TW201522083A - Substrate with organic function layer and method of manufacturing same - Google Patents

Abstract

A substrate with an organic function layer is provided, which includes: a substrate, an organic function layer disposed on the substrate, and a protective film disposed on the organic function layer. The protective film includes a silicon oxynitride represented by SiOxNy, wherein x and y satisfy 0.5 ≤ x ≤ 1.0, and -2.2y+2.1 ≤ x ≤ -2.2y+2.41. When a density of the protective film is set to [rho] (g/m3), 2.20(g/m3) ≤ [rho] ≤ 2.60(g/m3).

Description

Machine function layer substrate and manufacturing method thereof

The invention relates to an organic functional layer substrate comprising a protective film for protecting an organic functional layer and a manufacturing method thereof, in particular to a color filter, a photographic element, an organic solar cell and an organic electroluminescence ( An organic functional layer substrate with electroluminescence, EL) or the like and a method for producing the same.

Now, a color photographing apparatus using an organic photoelectric conversion layer has been proposed. A conventional color photographing apparatus includes: a pixel electrode formed on a semiconductor substrate on which a signal readout circuit is formed; an organic photoelectric conversion layer formed on a pixel electrode; and a counter electrode (upper electrode) formed on the organic photoelectric conversion layer And a protective film formed on the opposite electrode to protect the opposite electrode; a color filter or the like. The protective film contains a SiOxNy film formed by a plasma chemical vapor deposition (CVD) method. There have been various proposals for such a protective film since the prior art (see Patent Document 1, Patent Document 2, and Non-Patent Document 1).

Patent Document 1 describes a photography element including an organic photoelectric conversion layer. In the case, a hafnium oxynitride film (SiOxNy film) formed by a plasma CVD method is used as a protective film for protecting the counter electrode. It is described that when the protective film is a single layer, the internal stress of the entire protective film is -50 MPa to +60 MPa.

Patent Document 2 describes a gas barrier film in which a solvent resistant layer (acrylic hardening resin) and a phenolphthalein polymer layer (epoxy) are sequentially formed on both surfaces of a polyimide film. It is a hardening resin) and a ruthenium oxynitride layer. It is described that the ruthenium oxynitride layer is formed by a plasma CVD method.

Further, in addition to the above, a gas barrier film is formed which forms a SiOxNy layer as a gas barrier layer on a solvent resistant layer (acrylic cured resin) by sputtering, and forms a phenolphthalein-based polymer layer thereon. A ruthenium oxynitride layer is formed on the phenolphthalein-based polymer layer.

Patent Document 2 describes that the composition of SiNxOy suitable for barrier properties is x=0.5 to 1.5 and y=0.15 to 1. It is described that the preferred range of x is from 0.5 to 1.5, more preferably from 0.7 to 1.3, the preferred range of y is from 0.15 to 1, and more preferably from 0.3 to 0.7.

Non-Patent Document 1 describes a method of forming an SiOxNy film by a plasma CVD method at a substrate temperature of 350 °C. The composition and physical properties of the SiOxNy film are examined in Non-Patent Document 1, and the relationship between the composition of the SiOxNy film and the refractive index and density is shown. In addition to this, the relationship between the refractive index and the density of the SiOxNy film is shown.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-118363

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-241483

[Non-patent literature]

[Non-Patent Document 1] M. Jozwik et al., Thin Solid Films 468 (2004) 84-92.

As described above, the SiOxNy film used as the protective film has a description of internal stress, film composition, and film density. However, the SiOxNy film which is used as a protective film which is transparent and has a predetermined refractive index and has excellent barrier properties is not transparent and has excellent film stability.

An object of the present invention is to provide an organic functional layer substrate and a method for producing the same, which are provided with a protective film which is transparent and excellent in stability of a film, based on the problems of the prior art.

In order to achieve the object, a first aspect of the present invention provides a substrate with an organic functional layer, comprising: a substrate; an organic functional layer disposed on the substrate; and a protective film disposed on the organic functional layer; The protective film contains bismuth oxynitride represented by SiOxNy, x, y satisfies 0.5 ≦ x ≦ 1.0, and -2.2 y + 2.1 ≦ x ≦ - 2.2 y + 2.41, and the density of the protective film is set to ρ (g/m ^{3 )} When it is 2.20 (g/m ³ ) ≦ρ≦ 2.60 (g/m ³ ).

For example, it is preferable that the organic functional layer is an organic photoelectric conversion layer that generates charges when irradiated with light, the organic photoelectric conversion layer is provided with a lower electrode on the substrate side, and a transparent upper electrode is provided on the opposite side of the substrate, and the upper electrode is provided on the upper electrode. A protective film is disposed on the upper surface.

Moreover, for example, the organic functional layer is a color filter layer containing organic matter, in color A protective film is disposed on the color filter layer.

Further, it is preferable that x, y satisfy 0.5 ≦ x ≦ 1.0, and -2.2 y + 2.1 ≦ x ≦ - 2.2 y + 2.32. It is preferred that the density ρ (g/m ³ ) of the protective film is 2.30 (g/m ³ ) ≦ρ ≦ 2.60 (g/m ³ ).

According to a second aspect of the invention, there is provided a method of producing a substrate with an organic functional layer, comprising the step of forming a protective film comprising cerium oxynitride represented by SiOxNy on an organic functional layer disposed on a substrate. , x and y of SiOxNy satisfy 0.5≦x≦1.0, and -2.2y+2.1≦x≦-2.2y+2.41, when the density of the protective film is ρ(g/m ³ ), 2.20 (g/m) ³ ) ≦ρ≦ 2.60 (g/m ³ ).

According to the present invention, it is possible to provide an organic functional layer substrate comprising a protective film which is transparent and excellent in stability of a film.

Further, according to the present invention, an organic functional layer-attached substrate comprising a protective film which is transparent and excellent in stability of a film can be produced.

10‧‧‧With organic functional layer substrate

12‧‧‧Substrate

14‧‧‧Organic functional layer

16, 80‧‧‧ protective film

20‧‧‧Photographic components

30, 72‧‧‧ substrate

32‧‧‧Insulation

32a‧‧‧ Surface of the insulation

34‧‧‧ pixel electrodes (lower electrode)

35‧‧‧ circuit board

36‧‧‧Organic layer

38‧‧‧ opposite electrode (upper electrode)

40‧‧‧Protective film (sealing layer)

40a‧‧‧Surface of protective film

42‧‧‧Color filters

44‧‧‧Baffle

46‧‧‧Lighting layer

47‧‧‧ Surface of the light-shielding layer

48‧‧‧coating

50‧‧‧Electronic barrier

50a‧‧‧ Surface of the electronic barrier layer

52‧‧‧Photoelectric conversion layer

60‧‧‧Readout circuit

62‧‧‧ Counter electrode voltage supply unit

64‧‧‧1st connection

66‧‧‧2nd connection

68‧‧‧Wiring layer

70‧‧‧Organic solar cells

70a‧‧‧Organic EL components

74‧‧‧lower electrode

76‧‧‧Organic photoelectric conversion layer

78‧‧‧Transparent electrode (upper electrode)

82‧‧‧TFT

84‧‧‧ cathode

86‧‧‧Organic EL layer

88‧‧‧Power supply

L‧‧‧ incident light

Px‧‧‧unit pixels

Fig. 1 (a) is a schematic view showing an organic functional layer substrate according to an embodiment of the present invention, and Fig. 1 (b) is a schematic view showing a state before a protective film is formed in the organic functional layer substrate according to the embodiment of the present invention.

