JP2019194970A - Organic device, display device, imaging apparatus, lighting unit, mobile, and manufacturing method for organic device - Google Patents

Abstract

To provide a technology advantageous in improvement of the reliability of an organic device.SOLUTION: An organic device includes, on a surface of a substrate 201: an image region 10 in which a plurality of pixels including an organic functional layer 211 are arranged; and a peripheral region 20 including a pad electrode 30. A first layer 202, a sealing layer 300 and a resin layer 400 are stacked in that order from the surface side. The organic functional layer 211 is disposed between the first layer 202 and the sealing layer 300 in the pixel region 20. An opening for exposing the pad electrode 30 is provided in the peripheral region 20. The sealing layer 300 includes, from the surface side: a second layer 301 lower in moisture permeability than the first layer 202; a fourth layer 302 lower in defect density than the second layer 301; and a third layer 303. An end of the opening is covered with the second layer 301, the fourth layer 302, the third layer 303 and the resin layer 400.SELECTED DRAWING: Figure 4

Description

  The present invention relates to an organic device, an organic device, a display device, an imaging device, a lighting device, a moving body, and a method for manufacturing the organic device.

  2. Description of the Related Art Organic devices including an organic functional layer containing an organic compound are known, such as a light emitting device using an organic electroluminescence film and an imaging device using an organic photoelectric conversion film. Organic compounds tend to deteriorate in characteristics due to moisture. Patent Document 1 discloses that an organic functional layer is sealed using a sealing layer in which a silicon nitride film and an aluminum oxide film are stacked.

JP 2010-198969 A

  The inventors of the present invention provided an opening in the insulating layer and the sealing layer when an insulating layer using a material having a higher water permeability than the sealing layer is disposed under the organic functional layer throughout the device. It has been found that moisture may permeate from the pad electrode portion to the organic functional layer through the insulating layer. When moisture penetrates into the organic functional layer, the characteristics of the organic compound contained in the organic functional layer are deteriorated, and the reliability of the organic device can be lowered.

  An object of this invention is to provide the technique advantageous for the improvement of the reliability of an organic device.

  In view of the above problem, an organic device according to an embodiment of the present invention includes a pixel region in which a plurality of pixels including an organic functional layer are arranged on a surface of a substrate, and a peripheral region including a pad electrode. In the organic device, the first layer, the sealing layer, and the resin layer are stacked in this order from the surface side, and in the pixel region, between the first layer and the sealing layer. An organic functional layer is disposed, and in the peripheral region, the first layer, the sealing layer, and the resin layer each include an opening for exposing the pad electrode. A second layer and a third layer having a moisture permeability lower than that of the first layer, and a fourth layer having a defect density lower than that of the second layer, disposed between the second layer and the third layer. And an end of the opening of the first layer is covered by the second layer, the fourth layer, and the third layer, The step portion of the second layer caused by the end portion of the opening portion of the layer is covered by the fourth layer, and the step portion of the third layer caused by the end portion of the opening portion of the first layer is It is characterized by being covered with a resin layer.

  ADVANTAGE OF THE INVENTION According to this invention, the technique advantageous for the improvement of the reliability of an organic device can be provided.

The top view of the organic device which concerns on embodiment of this invention. Sectional drawing of the organic device of FIG. 1, and sectional drawing and a top view of pad electrode vicinity. Sectional drawing of the comparative example of the organic device of FIG. Sectional drawing of the organic device of FIG. 1, and sectional drawing of pad electrode vicinity. Sectional drawing of the comparative example of the organic device of FIG. Sectional drawing of the organic device of FIG. 1, and sectional drawing of pad electrode vicinity. Sectional drawing of the comparative example of the organic device of FIG. Sectional drawing of the organic device of FIG. The figure which shows an example of the display apparatus using the organic device of FIG. The figure which shows an example of the imaging device using the organic device of FIG. The figure which shows an example of the portable apparatus using the organic device of FIG. The figure which shows an example of the display apparatus using the organic device of FIG. The figure which shows an example of the illuminating device using the organic device of FIG. The figure which shows an example of the motor vehicle using the organic device of FIG.

  Hereinafter, specific embodiments of the organic device according to the present invention will be described with reference to the accompanying drawings. Note that, in the following description and drawings, common reference numerals are given to common configurations over a plurality of drawings. Therefore, a common configuration is described with reference to a plurality of drawings, and a description of a configuration with a common reference numeral is omitted as appropriate.

  With reference to FIGS. 1-14, the structure and manufacturing method of the organic device by embodiment of this invention are demonstrated. 1 is a plan view showing the structure of the organic device 100 according to the present invention, FIG. 2A is a cross-sectional view of the organic device 100 taken along the line AA ′ in FIG. 1, and FIGS. FIG. 8 is a cross-sectional view and a plan view of the vicinity of the pad electrode 30 of the organic device 100, respectively.

  As shown in FIG. 1, the organic device 100 includes a pixel region 10 in which a plurality of pixels are arranged, and a peripheral region 20 including a pad electrode 30. The pixels arranged in the pixel region 10 include an organic functional layer 211 using an organic light emitting material or an organic photoelectric conversion material, and the organic device 100 functions as a light emitting device including a light emitting element or an imaging device including a photoelectric conversion element. sell. As shown in FIG. 1, the peripheral region 20 may be disposed so as to surround the pixel region 10, or may be disposed along one or more sides of the pixel region 10. In the peripheral area 20, a circuit for controlling the pixel area 10 and the like can be arranged. The pad electrode 30 disposed in the peripheral region 20 can be used to exchange signals and the like between the organic device 100 and the outside of the organic device 100. For example, the pad electrode 30 may be used for outputting a signal generated in the organic device 100 to the outside, or for inputting a signal for controlling the organic device 100 from the outside to the organic device 100. May be used. Further, for example, the pad electrode 30 may be used to supply power for driving the organic device 100.

  As shown in FIG. 2A, the organic device 100 includes an insulating layer 202 (first layer), a sealing layer 300, and a resin layer 400 stacked in this order from the surface side of the substrate 201. The In the pixel region 10, a lower electrode 210, an organic functional layer 211, and an upper electrode 212 are disposed between the insulating layer 202 and the sealing layer 300. In the peripheral region 20, the insulating layer 202, the sealing layer 300, and the resin layer 400 each have an opening for exposing the pad electrode 30. In this specification, a surface of the substrate 201 on which the insulating layer 202, the sealing layer 300, the resin layer 400, and the like are disposed is referred to as a surface.

The insulating layer 202 is formed using an insulating material. The insulating layer 202 may include a compound containing at least oxygen and silicon, for example, an inorganic material such as a silicon oxide material. Further, for example, it may be formed using an organic material such as a thermosetting resin or a thermoplastic resin. In the present embodiment, the insulating layer 202 is formed using silicon oxide (SiO _x ). For example, the insulating layer 202 may be formed by a chemical vapor deposition method (CVD method) using tetraethoxysilane (TEOS). The insulating layer 202 is required to have good coverage, but TEOS can obtain silicon oxide with excellent coverage by a surface reaction via an ethoxy group. In addition, TEOS that does not spontaneously ignite can be handled safely compared to the case where the insulating layer 202 is formed using monosilane (SiH ₄ ) gas that has spontaneous ignitability. In order to ensure insulation and planarization, the thickness of the insulating layer 202 may be not less than 0.5 μm and not more than 5.0 μm.

  As the substrate 201, an insulating substrate such as glass or resin, a conductive substrate such as aluminum or stainless steel, or a semiconductor substrate such as silicon can be used. Electronic circuits (not shown) such as transistors and wiring patterns are disposed between the substrate 201 and the insulating layer 202.

  On the insulating layer 202, the lower electrode 210 is disposed in the pixel region 10. The lower electrode 210 is connected to an electronic circuit disposed between the substrate 201 and the insulating layer 202 by a plug electrode (not shown) formed of a conductive material such as tungsten. The lower electrode 210 may be a metal material having high conductivity. For the lower electrode 210, for example, a metal material such as aluminum, silver, an aluminum alloy, a silver alloy, titanium, or titanium nitride can be used.

  An organic functional layer 211 is disposed on the lower electrode 210. In the present embodiment, the organic functional layer 211 includes at least an organic light emitting material or an organic photoelectric conversion material. The material used for the organic functional layer 211 will be described later.

