JP2006049874A - Function element and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a function element with a sufficient photoelectric conversion characteristic and emission efficiency and to provide a manufacturing method for the element. <P>SOLUTION: The function element has a first electrode film 214, second electrode films 205 and 206, which are confronted with the first electrode film 214, function films 207, 208, 209 and 210 arranged between the first electrode film 214 and the second electrode films 205 and 206, and wiring 218 giving potential to the first electrode film 214 and the second electrode films 205 and 206 on a substrate 213. The element is also provided with a first insulating film 204 formed on the second electrode film 205 so that it covers a side wall of a function layer and a contact hole which is formed in the first insulating film 204 so that it penetrates to the second electrode films and in inside of which wiring 218 for second electrode film connection is installed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a functional element in which a photoelectric conversion film and a light emitting film are laminated on a substrate, and a method for manufacturing the functional element.

Devices using organic materials have made remarkable progress in recent years, with organic light-emitting devices as a representative, and organic EL displays, which are representative examples of organic light-emitting devices, have been successfully manufactured. Moreover, although the photoelectric conversion element using an organic semiconductor has not been successfully manufactured, it has made remarkable progress in recent years, and has the potential to overcome the problems of the conventional imaging element described below. In a conventional CCD solid-state image sensor or CMOS solid-state image sensor, a large number of photoelectric conversion elements (photodiodes) serving as light receiving portions and photoelectric conversion signals obtained by the respective photoelectric conversion elements are externally provided on the surface of a semiconductor substrate. A signal reading circuit for reading is formed. The signal readout circuit includes a charge transfer circuit and a transfer electrode in the case of the CCD type, and a MOS transistor circuit and a signal wiring in the case of the CMOS type.
Therefore, the conventional solid-state imaging device has a problem that a large number of light receiving portions and signal readout circuits must be formed on the surface of the same semiconductor substrate, and the area of the light receiving portions cannot be increased. If the area of the light receiving part cannot be increased, the light utilization efficiency will be greatly reduced. Therefore, in conventional solid-state image sensors, the light utilization efficiency is improved by concentrating light on the light receiving part by installing a microlens or inner lens above. Has compensated for the decline. However, problems such as an increase in optical reflection or the like are unavoidable, and it is said that there will be a loss of light amount of several tens of percent with the current image sensor. In addition, while miniaturization required for solid-state image sensors becomes more and more severe year by year, as the size of the light-receiving part advances, the difference in the light collection angle due to the difference in the light incident angle between the peripheral part and the central part of the image sensor. And shading occurs.

Therefore, for example, the structure of the solid-state imaging device described in Patent Document 1 below has been reviewed. In this solid-state imaging device, photosensitive layers are stacked on a semiconductor substrate having a signal readout circuit formed on the surface thereof, and these photosensitive layers serve as a light receiving portion, and photoelectric conversion signals obtained in the respective photosensitive layers are converted into signal readout circuits. Thus, a structure of taking out the light, that is, a photoelectric conversion film laminated type structure is obtained.
By adopting such a structure, it is possible to make the opening of the light receiving part large, and it is possible to solve the problem mentioned above, and in recent years, it is described in the following Patent Documents 2, 3, 4, and 5. Photoelectric conversion film laminated solid-state imaging devices have been proposed. The use of an element using an organic material for the photoelectric conversion film having such a structure is very desirable from the following viewpoints. By changing the structure of the compound of the organic material, the spectral wavelength can be adjusted relatively easily, and the photoelectric conversion element using the organic semiconductor can be realized with a thickness of the order of 100 nm. Even when laminated, the total film thickness can be reduced.
JP 58-103165 A Japanese Patent Laid-Open No. 2002-83946 Special Table 2002-502120 Special table 2003-502847 Japanese Patent No. 3405099

  However, in order to achieve further improvement of the functional element including an organic material or the like, it is necessary to finely process the electrode on the organic semiconductor film. However, when such fine processing is performed using a conventional method, the functional element The problem was that the performance of the camera deteriorated significantly.

As described above, the functional device manufactured based on the conventional method has a problem that the device characteristics are remarkably deteriorated.
The present invention has been made in view of the above situation, and an object thereof is to provide a functional element having good performance and a method for manufacturing the functional element.

The above object is achieved by the following configuration.
(1) On a substrate, a first electrode film, a second electrode film facing the first electrode film, a functional film disposed between the first electrode film and the second electrode film, A functional element having a wiring for applying a potential to one electrode film or the second electrode film, the first insulating film formed on the second electrode film so as to cover a side wall of the functional layer, and A contact hole formed in the first insulating film so as to penetrate to the second electrode film, and the wiring for connecting the second electrode film extending therein.

  According to this functional element, the first insulating film protects the sidewall of the functional film in the photolithography process when patterning the functional film, so that when the resist is patterned, the functional film is treated with a treatment liquid such as pure water. Can be protected from. In addition, when a resist for selectively removing a part of the first insulating film is patterned in the photolithography process for forming the contact hole, the functional film is not affected by the treatment liquid due to the resist formation. Thereby, it can prevent that the element performance of a functional film deteriorates within a manufacturing process.

(2) The functional element according to (1), wherein a second insulating film is interposed between the second electrode and the first insulating film.

  According to this functional element, when patterning a resist for selectively removing a part of the first insulating film in a photolithography process for forming a contact hole for connecting a wiring to the second electrode film, The second insulating film functions as a protective film for the functional film. Thereby, the element performance deterioration of the functional film at the time of element manufacture can be prevented.

(3) The functional element according to (2), wherein the contact hole is formed so as to penetrate the first insulating film and the second insulating film.

  According to this functional element, when the contact hole is formed by removing the first insulating layer and the second insulating layer by selective etching, the second insulating film is the functional layer while the first insulating layer is being removed. Therefore, the functional layer is not affected by the etching process. Therefore, the first insulating layer can be removed by wet etching, and the manufacturing process can be simplified.

(4) The multilayer structure including the first electrode film, the functional film, and the second electrode film is provided in a plurality of stages on the substrate, (1) to (3), Functional elements.

  According to this functional element, the functional film is always protected when forming each layer even in a configuration having a multi-layered structure. Also, deterioration of element performance is prevented.

(5) The functional element according to any one of (1) to (4), wherein a water permeability of the insulating film covering the functional film is 10 g / m ² · day or less.

  According to this functional element, pure water is used in the photolithography process for washing and the like, but by setting such conditions, the pure water reaches the photoelectric conversion film and degrades the element. Can be surely prevented.

(6) The functional element according to any one of (1) to (5), wherein the functional film includes an organic material.

  According to this functional element, even if the functional film is an organic material that is particularly susceptible to damage due to processing such as resist formation, it is possible to reliably prevent deterioration of element characteristics.

(7) The functional film includes at least a hole transporting organic material and an electron transporting organic material, and the functional film includes, from the substrate side, the first electrode, the hole transporting organic material, the electron transporting organic material, The functional device according to (6), wherein the functional elements are stacked in the order of the second electrode.

  According to this functional element, the photoelectric conversion film is laminated in the order of the first electrode, the hole transporting organic material, the electron transporting organic material, and the second electrode from the substrate side, thereby improving the performance of the functional film. be able to.

(8) The functional element according to any one of (1) to (7), wherein a length of a minimum side of the wiring extending from the contact hole is 1 mm or less.

  According to this functional element, it is possible to prevent the performance of the functional film from being deteriorated even when fine processing is performed in which the length of the minimum side of the wiring is 1 mm or less.

(9) The function according to any one of (1) to (8), wherein the second electrode includes at least one material of ITO, IZO, SnO ₂ , ATO, ZnO, TiO ₂ , and FTO. element.

According to this functional element, the use of at least one material of ITO, IZO, SnO ₂ , ATO, ZnO, TiO ₂ , or FTO as the second electrode makes it possible to further improve the element characteristics.

(10) The wiring includes at least one material of Al, Pt, W, Au, Ag, Ta, Cu, Cr, Mo, Ti, Ni, Pd, and Zn (1) to (9) The functional element according to any one of the above.

  According to this functional element, by using at least one material of Al, Pt, W, Au, Ag, Ta, Cu, Cr, Mo, Ti, Ni, Pd, and Zn as a wiring material, the element characteristics are adversely affected. Good electrical conductivity can be obtained without affecting

(11) The functional element according to any one of (1) to (10), wherein the functional element is a photoelectric conversion film stacked solid-state imaging element.

  According to this functional element, the performance of the photoelectric conversion stacked solid-state imaging device can be improved.

(12) The functional element according to any one of (1) to (10), wherein the functional element is an organic light emitting element.

  According to this functional element, the performance of the organic light emitting element can be improved.

(13) One of the functional films has a pixel arrangement in which one pixel is formed, and the contact hole in which the wiring is extended is formed in each pixel (11) or (12) ) Described functional element.

  According to this functional element, as the wiring is smaller, the area of the functional layer can be increased and the element performance can be improved.

(14) The functional element according to any one of (11) to (13), wherein the contact hole exists in each pixel portion and has a size of 5 μm or less.

  According to this functional element, the contact hole can be formed in the pixel portion with a size of 5 μm or less.

(15) A function comprising a first electrode film, a second electrode film facing the first electrode film, and an organic semiconductor layer disposed between the first electrode film and the second electrode film on the substrate. And a wiring for applying a potential to the first electrode film or the second electrode film, wherein the second electrode film is patterned on the second electrode film. A step of forming a resist pattern by photolithography in a state of being covered with the two insulating films, patterning the second insulating film using the resist pattern as a mask, and then patterning the second electrode film using the second insulating film as a mask The manufacturing method of the functional element containing a process.

  According to this method of manufacturing a functional element, the second insulating film is formed on the second electrode film, and thus functions through the second electrode film in the water washing step when forming the resist pattern when patterning the second electrode film. It is possible to prevent moisture from penetrating the membrane and causing deterioration. In addition, damage can be prevented even during the etching process.

(16) After the patterning step of the second electrode film, a step of forming a first insulating film so as to cover the second electrode film and a side wall of the functional film, and a step of forming a resist pattern by photolithography Forming a contact hole so as to penetrate the first insulating film and the second insulating film using the resist pattern as a mask, and forming the wiring so as to contact the second electrode film exposed in the contact hole (15) The manufacturing method of the functional element as described in the above.

  According to this method of manufacturing a functional element, the first insulating film covers the entire surface of the functional film when the resist pattern is formed on the first insulating film and the resist is removed by etching. Even so, the resist can be removed using a stripping solution. Further, when the first insulating film is removed with the resist, the functional film is not deteriorated through the second electrode film because the second insulating film is laid under the first insulating film.

(17) The method for producing a functional element according to (15) or (16), wherein the patterning step of the electrode film includes a step of dry etching in a state where the substrate is maintained at 150 ° C. or lower.

  According to this method of manufacturing a functional element, since the substrate is maintained at 150 ° C. or lower, generation of a substance that degrades element characteristics or a functional film due to a reaction with a functional film in the lower layer when the electrode film is patterned It is possible to achieve dry etching with high reliability without being caused to cause a reaction with.

(18) The method for manufacturing a functional element according to (17), wherein the second electrode film has a transmittance at a wavelength of 400 nm to 700 nm of 60% or more.

  According to this method for producing a functional element, when the second electrode film corresponds to the upper electrode of the photoelectric conversion element, the substrate temperature is likely to increase due to the translucency of the upper electrode. Since it can be considered to be able to suppress, it is possible to prevent deterioration of element characteristics.

(19) The method for manufacturing a functional element according to (17), including a step of processing with reducing plasma prior to the dry etching step.

  According to this method for manufacturing a functional element, when the second electrode film is a metal, it becomes a metal-rich film by reducing plasma such as hydrogen plasma, and can be easily etched by inert gas plasma. Etching can be easily performed at a low temperature.

(20) The method for manufacturing a functional element according to (19), wherein the dry etching step includes a treatment step using argon plasma.

