the like, silver nitrate dissolved in ethylene glycol in the presence of PVP was reduced to produce Ag nanowires (wire diameter: 35 nm, length: 2 μm). Dispersoid concentration was adjusted by adding ethylene glycol and PVP, and Ag nanowire was 0.2% by mass and PVP was 1% by mass to obtain a coating solution for forming the first electrode (anode).

(Application of coating solution for forming the first electrode (anode))
On the hole injection layer of the resin film A on which the prepared hole injection layer was formed, the whole surface was coated using an extrusion coater, followed by drying and heat treatment at 150 ° C. for 15 minutes, and a film thickness of 30 nm. One electrode (anode) was formed and wound into a roll and stored. The coating speed was 5 m / min. The film thickness is a value measured using a spectroscopic ellipsometer manufactured by Joban Yvon.

(Patterning of the first electrode (anode))
In the screen printing method, the first electrode (anode) having a size of 75 mm × 150 mm with an electrode width of 10 mm and an interval of 1 mm is arranged on the hole injection layer with an interval of 15 mm and two rows in the width direction. Formed continuously.

(Lamination of substrate 1)
On the first electrode (anode) of the resin film A formed up to the prepared first electrode (anode), a 15 μm thick UV curable liquid sealant (ThreeBond 3124C, manufactured by ThreeBond Co., Ltd.) is used for screen printing Subsequently, the prepared base materials 1 are stacked, pressed under pressure of 0.1 MPa in a reduced pressure environment of 1 × 10 ⁻² Pa, and irradiated with ultraviolet light having a main wavelength of 365 nm from the base material 1 side (100 mW After being cured and pasted at 90 cm / cm ^2, it was wound up and stored in a roll shape.

(Removal of resin film A)
The resin film A was peeled from the resin film A bonded to the prepared base material 1. By peeling the resin film, the base material 1 (PET film) in a state in which the adhesive / first electrode / hole injection layer is laminated in this order is obtained.

(Formation of hole transport layer (second organic functional layer 1))
(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.

(Application of coating liquid for hole transport layer formation)
Subsequently, on the entire upper surface of the hole injection layer laminated on the substrate 1 from which the resin film A was peeled off, in a nitrogen chamber (N 2 gas environment at 25 ° C., dew point temperature −20 ° C. or lower, under atmospheric pressure, and With the cleanliness class 5 or less (JIS B 9920), the prepared coating liquid for forming a hole transport layer was applied using a slit coater. After drying, UV irradiation was performed with a 100 W high-pressure mercury lamp for 180 seconds under a nitrogen atmosphere, photopolymerization / crosslinking was performed, a hole transport layer having a thickness of about 20 nm was formed, and the film was wound up and stored in a roll shape. 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.

(Formation of photoelectric conversion layer (second organic functional layer 2))
(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.

(Coating of coating liquid for photoelectric conversion layer formation)
Subsequently, after the base material 1 having been formed up to the hole transport layer was heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere, the prepared coating liquid for forming a photoelectric conversion layer was formed on the hole transport layer using a slit coater. The coating was applied while filtering through a filter, and the coating was left to dry at room temperature, followed by heat treatment at 150 ° C. for 15 minutes to form a photoelectric conversion layer having a film thickness of 100 nm, and wound and stored in a roll.

(Formation of electron injection layer)
Subsequently, the base material 1 formed up to the photoelectric conversion layer is transported to a vacuum deposition chamber, lithium fluoride (LiF) is used as a deposition raw material, and the photoelectric conversion is performed under a vacuum condition reduced to 5 × 10 ⁻⁴ Pa. The electron-injection layer having a thickness of 0.6 nm was formed by depositing a film on the layer so as to overlap the power generation region patterned.

(Formation of second electrode)
Subsequently, the base material 1 formed up to the electron injection layer was vacuumed under reduced pressure to 5 × 10 ⁻⁴ Pa, except for the external connection electrode part of the first electrode (the upper part of the first electrode ( The power generation region)) and the region leading to the lead portion are formed by mask deposition by vapor deposition using aluminum to form a second electrode (cathode) made of aluminum having a thickness of 100 nm, and the organic structure shown in FIG. A PV element was produced.

[Pasting of sealing member]
(Formation of adhesive layer)
An ultraviolet curable liquid adhesive (epoxy resin) was applied on the second electrode of the prepared organic PV element to a thickness of 10 μm by screen printing. 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. An organic PV panel was produced by sealing by irradiation and fixing for 15 minutes at an irradiation intensity of 15 mW / cm ² and a distance of 10 mm. 101.

