TW201523894A - Substrate with organic function layer and method of manufacturing same - Google Patents

Abstract

A substrate with organic function layer includes a substrate, an organic function layer disposed on the substrate, and a protection film disposed on the organic function layer. The protection film includes a plurality of silicon oxynitride layers represented by SiOxNy. An absolute value of difference of refractivity of each of the silicon oxynitride layers is within 0.1, and x and y satisfy 0.5 ≤ x ≤ 1.0 and -2.2y+2.1 ≤ x ≤ -2.2y+2.41. In the plurality of silicon oxynitride layers of the protection film, the x value of the silicon oxynitride layer at the side farther from the organic function layer is 0.05 or more larger than the silicon oxynitride layer formed at a position nearest to the organic function layer.

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 and a method for producing the same in an electrolumine event, EL, or the like.

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 discloses that a yttrium oxynitride film (SiOxNy film) formed by a plasma CVD method is used in an image pickup element including an organic photoelectric conversion layer. 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 curing resin), a phenolphthalein polymer layer (epoxy hardening resin), and nitrogen are sequentially formed on both surfaces of a polyimide film. Oxide 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-based cured resin) by sputtering, and a phenolphthalein polymer layer is formed thereon. A layer of oxynitride is formed on the phenolphthalein 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 discloses a transparent gas barrier material in which an SiON film is formed by reactive sputtering on a PET substrate. Non-Patent Document 1 shows the relationship between the composition of the SiOxNy film and the oxygen permeability. Non-Patent Document 1 shows that gas barrier properties are improved by increasing x from 0.6 to 1.0.

[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] S. Iwamori et al., "Vacuum" 68 (2003) 113-117.

As described above, in Patent Document 1 to Patent Document 3, the SiOxNy film used as the protective film has a description relating to internal stress, film composition, and gas barrier properties. However, if the compressive stress of the SiOxNy film is large, film peeling occurs, and if the tensile stress acts, the predetermined gas barrier property cannot be obtained. As described above, film peeling occurs due to the state of the film stress, and gas barrier properties are lowered, and the film stress has an appropriate range. The SiOxNy film having improved gas barrier properties has a high film stress and is peeled off.

Further, in Patent Document 1 to Patent Document 3, the stability of the SiOxNy film under high temperature and high humidity is not shown, and there is no consideration regarding the heat storage stability.

In the SiOxNy film used as the protective film, the SiOxNy film which does not have the above-mentioned appropriate film stress and which does not deteriorate the gas barrier properties even in a high-temperature and high-humidity environment is not used.

An object of the present invention is to provide an organic functional layer substrate including a protective film and a method for manufacturing the same according to the problems of the prior art, wherein the protective film has no loss due to reflected light, and the film stress is within a prescribed range. And excellent stability in high temperature and high humidity environment.

In order to achieve the object, a first aspect of the present invention provides a substrate with an organic function layer, comprising: a substrate; and an organic machine disposed on the substrate An energy layer and a protective film disposed on the organic functional layer; the protective film comprising a plurality of yttrium oxynitride layers represented by SiOxNy, wherein the absolute value of the refractive index difference of each yttrium oxynitride layer is within 0.1, more preferably within 0.05, x, y satisfy 0.5≦x≦1.0, and -2.2y+2.1≦x≦-2.2y+2.41, in the protective film, among the plurality of layers of oxynitride, the ruthenium oxynitride layer farther from the organic functional layer The value of x is larger than the value of x of the yttrium oxynitride layer formed at the position closest to the organic functional layer by 0.05 or more.

The protective film may have a configuration in which another layer is included between the respective ruthenium oxynitride layers.

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.

Further, for example, the organic functional layer is a color filter layer containing an organic substance, and 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.

According to a second aspect of the present invention, there is provided a method for producing a substrate having an organic functional layer, comprising: a protective film forming step of forming a plurality of SiOxNy by a plasma CVD method on an organic functional layer disposed on a substrate; The yttrium oxynitride layer is represented as a protective film; in the protective film forming step, only the high frequency power in the film forming conditions in the plasma CVD method is changed, and the value ratio of x is formed at a position closest to the organic functional layer. The value of x of the ruthenium oxynitride layer is 0.05 or more, more preferably 0.1 or more, still more preferably 0.15 or more, to form a ruthenium oxynitride layer farther from the organic functional layer.