Fig. 2 is a schematic cross-sectional view showing an image pickup element according to an embodiment of the present invention.

3(a) and 3(b) are schematic cross-sectional views showing a method of manufacturing an imaging element according to an embodiment of the present invention in order of steps.

4(a) and 4(b) are schematic cross-sectional views showing a method of manufacturing an imaging element according to an embodiment of the present invention in order of steps, and showing a post process of Fig. 3(b).

Fig. 5 (a) is a schematic cross-sectional view showing an organic solar cell according to an embodiment of the present invention, and Fig. 5 (b) is a schematic cross-sectional view showing an organic EL device according to an embodiment of the present invention.

Hereinafter, the organic functional layer-attached substrate of the present invention and a method for producing the same will be described in detail based on a preferred embodiment shown in the accompanying drawings.

Fig. 1 (a) is a schematic view showing an organic functional layer substrate according to an embodiment of the present invention, and Fig. 1 (b) is a schematic view showing a state before a protective film is formed in the organic functional layer substrate according to the embodiment of the present invention.

As shown in FIG. 1(a), the organic-functional layer substrate 10 includes a substrate 12, an organic functional layer 14, and a protective film 16.

The substrate 12 supports the organic functional layer 14 and the protective film 16. The substrate 12 can support the organic functional layer 14 and the protective film 16, and has a predetermined strength for heat or the like applied when the organic functional layer 14 and the protective film 16 are formed. For example, it consists of a flat plate. As the substrate 12, for example, a glass substrate, an insulating layer metal substrate, a resin substrate, a metal substrate, or the like can be used. In addition, as the base material 12, a conductive or insulating base material can be suitably used depending on the type of the organic functional layer 14 or the like.

The organic functional layer 14 contains an organic substance and exhibits a predetermined function, and has a heat resistance of 240 ° C or lower. The organic functional layer 14 is, for example, an organic photoelectric conversion layer used in a photographic element, a photoelectric conversion layer containing an organic substance used in an organic solar cell, An organic EL layer used in organic EL, a color filter, or the like.

The use form of the organic functional layer 14 includes a form of a single color filter such as a color filter, such as an organic photoelectric conversion layer used in a photographic element, and a photoelectric conversion layer containing an organic substance used in an organic solar cell. A form in which an electrode is provided, such as an organic EL layer, or the like.

The "heat resistance" is a temperature at which the function of the organic functional layer 14 can be maintained. In the present invention, it is 240 ° C or lower. Therefore, if the temperature exceeds 240 ° C, the function of the organic functional layer 14 is impaired. For example, in the case of a color filter, defects such as transmittance and color change occur, and the original spectral characteristics change. In the case of the organic photoelectric conversion layer, performance such as an increase in dark current is lowered. If it is an organic EL layer, the luminous intensity will fall.

The protective film 16 is for protecting the organic functional layer 14. The protective film 16 has a function of protecting the organic functional layer 14 for a long period of time in a high-temperature and high-humidity environment, and functions as a barrier film.

The protective film 16 is directly provided on the organic functional layer 14 in FIG. 1(a). However, if the organic functional layer 14 can be protected, the arrangement of the protective film 16 is not limited thereto. For example, the organic functional layer 14 may be provided with an electrode, a transparent electrode, another constituent portion, a structural portion, or the like, and the protective film 16 may be provided on the electrode, the other constituent portion or the structural portion.

The protective film 16 contains bismuth oxynitride represented by SiOxNy. The x and y of SiOxNy are compositions satisfying 0.5≦x≦1.0 and -2.2y+2.1≦x≦-2.2y+2.41. It is preferable to satisfy the composition of 0.5 ≦ x ≦ 1.0 and -2.2 y + 2.1 ≦ x ≦ - 2.2 y + 2.32.

Further, as a method of measuring the composition of the protective film 16, if the composition can be determined, It is not particularly limited, and various known measurement methods can be used. In addition, an example of the measurement method will be described in detail later.

The protective film 16 has a density of ρ (g/m ³ ) of 2.20 (g/m ³ ) ≦ρ ≦ 2.60 (g/m ³ ). Preferably, it is 2.30 (g/m ³ ) ≦ρ ≦ 2.60 (g/m ³ ).

Since SiOxNy is in the range of the above composition, the protective film 16 becomes a transparent and film-stable yttrium oxynitride film. Moreover, the refractive index is in the range of 1.65 to 1.75.

Here, "transparent" means that the light absorptivity is less than 0.2% in a wavelength range of a wavelength of 400 nm to 800 nm (visible light region). That is, "transparent" means that the maximum value of the light absorptance in the wavelength range of 400 nm to 800 nm is less than 0.2%. If the light absorptivity in the visible light region is 0.2%, light absorption can be ignored.

As the protective film 16, if it deviates from the range of the composition, it is not transparent, and the refractive index does not enter the range of 1.65 to 1.75. In addition, "opaque" means that the light absorptivity in the visible light region is 0.2% or more.

When the density ρ (g/m ³ ) of the protective film 16 is in the above range, it has predetermined heat resistance and can protect the organic functional layer 14 . If the density of the protective film 16 is less than 2.20 (g/m ³ ), the predetermined heat resistance cannot be obtained. On the other hand, when the density of the protective film 16 exceeds 2.60 (g/m ³ ), the film stress of the protective film 16 becomes high, which adversely affects the organic functional layer 14 of the lower layer.

Further, the protective film 16 preferably has a film thickness of 100 nm or more.

As the protective film 16 represented by SiOxNy, from the organic functional layer 14 From the viewpoint of heat resistance, it is formed by a plasma CVD method at a temperature of 240 ° C or lower in a reaction chamber such as a process chamber. By using the plasma CVD method, film formation can be performed at a faster deposition rate than vapor deposition.

For example, as shown in FIG. 1(b), after the organic functional layer 14 is formed on the substrate 12, the substrate temperature is 240 ° C or less as described above on the organic functional layer 14, and the plasma CVD method is used to form the A ruthenium oxynitride film in the range of composition is used as the protective film 16. With respect to the composition and density of the yttrium oxynitride film, the argon oxynitride film is formed by changing the flow rate of the reaction gas or the like in advance, and the film formation conditions (film formation temperature (substrate temperature) and pressure in the reaction chamber at the time of film formation are determined in advance ( Hereinafter, it is referred to as "pressure at the time of film formation", electric power at the time of film formation, gas type (SiH ₄ , NH ₃ , N ₂ O), gas mixing ratio, etc.), and it can be set in the range of the said composition, and it is set as the formation. The range of density of the yttrium oxynitride film.