  An upper electrode 212 is disposed on the organic functional layer 211. The upper electrode 212 is an electrode that emits light generated in the organic functional layer 211 when the organic functional layer 211 includes an organic light emitting material. The upper electrode 212 is an electrode that transmits light incident on the organic functional layer 211 when the organic functional layer 211 includes an organic light emitting material. In order to utilize a lot of light, the organic functional layer 211 can be made of a material having high light transmittance. For the upper electrode 212, a transparent oxide conductive material such as tin oxide, indium oxide, indium tin oxide, or indium zinc oxide may be used. The upper electrode 212 may be a thin metal electrode. In this case, for example, a thin film of gold, platinum, silver, aluminum, chromium, magnesium, or an alloy thereof can be used. When using a thin metal electrode, the film thickness may be 1 nm or more and 30 nm or less in order to achieve both high conductivity and suppression of light absorption by the metal. In addition, when magnesium is used for the upper electrode 212, since magnesium easily reacts with moisture, it is necessary to suppress intrusion of moisture as in the case of the organic functional layer 211.

  A sealing layer 300 is disposed on the upper electrode 212. In the present embodiment, the sealing layer 300 includes moisture suppression layers 301 (second layer) and 303 (third layer) having a moisture permeability lower than that of the insulating layer 202 from the surface side of the substrate 201. Further, the sealing layer 300 includes a defect suppression layer 302 (fourth layer) that is disposed between the moisture suppression layer 301 and the moisture suppression layer 303 and has a defect density lower than that of the moisture suppression layer 301. In the present embodiment, the sealing layer 300 has an organic functional layer having a laminated structure of moisture suppression layers 301 and 303 having a low moisture permeability and a defect suppression layer 302 having a very high coverage and a low defect density. 211 can suppress the influence of moisture in the external atmosphere.

The moisture suppression layers 301 and 303 may include a compound containing at least nitrogen and silicon, and more specifically include a silicon nitride-based material. For example, the moisture suppression layers 301 and 303 may be silicon nitride (SiN) or silicon oxynitride (SiON) formed using a CVD method. The moisture deterrence layers 301 and 303 using silicon nitride or silicon oxynitride formed by a CVD method have an extremely low moisture permeability of about 1 × 10 ⁻⁶ g / m ² · day. The moisture suppression layers 301 and 303 are not limited to silicon nitride and silicon oxynitride, and any method can be used as long as the moisture suppression layers 301 and 303 are formed so as to have high light transmittance like the upper electrode 212 and less moisture permeability than the insulating layer 202. Any material may be used. For example, the moisture suppression layers 301 and 303 can be formed so that the moisture permeability is 1 × 10 ⁻⁵ g / m ² · day or less. The moisture suppression layer 301 and the moisture suppression layer 303 may be, for example, the same material film layer such as silicon nitride, or different material film layers such that one is silicon nitride and the other is silicon oxynitride. There may be. Further, the film thickness of the moisture suppression layer 301 and the film thickness of the moisture suppression layer 303 may be the same film thickness, or may be different from each other.

The defect suppression layer 302 may include a compound containing at least oxygen and aluminum, and more specifically, may include an aluminum oxide-based material. For example, the defect suppression layer 302 may be aluminum oxide formed using an atomic layer deposition method (ALD method). The substrate 201 on which the moisture suppression layer 301 is formed is placed in a vacuum deposition chamber, and trimethylaluminum (TMA) gas is flowed to adsorb one atomic layer of TMA on the surface of the moisture suppression layer 301. Thereafter, the TMA gas is exhausted from the film forming chamber. Next, plasma is generated by supplying oxygen and applying high-frequency power, etc., and oxidize the TMA adsorbed on the surface of the moisture suppression layer 301. Subsequently, O ₂ in the film formation chamber is exhausted. As a result, a monoatomic layer of aluminum oxide is formed on the surface of the moisture suppression layer 301. By repeating this, the defect suppressing layer 302 using aluminum oxide having a desired thickness can be formed.

  The defect suppression layer 302 formed by the ALD method has a high film coverage at the concavo-convex portion and has a very high coverage. Therefore, the defect density in the film is lower than that of a thin film formed by a sputtering method or a CVD method. Is low. The ALD method requires a long film formation time. Therefore, in order to shorten the tact time for forming the defect suppression layer 302, the defect suppression layer 302 may have a film thickness of several tens nm to several hundreds nm. For example, the film thickness of the defect suppression layer 302 may be 10 nm or more and 500 nm or less, or may be 50 nm or more and 100 nm or less. In this embodiment, aluminum oxide formed using the ALD method is used as the defect suppression layer 302, but titanium oxide, zirconium oxide, or the like may be used. Further, the formation method is not limited to the ALD method, and it is only necessary to form the defect suppression layer 302 having a high film coverage at the uneven portion and high coverage.

  For the resin layer 400, a thermosetting resin, a thermoplastic resin, or the like can be used. For the resin layer 400, for example, phenol resin, epoxy resin, polyimide resin, polyethylene resin, polystyrene resin, acrylic resin, fluorine resin, or a mixed material thereof may be used. Further, the surface of the resin layer 400 may be subjected to surface treatment for improving water repellency. For example, the surface of the resin layer 400 may be roughened by etching, or the surface of the resin layer 400 may be subjected to plasma treatment using a fluorine-based gas to apply a fluorine coat to the surface of the resin layer 400. Also good.

  Next, the structure around the pad electrode 30 disposed in the peripheral region 20 in the present embodiment will be described in detail. 2B is a cross-sectional view in the vicinity of the pad electrode 30, and FIG. 2C is a plan view in the vicinity of the pad electrode 30. In the peripheral region 20, the insulating layer 202, the sealing layer 300, and the resin layer 400 each have an opening for exposing the pad electrode 30. As a result, the pad electrode 30 is exposed. A flexible cable for connecting the organic device 100 and the outside of the organic device 100 is connected to the exposed pad electrode 30 using, for example, an anisotropic conductive film (ACF). In the structure shown in FIG. 2C, the exposed portion of the pad electrode 30 is a square, but is not limited to this shape, and may be an arbitrary shape such as a rectangle, a trapezoid, or a circle. The material for forming the pad electrode 30 may be a metal material having high conductivity, and for example, a metal material such as aluminum, copper, silver, molybdenum, titanium, or titanium nitride can be used.

  In this embodiment, as shown in FIGS. 2A to 2C, the end a of the opening of the insulating layer 202 is formed by a moisture suppression layer 301, a defect suppression layer 302, and a moisture suppression layer 303. Covered. Further, the step S 1 of the moisture suppression layer 301 due to the end a of the opening of the insulating layer 202 is covered with the defect suppression layer 302, and the moisture suppression layer 303 due to the end a of the opening of the insulating layer 202. The step portion S <b> 2 is covered with the resin layer 400.

  In the present embodiment, the moisture suppression layer 301 is formed so as to cover the end a of the opening of the insulating layer 202. The insulating layer 202 using silicon oxide and having high moisture permeability is covered with the moisture suppressing layer 301 using a silicon nitride-based material having low moisture permeability that is not exposed around the pad electrode 30. For example, the moisture permeability of silicon oxide used for the insulating layer 202 is about 1 to 3 digits higher than that of a silicon nitride material used for the moisture suppression layer 301. As a result, moisture can be prevented from penetrating to the organic functional layer 211 through the insulating layer 202.

  As described above, the insulating layer 202 has a thickness of about 0.5 μm to 5.0 μm. Due to the thickness of the insulating layer 202, the moisture suppression layer 301 formed on the insulating layer 202 has a stepped portion S1. When silicon nitride or silicon oxynitride used for the moisture suppression layer 301 is formed by the CVD method, the growth direction and the growth speed are different at the top, side, and bottom of the uneven portion such as the stepped portion S1, and the film density at the stepped portion S1 is different. It may be low and dense. In addition, voids may be generated in portions where silicon nitride and silicon oxynitride grown in different directions collide with each other, and a gap may be formed in the moisture suppression layer 301. In this way, the stepped portion S1 of the moisture suppression layer 301 may have a vulnerability that increases the density of defects. When moisture enters from such a defect in the stepped portion S1 of the moisture suppression layer 301, moisture enters the insulating layer 202, and moisture penetrates to the organic functional layer 211 via the insulating layer 202. There is. Therefore, in the organic device 100 of the present embodiment, the defect suppression layer 302 is disposed so as to cover the stepped portion S1 of the moisture suppression layer 301. Since the aluminum oxide formed by the ALD method used for the defect suppression layer 302 has high film coverage at the concavo-convex portion and high coverage, defects such as the stepped portion S1 of the moisture suppression layer 301 are unlikely to occur. The coverage of the defect suppression layer 302 will be briefly described. For example, the film thickness of the portion of the defect suppression layer 302 that covers the side surface of the stepped portion S1 of the moisture suppression layer 301 is the film thickness of the portion of the defect suppression layer 302 that covers a relatively flat portion such as the portion that covers the pixel region 10. 95% or more and 105% or less. In addition, for example, the film thickness of a portion of the defect suppression layer 302 that covers the side surface of the stepped portion S1 of the moisture suppression layer 301 is a portion of the defect suppression layer 302 that covers a relatively flat portion such as a portion that covers the pixel region 10. It may be 98% or more and 102% or less of the film thickness. As described above, the defect suppressing layer 302 can more reliably cover the fragile portion of the stepped portion S <b> 1 of the moisture suppressing layer 301, thereby preventing moisture from entering the organic functional layer 211.