  According to this functional element manufacturing method, the metal-rich film can be easily removed by argon plasma without increasing the substrate temperature. Therefore, the functional film is not deteriorated.

  According to the present invention, deterioration of element performance can be suppressed even when fine processing is performed, and a functional element having good characteristics can be obtained.

The present invention provides on a substrate, a first electrode film, a second electrode film facing the first electrode film, a functional film disposed between the first electrode film and the second electrode film, A wiring that applies a potential to the first electrode film or the second electrode film, and a first insulating film formed on the second electrode film so as to cover a side wall of the functional layer; And a contact hole formed in the first insulating film so as to penetrate to the second electrode film, and the wiring for connecting the second electrode film extending therein.
Preferable examples of the functional film include a photoelectric conversion film and a light emitting film. In general, these functional elements have a configuration in which a wiring conducting to the bonding PAD is connected to each of the two electrode films in order to apply a potential to the two electrode films sandwiching the functional film. By adopting the above configuration, the present invention can perform micro processing on the micron order and sub micron order without deteriorating the characteristics of the functional film, and obtain good photoelectric conversion characteristics with this fine wiring structure. Is possible.

  As a functional element having such a feature, for example, a photoelectric conversion film stacked solid-state imaging element and a light emitting element can be given as examples. Hereinafter, the configuration and the manufacturing method thereof will be sequentially described. First, the photoelectric conversion film laminated solid-state imaging device will be described.

(First embodiment)
As a photoelectric conversion film stack type solid-state imaging device, three photoelectric conversion films sandwiched between two electrode films are stacked on a silicon substrate, and color imaging is possible by detecting three colors of light on the silicon substrate. A first photoelectric conversion film sandwiched between two electrode films is stacked on a silicon substrate, and two pn junctions are formed at different depths in the silicon substrate. Various configurations such as the second configuration as shown in FIG. 5 of Japanese Patent Laid-Open No. 2003-332551 that detects two colors of light and enables color imaging by detecting one color of light on a silicon substrate In this embodiment, the second configuration will be described as an example.

FIG. 1 is a schematic cross-sectional view of a photoelectric conversion film stacked solid-state imaging device for explaining the first embodiment of the present invention. In FIG. 1, a cross section for two pixels in a pixel portion, which is a portion that detects light and accumulates charges, wiring connected to an electrode in the pixel portion, bonding PAD connected to the wiring, and the like are formed. The cross section with the peripheral circuit part which is a part to be performed is also shown.
In this example, since the signal reading substrate itself also has photoelectric conversion capability, the description will be made in the form of stacked photoelectric conversion films. A silicon single crystal substrate 213 serves as an electromagnetic wave absorption / photoelectric conversion site for B light and R light and a charge storage / transfer / reading site for charges generated by photoelectric conversion. Usually, a p-type silicon substrate is used.

  In the p-type silicon substrate 213 of the pixel portion, an n-type impurity region 223, a p-type impurity region 222, and an n-type impurity region 221 are formed in order from the surface portion, and further on a part of the surface portion of the n-type impurity region 223. The p-type impurity region 224 is formed.

  The n-type impurity region 221 is an accumulation unit that accumulates red (R) component signal charges photoelectrically converted by a pn junction with the p-type silicon substrate 213. The change in the potential of the n-type impurity region 221 due to the accumulation of the R component signal charge occurs from the MOS transistor 226A formed on the surface of the p-type silicon substrate 213 through the metal wiring 219 connected to the MOS transistor 226A. The signal is read out to the signal readout PAD 227.

  The n-type impurity region 223 is an accumulation unit that accumulates a blue (B) component signal charge photoelectrically converted by a pn junction with the p-type impurity region 222. The potential change in the n-type impurity region 223 due to the accumulation of the B component signal charge occurs from the MOS transistor 226B formed on the surface of the p-type silicon substrate 213 through the metal wiring 219 connected to the MOS transistor 226B. The signal is read out to the signal readout PAD 227.

  In the p-type impurity region 224, a charge storage region 225 made of an n-type impurity region for storing a green (G) component signal charge generated in the photoelectric conversion film stacked above the p-type silicon substrate 213 is formed. Yes. The potential change in the charge storage region 225 due to the accumulation of the G component signal charge is caused by the MOS transistor 226C formed on the surface of the p-type silicon substrate 213 through the metal wiring 219 connected to the MOS transistor 226C. It is read out to the signal readout PAD 227. The signal readout PAD 227 is preferably provided separately for each transistor from which each color component is read out.

  Here, the p-type impurity region, the n-type impurity region, the transistor, the metal wiring, and the like are schematically shown. However, the structure of each is not limited to this, and an optimal one is appropriately selected. Since the B light and R light are separated according to the depth of the silicon substrate, it is important to select the depth from the surface of the silicon substrate such as a pn junction and the doping concentration of each impurity. As a CMOS circuit serving as a signal readout circuit of the photoelectric conversion film stacked solid-state imaging device, all of the preferable techniques used in ordinary CMOS image sensors can be used. A circuit configuration that reduces the number of transistors in the pixel portion, such as a low-noise readout column amplifier and a CDS circuit, can be naturally applied.

  In FIG. 1, the charge accumulation region 225 and the photodiode for detecting the R light and the B light are in a position where they overlap each other in plan view, but the present invention is not limited to this. For example, the charge storage region 225 and the photodiode that detects R light and B light may be formed at positions that do not overlap in plan view.

  A transparent insulating film 212 mainly composed of silicon oxide, silicon nitride or the like is formed on the p-type silicon substrate 213, and a transparent insulating film mainly composed of silicon oxide, silicon nitride or the like is formed on the insulating film 212. 211 is formed. The thickness of the insulating film 212 is preferably as small as possible, and is 5 μm or less, preferably 3 μm or less, more preferably 2 μm or less, and further preferably 1 μm or less.

  A plug 215 that electrically connects the photoelectric conversion film and the charge storage region 225 is formed in the insulating films 211 and 212. The plug 215 is relayed between the insulating film 211 and the insulating film 212 by a pad 216A. It is connected. For example, the plug 215 is preferably composed mainly of tungsten, and the pad 216A is preferably composed mainly of aluminum. In the insulating film 212, the metal wiring 219 and the gate electrodes of the transistors 226A, 226B, and 226C are formed. It is preferable that a barrier layer including a metal wiring is provided. The plug 215 is provided for each pixel.

  A light shielding film 217 is provided in the insulating film 211 in order to prevent noise during photoelectric conversion due to a pn junction between the p-type impurity region 224 and the n-type impurity region 225. As the light shielding film 217, a film mainly composed of tungsten, aluminum, or the like is usually used. In the insulating film 211, a bonding PAD 220 (PAD for supplying power from outside) and a signal readout PAD 227 are formed, and a metal for electrically connecting the bonding PAD 220 and a pixel electrode film 214 described later. Wiring (not shown) is also formed.

  A pad 216B is formed on the plug 215 of each pixel in the insulating film 211, and a pixel electrode film 214 which is a transparent first electrode film is formed on the pad 216B. The pad 216B is for improving the electrical connection between the plug 215 and the pixel electrode film 214, and aluminum, molybdenum, or the like is used. The pixel electrode film 214 is separated for each pixel, and the light receiving area is determined by this size. A bias is applied to the pixel electrode film 214 through the wiring from the bonding PAD 220. A structure in which electrons can be stored in the charge storage region 225 by applying a positive bias to the pixel electrode film 214 with respect to a counter electrode film described later is preferable.

  In order to realize this structure, a hole blocking layer 210, an n-type semiconductor layer 209, a p-type semiconductor layer 208, and an electron blocking layer 207 are stacked in this order on the pixel electrode film 214, and these layers emit G light. A photoelectric conversion film that detects and generates a signal charge corresponding to the detected signal is formed. The thickness of the photoelectric conversion film (207, 208, 209, 210) is preferably 0.5 μm or less, more preferably 0.3 μm or less, and particularly preferably 0.2 μm or less.

  A counter electrode film which is a transparent second electrode film is formed on the photoelectric conversion film. The counter electrode film has a two-layer structure in which the transparent electrode films 206 and 205 are laminated in this order, but may have a one-layer structure. Since the counter electrode film can be used in common for each pixel, it does not have to be separated for each pixel. Each thickness of the counter electrode film and the pixel electrode film 214 is preferably 0.2 μm or less.

  A protective film (first insulating film) 204 mainly composed of silicon nitride or the like having a function of protecting the photoelectric conversion film is formed on the counter electrode film. The protective film 204 is formed so as to cover the side wall of the photoelectric conversion film. An opening is formed in the transparent electrode film 205 and the protective film 204 at a position that does not overlap with the pixel electrode film 214 of the pixel portion, and an opening is formed in a part on the bonding PAD 220 in the insulating film 211 and the protective film 204. Yes. A wiring 218 made of aluminum or the like for electrically connecting the transparent electrode film 206 exposed by the two openings and the bonding PAD 220 and applying a potential to the counter electrode film is formed inside the opening and on the protective film 204. Is formed.

  A barrier metal 228 mainly composed of tungsten or the like is formed between the transparent electrode film 206 and the wiring 218. The barrier metal 228 can improve driving durability characteristics.

  A protective film 203 containing silicon nitride or the like as a main component for protecting the wiring 218 is formed over the wiring 218. Further, an infrared cut dielectric multilayer film 202 is formed on the protective film 203, and an antireflection film 201 is formed on the infrared cut dielectric multilayer film 202.

  The protective film 204 facilitates the manufacturing process of the layer containing an organic material. Although details will be described later, in particular, this layer can reduce damage to the photoelectric conversion film during the formation of the resist pattern during the formation of the connection electrode 218 and the like and during the etching. In addition, in order to avoid resist pattern creation, etching, etc., it is possible to manufacture with a mask. However, it is preferable to suppress the damage to the layer containing the organic material (photoelectric conversion film) by the structure in which the protective film 204 is formed. Can be processed in the micron order and the submicron order, which cannot be achieved by the mask method.

  With the above configuration, it is possible to perform color imaging by detecting light of BGR three colors with one pixel. In the configuration of FIG. 1, R and B are used as common values in two pixels, and only the G value is used separately. In other words, G is arranged so that the resolution of G is twice that of R and B. With such a configuration, the resolution of a high-sensitivity G signal that is particularly important when generating an image can be increased, and a good color image can be generated.

  Note that the pixel electrode film 214 need not have a single structure. A laminated structure of two or more layers made of different materials may be used. Even in the case of such a structure of two or more layers, the first electrode film will be collectively referred to.

  After laminating the photoelectric conversion layer on the first electrode film, the second electrode films 205 and 206 are further formed thereon. What are the basic materials for the first electrode film and the second electrode film? It doesn't matter. For example, a metal, an alloy, a metal oxide, an organic conductive compound, a mixture thereof, and the like are preferably exemplified. Specific examples include, for example, “Li, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Fr, Ra, Sc, Ti, Y, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Se, Te, Po, Br, I, At, B, C, Any combination selected from “N, F, O, S, N” may be used, but particularly preferred are Al, Pt, W, Au, Ag, Ta, Cu, Cr, Mo, Ti, Ni, Pd. , Zn. Any combination selected from Zn. The material for the wiring 218 and the bonding PAD 220 can be the same as the material for the first electrode film and the second electrode film.

Moreover, it is very preferable to use transparent materials as the first electrode film and the second electrode film. As specific materials, using conductive metal oxides such as tin oxide, zinc oxide, indium oxide, indium zinc oxide (IZO) and indium tin oxide (ITO), and metals such as gold, platinum, silver, chromium and nickel. Thin translucent electrodes prepared, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, organic materials such as polyaniline, polythiophene and polypyrrole Examples thereof include conductive materials and laminates of these and ITO. Also described in detail by Yutaka Sawada, "New development of transparent conductive film" (published by CMC, 1999), Japan Society for the Promotion of Science "Transparent conductive film technology" (Ohm, 1999), etc. May be used. Particularly preferable in the present invention is that the first electrode film and the second electrode film each include at least one of ITO, IZO, SnO ₂ , ATO, ZnO, TiO ₂ , and FTO.