Hereinafter, a specific example of the organic functional layer substrate of the present invention will be described. Specifically, the organic functional layer-attached substrate of the present invention may be referred to as "Complementary Metal Oxide Semiconductor (CMOS)".

Fig. 2 is a schematic cross-sectional view showing an image pickup element according to an embodiment of the present invention.

The photographic element 20 shown in FIG. 2 is referred to as an organic CMOS to convert visible light images into electrical signals. The photographic element 20 includes a substrate 30, an insulating layer 32, a pixel electrode (lower electrode) 34, an organic layer 36, a counter electrode (upper electrode) 38, a protective film (sealing layer) 40, a color filter 42, and a spacer. 44. A light shielding layer 46 and an overcoat layer 48. A readout circuit 60 is formed on the substrate 30, and the opposite direction is formed. The pole voltage supply unit 62.

The substrate 30 corresponds to the substrate 12 of the present invention (see FIG. 1(a)). As the substrate 30, for example, a glass substrate or a semiconductor substrate such as Si can be used. An insulating layer 32 containing a known insulating material is formed on the substrate 30. A plurality of pixel electrodes 34 are formed on the surface of the insulating layer 32. The pixel electrodes 34 are arranged in a matrix shape, for example, on the surface 32a of the insulating layer 32.

A first connecting portion 64 that connects the pixel electrode 34 and the readout circuit 60 is formed on the insulating layer 32. Further, a second connection portion 66 that connects the counter electrode 38 and the counter electrode voltage supply portion 62 is formed. The second connecting portion 66 is formed at a position that is not connected to the pixel electrode 34 and the organic layer 36. The first connecting portion 64 and the second connecting portion 66 are formed of a conductive material.

A wiring layer 68 containing a conductive material for connecting the readout circuit 60 and the counter electrode voltage supply unit 62 to the outside of the image pickup element 20 is formed inside the insulating layer 32.

As described above, the substrate on which the pixel electrodes 34 connected to the respective first connection portions 64 are formed on the surface 32a of the insulating layer 32 on the substrate 30 is referred to as "circuit substrate 35". Further, the circuit board 35 is also referred to as a "CMOS board."

The organic layer 36 is formed by covering the plurality of pixel electrodes 34 and avoiding the second connection portion 66. The organic layer 36 is formed to span the plurality of pixel electrodes 34. The organic layer 36 is a person who receives incident light L containing at least visible light and generates a charge corresponding to the amount of light, and includes a photoelectric conversion layer 52 and an electron blocking layer 50.

As for the organic layer 36, the electron blocking layer 50 is formed on the side of the pixel electrode 34, and is electrically The surface 50a of the sub-barrier layer 50 is formed with a photoelectric conversion layer 52. Further, the organic layer 36 may be a single layer of the photoelectric conversion layer 52 without providing the electron blocking layer 50.

The electron blocking layer 50 is a layer for suppressing injection of electrons from the pixel electrode 34 into the photoelectric conversion layer 52.

The photoelectric conversion layer 52 is a layer that generates electric charges corresponding to the amount of light received by the incident light L, for example, visible light or the like. The photoelectric conversion layer 52 is an organic photoelectric conversion layer mainly containing an organic material, and is formed on the electron blocking layer 50 across the plurality of pixel electrodes 34.

When the photoelectric conversion layer 52 and the electron blocking layer 50 have a fixed film thickness on the pixel electrode 34, the film thickness may not be fixed. In this case, the "film thickness" means the thickness of the region where the film thickness is fixed. Further, the photoelectric conversion layer 52 will be described in detail later.

The counter electrode 38 is an electrode opposed to the pixel electrode 34 and covers the photoelectric conversion layer 52. A photoelectric conversion layer 52 is provided between the pixel electrode 34 and the counter electrode 38.

In order to cause light to enter the photoelectric conversion layer 52, the counter electrode 38 includes a conductive material that is transparent with respect to the incident light L (light containing at least visible light). The counter electrode 38 is electrically connected to the second connection portion 66 disposed on the outer side of the photoelectric conversion layer 52, and is connected to the counter electrode voltage supply unit 62 via the second connection portion 66.

Examples of the material of the counter electrode 38 include a metal, a metal oxide, a metal nitride, a metal boride, an organic conductive compound, a mixture of these, and the like. Specific examples thereof include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (Indium Zinc Oxide, IZO), indium oxide tungsten (IWO), and titanium oxide. , TiN and other metal nitrides, gold a metal such as (Au), platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni), or aluminum (Al), and a mixture or laminate of the metal and the conductive metal oxide is further condensed. An organic conductive compound such as aniline, polythiophene or polypyrrole, or a laminate of ITO or the like. Particularly preferred as the material of the transparent conductive film are ITO, IZO, tin oxide, antimony tin oxide (ATO), Fluorine-doped Tin Oxide (FTO), zinc oxide, ytterbium-doped oxidation. Any material of zinc (Antimony Zinc Oxide, AZO) or gallium-doped Zinc Oxide (GZO). A particularly preferred material for the counter electrode 38 is ITO.

The light transmittance of the counter electrode 38 is preferably 60% or more, more preferably 80% or more, still more preferably 90% or more, and still more preferably 95% or more at the wavelength of visible light.

The counter electrode 38 preferably has a thickness of 5 nm to 30 nm. By making the counter electrode 38 a film thickness of 5 nm or more, the lower layer can be sufficiently coated to obtain uniform performance. On the other hand, when the film thickness of the counter electrode 38 exceeds 30 nm, the counter electrode 38 and the pixel electrode 34 are partially short-circuited, and a dark current is increased. By making the counter electrode 38 a film thickness of 30 nm or less, local short-circuiting can be suppressed.

The counter electrode voltage supply unit 62 applies a predetermined voltage to the counter electrode 38 via the second connection unit 66. When the voltage to be applied to the counter electrode 38 is higher than the power supply voltage of the imaging element 20, the voltage is boosted by a booster circuit such as a charge pump to supply the predetermined voltage.

The pixel electrode 34 is a charge trapping electrode for trapping charges generated in the photoelectric conversion layer 52. The pixel electrode 34 is connected to the readout circuit 60 via the first connection portion 64. The readout circuit 60 is provided corresponding to each of the plurality of pixel electrodes 34. On the substrate 30, a signal corresponding to the charge captured by the corresponding pixel electrode 34 is read.