  Since the defect suppression layer 302 and the moisture suppression layer 303 are formed so as to cover the stepped portion S1 of the moisture suppressing layer 301 caused by the end a of the opening of the insulating layer 202, the moisture suppressing layer 303 includes the stepped portion S2. Have Similarly to the step portion S1 of the moisture suppression layer 301, the step portion S2 of the moisture suppression layer 303 may have a vulnerability that increases the density of defects. When moisture enters from a defect in the stepped portion S2 of the moisture suppression layer 303, moisture may enter the defect suppression layer 302 using aluminum oxide, and the aluminum oxide may corrode (hydrolyze). Aluminum oxide is susceptible to corrosion (hydrolysis) when it comes into contact with a large amount of moisture at a high temperature. In order to suppress this corrosion, in the organic device 100 of this embodiment, the resin layer 400 is disposed so as to cover the stepped portion S2 of the moisture suppression layer 303. The resin layer 400 is not as low in moisture permeability as a thin film formed of an inorganic material. However, when the resin layer 400 covers the brittle portion of the stepped portion S2 of the moisture suppression layer 303, the defect suppression layer 302 can be prevented from coming into contact with a large amount of moisture.

  In this embodiment, as shown in FIGS. 2A to 2C, the end e of the opening of the resin layer 400 is the end of the opening of the insulating layer 202 in the orthogonal projection on the surface of the substrate 201. It is arranged at a position closer to the center p of the pad electrode 30 exposed than the part a. Further, in the orthogonal projection to the surface of the substrate 201, the end d of the opening of the moisture suppression layer 303 is the same position as the end e of the opening of the resin layer 400, or the end e of the opening of the resin layer 400. It is arranged at a position closer to the center p of the pad electrode 30 exposed. Further, in the orthogonal projection with respect to the surface of the substrate 201, the end c of the opening of the defect suppression layer 302 is the same position as the end d of the opening of the moisture suppression layer 303 or the end of the opening of the moisture suppression layer 303. It is arranged at a position closer to the center p of the pad electrode 30 exposed than the portion d. Further, in the orthogonal projection with respect to the surface of the substrate 201, the end b of the opening of the moisture suppression layer 301 is the same position as the end c of the opening of the defect suppression layer 302 or the end of the opening of the defect suppression layer 302. It is arranged at a position closer to the center p of the pad electrode 30 exposed than the portion c. Thus, moisture can be prevented from entering from the openings for exposing the pad electrodes 30 of the insulating layer 202, the sealing layer 300, and the resin layer 400, and the reliability of the organic device 100 can be improved. Is possible. Here, the center p of the exposed pad electrode 30 may be, for example, the geometric center of gravity of the exposed portion of the pad electrode 30 in an orthogonal projection with respect to the surface of the substrate 201.

  FIG. 3A shows a comparative organic device 110 in which the stepped portion S1 of the moisture suppression layer 301 is not covered by the defect suppression layer 302. FIG. Compared to the organic device 100 of the present embodiment described above, the end b of the opening of the moisture suppression layer 301 is closer to the center p of the pad electrode 30 exposed than the end c of the opening of the defect suppression layer 302. Arranged in position. In this case, moisture may enter from the defects that may exist in the step portions S 1 and S 2 of the moisture suppression layers 301 and 303, and moisture may penetrate to the organic functional layer 211 through the insulating layer 202. For example, when the organic device 110 is left for a long time in a high-temperature and high-humidity environment, or when it is left for a long time in water, characteristic deterioration of the organic device 110 is observed.

  FIG. 3B shows an organic device 111 of a comparative example in which the step portion S2 of the moisture suppression layer 303 is not covered with the resin layer 400. Compared with the organic device 100 of the present embodiment described above, the end a of the opening of the insulating layer 202 is closer to the center p of the pad electrode 30 exposed than the end e of the opening of the resin layer 400. Arranged. In this case, moisture may enter from the defects that may exist in the stepped portion S <b> 2 of the moisture suppression layer 303, and corrosion of aluminum oxide used for the defect suppression layer 302 may progress. For example, when the organic device 111 is left in a high temperature and high humidity environment for a long time or when it is left in water for a long time, characteristic deterioration of the organic device 111 is observed.

  Next, FIGS. 4A and 4B show a modification of the organic device 100 of the present embodiment. As shown in FIG. 4A, the organic device 100 may include a color filter 500 on the sealing layer 300. The color filter 500 includes a red filter 501, a green filter 502, and a blue filter 503 disposed on the resin layer 400 that is also used as a flattening layer of the color filter 500. A planarizing layer 402 is further disposed on the color filter 500. In the process of forming the color filter 500, the material application and the exposure / development are repeated for each color filter. In the configuration shown in FIG. 4A, the resin layer 400 also serves as a flattening layer of the color filter, but a flattening layer (not shown) is formed on the resin layer 400, and the color filter 500 is formed thereon. May be. FIG. 4B shows a cross-sectional view in the vicinity of the pad electrode 30. A resin layer 400 also serving as a flattening layer below the color filter 500 is disposed so as to cover the stepped portion S2 of the moisture suppression layer 303. The process of manufacturing the organic device 100 can be simplified by having the resin layer 400 also serve as a planarizing layer without forming the resin layer 400 and the planarizing layer below the color filter 500 by separate processes. And cost reduction.

  Here, the organic functional layer 211 will be specifically described. As described above, the organic functional layer 211 in the present embodiment includes at least an organic light emitting material or an organic photoelectric conversion material. When the organic functional layer 211 includes an organic light emitting material, the organic device 100 can function as a light emitting device. On the other hand, when the organic functional layer 211 includes an organic photoelectric conversion material, the organic device 100 can function as an imaging device.

  A known organic light emitting material can be used as the organic light emitting material. A light emitting material that functions as a single light emitting layer may be used, or a mixed layer of a light emitting layer host material and a light emitting material may be used. Organic light-emitting materials include condensed ring compounds (eg, fluorene derivatives, naphthalene derivatives, pyrene derivatives, perylene derivatives, tetracene derivatives, anthracene derivatives, rubrene, etc.), quinacridone derivatives, coumarin derivatives, stilbene derivatives, tris (8-quinolinolato) aluminum, etc. Organic aluminum complexes, iridium complexes, platinum complexes, rhenium complexes, copper complexes, europium complexes, ruthenium complexes, and polymer derivatives such as poly (phenylene vinylene) derivatives, poly (fluorene) derivatives, and poly (phenylene) derivatives. .

  Examples of the light emitting layer host material include aromatic hydrocarbon compounds or derivatives thereof, carbazole derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, organoaluminum complexes such as tris (8-quinolinolato) aluminum, and organic beryllium complexes.

As the organic photoelectric conversion material, either a known organic material or an organic / inorganic hybrid material can be used. As the organic photoelectric conversion material, for example, fullerene materials, phthalocyanine materials, metal complex materials, squalium materials, amine materials, indane materials, fluorene materials, and the like can be used. The organic functional layer 211 may be composed of one of these organic photoelectric conversion materials, or the organic functional layer 211 may be composed of a plurality of materials. Further, the organic functional layer 211 may have a configuration in which layers using these materials are stacked. As the organic / inorganic hybrid material, for example, a material for forming an organic / inorganic hybrid perovskite film can be used. The material constituting the organic-inorganic hybrid perovskite layer may be those represented by the general formula ABX _3. Here, in the general formula, A and B are cationic materials, and X is an anionic material. An example of the organic / inorganic hybrid material is CH ₃ NH ₃ PbI _{3 in} which any one of A, B, and X is an organic material, and A = CH ₃ NH ₃ , B = Pb, and X = I. .