  The first electrode film can be formed by using the above materials as an example, but any method may be used for patterning the first electrode film. Although a pattern may be created using a printing method or a mask method, a method by photolithography is preferable.

  In the present invention, a photoelectric conversion film is formed on the first electrode thus prepared. The photoelectric conversion film in the present invention includes a photoelectric conversion layer that absorbs light and converts it into electrons, and includes interelectrode materials and electrodes necessary for separating the electrons. As a preferable configuration, first, in the case where the photoelectric conversion film laminated on the substrate is one photoelectric conversion film, from the bottom [1] a lower electrode layer, an electron transporting material layer, a hole transporting material layer, and a transparent electrode Examples include a configuration, [2] a lower electrode layer, a hole transporting material layer, an electron transporting material layer, and a transparent electrode. However, the present invention is not limited to this. For example, the electron transporting material may be divided into two or more layers, or the hole transporting material layer may be divided into two or more. . For example, [3] lower electrode layer, electron transport material layer, electron transport material layer, hole transport material layer, transparent electrode [4] lower electrode layer, electron transport material layer, hole transport material layer, hole transport Material, transparent electrode [5] lower electrode layer, electron transport material layer, electron transport material layer, hole transport material layer, hole transport material, transparent electrode. Furthermore, when there are two photoelectric conversion films laminated on the substrate, a combination in the case of one photoelectric conversion film can be basically created. That is, for example, a combination of [1] and [1] from the bottom to the bottom electrode layer, electron transport material layer, hole transport material layer, transparent electrode, interlayer insulating film, bottom electrode layer (transparent electrode), electron Structure of transportable material layer, hole transportable material layer, transparent electrode, and lower electrode layer, electron transportable material layer, hole transportable material layer, transparent electrode, interlayer insulating film that is a combination of [1] and [2] , Lower electrode layer (transparent electrode), hole-transporting material layer, electron-transporting material layer, transparent electrode configuration, etc., and the configuration of such multiple layers is basically [1], [2], [ It may be arbitrarily configured with a combination selected from [3], [4], and [5], and other configurations other than [1], [2] [3], [4], and [5] and [1 ], [2], [3], [4], [5] may be arbitrarily combined. Laminating at least two photoelectric conversion films on a substrate increases the light utilization efficiency per unit area as compared with the case of one, and can be more preferably cited as a constituent requirement in the present invention.

  Further, although details will be described later, it is particularly preferable in the present invention to stack at least three photoelectric conversion films on the substrate because the light utilization efficiency can be further increased. In particular, in at least three cases, since a blue photoelectric conversion film, a green photoelectric conversion film, and a red photoelectric conversion film can be formed, a full-color image sensor can be formed. Therefore, it is very preferable in the present invention. As a matter of course, the configuration in the case of stacking at least three photoelectric conversion films on the substrate is the same as the two cases, and any combination selected from [1] and [2] and other configurations [1] , [2], and other combinations are possible.

  Moreover, although the material which comprises a photoelectric converting film may be an inorganic material or an organic material, when an organic material is contained in this invention, it can use especially preferably. For this reason, it is highly desirable to use an electron transporting organic material or a hole transporting organic material as the electron transporting material or hole transporting material described above.

  As the electron transporting organic material, for example, an acceptor organic semiconductor (compound) can be preferably used. An acceptor organic semiconductor (compound) is an organic compound that is typified by an electron-transporting organic compound and has a property of easily accepting electrons. More specifically, the organic compound having the higher electron affinity when two organic compounds are used in contact with each other. Therefore, as the acceptor organic compound, any organic compound can be used as long as it is an electron-accepting organic compound. For example, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), 5- to 7-membered heterocyclic compounds containing nitrogen atoms, oxygen atoms, and sulfur atoms (E.g. pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, Benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, o Metal complexes having ligands such as saziazole, imidazopyridine, pyralidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine), polyarylene compounds, fluorene compounds, cyclopentadiene compounds, silyl compounds, and nitrogen-containing heterocyclic compounds. Etc. Note that the present invention is not limited thereto, and any organic compound having an electron affinity higher than that of the organic compound used as the donor organic compound may be used as the acceptor organic semiconductor.

Examples of hole transporting organic materials include poly-N-vinylcarbazole derivatives, polyphenylene vinylene derivatives, polyphenylene, polythiophene, polymethylphenylsilane, polyaniline, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline. Derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, carbazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, porphyrin derivatives (phthalocyanines, etc.), aromatic tertiary amine compounds And styrylamine compounds, butadiene compounds, benzidine derivatives, polystyrene derivatives, triphenylmethane derivatives , Tetraphenyl benzene derivatives, starburst polyamine derivative or the like can be used.
It is also very preferable to use organic dyes. The above materials can have a structure that absorbs light, and other metal complex dyes, cyanine dyes, merocyanine dyes, phenylxanthene dyes, triphenylmethane. Chain compounds in which condensed polycyclic aromatic and aromatic or heterocyclic compounds such as naphthoquinone, anthraquinone dye, anthracene, pyrene, etc. are condensed , A cyanine-like dye bonded by two nitrogen-containing heterocycles such as quinoline, benzothiazole, and benzoxazole, a squarylium group, and a croconic methine group can be preferably used.
In the case of a metal complex dye, a dithiol metal complex dye, a metal phthalocyanine dye, a metal porphyrin dye or a ruthenium complex dye is preferable, and a ruthenium complex dye is particularly preferable. Examples of ruthenium complex dyes include, for example, U.S. Pat. Nos. 4927721, 4684537, 5084365, 5350644, 5463057, 5525440, JP-A-7-249790, JP-A-10-504512, WO98 / 50393. And complex dyes described in JP-A No. 2000-26487 and the like. Specific examples of polymethine dyes such as cyanine dyes, merocyanine dyes and squarylium dyes are disclosed in JP-A-11-35836, JP-A-11-67285, JP-A-11-86916, JP-A-11-97725, JP-A-11-97725. -158395, JP-A-11-163378, JP-A-11-214730, JP-A-11-214731, JP-A-11-238905, JP-A-2000-26487, European Patents 892411, 918441 and 991092 It is a dye described in each specification of No ..
These materials may be contained in the polymer binder as necessary. Examples of the polymer binder used as such include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, and ethyl cellulose. , Vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester, alkyd resin, epoxy resin, silicone resin, polyvinyl butyral, polyvinyl acetal, and the like.

  Although it is necessary to pattern such a photoelectric conversion film into a desired shape, any method may be used in the present invention. Among them, it is particularly preferable to form a film by a mask method or pattern the photoelectric conversion film using the second electrode as a mask.

A manufacturing process of the photoelectric conversion film laminated solid-state imaging device having the above configuration will be described with reference to the drawings.
2 to 11 are schematic cross-sectional views showing manufacturing steps of the photoelectric conversion film laminated solid-state imaging device shown in FIG. 1, and FIG. Since the structure up to FIG. 2 can be formed by a normal semiconductor process, the subsequent steps will be described in detail here.

  After forming the first electrode film 214, as shown in FIG. 3, the hole blocking layer 210, the n-type semiconductor layer 209, the p-type semiconductor layer 208, and the electron blocking layer 207 are formed on the first electrode film 214 in this order. Then, a photoelectric conversion film is formed. Next, as shown in FIG. 4, transparent electrode films 206 and 205 are formed in this order on the photoelectric conversion film to form a counter electrode film. Next, as shown in FIG. 5, the photoelectric conversion film and the counter electrode film on the peripheral circuit portion are selectively removed by etching.

  Next, as shown in FIG. 6, a protective film (first insulating film) 204 is formed. Then, in order to expose the transparent electrode film 206 which is a part of the counter electrode film, a part of the protective film 204 and a part of the counter electrode film are selectively etched away as shown in FIG. At this time, a resist pattern forming process is performed in which a resist is formed on the entire surface and selectively removed, but the photoelectric conversion films (207, 208, 209, 210) are protected by the protective film 204. At this time, a part of the protective film 204 on the bonding PAD 220 is also removed by etching. Next, a barrier metal 228 such as tungsten is formed only on the exposed surface of the transparent electrode film 206. The hole portion of the protective film 204 including the exposed surface of the transparent electrode film 206 becomes a contact hole for conducting with the transparent electrode 206. The size of the contact hole is preferably 5 μm or less, more preferably 1 μm or less, and still more preferably 0.5 μm or less. Next, as illustrated in FIG. 8, the insulating film 211 on the bonding PAD 220 is selectively removed by etching to expose a part of the bonding PAD 220.

  Next, as shown in FIG. 9, a wiring material 218 such as aluminum is formed. At this time, the wiring material 218 enters the opening on the transparent electrode film 206 and the opening on the bonding PAD 220, respectively. Next, while maintaining the state in which the transparent electrode film 206 and the bonding PAD 220 are connected by the wiring material 218, unnecessary wiring material 218 is selectively removed by etching as shown in FIG. . Next, as illustrated in FIG. 11, the protective film 203 is formed over the protective film 204 and the wiring 218. Further thereon, an infrared cut dielectric multilayer film 202 and an antireflection film 201 are formed in this order to obtain a photoelectric conversion film laminated solid-state imaging device as shown in FIG. Here, the length of the minimum side of the wiring extending from the contact hole is 1 mm or less, and even when such fine processing is used, the performance of the functional film can be prevented from being deteriorated.

  According to the manufacturing process as described above, when the mask pattern for forming the opening shown in FIG. 7 is formed by photolithography between FIGS. 6 and 7, the photoelectric conversion film (207 , 208, 209, 210) can be formed in a protected state. For this reason, in various processes such as patterning, there is an advantage that the photoelectric conversion film is reliably protected by the protective film 204 and characteristic deterioration of the photoelectric conversion film can be prevented. When the photoelectric conversion film contains an organic material, the method is more effective because characteristic deterioration due to the influence of the process is particularly concerned. Such an effect can be similarly obtained when forming a mask pattern when forming the wiring 218 in FIG.

In addition, it is preferable that the conditions of the protective film 204 required in order to prevent the characteristic deterioration of a photoelectric converting film have the low water permeability. Specifically, the water permeability is preferably 10 g / m ² · day or less, more preferably 1 g / m ² · day or less, more preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻² g. / M ² · day, more preferably 1 × 10 ⁻⁹ g / m ² · day to 1 × 10 ⁻² g / m ² · day or less, more preferably 1 × 10 ⁻⁹ g / m ² · day to 1 × 10 ⁻⁴ g / m ² · day or less. The water permeability can be measured, for example, with a water permeability measuring device manufactured by MOCON, USA.

  In general, when forming a resist pattern in photolithography, pure water is used by a washing process or the like. However, if such a condition is set, the pure water reaches the photoelectric conversion film. This can be surely prevented. In addition, the protective film 204 does not need to have a single layer structure, and may have a multilayer structure including a plurality of insulating films. In the case of a multilayer structure, the protection performance of the photoelectric conversion film can be further improved.

Here, the above manufacturing process will be described in more detail.
In the present embodiment, the patterning of the transparent electrode films 205 and 206 as the second electrode film is realized by performing a surface treatment with reducing plasma and then dry etching the substrate at a substrate temperature of 150 ° C. or lower.

  With this configuration, a reducing plasma treatment is performed to form a metal-rich film, and in this state, the substrate can be maintained at 150 ° C. or lower because it can be etched without being heated to a high temperature by hitting with Ar. In the patterning of the organic semiconductor film, the generation of a substance that deteriorates the device characteristics or the reaction with the film substance does not occur, and it is possible to realize highly reliable dry etching.