Examples of the material of the pixel electrode 34 include a metal, a conductive metal oxide, a metal nitride, a metal boride, an organic conductive compound, and a mixture thereof. Specific examples thereof include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), and titanium oxide, and titanium nitride (TiN). Conductive metal nitrides such as molybdenum nitride, nitrided group, and tungsten nitride; metals such as gold (Au), platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni), and aluminum (Al). Further, a mixture or laminate of the metal and the conductive metal oxide, an organic conductive compound such as polyaniline, polythiophene or polypyrrole, and a laminate with ITO may be mentioned. The material of the transparent conductive film is particularly excellent in ITO, IZO, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, antimony-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO). Any material. The most preferable material of the material of the pixel electrode 34 is any material of titanium nitride, molybdenum nitride, tantalum nitride, or tungsten nitride.

The readout circuit 60 includes, for example, a charge coupled device (CCD), a metal oxide semiconductor (MOS) circuit, or a thin film transistor (TFT) circuit, etc., by an insulating layer 32. The light shielding layer (not shown) provided inside shields light. Further, from the viewpoint of noise and high speed, it is preferable that the readout circuit 60 employs a CMOS circuit.

Further, although not shown, for example, the substrate 30 is formed with a high height surrounded by the p region. In the n region of the concentration, the first connecting portion 64 is connected to the n region. A readout circuit 60 is provided in the p region. The n region functions as a charge accumulation portion that accumulates charges of the photoelectric conversion layer 52. The signal charge accumulated in the n region is converted into a signal corresponding to the amount of charge by the read circuit 60, and is output to the outside of the image pickup device 20 via the wiring layer 68, for example.

In the image forming element 20, the organic layer 36 corresponds to the organic functional layer of the present invention, and has heat resistance of 240 ° C or lower. The protective film 40 is formed by covering the counter electrode 38. The protective film 40 is not directly provided on the organic layer 36. However, the protective film 40 can protect the organic layer 36 including the photoelectric conversion layer 52 from deterioration factors such as water molecules and oxygen.

By the protective film 40, in the respective manufacturing steps of the image forming element 20, the organic layer 36 is protected by preventing the factor of deterioration of the organic photoelectric conversion material contained in a solution such as an organic solvent or a plasma or the like from being impregnated. Further, after the production of the image sensor 20, the factor of deteriorating the organic photoelectric conversion material such as water molecules or oxygen is prevented from entering, and the organic layer 36 can be prevented from being deteriorated after long-term storage and long-term use. Further, when the protective film 40 is formed, the formed organic layer 36 is not deteriorated. Further, the incident light L passes through the protective film 40 to reach the organic layer 36. Therefore, the protective film 40 is transparent with respect to light of a wavelength detected by the organic layer 36, for example, visible light.

The protective film 40 is a single layer structure. The protective film 40 is a yttrium oxynitride film represented by SiOxNy having the same composition and density as the protective film 16 described above. The protective film 40 is formed by a plasma CVD method at a temperature of 240 ° C or lower.

Further, for example, the film thickness of the protective film 40 is 30 nm to 500 nm.

If the total film thickness of the protective film 40 is less than 30 nm, there is a decrease in barrier properties, and color The resistance of the filter to the developer is lowered. On the other hand, when the thickness of the protective film 40 exceeds 500 nm, when the pixel size is cut to 1 μm, it becomes difficult to suppress color mixture.

Further, for example, in the imaging element 20 having a pixel size of less than 2 μm, particularly about 1 μm, if the distance between the color filter 42 and the photoelectric conversion layer 52, that is, the thickness of the protective film 40 is thick, the protective film 40 is present. The influence of the oblique incident component of the incident light (visible light) becomes large, and the color mixture is caused. Therefore, it is preferable that the protective film 40 is thin.

The color filter 42 is formed on the protective film 40 at a position facing each of the pixel electrodes 34. The spacers 44 are disposed between the color filters 42 on the protective film 40 to improve the light transmission efficiency of the color filters 42. The light shielding layer 46 is formed on a region other than the region (effective pixel region) where the color filter 42 and the spacer 44 are provided on the protective film 40, and prevents light from entering the photoelectric conversion layer formed in a region other than the effective pixel region. 52. The color filter 42, the spacer 44, and the light shielding layer 46 can be formed, for example, by a photolithography method.

Further, although the configuration of the color filter 42 is provided, the color filter 42 may not be provided. In this case, since the spacer 44 and the light shielding layer 46 are not provided outside the color filter 42, the protective film 40 is the uppermost layer.

The coating layer 48 is used to protect the color filter 42 from a post process or the like, and covers the color filter 42, the spacer 44, and the light shielding layer 46.

In the imaging element 20, one of the pixel electrodes 34 on which the organic layer 36, the counter electrode 38, and the color filter 42 are provided is a unit pixel Px.

As the coating layer 48, a polymer material such as an acrylic resin, a polyoxyalkylene resin, a polystyrene resin, or a fluororesin, or an inorganic material such as cerium oxide or cerium nitride can be suitably used. When a photosensitive resin such as polystyrene is used, the coating layer 48 can be patterned by photolithography, and thus it is easy to perform the peripheral light shielding layer, the sealing layer, the insulating layer, and the like on the pad for soldering. It is preferable to use the photoresist at the time of opening, and it is easy to process the coating layer 48 itself into a microlens. On the other hand, the cladding layer 48 may be used as an antireflection layer, and it is also preferable to form a film of various low refractive index materials used as a spacer of the color filter 42. Further, in order to pursue the function as a protective layer for the post-process and the function as an anti-reflection layer, the clad layer 48 may have a configuration in which two or more layers of the material are combined.

The color filter 42 contains an organic substance and corresponds to the organic functional layer of the present invention. Therefore, the coating layer 48 can be made into a hafnium oxynitride film having the same composition and density as the protective film 16 in the same manner as the above-described protective film 40.

As the imaging element 20, the organic layer 36 can be protected for a long period of time by the protective film 40 even in a severe environment of high temperature and high humidity such as a temperature of 85 ° C and a relative humidity of 85%. Therefore, even in the severe environment of the high temperature and high humidity, the photographic element 20 can be used over a long period of time without deteriorating the performance. Therefore, the photographic element 20 is suitable for a use environment in which the use environment such as a monitoring camera is strict.

In the present embodiment, the pixel electrode 34 is formed on the surface of the insulating layer 32. However, the present invention is not limited thereto, and may be embedded in the surface portion of the insulating layer 32. Further, it is assumed that one second connection portion 66 and the counter electrode voltage are provided. The configuration of the supply unit 62 may be plural. For example, by supplying a voltage from the opposite ends of the counter electrode 38 to the counter electrode 38, the voltage drop of the counter electrode 38 can be suppressed. The number of components of the second connection portion 66 and the counter electrode voltage supply portion 62 can be appropriately increased or decreased in consideration of the wafer area of the element.

Next, the photoelectric conversion layer 52 and the electron blocking layer 50 constituting the organic layer 36 will be described in more detail.