  An additional functional layer may be disposed between the organic functional layer 211 and the lower electrode 210 or between the organic functional layer 211 and the upper electrode 212. Examples of the additional functional layer include a charge transport layer and a charge block layer. As a material for the charge transport layer, a material having a high mobility of holes and electrons can be used. In addition, as a material for the hole blocking layer in the charge blocking layer, a material having a deepest occupied level (HOMO) deep (energy far from the vacuum level) can be used. On the other hand, as the electron blocking layer in the charge blocking layer, a material having a shallowest unoccupied molecular orbital (LUMO) shallow (close to the vacuum level) can be used. HOMO and LUMO can be expressed as high or low based on the magnitude of the absolute value. Specifically, a deep HOMO can be expressed as a high HOMO. The same applies to other cases.

  A charge injection layer may be formed at the interface between the lower electrode 210 and the additional functional layer, or at the interface between the upper electrode 212 and the additional functional layer. Among the charge injection layers, an electron injection layer may be a thin film (for example, 0.5 to 1 nm) of an alkali (earth) metal or an alkali (earth) metal compound. For example, lithium fluoride (LiF), potassium fluoride (KF), or magnesium oxide (MgO) can be used for the electron injection layer. As the electron injection layer of the charge injection layer, a layer in which a metal or a metal compound that functions as a donor (electron donating) dopant is mixed with an organic compound can be used. In order to improve the electron injection efficiency, a metal having a low work function or a compound thereof may be used as a dopant. As the metal having a low work function, an alkali metal, an alkaline earth metal, or a rare earth can be used. An alkali metal compound that is relatively easy to handle in the atmosphere may be used as the electron injection layer. For example, the alkali metal compound may be a cesium compound, and cesium carbonate is stable in the air and easy to handle. The organic compound for the electron injection layer may be an electron transporting material, and a known material such as an aluminum quinolinol complex or a phenanthroline compound can be used. Since the alkali metal easily reacts with moisture, it is necessary to suppress the penetration of moisture as in the case of the organic functional layer 211.

  Here, application examples in which the organic device 100 of the present embodiment is applied to a display device, an imaging device, a portable device, a lighting device, and a moving object will be described with reference to FIGS. FIG. 9 is a schematic diagram illustrating an example of a display device using the organic device 100 of the present embodiment. The display device 1000 may include a touch panel 1003, a display panel 1005, a frame 1006, a circuit board 1007, and a battery 1008 between the upper cover 1001 and the lower cover 1009. The touch panel 1003 and the display panel 1005 are connected to flexible printed circuit FPCs 1002 and 1004. An active element such as a transistor is disposed on the circuit board 1007. The battery 1008 is not necessarily provided if the display device 1000 is not a portable device, and it is not necessary to provide the battery 1008 at this position even if it is a portable device. For the display panel 1005, the organic device 100 described above in which the organic functional layer 211 includes an organic light emitting material and functions as a light emitting device may be used. The organic device 100 functioning as the display panel 1005 is connected to an active element such as a transistor disposed on the circuit board 1007 and operates.

  The display device 1000 illustrated in FIG. 9 may be used in a display unit of an imaging device that includes an optical unit having a plurality of lenses and an imaging element that receives light that has passed through the optical unit. The imaging device may include a display unit that displays information acquired by the imaging device. Further, the display unit may be a display unit exposed to the outside of the imaging device or a display unit arranged in the viewfinder. The imaging device may be a digital camera or a digital video camera.

  FIG. 10 is a schematic diagram illustrating an example of an imaging apparatus using the organic device 100 of the present embodiment. The imaging device 1100 may include a viewfinder 1101, a rear display 1102, an operation unit 1103, and a housing 1104. The above-described organic device 100 in which the organic functional layer 211 includes an organic light emitting material and functions as a light emitting device may be used for the viewfinder 1101 as a display unit. In this case, the organic device 100 may display not only an image to be captured but also environmental information, an imaging instruction, and the like. The environmental information may include the intensity of external light, the direction of external light, the moving speed of the subject, the possibility of the subject being shielded by a shielding object, and the like.

  Since the timing suitable for imaging is often a short time, it is better to display information as soon as possible. Therefore, the organic device 100 in which the organic functional layer 211 described above includes an organic light emitting material can be used for the viewfinder 1101. This is because the organic light emitting material has a high response speed. The organic device 100 using an organic light-emitting material can be used more suitably for these devices where display speed is required than for a liquid crystal display device.

  The imaging device 1100 includes an optical unit (not shown). The optical unit includes a plurality of lenses, and forms an image on an image sensor (not shown) housed in a housing 1104 that receives light that has passed through the optical unit. The plurality of lenses can be adjusted in focus by adjusting their relative positions. This operation can also be performed automatically.

  The organic device 100 that functions as a light-emitting device may include a color filter that transmits red, green, and blue light. In the color filter, the red, green, and blue colors may be arranged in a delta arrangement.

  The above-described organic device 100 that includes an organic light-emitting material and functions as a light-emitting device may be used in a display unit of a mobile terminal. In that case, you may have both a display function and an operation function. Examples of portable terminals include mobile phones such as smartphones, tablets, and head mounted displays.

  FIG. 11 is a schematic diagram illustrating an example of a portable device using the organic device 100 of the present embodiment. The portable device 1200 includes a display unit 1201, an operation unit 1202, and a housing 1203. The housing 1203 may include a circuit, a printed board including the circuit, a battery, and a communication unit. The operation unit 1202 may be a button or a touch panel type reaction unit. The operation unit 1202 may be a biometric recognition unit that recognizes a fingerprint and releases a lock. A portable device having a communication unit can also be referred to as a communication device. For the display unit 1201, the organic device 100 described above in which the organic functional layer 211 includes an organic light emitting material and functions as a light emitting device may be used.

  12A and 12B are schematic views illustrating an example of a display device using the organic device 100 of the present embodiment. FIG. 12A shows a display device such as a television monitor or a PC monitor. The display device 1300 includes a frame 1301 and a display portion 1302. For the display unit 1302, the organic device 100 described above in which the organic functional layer 211 includes an organic light emitting material and functions as a light emitting device may be used. The display device 1300 may include a base 1303 that supports the frame 1301 and the display unit 1302. The base 1303 is not limited to the form shown in FIG. For example, the lower side of the frame 1301 may also serve as the base 1303. Further, the frame 1301 and the display portion 1302 may be bent. The curvature radius may be not less than 5000 mm and not more than 6000 mm.

  FIG. 12B is a schematic diagram illustrating another example of the display device using the organic device 100 of the present embodiment. The display device 1310 in FIG. 12B is configured to be bendable, and is a so-called foldable display device. The display device 1310 includes a first display portion 1311, a second display portion 1312, a housing 1313, and a bending point 1314. For the first display unit 1311 and the second display unit 1312, the organic device 100 described above in which the organic functional layer 211 includes an organic light emitting material and functions as a light emitting device may be used. The first display unit 1311 and the second display unit 1312 may be a single display device without a joint. The 1st display part 1311 and the 2nd display part 1312 can be divided by a bending point. The first display unit 1311 and the second display unit 1312 may display different images, or the first and second display units may display one image.

  FIG. 13 is a schematic diagram illustrating an example of a lighting apparatus using the organic device 100 of the present embodiment. The lighting device 1400 may include a housing 1401, a light source 1402, a circuit board 1403, an optical film 1404, and a light diffusion unit 1405. As the light source 1402, the organic device 100 described above in which the organic functional layer 211 includes an organic light emitting material and functions as a light emitting device may be used. The optical film 1404 may be a filter that improves the color rendering properties of the light source. The light diffusing unit 1405 can effectively diffuse the light of the light source such as light-up, and can deliver the light to a wide range. If necessary, a cover may be provided on the outermost part. The lighting device 1400 may include both the optical film 1404 and the light diffusing unit 1405, or may include only one of them.

  The lighting device 1400 is a device that illuminates a room, for example. The lighting device 1400 may emit white, day white, or any other color from blue to red. A dimming circuit for dimming them may be provided. The lighting device 1400 may include a power supply circuit connected to the organic device 100 that functions as the light source 1402. The power supply circuit is a circuit that converts an AC voltage into a DC voltage. Further, white has a color temperature of 4200K, and white white has a color temperature of 5000K. The lighting device 1400 may include a color filter. In addition, the lighting device 1400 may include a heat dissipation unit. The heat dissipating part releases the heat in the apparatus to the outside of the apparatus, and examples thereof include metals having high specific heat and liquid silicon.