In the present invention, a first electrode film, an organic semiconductor film, and a second electrode film facing the first electrode film are stacked in this order on a substrate on which a signal readout circuit is formed. After the lamination, it is necessary to finely process the second electrode film. When forming the first electrode film or the second electrode film by dry etching after forming the first electrode film or the second electrode film, it is important to set the substrate temperature to 150 ° C. or lower. The substrate temperature is preferably 80 ° C. or lower, more preferably 40 ° C. or lower. A transparent electrode is often used for the first electrode film or the second electrode film. The transmittance of the transparent electrode is preferably 60% or more at a wavelength of 400 nm to 700 nm, more preferably 80% or more, more preferably 90% or more, more preferably 95% or more. In such dry etching of the second electrode, it is common to apply a temperature to the substrate. However, when producing an element according to the present invention, it has been found that the element characteristics are extremely deteriorated unless the temperature is set to 150 ° C. or lower. This is because, under high temperature conditions in the presence of an etching gas, it is considered that a certain kind of substance that deteriorates device characteristics is generated or reacts with a film substance. Since this does not occur with normal liquid crystal displays, semiconductor devices, and conventional devices, this is a phenomenon specific to the device of the present invention and cannot be easily guessed.
The effect of the present invention is particularly effective when the first electrode film or the second electrode film contains at least one material selected from metal oxides such as ITO, IZO, SnO ₂ , ATO, ZnO, TiO ₂ and FTO. It is preferable because it functions effectively.

In addition, when dry etching is performed using at least one gas selected from HCl, HBr, HI, CH ₄ , CH ₃ OH, Ar, N ₂ , and O ₂ , the effect of the present invention is great. Therefore, it is more preferable to use these gases in the present invention, and it is desirable to carry out as follows in the present invention.
During dry etching, after treatment with reducing plasma, that is, plasma containing reducing molecules or atoms, in HCl, HBr, HI, CH ₄ , CH ₃ OH, Ar, N ₂ , Xe, Kr, and O ₂ It is preferable to perform dry etching using at least one gas selected from the group consisting of: More preferably, the reducing molecule or atom-containing plasma has an atom or molecule containing at least one element selected from carbon, hydrogen, nitrogen, sulfur, iodine, chlorine and bromine. The More preferably, the plasma containing the reducing molecule or atom contains at least one molecule selected from carbon monoxide, hydrogen, nitric oxide, sulfur monoxide, iodine, chlorine, bromine, Preference is given to containing carbon monoxide or hydrogen. In particular, it should be noted that it is not always necessary to supply these molecules in the form of a gas. For example, when an oxide such as the etching gas CHF ₃ is subjected to plasma treatment using CHF ₃ plasma, it is clear that nitrogen monoxide exists under normal conditions. This is because the oxide oxygen and the carbon of CHF ₃ are combined to produce carbon monoxide, and the present invention also applies to the case where molecules generated in the plasma treatment process and present in the plasma are used. It is effective to be included as a constituent requirement of the present invention.

In addition, when performing the dry etching using at least one gas selected from HCl, HBr, HI, CH ₄ , CH ₃ OH, Ar, N ₂ , and O ₂ , which is one of the present invention, In addition to maintaining the etching rate that could not be achieved at a substrate temperature of 150 ° C. or lower, various methods can be used for the method of processing with a plasma containing a functional molecule or an atom. It has been found that this also contributes to improving the performance. The dry etching method in the present invention is considered to have the same effect that can be obtained by any method regardless of inductive coupling type or capacitive coupling type.

  In addition, the first electrode film, the second electrode film, and the method for producing and forming the organic semiconductor film as the functional film in the present invention may be basically any method. Examples include a resistance heating vacuum deposition apparatus, an RF sputtering apparatus, a DC sputtering apparatus, a counter target sputtering apparatus, CVD, MBE, PLD, and a coating method. However, the present invention is not limited to this. Absent.

Next, for the structure of the present invention as described above, a structure different from the present invention is shown for comparison.
FIG. 12 shows a wiring structure having a structure different from that of the present invention. A part of the upper part of the wiring 2208 in this structure is in contact with the insulating film 2209, but the lower part is not in contact with the insulating film. At first glance, this structure is simple and only one type of insulating film 2209 exists on the second electrode 2207, and it seems that the process is superior. However, this method cannot provide good photoelectric conversion characteristics.

  In ordinary well-known semiconductor devices, such a difference is not so great. Rather, when it is desired to simplify the process, such a wiring structure is often provided. In general, when an organic material is used for the photoelectric conversion film (particularly when an organic semiconductor is used), this structure is adopted. When an organic material is used for the photoelectric conversion film (particularly when an organic semiconductor is used), this structure is taken because an element is formed by a mask method. Since it is impossible to make a fine contact hole by the mask method, wiring is performed in this way without installing an insulating film.

Next, a process for creating a wiring structure according to the present invention and a wiring structure different from the present invention will be compared. An example of a process for creating a wiring structure different from the present invention on a signal readout board prepared in the same manner as in FIG. 1 is presented here.
In FIG. 13, the first electrode 2204 is formed, the photoelectric conversion film 2206 and the second electrode film 2207 are formed on the entire surface, then a resist is applied on the entire surface, and a desired pattern is formed using a photolithography technique. It is a figure which shows the step after etching the 2nd electrode film 2207, resist peeling, and etching the photoelectric converting film 2206 using the 2nd electrode 2207 as a mask.

  From the stage of FIG. 13, etching is performed up to the second electrode PAD 2205 using the second electrode 2207 as a mask as shown in FIG. 14, and a wiring 2208 is formed on the entire surface as shown in FIG. From here on, the optical lithography technique is used to leave the wiring 2208 as shown in FIG. 16, and the insulating film 2209 is formed on the entire surface as shown in FIG.

The structure different from the present invention shown in FIG. 17 is deteriorated in photoelectric conversion characteristics as compared with the case where the structure of the present invention is created. Although the reason is not clear, it is presumed that this structure and the process for producing the structure cause damage to the photoelectric conversion film during the process. In the case of the structure of the present invention, the degree of damage is determined particularly when the second electrode contains at least one material of ITO, IZO, SnO ₂ , ATO, ZnO, TiO ₂ , or FTO, or when the wiring is made of Al, When at least one material of Pt, W, Au, Ag, Ta, Cu, Cr, Mo, Ti, Ni, Pd, and Zn is included, the effect is reduced.

  Note that supplementing the formation of the barrier metal, in the case where the barrier metal is also formed between the wiring 218 and the bonding PAD 220, in FIG. The barrier metal may be deposited on the exposed surface of the bonding PAD 220 in the next step.

  Alternatively, in FIG. 7, an opening is also formed in the insulating film 211 on the bonding PAD 220 to expose a part of the bonding PAD 220, and in the next step, a barrier metal is formed on the entire surface, and a wiring material 218 is formed thereon. Then, the barrier metal and the wiring material 218 are patterned together so that the barrier metal is interposed between the wiring 218 and the transparent electrode film 206 and between the wiring 218 and the bonding PAD 220. good.

  In the photoelectric conversion film stacked solid-state imaging device described above, the photoelectric conversion film includes at least a hole transporting organic material and an electron transporting organic material, and these are in the order of a hole transporting organic material and an electron transporting organic material from the bottom. It is particularly preferable to adopt a structure located at This is because, when a photoelectric conversion film is formed using a hole transporting organic material and an electron transporting organic material, it has been experimentally proved that the performance of the device is higher when the structure described above is used. .

The most preferred embodiment of the present invention will be described.
On the substrate, a first electrode film, a second electrode film facing the first electrode film, a functional film disposed between the first electrode film and the second electrode film, and the first electrode film And a wiring for applying a potential to the second electrode film,
(1) A first insulating film formed on the second electrode film so as to cover a side wall of the functional layer. (2) Formed through the first insulating film to the second electrode film, A contact hole in which the wiring for connecting the second electrode film extends (3) a second insulating film is installed between the second electrode and the first insulating film;
(4) The functional film includes at least a hole transporting organic material and an electron transporting organic material, and the functional film includes, from the substrate side, the first electrode, the hole transporting organic material, the electron transporting organic material, Are stacked in the order of the second electrode,
(5) A functional element having the contact hole in each pixel portion and a size of 5 μm or less.

The reason for this preference is as follows.
The performance of the functional film includes a hole transporting organic material and an electron transporting organic material, and the functional film includes the first electrode, the hole transporting organic material, the electron transporting organic material, and the second transporting material from the substrate side. The best performance can be achieved by stacking the electrodes in order.
However, when this structure is laminated on a substrate by a conventional method, in the case of a light emitting element, a PMOS must be used as a driving transistor of the substrate. In the case of a photoelectric conversion film, a signal charge is changed to a hole, Similarly, the performance on the substrate side deteriorates because a PMOS must be used, and the total performance cannot be maximized. However, the maximum force can be extracted by the following aspects of the present invention. A contact hole is formed in the first insulating film so as to penetrate to the second electrode film, and the wiring for connecting the second electrode film is formed therein, and the contact hole exists in each pixel portion. And the size is 5 μm or less. In addition, it is very difficult to form this embodiment without causing any performance degradation. However, using the most preferred example of the present invention, the shape is close to ideal. It has a first insulating film formed so as to cover the side wall of the functional layer above the second electrode film, and a second insulating film between the second electrode and the first insulating film Is installed. This insulating film two-layer structure can bring out the performance of the device to the maximum without causing deterioration of the functional film. The second insulating film protects the functional film from the photolithography process, and the first insulating film prevents the functional film from being exposed to the atmosphere.

Next, a modified example of the photoelectric conversion film stacked solid-state imaging device will be described.
This modification is formed on the second electrode film so as to cover the side wall of the functional layer, and is formed so as to penetrate through the first insulating film to the second electrode film. And a second insulating film interposed between the second electrode and the first insulating film. In the case of this configuration, the effect of the present invention is further increased.
2 to 4 can be described as a common process so that it can be compared with the aforementioned process. As a subsequent process, an insulating film (second insulating film) 2301 is formed as shown in FIG. 18 without etching the second electrodes (205, 206) as described above. A resist 2310 is formed thereon by photolithography as shown in FIG. 19, and the insulating film 2301 is first etched according to the resist pattern as shown in FIG. Thereafter, before etching the second electrode 2207, the resist 2310 is removed as shown in FIG. The resist 2310 is removed by a dry process such as oxygen ashing. However, when the second electrode 2207 plays a large role in protecting the photoelectric conversion layer 2206, ashing using a normal stripping solution can be performed. This point is very important, and is a great effect that is useful for simplifying the manufacturing process and reducing costs. Further, as shown in FIG. 22, the insulating film is etched using 2301 as a mask. After that, an insulating film (first insulating film) 2302 is formed, a resist pattern 2311 is formed on the insulating film 2302 as shown in FIG. 23, PAD is removed as shown in FIG. 24, and the resist 2311 is removed. Then, a wiring material is formed. Then, after forming the wiring 2303 as shown in FIG. 25, an insulating film 2304 is finally formed as shown in FIG.

The structure of this modification is effective from the following viewpoints. Since the second electrode 2207 covers the entire surface of the photoelectric conversion film 2206 when removing the resist in FIG. 21, the resist can be removed using a stripping solution even if the photoelectric conversion film 2206 is easily damaged. is there. This is a significant effect over the example described above. In particular, when the photoelectric conversion film 2206 uses an organic material, this effect is very large, and when the photoelectric conversion film 2206 includes at least a hole transporting organic material and an electron transporting organic material, the effect is extremely high. Is big.
In addition, when the insulating film 2302 is removed with the resist 2311 in FIG. 23, since the insulating film 2207 is laid under the insulating film 2302, the photoelectric conversion film 2206 does not deteriorate through the second electrode film 2207. Therefore, wet etching can also be used to remove the insulating film 2302. Further, since the insulating film 2302 covers the side wall of the photoelectric conversion film 2206 at the time of removing the resist in FIG. 23, the characteristic deterioration of the photoelectric conversion film 2206 due to the resist removal is prevented.