The photoelectric conversion layer 52 includes a p-type organic semiconductor material and an n-type organic semiconductor material. The exciton dissociation efficiency can be increased by forming a donor acceptor interface by bonding a p-type organic semiconductor material to an n-type organic semiconductor material. Therefore, the photoelectric conversion layer formed by bonding the p-type organic semiconductor material and the n-type organic semiconductor material exhibits high photoelectric conversion efficiency. In particular, it is preferable that the junction interface of the photoelectric conversion layer in which the p-type organic semiconductor material and the n-type organic semiconductor material are mixed is increased to improve the photoelectric conversion efficiency.

The p-type organic semiconductor material (compound) is a donor organic semiconductor material (compound), and is mainly represented by a hole transporting organic compound, and is an organic compound having a property of easily providing electrons. More specifically, it means an organic compound having a small ionization potential when two kinds of organic materials are used in contact with each other. Therefore, any organic compound can be used if the donor organic compound is an organic compound having electron donability. For example, a metal complex or the like having a compound as a ligand can be used: a triarylamine compound, a benzidine compound, a pyrazoline compound, a styrylamine compound, an anthracene compound, a triphenylmethane compound, a carbazole compound, Polydecane compound, thiophene compound, phthalocyanine compound, cyanine compound, merocyanine compound, oxonium compound, polyamine compound, hydrazine compound, pyrrole compound, pyrazole compound, polyaryl compound, condensed aromatic carbocyclic ring compound (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene fused derivatives, pyrene derivatives, perylene derivative, fluoranthene (fLUORANTHENE) derivatives), a nitrogen-containing heterocyclic compound. In addition, the organic compound having a smaller free potential of the organic compound used as the n-type (acceptor) compound as described above can also be used as a donor organic semiconductor.

The n-type organic semiconductor material (compound) is an acceptor organic semiconductor material, and is mainly represented by an electron-transporting organic compound, and is an organic compound having a property of easily accepting electrons. More specifically, the "n-type organic semiconductor" refers to an organic compound having a large electron affinity when the two organic compounds are brought into contact with each other. Therefore, if the acceptor organic compound is an organic compound having electron acceptability, any organic compound can be used. For example, a metal complex or the like having a compound as a ligand: a condensed aromatic carbocyclic compound (naphthalene derivative, an anthracene derivative, a phenanthrene derivative, a thick tetraphenyl derivative, an anthracene derivative, an anthracene derivative, or the like) a fluoranthene derivative), a 5- to 7-membered heterocyclic compound containing a nitrogen atom, an oxygen atom, or a sulfur atom (for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline) , pyridazine, porphyrin, isoquinoline, acridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, oxazole, benzimidazole, benzotriazole, benzo Oxazole, benzothiazole, oxazole, hydrazine, triazolopyrazine, triazolopyrimidine, tetrazaindene, oxadiazole, imidazopyridine, pyrrolidine, pyrrolopyridine, thiadiazole Pyridine, dibenzoazepine, tribenzoazepine, etc., poly-arylene compounds, An anthracene compound, a cyclopentadiene compound, a fluorenyl compound, or a nitrogen-containing heterocyclic compound. Further, the present invention is not limited thereto, and an organic compound having a larger electron affinity than an organic compound having a p-type (donor) compound as described above may be used as an acceptor organic semiconductor.

Any organic pigment may be used as the p-type organic semiconductor material or the n-type organic semiconductor material, and preferably, a cyanine dye, a styryl dye, a hemicyan pigment, a merocyanine dye (including zero) may be used. Hypomethyl part cyanine (simple part cyanine)), 3 nucleus cyanine pigment, 4 nucleus cyanine pigment, rhodamine pigment, miscellaneous cyanine pigment, staggered cyanine pigment, Aropole Alopolar dye, oxonium pigment, sulfonium pigment, squarylium dye, croconium dye, aza-methine pigment, coumarin pigment, arylene pigment , anthraquinone pigment, triphenylmethane pigment, azo dye, azo methine dye, spiro compound, metallocene pigment, anthrone dye, fulgide dye, anthraquinone pigment, purple ring ketone pigment, morphazine pigment , phenothiazine, anthraquinone, diphenylmethane, polyene, acridine, acridone, diphenylamine, quinacridone, quinacridone, phenoxazine, Anthraquinone pigment, diketopyrrolopyrrole pigment, dioxane pigment, porphyrin pigment , chlorophyll pigment, phthalocyanine pigment, metal complex pigment, condensed aromatic carbocyclic dye (naphthalene derivative, anthracene derivative, phenanthrene derivative, thick tetraphenyl derivative, anthracene derivative, anthracene derivative, fluoranthene) derivative).

As the n-type organic semiconductor material, it is particularly preferable to use a fullerene or a fullerene derivative excellent in electron transport property. The term "fullerene" means fullerene C ₆₀ , fullerene C ₇₀ , fullerene C ₇₆ , fullerene C ₇₈ , fullerene C ₈₀ , fullerene C ₈₂ , fullerene C ₈₄ , Fullerene C ₉₀ , fullerene C ₉₆ , fullerene C ₂₄₀ , fullerene C ₅₄₀ , mixed fullerenes, fullerene nanotubes, so-called "fullerene derivatives" are expressed in these rich A compound having a substituent added to the olefin.

The substituent of the fullerene derivative is preferably an alkyl group, an aryl group or a heterocyclic group. More preferably, the alkyl group is an alkyl group having 1 to 12 carbon atoms, and the aryl group and the heterocyclic group are preferably a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, a terphenyl group, and a thick tetraphenyl group. Ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, pyridazine ring, anthracene ring, benzo Furan ring, benzothiophene ring, isobenzofuran ring, benzimidazole ring, imidazopyridine ring, quinazine ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring, quinoxaline ring , isoquinoline ring, indazole ring, phenazin ring, acridine ring, phenanthroline ring, thioxan ring, benzopyran ring, dibenzopyran ring, phenoxathiine ring, phenothiazine (phenothiazine) ring, or phenazine ring, more preferably a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyridine ring, an imidazole ring, an oxazole ring, or a thiazole ring, particularly preferably a benzene ring, Naphthalene ring, or pyridine ring. These may further have a substituent which may also bond as much as possible to form a ring. Further, it may have a plurality of substituents which may be the same or different. Moreover, a plurality of substituents may also be bonded as much as possible to form a ring.

The photoelectric conversion layer can rapidly transfer electrons generated by photoelectric conversion to the pixel electrode 34 or by means of a fullerene molecule or a fullerene derivative molecule by containing a fullerene or a fullerene derivative molecule. Electrode 38. If a path in which a fullerene molecule or a fullerene derivative molecule is connected to form an electron, the electron transport property is improved. Highly, high-speed responsiveness of the photoelectric conversion element can be achieved. Therefore, it is preferred to contain 40% (by volume) or more of fullerene or fullerene derivative in the photoelectric conversion layer. When the fullerene or fullerene derivative is too large, the p-type organic semiconductor decreases, and the bonding interface becomes small, resulting in a decrease in exciton dissociation efficiency.