  FIG. 14 is a schematic diagram of an automobile having a tail lamp that is an example of a vehicle lamp using the organic device 100 of the present embodiment. The automobile 1500 may have a tail lamp 1501 and turn on the tail lamp 1501 when a brake operation or the like is performed. An automobile is an example of a mobile object, and the mobile object may be a ship or a drone. The moving body may include an airframe and a lamp provided thereon. The lamp may inform the current position of the aircraft.

  For the tail lamp 1501, the organic device 100 described above in which the organic functional layer 211 includes an organic light emitting material and functions as a light emitting device may be used. The tail lamp 1501 may include a protective member that protects the organic device 100 that functions as the tail lamp 1501. The protective member has a certain degree of strength and can be made of any material as long as it is transparent, but may be made of polycarbonate or the like. In addition, the protective member may be a polycarbonate mixed with a furandicarboxylic acid derivative, an acrylonitrile derivative, or the like.

  The automobile 1500 may have a vehicle body 1503 and a window 1502 attached thereto. The window may be a window for confirming the front and rear of the automobile, or may be a transparent display. In the transparent display, the organic device 100 described above in which the organic functional layer 211 includes an organic light emitting material and functions as a light emitting device may be used. In this case, a constituent material such as an electrode included in the organic device 100 is formed of a transparent member.

  Hereinafter, examples and comparative examples of the organic device 100 of the present embodiment will be described.

First Example An organic device 100 shown in FIGS. 4A and 4B was produced. In this embodiment, the organic functional layer 211 includes an organic light emitting material. Therefore, the organic device 100 functions as a light emitting device.

  First, a silicon substrate was prepared as the substrate 201. After the electronic circuit (not shown) and the pad electrode 30 were formed on the substrate 201, the insulating layer 202 was formed on the surface of the substrate 201 on which the electronic circuit (not shown) and the pad electrode 30 using an aluminum alloy were disposed. . In this embodiment, silicon oxide is formed with a thickness of 1 μm as the insulating layer 202. Next, using a mask pattern having an opening on the pad electrode 30, the insulating layer 202 in the opening portion of the mask pattern was etched to perform an etching process for exposing the pad electrode 30. First, a mask pattern having a desired opening was formed using a resist coating and exposure / development process, and then the insulating layer 202 was etched by plasma etching using a reactive gas in a dry etching apparatus. After etching the insulating layer 202, the mask pattern was removed with a stripping solution.

  Next, a pixel formation step of forming a plurality of pixels on the insulating layer 202 in the pixel region 10 was performed. First, the lower electrode 210 in which an aluminum alloy and indium tin oxide were sequentially laminated from the surface side of the substrate 201 was formed on the insulating layer 202. As described above, the lower electrode 210 was connected to the electronic circuit disposed on the substrate 201 side of the insulating layer 202 by the plug electrode provided in the insulating layer 202.

  After forming the lower electrode 210, an organic functional layer 211 containing an organic light emitting material was formed on the lower electrode 210 in the pixel region 10. As a method for forming the organic functional layer 211, a vacuum vapor deposition method using a vapor deposition mask having an opening for desired patterning can be used.

  After forming the organic functional layer 211, an electron injection layer (not shown) using lithium fluoride (LiF) is formed on the organic functional layer 211 with a thickness of 0.5 nm, and silver is formed on the electron injection layer. An upper electrode 212 using a mixed film of magnesium and magnesium (volume ratio of 1: 1) was formed to a thickness of 10 nm. As a method for forming the upper electrode 212, a vacuum evaporation method using an evaporation mask having an opening for desired patterning can be used.

  On the insulating layer 202, the sealing layer 300 and the resin layer 400 were laminated in this order after the pixel formation step of forming a plurality of pixels. First, the sealing layer 300 was formed so as to cover the entire substrate 201. First, silicon nitride with a film thickness of 1500 nm was formed as a moisture suppression layer 301 on the entire surface of the substrate 201 by a CVD method. Next, an aluminum oxide film having a thickness of 100 nm was formed as the defect suppression layer 302 using the ALD method so as to cover the entire surface of the substrate 201 with the moisture suppression layer 301. Further, a silicon nitride film having a thickness of 500 nm was formed as the moisture suppression layer 303 using a CVD method so as to cover the entire surface of the substrate 201 with the defect suppression layer 302. Next, a resin having a thickness of 400 nm was applied as a resin layer 400 using a spin coating method so as to cover the moisture suppression layer 303 on the entire surface of the substrate 201, and then baked at a high temperature. As described above, the resin layer 400 also functions as a planarizing layer below the color filter 500.

  Next, a color filter 500 was formed in the pixel region 10. For the red filter 501, the green filter 502, and the blue filter 503, the material application and the exposure / development process were repeated for each color filter. After the color filter 500 was formed, the planarization layer 402 was formed by applying a resin with a film thickness of 400 nm by a spin coating method and then baking at a high temperature.

  After the formation of the planarization layer 402, the planarization layer 402, the resin layer 400, and the sealing layer 300 on the pad electrode 30 were etched by dry etching to expose the pad electrode 30. By etching the planarization layer 402, the resin layer 400, and the sealing layer 300 in one etching process, the manufacturing process of the organic device 100 can be simplified and the cost can be reduced. Specifically, first, in orthographic projection onto the surface of the substrate 201, a mask pattern having an opening inside the end portion of the insulating layer 202 opened by the above-described etching process of the insulating layer 202 is applied to resist and exposed. -It formed using the image development process. Next, the planarization layer 402, the resin layer 400, and the sealing layer 300 were etched by plasma etching using a reactive gas with a dry etching apparatus. After etching the planarization layer 402, the resin layer 400, and the sealing layer 300, the mask pattern was removed with a stripping solution.

  Through the above steps, the moisture suppression layer 301 was formed so as to cover the end a of the opening of the insulating layer 202 as shown in FIG. Furthermore, the defect suppression layer 302 was formed so as to cover the stepped portion S1 of the moisture suppression layer 301. Furthermore, the resin layer 400 was formed so as to cover the stepped portion S2 of the moisture suppression layer 303. The mask pattern opening and dry etching conditions in each step were adjusted so that the defect suppression layer 302 covering the stepped portion S1 of the moisture suppression layer 301 was not removed by side etching or the like. Similarly, the opening of the mask pattern and the dry etching conditions in each step were adjusted so that the resin layer 400 covering the stepped portion S2 of the moisture suppression layer 303 was not removed.

  Further, through the above-described steps, the end e of the opening of the resin layer 400 is closer to the center p of the pad electrode 30 exposed than the end a of the opening of the insulating layer 202 in the orthogonal projection with respect to the surface of the substrate 201. Arranged in position. Further, in the orthogonal projection to the surface of the substrate 201, the end d of the opening of the moisture suppression layer 303 is the same position as the end e of the opening of the resin layer 400, or the end e of the opening of the resin layer 400. It is arranged at a position closer to the center p of the pad electrode 30 exposed. Further, in the orthogonal projection with respect to the surface of the substrate 201, the end c of the opening of the defect suppression layer 302 is the same position as the end d of the opening of the moisture suppression layer 303 or the end of the opening of the moisture suppression layer 303. The pad electrode 30 was disposed at a position closer to the center p of the pad electrode 30 exposed than the portion d. Further, in the orthogonal projection with respect to the surface of the substrate 201, the end b of the opening of the moisture suppression layer 301 is the same position as the end c of the opening of the defect suppression layer 302 or the end of the opening of the defect suppression layer 302. The pad electrode 30 was exposed at a position closer to the center p than the portion c. Since the upper layer is scraped to the inner side by side etching when dry-etching the sealing layer 300 and the resin layer 400 using the same mask pattern, the positional relationship between the end portions a to e of such an opening is obtained. .

  The organic device 100 of the present example was able to suppress moisture from entering the organic functional layer 211. Specifically, the organic device 100 of the present invention is a light emitting device as described above, and the light emission efficiency (cd / A) when a desired voltage was applied was measured. In addition, the moisture resistance test was performed with a pressure cooker capable of testing in a high-density steam atmosphere. When the luminous efficiency (cd / A) of the organic device 100 was measured after being left in a high-density water vapor atmosphere at 100 ° C. or higher for 1000 hours or more, no significant decrease in luminous efficiency could be confirmed.

First Comparative Example As an organic device of a comparative example, an organic device 112 shown in FIG. In the first embodiment described above, the etching process for exposing the pad electrode 30 was performed in two steps. Specifically, after performing etching for exposing the pad electrode 30 of the insulating layer 202, the sealing layer 300 and the resin layer 400 are formed, and the pad electrode 30 of the sealing layer 300 and the resin layer 400 is exposed. Etching was performed. On the other hand, in this comparative example, all layers of the insulating layer 202, the sealing layer 300, and the resin layer 400 (and the planarization layer 402) were etched by dry etching using the same mask pattern. As a result, the end of the opening of the insulating layer 202 was not covered with the moisture suppression layer 301, and the end of the opening of the insulating layer 202 was exposed. In other steps, the organic device 112 was manufactured using the same steps as those in the first embodiment.