  The insulating film 2302 that covers the photoelectric conversion film 2206 and exists below the wiring 2303 is an important characteristic particularly with respect to the water permeability described above. The effect of this characteristic is great when an organic material is used for the photoelectric conversion film 2206, and when the photoelectric conversion film 2206 includes at least a hole transporting organic material and an electron transporting organic material, the effect is extremely large. It will be a thing.

(Second embodiment)
Next, an example in which the functional element according to the present invention is a light emitting element will be described. In addition, when setting it as a photoelectric conversion film laminated | stacked solid-state image sensor as a similar form, what was described in 1st embodiment as a board | substrate, and what was used for the below-mentioned 3rd and 4th embodiment can be utilized. The light emitting element here is an element used for a display or the like, and will be described below assuming that a portion emitting light for expressing one pixel of an image is one pixel.

FIG. 27A is a schematic surface view illustrating a schematic configuration of two pixels of the light emitting element, and FIG. 27B is a schematic cross-sectional view taken along the line α-α ′ illustrated in FIG. (C) is an example of a substrate circuit that can be used in this embodiment, and (d) is an example of a substrate circuit that is often used in the prior art. The feature (c) is that an NMOS can be used as a drive transistor of the light emitting element, which is realized by the structure of this embodiment.
The light emitting element is formed on the second electrode film so as to cover the side wall of the functional layer, and is formed so as to penetrate through the first insulating film up to the second electrode film. And a second insulating film interposed between the second electrode and the first insulating film.

  As shown in FIG. 27B, a p-well layer 2408 is formed on the surface portion of the silicon substrate 2407, and a drain 2404 of the driving transistor is formed here. An insulating film 2412 is formed on the p-well layer 2408, and an insulating film 2413 is formed thereon. A plug 2410A is formed on the current supply portion 2404 in the insulating film 2412, and the plug 2410A is connected to an electrode pad 2411A formed in the insulating film 2413. A plug 2410B is formed on the electrode pad 2411A, and the plug 2410B is connected to the electrode pad 2411B formed in the insulating film 2415. In this way, the electrode pad 2411B and the drain 2404 of the driving transistor are electrically connected.

  In the insulating film 2413, a metal wiring (not shown) for electrically connecting the electrode pad 2411A and the first electrode film 2402 is formed. In the insulating film 2415, a first electrode film 2402, a light emitting film 2405, a second electrode film 2401, and an insulating protective film (second insulating film) 2414 are formed in this order from the bottom. It is desirable that the light emitting film is positioned as a hole transporting material and an electron transporting material in order from the bottom. An opening is formed in part of the insulating film (first insulating film) 2415 on the second electrode film 2401 and part of the electrode pad 2411B, and a barrier metal 2406 is formed in the opening and on the insulating film 2401. Has been. A wiring 2403 for electrically connecting the second electrode film 2401 and the electrode pad 2411B is formed on the barrier metal 2406. A protective film 2416 for protecting the wiring 2403 is formed over the wiring 2403. In the present embodiment, a portion overlapping the first electrode film 2402 in plan view is defined as a pixel portion.

  As shown in FIG. 13C, the driving circuit of the light emitting element of this embodiment includes an NMOS transistor 2420, an NMOS transistor 2421 as a driving transistor, a capacitor 2422, a diode 2423, a scanning signal line 2424, a power source. A supply line 2425 and a data signal line 2426 are provided. As shown in FIG. 13D, the conventional driving circuit uses a PMOS transistor 2421 'as a driving transistor. Thus, according to the configuration of the light emitting element of the present embodiment, an NMOS transistor can be used as the drive transistor of the drive circuit.

  An NMOS transistor has high mobility because carriers are electrons, and the area of the transistor can be reduced to about half. In particular, when an organic material is included in the light-emitting element, the driving current is large and the area is likely to be relatively large. In addition, when a Si single crystal substrate is used as the substrate, in order for the NMOS transistor and the PMOS transistor to coexist, one of them must be formed on a well having a reverse characteristic to that of the carrier. This well creation gives a very large constraint on the design rule (for example, if the PMOS side is created on the Nwell, the distance between the Nwell and the NMOS transistor must be sufficiently large). These two effects decisively affect the difference in performance in a functional element with a small pixel portion.

  In addition, since the barrier metal 2406 is interposed between the wiring 2403 and the second electrode film 2401 in the light emitting element shown in FIG. 27, the driving durability characteristics can be improved as in the first embodiment. . The materials described in the first embodiment can be used as they are for the first electrode film, the second electrode film, the barrier metal, the plug, the wiring, and the electrode pad described in the present embodiment. When a light emitting film containing an organic material is used, an effect of preventing characteristic deterioration can be further obtained.

The water permeability of the insulating film 2415 and the protective film 2414 is preferably 10 g / m ² · day or less, more preferably 1 g / m ² · day or less, and more preferably 1 × 10 ⁻⁹ to 1 ×. 10 ⁻² g / m ² · day, more preferably 1 × 10 ⁻⁹ g / m ² · day to 1 × 10 ⁻² g / m ² · day, more preferably 1 × 10 ⁻⁹ g / m ^2. It is not less than day and not more than 1 × 10 ⁻⁴ g / m ² · day. Further, the barrier metal may be provided between the first electrode film 2402 and the metal wiring connected thereto.

A manufacturing process of the light-emitting element having the above structure will be described with reference to the drawings.
28 to 39 are schematic cross-sectional views showing manufacturing steps of the light-emitting element shown in FIG. FIG. 28 shows a state where up to the first electrode film 2402 has been formed, and up to this point, it can be formed by a normal semiconductor process. Therefore, the subsequent steps will be described in detail.

  After forming the first electrode film 2402, as shown in FIG. 29, a light emitting film 2405 and a second electrode film 2401 are laminated in this order on the first electrode film 2402. Next, as shown in FIG. 30, a protective film 2414 for protecting the light emitting film 2405 is formed on the second electrode film 2401. Next, in order to separate the light emitting film 2405 for each pixel, a predetermined resist pattern R is formed on the protective film 2414 as shown in FIG.

  Next, as shown in FIG. 32, the protective film 2414 is etched using the resist pattern R as a mask. Next, as shown in FIG. 33, the resist pattern R is removed. Next, as shown in FIG. 34, the first electrode film 2402, the light emitting film 2405, and the second electrode film 2401 are etched using the protective film 2414 as a mask. Next, as shown in FIG. 35, an insulating film 2415 is formed on the entire surface. Next, as shown in FIG. 36, a resist pattern R is formed on the insulating film 2415. Next, the insulating film 2415 and the protective film 2415 are etched using the resist pattern R as a mask to form openings in a part on the second electrode film 2401 and a part on the electrode pad 2411B as shown in FIG. To do.

  Next, after the barrier metal 2406 is formed on the entire surface, as shown in FIG. 38, the barrier metal 2406 is patterned leaving only a portion connecting the second electrode film 2401 and the electrode pad 2411B. In this state, the barrier metal 2406 is buried in the openings on the second electrode film 2401 and the electrode pad 2411B. Next, after forming a wiring material, patterning is performed so that the wiring material remains only on the barrier metal 2406 to form a wiring 2403 as shown in FIG. Finally, a protective film 2416 is formed over the wiring 2403 to obtain a light emitting element as shown in FIG. Note that the wiring 2403 and the barrier metal 2406 may be patterned at the same time.

  The preferable point in this example is that the insulating protective film can be disposed on the entire surface of the functional film when the resist is formed, and that the resist removal can be removed under the protection of the second electrode. That is, in this manufacturing method, the barrier metal 2406 and the wiring 2403 can be formed by patterning in a state where the two insulating films of the protective film 2414 and the insulating film 2415 exist on the light emitting film 2405 which is a functional film. Therefore, in the photolithography process when forming the barrier metal 2406 and the wiring 2403, damage to the light emitting film 2405 can be reduced as much as possible, and performance deterioration of the light emitting film 2405 can be prevented. In the structure of the light emitting element shown in FIG. 27, since the wiring 2403 is formed in the pixel portion, there is an effect that the smaller the wiring 2403 is, the larger the light emitting area can be. Note that this embodiment can also be applied to a three-layer structure as in the following example.

(Third embodiment)
Next, the functional element according to the present invention is a photoelectric conversion film laminated solid-state imaging device, and as its configuration, three photoelectric conversion films sandwiched between two electrode films are stacked on a silicon substrate, The first configuration described above that enables color imaging by detecting three colors of light will be described.
FIG. 40 is a schematic view of the surface of a photoelectric conversion film laminated solid-state imaging device for explaining a third embodiment of the present invention. In the photoelectric conversion film stacked solid-state imaging device 1100 shown in FIG. 40, a large number of light receiving portions (pixels) 1101 are arranged in a grid pattern in the vertical and horizontal directions in this example. Here, the basic structure of the photoelectric conversion film laminated solid-state imaging device will be described first, and the structure having the characteristic portion of the present invention will be described separately later.

  On the surface of the semiconductor substrate provided below the light receiving unit 1101 of the photoelectric conversion film stacked solid-state imaging device 1100 as the basic structure, three lines corresponding to each column of the light receiving units 1101 arranged in the column direction are provided. Vertical transfer paths (column direction CCD registers) 1102b, 1102g, and 1102r (subscripts b, g, and r are the same in the following, but correspond to blue (B), green (G), and red (R), respectively. .) And a horizontal transfer path (row direction CCD register) 1103 is formed on the lower side of the semiconductor substrate.

  An amplifier 1104 is provided at the exit of the horizontal transfer path 1103, and signal charges detected by each light receiving unit 1101 are first transferred to the horizontal transfer path 1103 by the vertical transfer paths 1102b, 1102g, and 1102r, and then transferred horizontally. The signal is transferred to the amplifier 1104 through the path 1103 and output from the amplifier 1104 as the output signal 1105.

  On the surface of the semiconductor substrate, electrode terminals 1106, 1107, 1108, and 1109 are connected to four-phase transfer electrodes (not shown) provided on the vertical transfer paths 1102b, 1102g, and 1102r and to which four-phase transfer pulses are applied. Electrode terminals 1110 connected to a second electrode film, which will be described later, and two-phase transfer electrode terminals 1111 and 1112 of the horizontal transfer path 1103 are provided.

  FIG. 41A is an enlarged schematic diagram within the dotted rectangular frame II shown in FIG. 40. The light receiving portion 1101 for nine pixels and the vertical wiring 1119 portion for the second electrode film to which the electrode terminal 1110 is connected are shown. It is shown. In FIG. 41A, the vertical transfer paths 1102r, 1102g, and 1102b shown in FIG. 40 are omitted.

  Each light receiving portion 1101 is defined by a rectangular first electrode film 1120 (also referred to as a pixel electrode film because it is separated for each pixel). As shown in FIG. 41B, the first electrode film 1120 shown in FIG. 41A has three first electrode films 1120r, 1120g, and 1120b in the light incident direction through the photoelectric conversion films described later. They are arranged side by side.

  The first electrode film 1120r for red is provided with a vertical wiring connection pad 1117r on the same plane as the first electrode film 1120r, and the first electrode film 1120g for green is similarly connected to the vertical wiring connection. A pad 1117g is provided in a protruding manner, and a vertical wiring connecting pad 1117b is provided in a protruding manner in the blue first electrode film 1120b. As shown in FIG. 41A, the pads 1117r, 1117g, and 1117b of the same pixel (light receiving unit) 1101 are provided so as to be displaced in position.

  The code | symbol 1122 shown to Fig.41 (a) shows a 2nd electrode film. In the basic structure of the present embodiment, the second electrode film 1122 also includes a red second electrode film 1122r, a green second electrode film 1122g, and a blue second electrode film 1122b, as will be described later. They are provided so as to overlap each other via a photoelectric conversion film or the like.