The p-type organic semiconductor material which is mixed with the fullerene or the fullerene derivative in the photoelectric conversion layer 52 can be expressed by using the triarylamine compound described in Japanese Patent No. 4213832 or the like. The high SN ratio of the photoelectric conversion element is particularly excellent. When the ratio of the fullerene or fullerene derivative in the photoelectric conversion layer is too large, the amount of the triarylamine compound decreases and the amount of absorption of incident light decreases. Thereby, the photoelectric conversion efficiency can be reduced. Therefore, it is preferable that the fullerene or fullerene derivative contained in the photoelectric conversion layer has a composition of 85% by volume or less.

An electronic organic material can be used in the electron blocking layer 50. Specifically, N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD) and 4,4'- can be used as the low molecular material. An aromatic diamine compound such as bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD), oxazole, oxadiazole, triazole, imidazole, imidazolidinone, stilbene Derivatives, pyrazoline derivatives, tetrahydroimidazole, polyarylalkanes, butadiene, 4,4',4"-tris(N-(3-methylphenyl)N-phenylamino) a phenylamine (m-MTDATA), a porphin, a tetraphenylporphyrin copper, a phthalocyanine, a copper phthalocyanine, a titanium phthalocyanine oxide, or the like, a triazole derivative, an oxadiazole derivative, an imidazole derivative a polyarylalkane derivative, a pyrazoline derivative, a pyrazolone derivative, a phenylenediamine derivative, an annealing amine derivative, an amine-substituted chalcone derivative, an oxazole derivative, Styryl hydrazine derivative, anthrone derivative, anthracene derivative, decazane derivative, carbazole derivative, As the polymer material, a polymer such as phenylenevinylene, hydrazine, carbazole, hydrazine, hydrazine, pyrrole, picoline, thiophene, acetylene or diacetylene, and derivatives thereof can be used as the polymer material. Even if it is not provided with an electronic compound, it can also be used as a compound which has sufficient hole-transportability.

An inorganic material can also be used for the electron blocking layer 50. In general, the inorganic material has a larger dielectric constant than the organic material. Therefore, in the case of use in the electron blocking layer 50, a large voltage can be applied to the photoelectric conversion layer, and the photoelectric conversion efficiency can be improved. The material which can be the electron blocking layer 50 is calcium oxide, chromium oxide, copper chromium oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium oxide copper, copper beryllium oxide, cerium oxide, molybdenum oxide or indium copper oxide. Indium oxide silver, ruthenium oxide, and the like.

In the electron blocking layer including the plurality of layers, the layer adjacent to the photoelectric conversion layer 52 in the plurality of layers is preferably a layer containing the same material as the p-type organic semiconductor contained in the photoelectric conversion layer 52. As described above, since the same p-type organic semiconductor is also used in the electron blocking layer 50, an intermediate level can be suppressed from being formed at the interface of the layer adjacent to the photoelectric conversion layer 52, and dark current can be further suppressed.

When the electron blocking layer 50 is a single layer, the layer may be a layer containing an inorganic material, and in the case of a plurality of layers, one or two or more layers may be a layer containing an inorganic material.

Next, a method of manufacturing the imaging element 20 will be described.

3(a) and 3(b) are schematic cross-sectional views showing a method of manufacturing an imaging element according to an embodiment of the present invention in order of steps, and Figs. 4(a) and 4(b) are diagrams showing the steps in order. Description of a method of manufacturing an imaging element according to an embodiment of the present invention The intentional cross-sectional view shows the post-process of Figure 3(b).

In the method of manufacturing the imaging device 20 according to the embodiment of the present invention, first, as shown in FIG. 3(a), a circuit board 35 (CMOS substrate) is prepared, and a readout circuit 60 and a counter electrode voltage supply unit are formed. On the substrate 30 of 62, the first connection portion 64 and the second connection portion 66, the insulating layer 32 provided with the wiring layer 68, and the surface 32a of the insulating layer 32 are formed with the first connection portion 64. Prime electrode 34. In this case, as described above, the first connection portion 64 is connected to the readout circuit 60, and the second connection portion 66 is connected to the counter electrode voltage supply portion 62. The pixel electrode 34 is formed, for example, by TiN.

Next, the film is transported in a film forming chamber (not shown) of the electron blocking layer 50 by a predetermined transport path, and as shown in FIG. 3(b), for example, a vapor deposition method is used to block electrons under a predetermined vacuum. The material is formed into a film to form an electron blocking layer 50 covering all of the pixel electrodes 34 except for the second connecting portion 66. The electron blocking material uses, for example, a carbazole derivative, and more preferably a diterpene derivative.

Then, it is transported in a film forming chamber (not shown) of the photoelectric conversion layer 52 by a predetermined transport path, and a photoelectric conversion layer is formed on the surface 50a of the electron blocking layer 50 by a vapor deposition method under a predetermined vacuum. 52. As the photoelectric conversion material, for example, a p-type organic semiconductor material and a fullerene or a fullerene derivative can be used. Thereby, the photoelectric conversion layer 52 is formed, and the organic layer 36 is formed.

Then, after being transported in a film forming chamber (not shown) of the counter electrode 38 by a predetermined transport path, the organic layer 36 (the photoelectric conversion layer 52 and the electron blocking layer 50) is covered and formed in the second connection. The pattern on portion 66, using, for example, sputtering The counter electrode 38 is formed under a prescribed vacuum.

Then, the film is conveyed in a film forming chamber (not shown) of the protective film 40 by a predetermined transport path, and as shown in FIG. 4(a), the counter electrode 38 and the surface 32a of the insulating layer 32 are covered. As the protective film 40, a hafnium oxynitride film (SiOxNy film) having a thickness of 300 nm is formed by, for example, a plasma CVD method.

In this case, as the protective film 40, a ruthenium oxynitride film having the above composition and density is formed by a plasma CVD method at a substrate temperature of 240 ° C or lower. With respect to the composition and density of the yttrium oxynitride film, the yttrium oxynitride film is formed by changing the flow rate of the reaction gas or the like in advance, and the film formation conditions (film formation temperature (substrate temperature), pressure at the time of film formation, and electric power at the time of film formation are determined in advance. The gas type (SiH ₄ , NH ₃ , N ₂ O) and the mixing ratio of the gas, etc., may be in the range of the composition, and a cerium oxynitride film having a density in the range described above may be formed.

Next, as shown in FIG. 4(b), the color filter 42, the spacer 44, and the light shielding layer 46 are formed on the surface 40a of the protective film 40 by, for example, photolithography. The color filter 42, the spacer 44, and the light shielding layer 46 are used by those skilled in the art of organic solid-state imaging devices. The steps of forming the color filter 42, the spacer 44, and the light shielding layer 46 may be performed under a predetermined vacuum or under a vacuum.