According to the present invention, it is possible to provide an organic functional layer substrate including a protective film which can suppress loss due to reflected light, has a film stress within a predetermined range, and is excellent in stability in a high temperature and high humidity environment. In particular, in the case where an organic photoelectric conversion layer is used in the organic functional layer, sensitivity loss due to reflected light can be reduced.

Further, according to the present invention, it is possible to manufacture an organic functional layer substrate including a protective film which can suppress loss due to reflected light, has a film stress in a predetermined range, and is excellent in stability in a high-temperature and high-humidity environment.

10‧‧‧With organic layer substrate

10a, 10b‧‧‧ with organic functional layer substrate

12‧‧‧Substrate

14‧‧‧Organic functional layer

16, 80‧‧‧ protective film

16a, 41a, 81a‧‧‧1st bismuth oxynitride layer

16b, 41b, 81b‧‧‧2nd bismuth oxynitride layer

17‧‧‧3rd bismuth oxynitride layer

19‧‧‧Other constituent layers

20‧‧‧Photographic components

20a‧‧‧Photographic components

30, 72, 100‧‧‧ substrates

32‧‧‧Insulation

32a‧‧‧ Surface of insulating layer 32

34‧‧‧ pixel electrodes (lower electrode)

35‧‧‧Circuit board (CMOS board)

36‧‧‧Organic layer

38‧‧‧ opposite electrode (upper electrode)

40‧‧‧Protective film (sealing layer)

40a‧‧‧ Surface of protective film 40

42‧‧‧Color filters

44‧‧‧Baffle

46‧‧‧Lighting layer

47‧‧‧ Surface of the light-shielding layer 46

48‧‧‧Protective layer

49a‧‧‧1st bismuth oxynitride layer

49b‧‧‧2nd bismuth oxynitride layer

50‧‧‧Electronic barrier

50a‧‧‧ Surface of the electronic barrier layer 50

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

102‧‧‧film

200‧‧‧Measurement device

202‧‧‧Laser Department

204‧‧‧Separator

206‧‧‧Mirror

208‧‧‧1st detection department

210‧‧‧2nd detection department

h‧‧‧Thickness of substrate 100

L‧‧‧ incident light

Px‧‧‧unit pixels

R‧‧‧ radius of curvature

t‧‧‧Thickness of film 102

σ _c ‧‧‧compressive stress

σ _t ‧‧‧ tensile stress

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 another example of the organic functional layer substrate according to the embodiment of the present invention, and Fig. 1 (c) It is a schematic view showing another example of the organic functional layer substrate according to the embodiment of the present invention, and FIG. 1(d) is a schematic view showing a state before the protective film is formed in the organic functional layer substrate of FIG. 1(a).

Fig. 2 (a) is a schematic cross-sectional view showing an image pickup element according to an embodiment of the present invention, and Fig. 2 (b) is a schematic cross-sectional view showing another example of the image pickup element according to the 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 diagrams showing an embodiment of the present invention in order of steps A schematic cross-sectional view of a method of manufacturing a photographic element, showing the 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.

6(a) and 6(b) are schematic cross-sectional views for explaining stress on a film formed on a substrate, respectively.

FIG. 7 is a schematic view showing a measuring device for measuring the amount of warpage of a substrate on which a thin film is formed.

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 another example of the organic functional layer substrate according to the embodiment of the present invention, and Fig. 1 (c) It is a schematic view showing another example of the organic functional layer substrate according to the embodiment of the present invention, and FIG. 1(d) is a schematic view showing a state before the protective film is formed in the organic functional layer substrate of FIG. 1(a).

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, a metal substrate with an insulating layer, a resin substrate, and gold can be used. Is a substrate or the like. 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 heat resistance of 245 ° 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 an organic EL element, and a color filter.

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 245 ° C or lower. Therefore, if the temperature exceeds 245 ° 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 a multilayer structure in which a plurality of ruthenium oxynitride layers represented by SiOxNy are laminated. In the example shown in FIG. 1(a), the protective film 16 is the first yttria layer 16a and the second yttrium oxynitride layer 16b. However, the number of layers is not particularly limited. Moreover, in the protective film 16 of FIG. 1(a), it is directly provided on the organic functional layer 14, but if it can be protected In the organic functional layer 14, 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.