  42 is a schematic cross-sectional view taken along the line III-III in FIG. 41A, showing cross sections of the pads 1117r, 1117g, and 1117b, and FIG. 43 is a schematic cross-sectional view taken along the line IV-IV in FIG. Yes, and shows a cross section of the central portion of the pixel.

  A P well layer 1131 is formed on the surface portion of the n-type semiconductor substrate 1130, and charge storage portions 1138 r, 1138 g, and 1138 b, which are n-type regions, are formed on the surface portion of the P well layer 1131, and a channel stop 1115 is formed. The defined vertical transfer paths (n-type semiconductor layers) 1102r, 1102g, and 1102b are formed. Vertical wiring connection portions 1137r, 1137g, and 1137b, which are n + regions, are formed at the central portions of the charge storage portions 1138r, 1138g, and 1138b.

  A gate insulating film 1132 is formed on the surface of the semiconductor substrate 1130, a transfer electrode 1139 made of polysilicon is formed thereon, and an insulating film 1134 is formed thereon. A light shielding film 1133 is formed in the insulating film 1134 so that incident light does not enter the vertical transfer path.

  A conductive film is formed over the insulating film 1134 and patterned to form the horizontal wirings 1124r, 1124g, and 1124b shown in FIG. The vertical wiring connecting portions 1137r, 1137g, 1137b of the charge storage units 1138r, 1138g, 1138b and the horizontal wirings 1124r, 1124g, 1124b are connected by the first vertical wirings 1126r, 1126g, 1126b.

  An insulating layer 1125 is formed on the layer provided with the horizontal wirings 1124r, 1124g, and 1124b, and a transparent conductive film is stacked thereon. This conductive film is patterned to form a first electrode film 1120r divided for each light receiving portion 1101. Further, by this patterning, the pad 1117r shown in FIG. 41B is formed, and the conductive films 1116b and 1116g that are aligned in the light incident direction and separated from the other are left on the pads 1117b and 1117g.

  A photoelectric conversion film 1121r for detecting red (R) is laminated on the first electrode film 1120r, the pad 1117r, and the conductive films 1116b and 1116g. The photoelectric conversion film 1121r does not need to be provided separately for each light receiving unit, and is laminated in a single configuration on the entire light receiving surface where the light receiving units 1101 gather.

  On the photoelectric conversion film 1121r, a single second electrode film (also referred to as “counter electrode film” because it faces the first electrode film) 1122r common to each light receiving unit 1101 that detects a red signal is also one sheet. A transparent insulating film (first insulating film) 1127 is stacked on the top of the stacked layers.

  A transparent conductive film is stacked on the insulating film 1127, and the conductive film is patterned. Similarly to the above, the first electrode film 1120g and the pad 1117g divided for each light receiving portion 1101 are separated from the others. A conductive film 1118b aligned with the pad 1117b shown in FIG. 41B is formed. On these first electrode films 1120g, etc., a photoelectric conversion film 1121g for detecting green (G) is laminated in a single configuration as described above, and further a second electrode film 1122g is laminated thereon, A transparent insulating film (first insulating film) 1128 is laminated thereon.

  A transparent conductive film is stacked on the insulating film 1128 and patterned to form a first electrode film 1120b and a pad 1117b divided for each light receiving unit 1101, and a blue (B The photoelectric conversion film 1121b for detecting) is laminated in the same manner as described above, the second electrode film 1122b is laminated thereon, and the transparent protective film 1129 is laminated on the uppermost layer.

  The horizontal wiring 1124b and the pad 1117b of the blue first electrode film 1120b are connected by a second vertical wiring 1114b, and the horizontal wiring 1124g and the pad 1117g of the green first electrode film 1120g are connected by a second vertical wiring 1114g. 1124r and the pad 1117r of the red first electrode film 1120r are connected by the second vertical wiring 1114r. Each vertical wiring 1114r, 1114g, 1114b, 1126r, 1126g, 1126b is electrically insulated from the corresponding first electrode film pad, conductive films 1116g, 1116b, 1118b and other than the horizontal wiring, as will be described in detail later. Manufactured.

  44 is a schematic cross-sectional view taken along the line VV of FIG. 41A, and shows a connection configuration between the electrode terminal 1110 of FIG. 40 and the second electrode films 1122b, 1122g, and 1122r. A high concentration P layer 1141 is formed on the surface portion of the P well layer 1131 formed on the surface portion of the n-type semiconductor substrate 1130, and a field region (insulating film) 1142 is formed thereon.

  The high-concentration P layer 1141 may be formed in the same process as the channel stop 1115 shown in FIGS. 42 and 43, or may be formed in a separate process. The insulating film 1142 is formed simultaneously with the formation of the gate insulating film 1132 shown in FIGS. 42 and 43, and the insulating film forming process is continued after the formation of the gate insulating film 1132 so that the film thickness becomes thicker than that of the gate insulating film 1132. .

  The same insulating film 1134 as in FIGS. 42 and 43 is formed over the insulating film 1142, and a conductive film 1124k is stacked thereover. The conductive film 1124k is formed by patterning the conductive film that forms the horizontal wirings 1124r, 1124g, and 1124b shown in FIGS. 42 and 43, and the electrode terminal 1110 shown in FIG. 40 is connected to the conductive film 1124k.

  By patterning the conductive film forming the first electrode film 1120r, the conductive film 1120k-1 is formed, and the vertical wiring 1143-1 is formed between the conductive film 1124k and the conductive film 1120k-1.

  Similarly, a conductive film 1120k-2 is formed by patterning a conductive film that forms the first electrode film 1120g, and a vertical wiring 1143-2 is formed between the second electrode film 1122r and the conductive film 1120k-2. In addition, the vertical wiring 1143-3 is formed between the conductive film 1120k-2 and the conductive film 1120k-1. Accordingly, the second electrode film 1122r and the conductive film 1124k are electrically connected, and the second electrode film 1122r is connected to the electrode terminal 1110.

  Similarly, the conductive film 1120k-3 is formed by patterning the conductive film forming the first electrode film 1120b, and the vertical wiring 1143-4 is formed between the second electrode film 1122g and the conductive film 1120k-3. In addition, the vertical wiring 1143-5 is formed between the conductive film 1120k-3 and the conductive film 1120k-2. Thereby, the second electrode film 1122g and the conductive film 1124k are electrically connected, and the second electrode film 1122g is connected to the electrode terminal 1110.

  A transparent conductive film 1144 is laminated at the corner of the upper surface of the protective film 1129, and a vertical wiring 1143-6 is formed between the second electrode film 1122b and the conductive film 1144, and the conductive film 1144 and the conductive film 1120k-3. Vertical wiring 1143-7 is formed between the two. Accordingly, the second electrode film 1122b and the conductive film 1124k are electrically connected, and the second electrode film 1122b is connected to the electrode terminal 1110.

  The photoelectric conversion film stacked solid-state imaging device as the basic structure of the present embodiment includes two different electrodes, for example, between the second electrode film 1122r and the vertical wiring 1143-2, and between the second electrode film 1122g and the vertical wiring 1143. -4, between the second electrode film 1122b and the vertical wiring 1143-6, between the conductive film 1120k-1 and the vertical wiring 1143-3, between the conductive film 1120k-2 and the vertical wiring 1143-5, A barrier metal 1200 is interposed between the film 1120k-3 and the vertical wiring 1143-7 as shown in FIG. With this configuration, driving durability characteristics can be improved. The same material as that of the first embodiment can be used as the material for the second electrode film and the barrier metal. In addition, the barrier metal should just exist in at least one between the above-mentioned.

The homogeneous transparent electrode films 1122r, 1122g, 1122b, 1120r, 1120g, 1120b and the like include tin oxide (SnO ₂ ), titanium oxide (TiO ₂ ), indium oxide (InO ₂ ), and indium oxide-tin (ITO) thin film. However, the present invention is not limited to this.

  The photoelectric conversion films 1121r, 1121, and 1121b may be a single layer film or a multilayer film, and the film materials are composed of inorganic materials such as silicon and compound semiconductors, organic semiconductors, organic materials including organic dyes, and nanoparticles. Various materials such as a quantum dot deposited film can be used. A preferred configuration is the configuration described in the first embodiment.

  In the basic structure of this embodiment, a plurality of photoelectric conversion films are stacked on a silicon substrate. For example, when two photoelectric conversion films are stacked on a silicon substrate, the configuration of each photoelectric conversion film is the same as the configuration example [1], [2], [3], [4], [ It may be configured in any combination selected from [5], and other configurations other than [1], [2], [3], [4], [5] and [1], [2], [ [3], [4], and [5] may be arbitrarily combined. Laminating a plurality of photoelectric conversion films on a silicon substrate increases the light utilization efficiency per unit area as compared with a single case, and therefore can be more preferably cited as a constituent requirement in the present invention. Furthermore, as in the basic structure of this embodiment, it is particularly preferable in the present invention to stack three or more photoelectric conversion films on a silicon substrate because the light utilization efficiency can be further increased. In particular, in the case of three or more, since a blue photoelectric conversion film, a green photoelectric conversion film, and a red photoelectric conversion film can be created, a full-color imaging device can be created. Therefore, it is very preferable in the present invention. As a matter of course, the configuration in the case where three or more photoelectric conversion films are stacked on the substrate is the same as in the case of two configurations [1], [2], [3], [4], [5] ] Or any combination of other configurations and configuration examples [1], [2], [3], [4], [5]. Of course, other combinations may be used. .

  When light from the subject is incident on the photoelectric conversion film stacked solid-state imaging device 1100 having such a configuration, a photoelectric charge corresponding to the amount of blue light in the incident light is generated in the blue photoelectric conversion film 1121b, and this photoelectric charge is generated. The charge is accumulated in the charge accumulation unit 1138b through the vertical wiring 1114b, the horizontal wiring 1124b, and the vertical wiring 1126b. Similarly, the photocharge corresponding to the green incident light amount is accumulated in the charge accumulation unit 1138g, and the photocharge corresponding to the red incident light amount is accumulated in the charge accumulation unit 1138r. The charges (signal charges) stored in the charge storage units 1138r, 1138g, and 1138b are read to the vertical transfer paths 1102r, 1102g, and 1102b, transferred to the horizontal transfer path 1103, and transferred to the horizontal transfer path 1103. It is output from the photoelectric conversion film stacked solid-state imaging device 1100.

  45 to 59 are diagrams showing a manufacturing procedure of the photoelectric conversion film laminated solid-state imaging device shown in FIGS. 42 to 44, and each figure (a) is a schematic sectional view at the same position as FIG. Each drawing (b) is a schematic sectional view at the same position as FIG. 59 (a) showing the completion of manufacture is the same as FIG. 42, and FIG. 59 (b) is the same as FIG.

  Up to the state shown in FIG. 45, the semiconductor device is manufactured by the same semiconductor manufacturing procedure as that of the conventional CCD type and CMOS type solid-state imaging device, and charge storage units 1138r, 1138g, 1138b and vertical transfer are transferred to the P well layer 1131 of the semiconductor substrate 1130. The paths 1102r, 1102g, and 1102b are formed, and the insulating film 1134 is formed on the surface portion. After openings for the first vertical wirings 1126r, 1126g, and 1126b are formed in the insulating film 1134 by etching, each opening is filled with a metal such as tungsten or copper, or conductive polycrystalline silicon, and the first vertical wirings are formed. 1126r, 1126g, and 1126b are formed. Then, a transparent conductive film is formed on the surface portion and patterned to form horizontal wirings 1124r, 1124g, 1124b and a conductive film 1124k. The patterning is performed, for example, in the order of resist coating, exposure, development, and etching.

  Next, as shown in FIG. 46, an insulating film 1125 is laminated on the surface, and as shown in FIG. 47, openings 1150r, 1150g, 1150b, 1150k reaching the horizontal wirings 1124r, 1124g, 1124b and the conductive film 1124k, respectively. Is formed by etching. As shown in FIG. 48, openings 1150r, 1150g, 1150b, 1150k (see FIG. 47) are filled with a transparent conductive material, and a part of vertical wirings 1114r, 1114g, 1114b and the vertical wiring described in FIG. 1143-1 is formed. Further, as shown in FIG. 49, a transparent conductive film 1151 is formed on the surface portion.