<Sample No. Production of 102>
Sample No. was changed except that the base material to be bonded was changed to the base material 2. An organic PV panel was prepared under the same conditions as in sample 101, and sample no. 102.

<Sample No. 103 production>
Sample No. was changed except that resin film A was changed to resin film B. An organic PV panel was prepared under the same conditions as in sample 101, and sample no. 103.

<Sample No. Production of 104>
Sample Nos. Were changed except that the resin film A was changed to the resin film B and the substrate 1 was changed to the substrate 2. An organic PV panel was prepared under the same conditions as in sample 101, and sample no. 104.

<Comparative Sample No. Production of 105>
(Preparation of base material)
Sample No. Substrate 1 used to make 101 The same substrate was used.

(Formation of the first electrode (anode))
On the prepared base material, the sample No. The same first electrode (anode) forming coating solution as the first electrode (anode) forming coating solution used for the production of the first electrode (anode) of No. 102 was prepared. After coating by the same coating method as that of No. 102, patterning was performed by the same method to form a first electrode (anode).

(Formation of hole injection layer)
Sample No. 1 was placed on the first electrode (anode). The same coating solution for forming a hole injection layer as that used for the preparation of Sample No. The hole injection layer was formed by applying in the same manner as in the preparation of 102.

(Formation of organic PV panels)
Thereafter, a hole transport layer, a photoelectric conversion layer, an electron injection layer, and a second electrode are provided on the hole injection layer with sample No. After forming under the same conditions as in sample 102, sample no. A sealing member was bonded under the same conditions as in No. 102 to produce an organic PV panel. 105.

(Evaluation)
The prepared sample No. Nos. 101 to 105, whether or not leaks occur, performance characteristics immediately after fabrication of series resistance Rs (Ωcm ² ), parallel resistance Rsh (Ωcm ² ), energy conversion efficiency η (%) as a substitute characteristic for function degradation due to leak current, and storage Table 1 shows the results of measuring performance (energy conversion efficiency η (%)) by the method shown below.

  The term “immediately after production” refers to a state of storage for 12 hours in an environment of 25 ° C. and 50% RH.

(Performance immediately after fabrication)
Measurement of series resistance Rs (Ωcm ² ) and parallel resistance Rsh (Ωcm ² ) The solar simulator is a solar simulator (ES-500XIL manufactured by Eihiro Seiki Co., Ltd.) calibrated in advance with a secondary reference solar cell (RC2-G5 manufactured by PV Measurements). Use a AM1.5G filter to irradiate light with an intensity of 100 mW / cm ² , and overlay a mask with an effective area of 1 cm ² on the light receiving part, and use a source meter (2400 made by Keithley) for series resistance Rs (Ωcm ² ), parallel resistance Rsh (Ωcm ² ) was measured.

Measurement of energy conversion efficiency η (%) When measuring series resistance Rs (Ωcm ² ) and parallel resistance Rsh (Ωcm ² ), short-circuit current density Jsc (mA / cm ² ) and open circuit voltage Voc (V ), The energy conversion efficiency η (%) was obtained from the measurement result of the fill factor FF according to Equation 1.

(Formula 1) η (%) = Jsc (mA / cm ² ) × Voc (V) × FF
(Storability)
After standing for 168 hours in room temperature air (25 ° C., 50% RH), the same measurement was performed on the energy conversion efficiency η (%), and evaluation was performed according to the following evaluation rank.

Evaluation rank ◎: Energy conversion efficiency is 90% or more with respect to the measured energy efficiency immediately after the production ○: Energy conversion efficiency is 70% or more and less than 90% with respect to the energy efficiency measured immediately after the production △: Energy conversion efficiency is produced 50% or more and less than 70% with respect to the immediately measured energy efficiency value X: Energy conversion efficiency is less than 50% with respect to the immediately measured energy efficiency measured value Presence or absence of leakage occurrence Sample of 850 nm infrared light emitted at a frequency of 3 Hz Then, an infrared camera (SC5200 manufactured by FLIR ATR) was used to photograph the sample, and the presence or absence of a heat generation point due to leak was visually observed using a lock-in thermobluff.

Sample No. produced by the production method of the present invention. 101 to No. No leakage occurs, the function immediately after fabrication is not deteriorated due to short or leakage current, the series resistance Rs (Ωcm ² ), the parallel resistance Rsh (Ωcm ² ), and the energy conversion efficiency η (%) are compared. Sample No. It was confirmed that all of them showed superior performance as compared with 105. It was confirmed that all showed excellent performance. Note that the parallel resistance Rsh [Ωcm ² ] is the comparative sample No. Although the value is higher than 105, it is determined that there is no occurrence of functional degradation due to leakage current.