In the yttrium oxynitride layer constituting the protective film 16, x and y of SiOxNy satisfy 0.5 ≦ x ≦ 1.0, and -2.2 y + 2.1 ≦ x ≦ - 2.2 y + 2.41 (0.5 ≦ y ≦ 0.86). It is preferable to satisfy 0.5 ≦ x ≦ 1.0 and -2.2 y + 2.1 ≦ x ≦ - 2.2 y + 2.32.

In the protective film 16, a plurality of ruthenium oxynitride layers are different in composition, and among the plurality of ruthenium oxynitride layers, the value of x of the ruthenium oxynitride layer farther from the organic functional layer 14 is formed closer to the organic functional layer. The value of x in the niobium oxynitride layer at the position is 0.05 or more. Specifically, in the case of FIG. 1( a ), the first bismuth oxynitride layer 16 a is formed directly above the organic functional layer 14 , and the second bismuth oxynitride layer 16 b corresponds to nitrogen farther from the organic functional layer 14 . Oxide layer. In the case of FIG. 1(a), when the second bismuth oxynitride layer 16b is compared with the first bismuth oxynitride layer 16a, the value of x of the SiOxNy of the second bismuth oxynitride layer 16b is set to x _{2 .} When the value of x of SiOxNy of the first bismuth oxynitride layer 16a is x ₁ , x ₁ + 0.05 ≦ x ₂ .

In the case of two or more layers, the value of x of SiOxNy of the yttria layer is different due to the relative positional relationship with respect to the organic functional layer 14, and the value of x from the side of the organic functional layer 14 is sequentially at least 0.05. In the protective film 16, as the yttrium oxynitride layer becomes the uppermost layer, the value of x takes a large value within the range of the composition. The value of y of the uppermost layer of the protective film 16 is preferably 0.60 to 0.68, and more preferably the value of y is 0.62 to 0.66.

In addition, although the value of x is at least 0.05 or more, it is more preferably 0.1. More preferably, the above is 0.15 or more.

For example, when the protective film 16 is a three-layer structure of the first yttria layer 16a to the third yttrium oxynitride layer 17 as in the organic functional layer substrate 10a shown in FIG. 1(b), the first nitrogen oxide is used. The uppermost third arsenic oxynitride layer 17 of the ruthenium layer 16a to the third ruthenium oxynitride layer 17 takes the value of x which is the largest in the composition range. However, the present invention is not limited thereto, and in the case of three or more layers, the first oxynitride layer 16a and the second oxynitride layer 16b have a composition satisfying the above composition, and the first oxynitride layer 16a and the first layer can be used. When the ruthenium oxynitride layer 16b functions as the protective film 16, the third ruthenium oxynitride layer 17 of the uppermost layer may not satisfy the composition of the ruthenium oxynitride layer.

On the other hand, when the second oxynitride layer 16b and the uppermost argon oxynitride layer 17 satisfy the above composition, the second oxynitride layer 16b and the uppermost third arsenide layer 17 can function as a protective film. In the function of 16, the first yttria layer 16a may not satisfy the composition of the yttrium oxynitride layer.

Further, the protective film 16 does not need to be the uppermost layer with the organic functional layer substrate, and a film may be further formed on the protective film 16. In this case, the constitution and composition of the film are not particularly limited.

Further, as in the organic functional layer-attached substrate 10b shown in FIG. 1(c), another constituent layer may be present between the first hafnium oxynitride layer 16a and the second hafnium oxynitride layer 16b. The other constituent layer is, for example, a transparent electrode, a resin layer or an adhesive layer. It can also be applied to the organic functional layer substrate 10a having a three-layer structure as shown in Fig. 1(b).

In the present invention, it is preferable that the total thickness of the protective film 16 is 50 nm or more regardless of the constitution of the protective film 16.

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

Here, the term "transparent" means that the light absorptivity is less than 0.2% in a wavelength range of 400 nm to 800 nm (visible light region). That is, the term "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.