  The moisture resistance test of the organic device 112 of this comparative example was performed with a pressure cooker capable of testing in a high-density steam atmosphere. When the light emission efficiency (cd / A) of the organic device 112 was measured after being left in a high-density water vapor atmosphere at 100 ° C. or higher for 1000 hours or more, the light emission efficiency was reduced by about 20%.

Second Comparative Example An organic device 113 was manufactured using the same process as in the first example described above. 5B, when the sealing layer 300 and the resin layer 400 are etched in the organic device 113, the defect suppression layer 302 that covers the stepped portion S1 of the moisture suppression layer 301 is removed by side etching. It was. For this reason, the side surface of the stepped portion S1 of the moisture suppression layer 301 is exposed.

  The moisture resistance test of the organic device 113 of this comparative example was performed with a pressure cooker capable of testing in a high-density steam atmosphere. When the light emission efficiency (cd / A) of the organic device 113 was measured after being left in a high-density water vapor atmosphere at 100 ° C. or higher for 1000 hours or more, the light emission efficiency was reduced by about 12%.

Third Comparative Example An organic device 114 was manufactured using the same process as in the first example described above. As shown in FIG. 5C, the organic device 114 has a resin layer 400 (and planarization) that covers the stepped portion S2 of the moisture suppression layer 303 by side etching when the sealing layer 300 and the resin layer 400 are etched. Layer 402) was removed. For this reason, the side surface and the bottom of the stepped portion S2 of the moisture suppression layer 303 are exposed.

  The moisture resistance test of the organic device 114 of this comparative example was performed with a pressure cooker capable of testing in a high-density water vapor atmosphere. When the light emission efficiency (cd / A) of the organic device 113 was measured after being left in a high-density water vapor atmosphere at 100 ° C. or higher for 1000 hours or more, the light emission efficiency was reduced by about 5%.

Second Example An organic device 101 shown in FIGS. 6A and 6B was manufactured. In the present embodiment, the organic functional layer 211 includes an organic photoelectric conversion material. Therefore, the organic device 101 functions as an imaging device.

  First, a silicon substrate was prepared as the substrate 201. After the electronic circuit (not shown) and the pad electrode 30 were formed on the substrate 201, the insulating layer 202 was formed on the surface of the substrate 201 on which the electronic circuit (not shown) and the pad electrode 30 using an aluminum alloy were disposed. . In this example, silicon oxide was formed to a thickness of 1.5 μm as the insulating layer 202. Next, using a mask pattern having an opening on the pad electrode 30, the insulating layer 202 in the opening portion of the mask pattern was etched to perform an etching process for exposing the pad electrode 30. First, a mask pattern having a desired opening was formed using a resist coating and exposure / development process, and then the insulating layer 202 was etched by plasma etching using a reactive gas in a dry etching apparatus. After etching the insulating layer 202, the mask pattern was removed with a stripping solution.

  Next, a pixel formation step of forming a plurality of pixels on the insulating layer 202 in the pixel region 10 was performed. First, the lower electrode 210 using titanium nitride was formed on the insulating layer 202. As described above, the lower electrode 210 was connected to the electronic circuit disposed on the substrate 201 side of the insulating layer 202 by the plug electrode provided in the insulating layer 202.

  After forming the lower electrode 210, an organic functional layer 211 containing an organic light emitting material was formed on the lower electrode 210 in the pixel region 10. As a method for forming the organic functional layer 211, a vacuum vapor deposition method using a vapor deposition mask having an opening for desired patterning can be used.

  After the organic functional layer 211 was formed, the upper electrode 212 using indium zinc oxide was formed to a thickness of 30 nm. As a method for forming the upper electrode 212, a sputtering method using a film formation mask having a desired patterning opening can be used.

  On the insulating layer 202, the sealing layer 300 and the resin layer 400 were laminated in this order after the pixel formation step of forming a plurality of pixels. First, the sealing layer 300 was formed so as to cover the entire substrate 201. First, silicon oxynitride with a film thickness of 2000 nm was formed as a moisture suppression layer 301 over the entire surface of the substrate 201 by a CVD method. Next, an aluminum oxide film having a thickness of 50 nm was formed as the defect suppression layer 302 using the ALD method so as to cover the entire surface of the substrate 201 with the moisture suppression layer 301. Further, a silicon oxynitride film having a thickness of 500 nm was formed as the moisture suppression layer 303 by a CVD method so as to cover the entire surface of the substrate 201 with the defect suppression layer 302. Next, a resin having a thickness of 600 nm was applied as a resin layer 400 using a spin coating method so as to cover the moisture suppression layer 303 on the entire surface of the substrate 201, and then baked at a high temperature. As described above, the resin layer 400 also functions as a planarizing layer below the color filter 500.

  Next, a color filter 500 was formed in the pixel region 10. For the red filter 501, the green filter 502, and the blue filter 503, the material application and the exposure / development process were repeated for each color filter.

  After the color filter 500 was formed, the resin layer 400 and the sealing layer 300 on the pad electrode 30 were etched by dry etching to expose the pad electrode 30. By etching the resin layer 400 and the sealing layer 300 in a single etching process, the manufacturing process of the organic device 101 can be simplified and the cost can be reduced. Specifically, first, in orthographic projection onto the surface of the substrate 201, a mask pattern having an opening inside the end portion of the insulating layer 202 opened by the above-described etching process of the insulating layer 202 is applied to resist and exposed. -It formed using the image development process. Next, the resin layer 400 and the sealing layer 300 were etched by plasma etching using a reactive gas with a dry etching apparatus. After the etching of the resin layer 400 and the sealing layer 300, the mask pattern was removed with a stripping solution.

  Through the above steps, the moisture suppression layer 301 was formed so as to cover the end a of the opening of the insulating layer 202 as shown in FIG. Furthermore, the defect suppression layer 302 was formed so as to cover the stepped portion S1 of the moisture suppression layer 301. Furthermore, the resin layer 400 was formed so as to cover the stepped portion S2 of the moisture suppression layer 303. In this embodiment, a resin layer 400 is formed on the pixel region 10 and the stepped portion S2 of the moisture suppression layer 303. This is because the portion of the resin layer 400 is removed together with the mask pattern by dry etching for etching the sealing layer 300 and the resin layer 400. When the moisture suppression layers 301 and 303 using silicon nitride or silicon oxynitride are formed using a CVD method or the like, the film density is low and dense in the stepped portions S1 and S3 where the side surface, the side surface, and the bottom portion intersect. Defects such as lack of properties and voids are likely to occur. For this reason, as shown in FIG. 6B, in the peripheral region 20, the resin layer 400 covers at least the side surface of the stepped portion S <b> 2 of the moisture suppressing layer 303, so that moisture is stepped in the moisture suppressing layer 303. It is possible to suppress entry into the defect suppression layer 302 via the. Since the resin layer 400 covers the side surface of the stepped portion S2 of the moisture suppressing layer 303, the portion where the side surface and the bottom of the stepped portion S2 of the moisture suppressing layer 303 intersect can be covered at the same time. In the structure shown in FIG. 6B as well, the reliability of the organic device 101 can be improved as in the organic device 100 described above. Further, when the organic functional layer 211 of the organic device 101 includes an organic light emitting material, the organic device 101 can function as a light emitting device. In this case, the organic device 101 can be applied to the display devices 1000, 1300, and 1310, the imaging device 1100, the mobile device 1200, the lighting device 1400, the automobile 1500, and the like shown in FIGS.

  After the pad electrode 30 was exposed, a resin was applied to the planarizing layer 402 with a film thickness of 600 nm by a spin coat method, and was patterned into a desired shape. As shown in FIG. 6B, the peripheral region 20 may include a portion where the moisture suppression layer 303 is exposed. Next, a microlens (not shown) for increasing the light collection efficiency was formed on the planarization layer 402. In order to accurately form the shape of the microlens, higher planarization property of the planarization layer 402 is necessary.