  Next, the conductive film 1151 is patterned to form a first electrode film 1120r (see FIG. 43). As shown in FIG. 50, the conductive films 1116b, 1116g, and 1120k− described with reference to the pad 1117r and FIG. 1 is formed. Thereafter, as shown in FIG. 51, a red detection photoelectric conversion film 1121r is laminated on the surface portion, and further, as shown in FIG. 52, a second electrode film 1122r is laminated on the photoelectric conversion film 1121r. .

  Next, as shown in FIG. 53, a resist film 1152 is formed on the surface, openings 1153b and 1153g aligned with the positions of the conductive films 1116r and 1116g are formed by etching, and photoelectric conversion on the conductive film 1120k-1 is performed. The ends of the film 1121r and the second electrode film 1122r are cut as shown in FIG.

  As described above, in the basic structure of this embodiment, the second electrode film 1122r is continuously stacked following the step of stacking the photoelectric conversion film 1121r, and the second electrode film 1122r and the photoelectric conversion film 1121r are etched together. Thus, since the openings 1153g and 1153b are formed, the interface between the photoelectric conversion film 1121r and the second electrode film 1122r is not roughened, and the number of etchings of the vertical wiring openings can be reduced. In addition, since the conductive films 1116g and 1116b are provided at the bottom of the opening when etching is performed, the etching can be accurately stopped at the positions of the conductive films 1116g and 1116b.

  After the openings 1153b and 1153g are formed, as shown in FIG. 54, an insulating film 127 is stacked on the surface portion to fill the openings 1153b and 1153g, and the insulating film 1127 is formed in the cut portion shown in FIG. Are laminated. Then, as shown in FIG. 55, openings 1154g and 1154b having diameters smaller than the openings 1153b and 1153g are opened by etching, and an opening 1154k− reaching the second electrode film 1122r at the end (FIG. 55B). 1 and an opening 1154-2 reaching the conductive film 1120 k-1 is opened.

  Next, as shown in FIG. 55B, a barrier metal is selectively grown on the second electrode film 1122r and the conductive film 1120k-1 exposed by the openings 1154k-1 and 1154k-2. To do.

  Next, the openings 1154g, 1154b, 1154k-1, and 1154k-2 are filled with a transparent conductive material as shown in FIG. 56 to form vertical wirings 1114g, 1114b, 1143-2, and 1143-3. After each opening is filled with a transparent conductive material, the surface is smoothed. This is performed by, for example, etch back or CMP (Chemical Mechanical Polishing).

  As described above, in the basic structure of this embodiment, the vertical wirings 1114g and 1114b penetrating the three layers of the insulating film 1127, the second electrode film 1122r, and the photoelectric conversion film 1121r are manufactured in the same process. The number decreases.

  Then, by repeating the same procedure as the manufacturing procedure of FIGS. 49 to 56, as shown in FIG. 57, the vertical wiring 1114b penetrating the photoelectric conversion film 1121g for green detection and the second electrode film 1122g is formed. The vertical wirings 1143-3 and 1143-5 are formed at the ends.

  Further, as shown in FIG. 58, a first electrode film 1120b (see FIG. 43) and a pad 1117b are formed, and a blue detection photoelectric conversion film 1121b, a second electrode film 1122b, and a transparent protective film 1129 are formed thereon. Then, an opening is opened in a predetermined portion of the transparent protective film 1129 by etching and filled with a conductive material, thereby forming vertical wirings 1143-6 and 1143-7. Finally, as shown in FIG. 59, a conductive film 1144 for connecting the vertical wiring 1143-6 and the vertical wiring 1143-7 is formed.

  As described above, in the basic structure of this embodiment, the second electrode film is continuously stacked following the photoelectric conversion film stacking process, and the second electrode film and the photoelectric conversion film are etched together. Since the opening is provided, the interface between the photoelectric conversion film and the second electrode film is not roughened, and the number of etchings of the vertical wiring opening can be reduced. Thereby, the photoelectric conversion performance can be improved and the manufacturing cost can be reduced.

The basic example of the three-layer laminated structure as described above has been described. However, the above basic configuration includes a step of forming a resist pattern on the photoelectric conversion film via the electrode film, which causes deterioration of the photoelectric conversion film. become. A configuration example according to the present invention that can solve this problem will be described below.
Here, the first insulating film formed so as to cover the side wall of the functional layer on the second electrode film, which is a feature of the present invention, and formed through the first insulating film to the second electrode film, A contact hole in which wiring for connecting the second electrode film extends, and a photoelectric conversion film stacked solid in which a second insulating film is interposed between the second electrode and the first insulating film The structure of the image sensor and the manufacturing method thereof will be described.
60 to 66 are views showing changes to the manufacturing steps from FIGS. 38 to 55, and are schematic cross-sectional views at the same position as FIG. 60 to 66, only the portion located below the opening 1154b shown in FIG. 55 (a) is shown.

  In the photoelectric conversion film stacked solid-state imaging device according to the present invention, after forming the second electrode film 1122r, an insulating film (second insulating film) 1201 is formed as shown in FIG. Next, as shown in FIG. 61, a resist pattern 1202 is formed on the insulating film 1201. Using this resist pattern 1202, only the insulating film 1201 is etched as shown in FIG. Next, as shown in FIG. 63, the resist pattern 1202 is removed. If the second electrode film 1122r has a protective function, the resist pattern can be removed by a wet treatment with a stripping solution. Of course, if there is a resist treatment that does not damage the photoelectric conversion film 1121r, the second electrode film 1122r and the photoelectric conversion film 1121r can be etched from the state of FIG. Next, using the insulating film 1201 as a mask, the second electrode film 1122r and the photoelectric conversion film 1121r are etched as shown in FIG. Next, an insulating film (first insulating film) 1127 is formed and smoothed as shown in FIG. 65, and then a via hole 1154b is formed as shown in FIG.

When the photoelectric conversion film is easily damaged, it is difficult to reliably protect the photoelectric conversion film because the lower layer has only the second electrode film when forming the resist in FIG. When forming a resist, steps such as solvent coating, alkaline developer treatment, and water washing are performed. Therefore, if these treatments are easily damaged, device characteristics are deteriorated. This is particularly remarkable when the photoelectric conversion film contains an organic material. However, as shown in FIG. 61, since the entire surface of the photoelectric conversion film is protected by the insulating film when the resist is formed, the photoelectric conversion film is not deteriorated, and the element characteristics can be reliably prevented from being deteriorated.
In addition, important features in the present embodiment will be further described. In FIG. 62, after the resist is formed on the insulating film, the second insulating film up to FIG. 65 can be formed in a consistent vacuum using a dry etching process and a vacuum film forming technique. . In and after FIG. 66, even if an element containing an organic material sensitive to oxygen or water is exposed to the atmosphere, the organic material is not deteriorated because it is protected by the second insulating film. That is, this two-layer structure of the insulating film is a specific structure that is deeply considered not to deteriorate the organic material in the functional film formation process.

(Fourth embodiment)
Next, a fourth embodiment of the functional element according to the present invention will be described.
Although the arrangement of the charge storage portions formed on the silicon substrate of the photoelectric conversion film stacked solid-state imaging device described in the third embodiment is a square lattice arrangement, the arrangement is not limited to this, and various arrangements can be employed. For example, a so-called honeycomb arrangement in which the odd-numbered columns and the even-numbered columns of the charge accumulation unit rows formed of the charge accumulation units arranged in the vertical direction are shifted by approximately ½ of the vertical arrangement pitch of the charge accumulation units may be employed. A detailed configuration of the honeycomb arrangement is disclosed in Japanese Patent Laid-Open No. 10-136391.

FIG. 67 is a schematic view of the surface of a photoelectric conversion film stacked solid-state imaging device for explaining a fourth embodiment of the present invention.
In the photoelectric conversion film laminated solid-state imaging device 2100, a large number of charge storage portions 2101 are arranged on the surface of a silicon substrate 2107, and the arrangement is a honeycomb arrangement as disclosed in JP-A-10-136391. A vertical transfer path (column direction CCD register) 2102 is formed on the surface of the silicon substrate 2107 corresponding to each column of the charge storage units 2101 arranged in the column direction, and a horizontal transfer path is formed on the lower side of the silicon substrate 2107. (Row direction CCD register) 2103 is formed. An amplifier 2104 is installed at the exit of the horizontal transfer path 2103, and the signal charge is amplified here and output as an output signal 2105. A bonding PAD 2106 for supplying power is provided at both ends of the silicon substrate 2107. The bonding PAD 2106 sandwiches the three photoelectric conversion films 2108 stacked on the silicon substrate 2107, and separates the first electrode film 2109 separated for each pixel. And connected to the second electrode film 2110 that is not separated for each pixel through a wiring.

  68 is a partially enlarged view of the solid-state imaging device shown in FIG. In the solid-state imaging device shown in FIG. 68, as described above, the charge storage unit 2101 and the vertical transfer channel 2102 including the vertical transfer channel 106 and the transfer electrodes 111 to 114 adjacent thereto are arranged in a two-dimensional plane. . Transfer electrodes 111 to 114 for supplying four-phase transfer pulses φ1 to φ4 to one charge storage unit 2101 are arranged. Each of the transfer electrodes 111 to 114 extends in the row direction, and is formed to meander while avoiding the charge storage portion 2101.

  The signal charge generated in the photoelectric conversion film and accumulated in the charge accumulation unit 2101 is read out to the vertical transfer channel 106 from the read gate 107 provided at the lower right in the drawing. In FIG. 68, the vertical transfer channel 106 adjacent to each charge storage unit 2101 is continuous in the vertical direction from the top to the bottom, and extends in the column direction while meandering between the charge storage units 2101 arranged in a honeycomb shape. In addition, a vertical transfer path 2102 is formed together with the transfer electrodes 111 to 114. The end of each vertical transfer path 2102 is connected to a light-shielded horizontal transfer path 2103. Further, an amplifier 2104 having a floating diffusion amplifier (FDA) or the like is connected to the end of the horizontal transfer path 2103, and a signal corresponding to the signal charge is output therefrom.

FIG. 69 shows an AA cross section (a) of FIG. 68 and an enlarged cross sectional view (b) of the photoelectric conversion portion.
As shown in FIG. 69, the charge storage portion 2101 has a configuration in which an n ⁺ region 105 which is an N-type high concentration impurity layer is formed. A plug 3001 is provided on the n ⁺ region 105, and a photoelectric conversion portion 3009 in which a first electrode film 3003, a photoelectric conversion film 3005, a second electrode film 3007, and the like are stacked is provided. Transfer electrodes 111, 112, 113, 114 (see FIG. 68) are formed on the vertical transfer channel 106 by polysilicon electrodes having a two-layer structure. In the two-layer polysilicon electrode, transfer electrodes 111 and 113 are formed, and then transfer electrodes 112 and 114 are formed through an insulating film 109 so that ends thereof overlap. These transfer electrodes 111, 112, 113, 114 can apply a four-phase transfer pulse of, for example, φ1, φ2, φ3, and φ4 to drive the vertical transfer path 2102 to read out all pixels.

  On one side of the outer periphery of the N-type high-concentration impurity layer 105, a read gate 107 is provided for reading out charges accumulated by photoelectric conversion to the vertical transfer channel 106, and the other side is adjacent in the vertical direction. An element isolation region (channel stop) 108 made of P-type high-concentration impurities is formed so that electric charges do not flow in the vertical transfer channel of the pixel column.