  Further, Sample No. produced using the resin film B having a fine structure was used. 103 and sample no. Sample No. 104 produced using resin film A having no fine structure. 101 and sample no. Compared to 102, the series resistance was low. This is considered to be because the contact area between the second organic functional layer (photoelectric conversion layer) and the fine structure formed on the surface of the first organic functional layer (hole transport layer) is increased. As a result, it was confirmed that high energy conversion efficiency was obtained.

  Further, Sample 102 and Sample No. 2 prepared using the base material 2 having a barrier layer. 104, sample No. 104 produced using the substrate 1 having no barrier layer. 101 and sample no. Compared to 103, no difference was found in the energy conversion efficiency immediately after fabrication, but it was confirmed that a large difference was obtained in storage stability.

Comparative sample No. 1 produced using the substrate 1 having no barrier layer. Sample No. 105 was prepared using the base material 1 having no barrier layer in terms of storage stability. Although the same performance as 101 and 103 was shown, a heat generation point due to leakage was confirmed, and all of the series resistance Rs (Ωcm ² ), the parallel resistance Rsh (Ωcm ² ), and the energy conversion efficiency η (%) immediately after fabrication were samples. No. It was confirmed that it was inferior to 101 and 103. The effectiveness of the present invention was confirmed.

1 'organic electronics panel continuum 1'a organic electronics panel 101' base material 102 'first electrode (anode)
103 'organic functional layer 104' second electrode (cathode)
105 'Sealing layer 106', 107 'Adhesive layer 1 to 4 Manufacturing process 1a to 3a First organic functional layer forming process 1b, 3b First electrode forming process 1c Pattern forming process 1d, 3c Substrate bonding process 1e, 3d peeling process 1f, 3e, 3f 2nd organic functional layer formation process 1g, 3f 2nd electrode formation process 1h, 3g Sealing material bonding process 401 Band-shaped base film 402 Resin layer 1a11, 3a11, 403 Band-shaped resin film

Claims (7)

Organic electronics having a first electrode, a second electrode, a sealing layer, and at least one organic functional layer including an organic material layer between the first electrode and the second electrode on a substrate. In the panel manufacturing method,
The organic functional layer has a first organic functional layer,
A first organic functional layer forming step of forming the first organic functional layer on a belt-shaped resin film;
An organic electronics panel manufacturing method comprising: a first electrode forming step of forming the first electrode on the first organic functional layer formed on the belt-shaped resin film.   2. The method of manufacturing an organic electronics panel according to claim 1, wherein a surface of the belt-shaped resin film on which the first organic functional layer is formed has a fine structure.   The method for producing an organic electronics panel according to claim 1, wherein the base material has a gas barrier layer. In the manufacturing method of the organic electronics panel of any one of Claim 1 to 3, The said organic functional layer has a said 1st organic functional layer and a 2nd organic functional layer,
And the manufacturing method of the organic electronics panel characterized by having each next process sequentially.
A) Said 1st organic functional layer formation process B) 1st electrode formation process C) Pattern formation process which forms a pattern in said 1st electrode D) Base material sticking which bonds the said base material on said 1st electrode Combined Step E) Peeling Step of Peeling the Strip-shaped Resin Film F) Second Organic Forming the Second Organic Functional Layer on the Surface of the First Organic Functional Layer from which the Strip-shaped Resin Film has been Stripped Functional layer forming step G) Second electrode forming step of forming the second electrode on the second organic functional layer H) Sealing layer forming step of forming the sealing layer on the second electrode 4. The method of manufacturing an organic electronics panel according to claim 1, wherein the organic functional layer includes the first organic functional layer and a second organic functional layer, and the first electrode forming step includes: It is formed by vapor deposition using a mask,
And the manufacturing method of the organic electronics panel characterized by having each next process sequentially.
A) Said 1st organic functional layer formation process B) Said 1st electrode formation process C) Base material bonding process which bonds the said base material on the said 1st electrode D) Peeling which peels the said strip | belt-shaped resin film Step E) Second organic functional layer forming step of forming the second organic functional layer on the surface of the first organic functional layer from which the band-shaped resin film has been peeled. F) of the second organic functional layer Second electrode forming step for forming the second electrode on top G) Sealing layer bonding step for forming the sealing layer on the second electrode   The method for producing an organic electronics panel according to any one of claims 1 to 5, wherein the organic electronics panel is an organic photoelectric conversion element.   The said organic electronics panel is an organic electroluminescent panel, The manufacturing method of the organic electronics panel of any one of Claim 1 to 5 characterized by the above-mentioned.

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