The organic device 101 of the present example was able to suppress moisture from entering the organic functional layer 211. Specifically, the organic device 101 of the present invention is an imaging device as described above, and the sensitivity (e ⁻ / lx · s · μm ² ) per unit area when applying a desired voltage was measured. In addition, the moisture resistance test was performed with a pressure cooker capable of testing in a high-density steam atmosphere. When the sensitivity (e ⁻ / lx · s · μm ² ) was measured after being left in a high-density water vapor atmosphere at 100 ° C. or higher for 1000 hours or more, no significant decrease in sensitivity could be confirmed.

Third Example An organic device 118 shown in FIG. 8 was produced. In the present embodiment, the organic functional layer 211 includes an organic photoelectric conversion material. Therefore, the organic device 101 functions as an imaging device.

  First, a silicon substrate was prepared as the substrate 201. After the electronic circuit (not shown) and the pad electrode 30 were formed on the substrate 201, the insulating layer 202 was formed on the surface of the substrate 201 on which the electronic circuit (not shown) and the pad electrode 30 using an aluminum alloy were disposed. . In this example, silicon oxide was formed to a thickness of 1.5 μm as the insulating layer 202.

  Next, a pixel formation step of forming a plurality of pixels on the insulating layer 202 in the pixel region 10 was performed. First, the lower electrode 210 using a single layer or a laminated alloy containing titanium or aluminum was formed on the insulating layer 202. As described above, the lower electrode 210 was connected to the electronic circuit disposed on the substrate 201 side of the insulating layer 202 by the plug electrode provided in the insulating layer 202.

  Next, an insulating layer 801 for reducing current leakage between the electrodes was formed on the surface of the substrate 201 provided with the lower electrode 210 and the insulating layer 202. Next, using a mask pattern having an opening on the pad electrode 30, the insulating layer 202 and the insulating layer 801 in the opening portion of the mask pattern were etched, and an etching process for exposing the pad electrode 30 was performed. First, a mask pattern having a desired opening was formed using a resist coating and exposure / development process, and then the insulating layer 202 was etched by plasma etching using a reactive gas in a dry etching apparatus. After etching the insulating layer 202, the mask pattern was removed with a stripping solution.

  Next, using the mask pattern having an opening on the lower electrode 210, the insulating layer 801 in the opening portion of the mask pattern was etched, and an etching process for exposing the lower electrode 210 was performed. First, a mask pattern having a desired opening is formed using a resist coating and exposure / development process, and then the insulating layer 801 is etched by plasma etching using a reactive gas in a dry etching apparatus. An insulating layer 801 covering the side surface was formed. After the etching for forming the insulating layer 801, the mask pattern was removed with a stripping solution. In order to suppress the generation of the modified layer due to the stripping solution on the surface of the lower electrode 210, the insulating layer 202 on the pad electrode 30 and the insulating layer 801 are etched on the lower electrode 210 as shown in this embodiment. The insulating layer 801 may be etched.

  After the insulating layer 801 on the lower electrode 210 was etched, an organic functional layer 211 containing an organic light emitting material was formed on the lower electrode 210 in the pixel region 10. As a method for forming the organic functional layer 211, a vacuum vapor deposition method using a vapor deposition mask having an opening for desired patterning can be used. Through this step, a plurality of lower electrodes 210 are disposed between the insulating layer 202 and the organic functional layer 211.

  After forming the organic functional layer 211, the upper electrode 212 using silver and magnesium was formed with a film thickness of 30 nm. As a method for forming the upper electrode 212, a sputtering method using a film formation mask having a desired patterning opening can be used.

  On the insulating layer 202, the sealing layer 300 and the resin layer 400 were laminated in this order after the pixel formation step of forming a plurality of pixels. First, the sealing layer 300 was formed so as to cover the entire substrate 201. First, silicon oxynitride with a film thickness of 2000 nm was formed as a moisture suppression layer 301 over the entire surface of the substrate 201 by a CVD method. Next, an aluminum oxide film having a thickness of 50 nm was formed as the defect suppression layer 302 using the ALD method so as to cover the entire surface of the substrate 201 with the moisture suppression layer 301. Further, a silicon oxynitride film having a thickness of 500 nm was formed as the moisture suppression layer 303 by a CVD method so as to cover the entire surface of the substrate 201 with the defect suppression layer 302. Next, a resin having a thickness of 600 nm was applied as a resin layer 400 using a spin coating method so as to cover the moisture suppression layer 303 on the entire surface of the substrate 201, and then baked at a high temperature. As described above, the resin layer 400 also functions as a planarizing layer below the color filter 500.

  Next, a color filter 500 was formed in the pixel region 10. For the red filter 501, the green filter 502, and the blue filter 503, the material application and the exposure / development process were repeated for each color filter.

  After the color filter 500 was formed, the resin layer 400 and the sealing layer 300 on the pad electrode 30 were etched by dry etching to expose the pad electrode 30. By etching the resin layer 400 and the sealing layer 300 in a single etching process, the manufacturing process of the organic device 101 can be simplified and the cost can be reduced. Specifically, first, in orthographic projection onto the surface of the substrate 201, a mask pattern having an opening inside the end portion of the insulating layer 202 opened by the above-described etching process of the insulating layer 202 is applied to resist and exposed. -It formed using the image development process. Next, the resin layer 400 and the sealing layer 300 were etched by plasma etching using a reactive gas with a dry etching apparatus. After the etching of the resin layer 400 and the sealing layer 300, the mask pattern was removed with a stripping solution.

  Through the above steps, the moisture suppression layer 301 was formed so as to cover the end a of the opening of the insulating layer 202 as shown in FIG. Furthermore, the defect suppression layer 302 was formed so as to cover the stepped portion S1 of the moisture suppression layer 301. Furthermore, the resin layer 400 was formed so as to cover the stepped portion S2 of the moisture suppression layer 303. The organic device 118 according to the present embodiment has a structure in which an insulating layer 801 that covers the side surface of each lower electrode 210 is added to the above-described organic device 101 in order to suppress a leakage current between the lower electrodes 210. . For this reason, the process after forming the resin layer 400 may be the same as that of the above-mentioned 2nd Example, and abbreviate | omits description here.

  The organic device 118 of the present example was able to suppress moisture from entering the organic functional layer 211. In addition, a moisture resistance test similar to that of the organic device 101 described above was performed, but no significant reduction in sensitivity could be confirmed. That is, also in the structure shown in FIG. 8, the reliability of the organic device 118 can be improved as in the organic device 101 described above. In addition, when the organic functional layer 211 of the organic device 118 includes an organic light emitting material, the organic device 118 can function as a light emitting device. In this case, the organic device 118 can be applied to the display devices 1000, 1300, and 1310, the imaging device 1100, the portable device 1200, the lighting device 1400, the automobile 1500, and the like shown in FIGS.

Fourth Comparative Example An organic device 115 shown in FIG. 7A was manufactured as an organic device of a comparative example. In the second embodiment described above, the etching process for exposing the pad electrode 30 was performed in two steps. Specifically, after performing etching for exposing the pad electrode 30 of the insulating layer 202, the sealing layer 300 and the resin layer 400 are formed, and the pad electrode 30 of the sealing layer 300 and the resin layer 400 is exposed. Etching was performed. On the other hand, in this comparative example, all of the insulating layer 202, the sealing layer 300, and the resin layer 400 were etched by dry etching using the same mask pattern. As a result, the end of the opening of the insulating layer 202 was not covered with the moisture suppression layer 301, and the end of the opening of the insulating layer 202 was exposed. In other steps, the organic device 115 was manufactured using the same steps as those in the first embodiment.

The moisture resistance test of the organic device 115 of this comparative example was performed with a pressure cooker capable of testing in a high-density steam atmosphere. When the sensitivity (e ⁻ / lx · s · μm ² ) of the organic device 115 was measured after being left in a high-density water vapor atmosphere at 100 ° C. or higher for 1000 hours or more, the sensitivity was reduced by about 22%.

Fifth Comparative Example An organic device 116 was manufactured using the same process as in the second example described above. As shown in FIG. 7B, in the organic device 116, when the sealing layer 300 and the resin layer 400 are etched, the defect suppression layer 302 covering the stepped portion S1 of the moisture suppression layer 301 is removed by side etching. It was. For this reason, the side surface of the stepped portion S1 of the moisture suppression layer 301 is exposed.

The moisture resistance test of the organic device 116 of this comparative example was performed with a pressure cooker capable of testing in a high-density water vapor atmosphere. When the sensitivity (e ⁻ / lx · s · μm ² ) of the organic device 116 was measured after being left in a high-density water vapor atmosphere at 100 ° C. or higher for 1000 hours or more, the sensitivity was reduced by about 16%.