  In the solid-state imaging device having such a configuration, even if the transfer electrode for driving the column direction CCD register has a two-layer polysilicon structure, it can cope with all pixel readout, so that the manufacturing process can be simplified. Further, four electrodes can be arranged per one charge storage portion. In this case, driving with a four-phase transfer pulse can increase the amount of charge to be handled by about 1.5 times that in the case of three-phase driving. In the honeycomb CCD structure, the area of the charge storage part can be made relatively large compared to the conventional square lattice CCD, and the horizontal and vertical resolution is high, so miniaturization (higher density, more pixels) has been achieved. Even in such a case, a highly sensitive solid-state imaging device can be obtained.

  In this embodiment, in order to lower the electrical resistance of the polysilicon electrodes used as the transfer electrodes 111 to 114, an electrode material having a specific resistance smaller than that of polysilicon, such as Al (aluminum) or W (tungsten), is used as the metal wiring 125. A so-called metal backing structure is formed by laminating an insulating film on a polysilicon electrode. The metal wiring 125 is electrically connected to the transfer electrodes 111 to 114 via the contact holes 126. In the honeycomb arrangement as in the present embodiment, unlike the conventional square lattice arrangement, all phases are meandering along the longitudinal direction of the polysilicon electrode having a two-layer structure, that is, in the lateral direction (horizontal direction) in FIG. A metal wiring 125 can be laid corresponding to the (layer) transfer electrodes 111 to 114.

  The metal wiring 125 extends in the horizontal direction in FIG. 68, and is electrically connected to a wiring pattern 130 for transmitting driving transfer pulses φ1 to φ4 supplied from the outside of the element. In the example of FIG. 55, the metal wiring 125 and the wiring pattern 130 are made of Al, and the wiring pattern 130 is formed on the polysilicon electrode via an insulating film at a portion where the metal wiring 125 and the wiring pattern 130 of another phase intersect. It shows a configuration in which the metal wiring 125 and the wiring pattern 130 are electrically connected to the polysilicon electrode at the contact portion.

  As electrode materials, Al, W, Cu (copper), Ti (titanium), Co (cobalt), Ni (nickel), Pd (palladium), Pt (platinum), or nitrides thereof (WSi (tungsten silicon)) Etc.), silicides (TiSi (titanium silicon), etc.), alloys, compounds, and composites are suitable. Al is easy to process, easy to handle, and has low electrical resistance, so it is often used for backing metal wiring. Since W does not form an alloy with polysilicon as compared with Al, potential shift (partial change in potential) due to the alloy hardly occurs, and efficient charge transfer is possible in the vertical transfer path. Further, since W is used for the light shielding film of the solid-state imaging device, it may be used together with the light shielding film portion.

  In each of the embodiments described above, a piece of functional film has a pixel array in which one pixel is formed, and the first electrode film is divided and arranged for each pixel. However, the present invention is not limited to this configuration. The second electrode film may be divided for each pixel, or both may be divided for each pixel. In particular, the present invention is highly effective when the second electrode film is divided for each pixel.

It is a cross-sectional schematic diagram of the photoelectric conversion film laminated | stacked solid-state image sensor for demonstrating 1st embodiment of this invention. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the wiring structure which has a structure different from this invention. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process with respect to the modification of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process with respect to the modification of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process with respect to the modification of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process with respect to the modification of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process with respect to the modification of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process with respect to the modification of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process with respect to the modification of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process with respect to the modification of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process with respect to the modification of the photoelectric converting film laminated | stacked solid-state image sensor shown in FIG. (A) is a schematic surface diagram showing a schematic configuration of two pixels of a light emitting element, (b) is a schematic cross-sectional view taken along the line α-α ′ shown in (a), and (c) is used in this embodiment. The figure of an example of the board | substrate circuit which can be performed, (d) is a figure of the example of the board | substrate circuit often used with a prior art It is a cross-sectional schematic diagram which shows the manufacturing process of the light emitting element shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the light emitting element shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the light emitting element shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the light emitting element shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the light emitting element shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the light emitting element shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the light emitting element shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the light emitting element shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the light emitting element shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the light emitting element shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the light emitting element shown in FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the light emitting element shown in FIG. It is a surface schematic diagram of the photoelectric conversion film laminated | stacked solid-state image sensor for demonstrating 3rd embodiment of this invention. (A) is an expansion schematic diagram in the dotted-line rectangular frame II shown in FIG. 40, (b) is explanatory drawing which shows the 1st electrode film shown in (a). FIG. 42 is a schematic cross-sectional view taken along the line III-III in FIG. FIG. 42 is a schematic cross-sectional view taken along the line IV-IV in FIG. FIG. 42 is a schematic cross-sectional view taken along the line VV in FIG. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. FIG. 45 is a diagram illustrating a manufacturing procedure of the photoelectric conversion film stacked solid-state imaging device illustrated in FIGS. 42 to 44, in which (a) is a schematic cross-sectional view at the same position as FIG. 42, and (b) is a cross-sectional view at the same position as FIG. It is a schematic diagram. It is a figure which shows the change with respect to the manufacturing process of FIGS. 38-55, and is a cross-sectional schematic diagram in the same position as FIG. It is a figure which shows the change with respect to the manufacturing process of FIGS. 38-55, and is a cross-sectional schematic diagram in the same position as FIG. It is a figure which shows the change with respect to the manufacturing process of FIGS. 38-55, and is a cross-sectional schematic diagram in the same position as FIG. It is a figure which shows the change with respect to the manufacturing process of FIGS. 38-55, and is a cross-sectional schematic diagram in the same position as FIG. It is a figure which shows the change with respect to the manufacturing process of FIGS. 38-55, and is a cross-sectional schematic diagram in the same position as FIG. It is a figure which shows the change with respect to the manufacturing process of FIGS. 38-55, and is a cross-sectional schematic diagram in the same position as FIG. It is a figure which shows the change with respect to the manufacturing process of FIGS. 38-55, and is a cross-sectional schematic diagram in the same position as FIG. It is a surface schematic diagram of the photoelectric conversion film laminated | stacked solid-state image sensor for demonstrating 4th embodiment of this invention. FIG. 68 is a partially enlarged view of the solid-state imaging device shown in FIG. 67. FIG. 70 is an AA cross section (a) of FIG. 68 and an enlarged cross sectional view (b) of the photoelectric conversion unit.

Explanation of symbols

204 Protective film (first insulating film)
205, 206 Second electrode film 207 Electron blocking layer 208 p-type impurity layer 209 n-type impurity layer 210 hole blocking layer 213 silicon substrate 214 first electrode film 218 wiring 1100 photoelectric conversion film stacked solid-state imaging device 1120 first electrode film 1120g Green first electrode film 1120r Red first electrode film 1120b Blue first electrode film 1121r, 1121, 1121b Photoelectric conversion films 1122r, 1122g, 1122b Second electrode films 1124r, 1124g, 1124b Horizontal wiring 1125 Insulating films 1126r, 1126g, 1126b Wiring 1127 Insulating film 1128 Insulating film 1129 Transparent protective film 1130 N-type semiconductor substrate 1131 Well layer 1132 Gate insulating film 1133 Light shielding film 1134 Insulating films 1137r, 1137g, 1137b Vertical wiring connecting portion 11 38r, 1138g, 1138b Charge storage portion 1139 Transfer electrode 1141 High-concentration P layer 1142 Field region (insulating film)
1143 Vertical wiring 1144 Transparent conductive film 1150r, 1150g, 1150b, 1150k Opening 1151 Conductive film 1152 Resist film 1153b, 1153g Opening 1154g, 1154b Opening 1154 Opening 1154k Opening 1201 Insulating film (second insulating film)
2100 Photoelectric conversion film stacked solid-state imaging device 2109 First electrode film 2110 Second electrode 2121 Wiring 2206 Photoelectric conversion film 2207 Second electrode film 2301 Insulating film (second insulating film)
2302 Insulating film (first insulating film)
2303 Wiring 2401 Second electrode film 2403 Wiring 2407 Silicon substrate 2414 Protective film (second insulating film)
2415 Insulating film (first insulating film)
3003 First electrode film 3005 Photoelectric conversion film 3007 Second electrode film 3009 Photoelectric conversion unit

Claims (20)

On the substrate, a first electrode film, a second electrode film facing the first electrode film, a functional film disposed between the first electrode film and the second electrode film, and the first electrode film Or a functional element having a wiring for applying a potential to the second electrode film,
A first insulating film formed on the second electrode film so as to cover a side wall of the functional layer;
A functional element comprising: a contact hole formed in the first insulating film so as to penetrate to the second electrode film; and the wiring for connecting the second electrode film is extended inside the functional element. . The functional element according to claim 1,
A functional element, wherein a second insulating film is interposed between the second electrode and the first insulating film. The functional element according to claim 2,
The functional element, wherein the contact hole is formed so as to penetrate the first insulating film and the second insulating film. The functional element according to any one of claims 1 to 3,
A functional element comprising a plurality of layers having a layer structure including the first electrode film, the functional film, and the second electrode film on the substrate. 5. The functional element according to claim 1, wherein a water permeability of the insulating film covering the functional film is 10 g / m ² · day or less. . The functional element according to any one of claims 1 to 5,
The functional element, wherein the functional film includes an organic material. The functional element according to claim 6,
The functional film includes at least a hole transporting organic material and an electron transporting organic material, and the functional film includes the first electrode, the hole transporting organic material, the electron transporting organic material, and the second from the substrate side. Functional element characterized by being stacked in the order of electrodes A functional element according to any one of claims 1 to 7,
A functional element, wherein a length of a minimum side of a wiring extending from the contact hole is 1 mm or less. A functional element according to any one of claims 1 to 8,
The second electrode is _{ITO, IZO, SnO 2, ATO} , ZnO, functional element which comprises at least one material of TiO _2, FTO. A functional element according to any one of claims 1 to 9,
The functional element, wherein the wiring includes at least one material of Al, Pt, W, Au, Ag, Ta, Cu, Cr, Mo, Ti, Ni, Pd, and Zn. The functional element according to any one of claims 1 to 10,
The functional element is a photoelectric conversion film laminated solid-state imaging element. The functional element according to any one of claims 1 to 10,
The functional element is an organic light emitting element. A functional element according to claim 11 or claim 12,
A functional element having a pixel array in which one piece of the functional film is one pixel, and the contact hole in which the wiring is extended is formed in each pixel. A functional element according to any one of claims 11 to 13,
The functional element, wherein the contact hole exists in each pixel portion and has a size of 5 μm or less. On the substrate, a first electrode film, a second electrode film facing the first electrode film, a functional film made of an organic semiconductor layer disposed between the first electrode film and the second electrode film, A wiring for applying a potential to the first electrode film or the second electrode film;
The patterning step of the second electrode film includes
Forming a resist pattern by photolithography in a state where the second electrode film is coated with the first insulating film;
After patterning the first insulating film using the resist pattern as a mask,
A method for manufacturing a functional element, comprising a step of patterning a second electrode film using the first insulating film as a mask. It is a manufacturing method of the functional element according to claim 15,
After the patterning step of the second electrode film, a step of forming a second insulating film so as to cover the second electrode film and the side walls of the functional film;
Forming a resist pattern by photolithography,
Forming a contact hole so as to penetrate the second insulating film and the first insulating film using the resist pattern as a mask;
Forming the wiring so as to contact the second electrode film exposed in the contact hole. A method for manufacturing a functional element according to claim 15 or 16,
The method of manufacturing a functional element, wherein the patterning step of the electrode film includes a step of dry etching with the substrate maintained at 150 ° C. or lower. A method for producing a functional element according to claim 17,
The said 2nd electrode film is a manufacturing method of the functional element whose transmittance | permeability with a wavelength of 400 nm-700 nm is 60% or more. A method for producing a functional element according to claim 17,
Prior to the dry etching step, a functional element manufacturing method including a processing step using reducing plasma. A method for manufacturing a functional element according to claim 19,
The said dry etching process is a manufacturing method of the functional element containing the process process using argon plasma.

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