Next, a coating layer 48 covering the surface 47 of the color filter 42, the spacer 44, and the light shielding layer 46 is formed by, for example, a coating method. Thereby, the photographic element 20 as shown in FIG. 2 can be formed. The cover layer 48 can be used by a person skilled in the art of organic solid-state imaging elements. The step of forming the cladding layer 48 can be carried out under a prescribed vacuum or under a vacuum.

When the coating layer 48 is formed by a hafnium oxynitride film (SiOxNy film), it can be formed by the same method as the protective film 40.

Hereinafter, other specific examples of the organic functional layer substrate will be described.

The organic functional layer substrate of the present invention may be, for example, an organic solar cell or an organic EL device.

Fig. 5 (a) is a schematic cross-sectional view showing an organic solar cell according to an embodiment of the present invention, and Fig. 5 (b) is a schematic cross-sectional view showing an organic EL device according to an embodiment of the present invention.

The organic solar cell 70 shown in FIG. 5(a) includes an organic photoelectric conversion layer 76. The organic photoelectric conversion layer 76 corresponds to the organic functional layer of the present invention, and has heat resistance of 240 ° C or lower. The organic solar cell 70 is formed by sequentially laminating a lower electrode 74, an organic photoelectric conversion layer 76, a transparent electrode (upper electrode) 78, and a protective film 80 on a substrate 72. The incident light L is incident from the side of the transparent electrode 78.

The protective film 80 has the same composition and density as the protective film 16, and is formed by the same manufacturing method as the protective film 16. Therefore, the detailed description thereof will be omitted. The substrate 72 corresponds to the substrate 12 of the present invention (see FIG. 1(a)).

The lower electrode 74, the organic photoelectric conversion layer 76, and the transparent electrode 78 are included in a general user of a known organic solar cell. Therefore, the detailed description thereof will be omitted.

The current generated in the organic photoelectric conversion layer 76 by the irradiation of the incident light L can be taken out to the outside by the lower electrode 74 and the transparent electrode 78.

In the organic solar cell 70 of such a configuration, it is possible to protect the organic solar cell 70 in a high-temperature and high-humidity environment for a long period of time by providing the same protective film 80 as the protective film 16. Organic photoelectric conversion layer 76. Thereby, the durability of the organic solar cell 70 can be improved. Further, the protective film 80 is transparent as described above, and does not prevent the incident light L from entering the organic photoelectric conversion layer 76.

The organic EL element 70a shown in FIG. 5(b) is a light-emitting element using the organic EL layer 86, and is referred to as a "top emission method". In the organic EL element 70a, the same components as those of the organic solar cell 70 shown in Fig. 5(a) are denoted by the same reference numerals, and detailed description thereof will be omitted.

The organic EL layer 86 corresponds to the organic functional layer of the present invention, and has heat resistance of 240 ° C or lower. The organic EL element 70a has a TFT 82, a cathode 84, an organic EL layer 86, a transparent electrode (upper electrode) 78, and a protective film 80 laminated on the substrate 72 in this order. A power source 88 is connected to the TFT 82, the cathode 84, and the transparent electrode 78. The protective film 80 is the same as the organic solar cell 70 shown in Fig. 5(a).

The organic EL layer 86 is a portion where light is emitted, and a hole injection layer, a hole transport layer, a light emitting layer, and electron injection are sequentially laminated. Transport layer, etc.

The cathode 84 and the transparent electrode 78 are for applying a voltage required to cause the organic EL layer 86 to emit light, and the TFT 82 is a light source for controlling the organic EL element 70a.

The power source 88 generates a voltage required to cause the organic EL layer 86 to emit light, and drives the TFT 82.

Further, the TFT 82, the cathode 84, the organic EL layer 86, and the transparent electrode 78 are suitably configured by a general one used in a known organic EL device. Therefore, the detailed description thereof will be omitted.

In the organic EL element 70a of such a configuration, it is also possible to provide The protective film 80 of the same protective film 16 is used to protect the organic EL layer 86 for a long period of time in a high-temperature and high-humidity environment. Thereby, the durability of the organic EL element 70a can be improved. Further, the protective film 80 is transparent as described above, and does not affect the light emission of the organic EL layer 86.

The protective film of the present invention is not limited to the above-described examples, and can protect the organic functional layer having a heat resistance of 240 ° C or less over a long period of time in a high-temperature and high-humidity environment, and the requirement is not to hinder the incidence of light into the organic functional layer and from the organic The transparency of the light emission of the functional layer is suitably used.

The invention is basically constructed as described above. The above-described organic functional layer substrate and the method for producing the same according to the present invention have been described in detail, but the present invention is not limited to the above-described embodiments, and various modifications and changes can be made without departing from the spirit and scope of the invention. .

[Examples]

Hereinafter, the effect of the protective film of the present invention will be specifically described.

In the present Example, samples of Examples 1 to 9 and Comparative Examples 1 to 7 were prepared, and the effects of the protective film of the present invention were confirmed.

In the present embodiment, the following photoelectric conversion element body is used as a sample: on the substrate, a pixel electrode is formed on a portion of the surface of the substrate, the pixel electrode is covered, and an organic functional layer is formed on the substrate as photoelectric conversion. In the layer, a counter electrode is formed on the organic functional layer, and a photoelectric conversion element body having a simplified structure in which a protective film covering the counter electrode is formed is formed.

Further, a ruthenium oxynitride film represented by SiOxNy is used for the protective film.

In the samples of Examples 1 to 9 and Comparative Examples 1 to 7, the element units described later, which have the same configuration except for the protective film, were used.

Hereinafter, the element unit will be described.

Element units formed as follows were prepared for each sample.

An alkali-free glass substrate having a thickness of 0.7 mm was prepared as a substrate, and an indium tin oxide (ITO) film having a thickness of 100 nm was formed as a pixel electrode on the substrate by a sputtering method.

Next, the material represented by the following Chemical Formula 1 was deposited on the substrate by a resistance heating vapor deposition method at a deposition rate of 10 nm/s to 20 nm/s to a thickness of 100 nm to serve as an electron barrier covering the image electrode. Floor. Next, at a vapor deposition rate of 16 nm/s to 18 nm/s and 25 nm/s to 28 nm/s, the volume ratio of the material represented by the following chemical formula 2 to the material represented by the following chemical formula 3 is 1:3. On the other hand, the material represented by the following Chemical Formula 2 (fullerene C ₆₀ ) and the material represented by the following Chemical Formula 3 were co-deposited to have a thickness of 400 nm as an organic layer (photoelectric conversion layer).

[Chemical 2]

Next, an indium tin oxide (ITO) film having a thickness of 10 nm was formed on the organic layer and the substrate by sputtering to serve as a counter electrode.

The sample of Example 1 can be produced as follows.