Sixth Comparative Example An organic device 117 was manufactured using the same steps as those in the second example. In the organic device 117, as illustrated in FIG. 7C, when the sealing layer 300 and the resin layer 400 are etched, the resin layer 400 covering the stepped portion S2 of the moisture suppression layer 303 is removed by side etching. . For this reason, the side surface and the bottom of the stepped portion S2 of the moisture suppression layer 303 are exposed.

The moisture resistance test of the organic device 117 of this comparative example was performed with a pressure cooker capable of testing in a high-density water vapor atmosphere. When the sensitivity (e ⁻ / lx · s · μm ² ) of the organic device 117 was measured after being left in a high-density water vapor atmosphere at 100 ° C. or higher for 1000 hours or more, the sensitivity decreased by about 7%.

  As described above, in the organic device 100 of the first example, the emission efficiency did not decrease as compared with the organic devices 112 to 114 of the first to third comparative examples. In addition, the organic devices 101 and 118 of the second and third examples did not decrease in sensitivity as compared with the organic devices 115 to 117 of the fourth to sixth comparative examples. Thus, the reliability of the organic device can be improved by using the structure shown in this embodiment.

  As mentioned above, although embodiment and the Example which concern on this invention were shown, it cannot be overemphasized that this invention is not limited to these Embodiment and Example, In the range which does not deviate from the summary of this invention, embodiment mentioned above Can be changed or combined as appropriate.

10: Pixel region, 20: Peripheral region, 30: Pad electrode, 100, 101, 118: Organic device, 201: Substrate, 211: Organic functional layer, 300: Sealing layer, 400: Resin layer, 1000: Display device 1001: upper cover, 1002: flexible printed circuit, 1003: touch panel, 1004: flexible printed circuit, 1005: display panel, 1006: frame, 1007: circuit board, 1008: battery, 1009: lower cover, 1100: imaging device, 1101 : Viewfinder, 1102: Rear display, 1103: Operation unit, 1104: Case, 1200: Portable device, 1201: Display unit, 1202: Operation unit, 1203: Case, 1300: Display device, 1301: Frame, 1302: Display unit: 1303: Base, 1310: Display device 1311: First display unit, 1312: Second display unit, 1313: Housing, 1314: Bending point, 1400: Lighting device, 1401: Housing, 1402: Light source, 1403: Circuit board, 1404: Optical film, 1405 : Light diffusing section, 1500: automobile, 1501: tail lamp, 1502: window, 1503: vehicle body

Claims (22)

An organic device including a pixel region in which a plurality of pixels including an organic functional layer are disposed on a surface of a substrate, and a peripheral region including a pad electrode,
In the organic device, the first layer, the sealing layer, and the resin layer are laminated in this order from the surface side,
In the pixel region, the organic functional layer is disposed between the first layer and the sealing layer,
In the peripheral region, the first layer, the sealing layer, and the resin layer each include an opening for exposing the pad electrode,
The sealing layer includes, from the surface side, a second layer and a third layer having a moisture permeability lower than that of the first layer, and between the second layer and the third layer. And a fourth layer having a defect density lower than that of the second layer,
An end of the opening of the first layer is covered by the second layer, the fourth layer, and the third layer;
The step portion of the second layer resulting from the end of the opening of the first layer is covered by the fourth layer;
An organic device, wherein a step portion of the third layer caused by an end portion of the opening of the first layer is covered with the resin layer. An organic device including a pixel region in which a plurality of pixels including an organic functional layer are disposed on a surface of a substrate, and a peripheral region including a pad electrode,
In the organic device, a first layer containing a compound containing at least oxygen and silicon, a sealing layer, and a resin layer are laminated in this order from the surface side.
In the pixel region, the organic functional layer is disposed between the first layer and the sealing layer,
In the peripheral region, the first layer, the sealing layer, and the resin layer each include an opening for exposing the pad electrode,
The sealing layer is arranged between the second layer and the third layer containing a compound containing at least nitrogen and silicon, and between the second layer and the third layer from the surface side, A fourth layer comprising a compound comprising at least oxygen and aluminum,
An end of the opening of the first layer is covered by the second layer, the fourth layer, and the third layer;
The step portion of the second layer resulting from the end of the opening of the first layer is covered by the fourth layer;
An organic device, wherein a step portion of the third layer caused by an end portion of the opening of the first layer is covered with the resin layer. In orthographic projection to the surface,
An end of the opening of the resin layer is disposed at a position closer to the center of the pad electrode exposed than an end of the opening of the first layer,
The end of the opening of the third layer is at the same position as the end of the opening of the resin layer, or at a position closer to the center of the pad electrode exposed than the end of the opening of the resin layer. Arranged,
The end of the opening of the fourth layer is at the same position as the end of the opening of the third layer, or the center of the pad electrode exposed from the end of the opening of the third layer Placed near the
The end of the opening of the second layer is at the same position as the end of the opening of the fourth layer, or the center of the pad electrode exposed from the end of the opening of the fourth layer The organic device according to claim 1, wherein the organic device is disposed at a position close to.   4. The organic device according to claim 1, wherein a thickness of the first layer is 0.5 μm or more and 5.0 μm or less.   The organic device according to any one of claims 1 to 4, wherein the first layer includes a silicon oxide-based material.   The organic device according to claim 1, wherein the second layer includes a silicon nitride-based material.   The organic device according to claim 1, wherein the third layer includes a silicon nitride-based material.   The organic device according to any one of claims 1 to 6, wherein the fourth layer includes an aluminum oxide-based material. 9. The organic material according to claim 1, wherein moisture permeability of the second layer and the third layer is 1 × 10 ⁻⁵ g / m ² · day or less. device.   The thickness of the portion of the fourth layer that covers the side surface of the step portion of the second layer is 95% or more and 105% or less of the thickness of the portion of the fourth layer that covers the pixel region. The organic device according to any one of claims 1 to 9, wherein the organic device is provided.   11. The device according to claim 1, wherein in the peripheral region, the resin layer includes at least a side surface of the step portion of the third layer and the third layer is exposed. The organic device according to item.   The organic device according to claim 1, further comprising a color filter disposed on the resin layer in the pixel region.   The organic device according to claim 1, wherein the organic functional layer contains an organic light emitting material.   The organic functional layer according to claim 1, wherein the organic functional layer includes an organic photoelectric conversion material. A plurality of lower electrodes are disposed between the first layer and the organic functional layer,
The organic device according to any one of claims 1 to 14, wherein each side surface of the plurality of lower electrodes is covered with an insulating layer.   A display device comprising: the organic device according to claim 1; and an active element connected to the organic device. An optical unit having a plurality of lenses, an image sensor that receives light that has passed through the optical unit, and a display unit that displays an image,
The image display apparatus according to claim 1, wherein the display unit is a display unit that displays an image captured by the image sensor, and includes the organic device according to claim 1. A lighting device having a light source and at least one of a light diffusion portion and an optical film,
The said light source has an organic device of any one of Claims 1 thru | or 15, The illuminating device characterized by the above-mentioned. A fuselage and a lamp provided in the fuselage,
The said lamp has the organic device of any one of Claims 1 thru | or 15, The moving body characterized by the above-mentioned. A method of manufacturing an organic device, comprising: a pixel region in which a plurality of pixels including an organic functional layer are disposed on a surface of a substrate; and a peripheral region including a pad electrode,
Forming a first layer on the surface of the substrate on which the pad electrode is disposed;
Etching the first layer using a mask pattern having an opening on the pad electrode to expose the pad electrode;
Forming a plurality of pixels on the first layer in the pixel region; and
After the pixel formation step, a step of laminating a sealing layer and a resin layer in this order;
In the orthogonal projection on the surface, the pad layer is formed by etching the sealing layer and the resin layer using a mask pattern having an opening inside the end portion opened by the etching process in the first layer. Exposing, and
The sealing layer is formed between the second layer and the third layer having a moisture permeability lower than that of the first layer, and between the second layer and the third layer from the surface side. And a fourth layer having a defect density lower than that of the second layer,
In the portion where the pad electrode is exposed, an end of the opening of the first layer is covered with the second layer, the fourth layer, and the third layer,
The step portion of the second layer resulting from the end of the opening of the first layer is covered by the fourth layer;
The method of manufacturing, wherein the step portion of the third layer caused by the end of the opening of the first layer is covered with the resin layer.   21. The manufacturing method according to claim 20, wherein the fourth layer is formed by an atomic layer deposition method.   The manufacturing method according to claim 20 or 21, wherein the first layer is formed by a chemical vapor deposition method using tetraethoxysilane.

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