A ruthenium oxynitride film (SiOxNy film) having a thickness of 300 nm was formed as a protective film on the counter electrode and the substrate of the element unit prepared as described above by a plasma CVD method. The sample of Example 1 was prepared as described above.

The compositions of the protective films of the samples of Examples 1 to 9 and Comparative Examples 1 to 7 are shown in Table 1 below. In addition, the protective film can be obtained in advance as a film forming condition (film forming temperature (substrate temperature), film forming pressure, film forming power, gas type (SiH ₄ , NH ₃ , N). ₂ O) and the mixing ratio of the gas, etc., and film formation is carried out under the production conditions. In Example 1 to Example 9, Comparative Example 1, and Comparative Example 6, the substrate temperature was 154 °C.

In the present Example, the film density and the film composition were measured for the protective films of the respective samples of Examples 1 to 9 and Comparative Examples 1 to 7, and the refractive index at a wavelength of 550 nm was measured using an ellipsometer. The results are shown in Table 1 below.

Further, each of the samples of Examples 1 to 9 and Comparative Examples 1 to 7 was placed in an environment having a temperature of 85 ° C and a relative humidity of 85%, and the dark current after being placed in the environment was measured. The time before the value of 2 times is placed in the environment. This measurement time was taken as the life. The results are shown in Table 1 below.

The film density can be measured as described below.

For the measurement of the film density, ATX-G manufactured by RIGAKU Co., Ltd. was used. The X-ray source uses a Cu target to generate X-rays at 50 keV-300 mA. The S1 slit is 0.5 mm wide and 5 mm high. The incident side optical element is a Ge (220) crystal. The S2 slit is 0.05 mm wide and 10 mm high. The receiving slit is 0.1 mm wide and 10 mm high. There is no light receiving side optical element. The Guard slit is 0.2 mm wide and 20 mm high. The scanning axis is 2θ/ω, the scanning range is 0°~2°, the sampling range is 0.001°, and the scanning speed is 0.1°/min. The film density was calculated by fitting simulation of the measured profiles.

The composition of the film can be determined as described below (XPS).

The measurement apparatus for the film composition used QuanteraSXM manufactured by PHI, and the X-ray source used monochromated Al-Kα rays of 15 kV to 25 W. The depth direction analysis was performed by Ar ⁺ etching / XPS. Regarding the Ar ⁺ etching, the acceleration voltage of Ar ⁺ was set to 3 kV, and the etching area was set to 2 × 2 mm ² . Regarding XPS, the X-ray irradiation range and the analysis range were set to 300 × 300 μm ² , the Pass Energy was set to 112 eV, and the step (Step) was set to 0.2 eV. The charging correction is set to (with an electron gun and a low-speed ion gun), and the respective intensities of C1s, O1s, N1s, and Si2p are corrected by the sensitivity coefficient, and converted into an atomic ratio.

Further, on the dark current, in a state where the photoelectric conversion element main body for shielding, at 60 ℃ environment, in an electric field is applied to 2 × 10 ⁵ V / cm to the electrode side, the use of power meter (Kat in this state The value of the current measured by Keithley's 6430) was used as the dark current.

Further, in Comparative Example 2 to Comparative Example 5 and Comparative Example 7, when the protective film was formed, the substrate temperature was as high as 370 ° C, and the protective film was formed, but the organic layer (photoelectric conversion layer) was damaged. Therefore, it is referred to as "organic destruction" in the column of "85 ° C, 85% RH withstand time (relative time)" in Table 1 below.

As shown in Table 1, in Examples 1 to 9, even in the environment of a temperature of 85 ° C and a relative humidity of 85%, the time until the dark current was doubled was as long as 100 hours as in Example 1. Improve durability.

On the other hand, in Comparative Example 1, the value of x exceeded the upper limit of the present invention, and the formula of y was not satisfied, and the density was also less than the lower limit of the present invention. Comparative Example 1 had a low refractive index, and the temperature was 85 ° C, and the relative humidity of 85% was also as low as 10 hours.

In Comparative Example 6, the film density of the protective film was less than the lower limit of the present invention, and the refractive index was low, and the temperature was 85 ° C and the relative humidity of 85% was also as low as 50 hours.

In Comparative Example 2 to Comparative Example 5 and Comparative Example 7, the substrate temperature as described above Up to 370 ° C, resulting in organic damage. Further, in Comparative Example 2, the protective film did not satisfy the formula of y, and the density exceeded the upper limit of the present invention.

In Comparative Example 3, regarding the protective film, the value of x is also less than the lower limit of the present invention, and the formula of y is not satisfied. In Comparative Example 4, the protective film did not satisfy the formula of y, and the density also exceeded the upper limit of the present invention.

In Comparative Example 5, the protective film did not satisfy the formula of y. In Comparative Example 7, the density of the protective film exceeded the upper limit of the present invention.

10‧‧‧With organic functional layer substrate

12‧‧‧Substrate

14‧‧‧Organic functional layer

16‧‧‧Protective film

Claims (7)

A substrate with an organic functional layer, comprising: a substrate; an organic functional layer disposed on the substrate; a protective film disposed on the organic functional layer; and the protective film comprising nitrogen represented by SiOxNy矽 矽, x, y satisfy 0.5≦x≦1.0, and -2.2y+2.1≦x≦-2.2y+2.41, when the density of the protective film is ρ(g/m ³ ), 2.20 (g) /m ³ ) ≦ρ≦ 2.60 (g/m ³ ). The organic functional layer substrate according to claim 1, wherein the organic functional layer is an organic photoelectric conversion layer that generates light by irradiating light, and the organic photoelectric conversion layer is provided with a lower electrode on the substrate side. A transparent upper electrode is provided on the opposite side of the substrate, and the protective film is disposed on the upper electrode. The organic functional layer substrate according to claim 1, wherein the organic functional layer is a color filter layer containing an organic material, and the protective film is disposed on the color filter layer. The organic functional layer substrate according to any one of claims 1 to 3, wherein x, y satisfy 0.5 ≦ x ≦ 1.0, and -2.2 y + 2.1 ≦ x ≦ - 2.2 y + 2.32. The organic functional layer substrate according to any one of claims 1 to 3, wherein the protective film has a density ρ (g/m ³ ) of 2.30 (g/m ³ ) ≦ρ ≦ 2.60. (g/m ³ ). The organic functional layer substrate according to claim 4, wherein the protective film has a density ρ (g/m ³ ) of 2.30 (g/m ³ ) ≦ρ ≦ 2.60 (g/m ³ ). A method for producing a substrate with an organic functional layer, comprising: forming a protective film comprising cerium oxynitride represented by SiOxNy on an organic functional layer disposed on a substrate, wherein x, y of SiOxNy is satisfied 0.5≦x≦1.0, and -2.2y+2.1≦x≦-2.2y+2.41, when the density of the protective film is ρ(g/m ³ ), 2.20 (g/m ³ )≦ρ≦ 2.60 (g/m ³ ).