In the protective film 16, the absolute value of the refractive index difference of each of the yttrium oxynitride layers is within 0.1, more preferably within 0.05. Specifically, in the example shown in FIG. 1( a ), the absolute value of the refractive index difference between the first argon oxynitride layer 16 a and the second bismuth oxynitride layer 16 b is within 0.1. Further, when the number of layers of the protective film 16 is 3 or more, the absolute value of the refractive index difference of all the ruthenium oxynitride layers is 0.1 or less. That is, in the protective film 16, the difference between the maximum value and the minimum value of the refractive index of the yttrium oxynitride layer is within 0.1. Thereby, the incident light L can be suppressed from being reflected at the interface between the first yttria layer 16a and the second yttrium oxynitride layer 16b of the protective film 16. Further, it is preferable that the absolute value of the refractive index difference is within 0.03.

Here, the compressive film stress of the durable yttria layer (SiON film) is large. When the film thickness of the protective film is thinned to prevent the film from peeling off, the optical path length is changed, the reflectance of the incident light L is increased, and if the organic functional layer 14 is a photoelectric conversion layer, It cannot be used due to its reduced sensitivity. Moreover, stress and durability cannot be achieved in a single layer film. Therefore, by setting the film structure to a multilayer structure and setting the composition and refractive index difference of each layer to the range of the present invention, it is possible to provide the high stress layer only on the surface without changing the overall film thickness. Both the suppression of the film peeling of the protective film and the suppression of the increase in the reflectance are both.

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 ).

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.

The protective film 16 represented by SiOxNy is formed by a plasma CVD method at a temperature of 245 ° C or lower from the viewpoint of heat resistance of the organic functional layer 14 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.

In the organic functional layer substrate 10 of FIG. 1(a), for example, as shown in FIG. 1(d), after the organic functional layer 14 is formed on the substrate 12, the substrate temperature is as described above on the organic functional layer 14 ( The film formation temperature is 245 ° C or lower, and a ruthenium oxynitride layer in the range of the composition is formed by a plasma CVD method to serve as the protective film 16 . The composition and density of the yttrium oxynitride layer are changed to form a ruthenium oxynitride layer 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", high-frequency power at the time of film formation, gas type (SiH ₄ , NH ₃ , N ₂ O), and gas mixing ratio, etc., and nitrogen oxidation in the range of the composition can be formed.矽 layer.

In the protective film 16, a plurality of ruthenium oxynitride layers are formed, and the compositions are different. In this case, by merely changing the high-frequency power in the film formation conditions in the plasma CVD method, the value of x of SiOxNy of the yttria layer can be made to be higher than that of the yttrium oxynitride formed at the position closest to the organic functional layer 14. The value of x of the layer is greater than 0.05. In the case of a plurality of ruthenium oxynitride layers, it is also possible to continuously form a plurality of yttrium oxynitride layers by merely changing the high frequency power as a film formation condition without stopping the supply of the material gas. Further, it is also possible to stop the supply of the material gas and continuously change the high frequency power to continuously form a plurality of ruthenium oxynitride layers. The composition of the yttrium oxynitride layer can be changed by changing only the high frequency power as described above to form a plurality of ruthenium oxynitride layers. Therefore, a reaction chamber such as a process chamber required for formation of a plurality of ruthenium oxynitride layers is 1 Just one. Therefore, it is possible to suppress an increase in the film formation time of the protective film, and further reduce the production cost, without requiring a time required for the substrate to be fed and fed, and the film formation environment.

Further, in the protective film 16, the composition of the yttrium oxynitride layer can be changed, whereby the film stress of the protective film 16 can be adjusted. Further, the film stress and its measuring method will be described in detail later. The film stress of the protective film 16 is a value of stress in the multilayer structure. When the protective film has a configuration in which another layer is provided between the yttria layers as shown in FIG. 1(c), the film stress is a value of the stress in the state of the multilayer structure.

Hereinafter, a specific example of the organic functional layer substrate of the present invention will be described. The organic functional layer substrate of the present invention may be specifically referred to as an organic complementary gold, for example. It is an oxide semiconductor (Complementary Metal Oxide Semiconductor, CMOS).

Fig. 2 (a) is a schematic cross-sectional view showing an image pickup element according to an embodiment of the present invention, and Fig. 2 (b) is a schematic cross-sectional view showing another example of the image pickup element according to the embodiment of the present invention.

The photographic element 20 shown in Fig. 2(a) is referred to as an organic CMOS, and converts a visible light image into an electrical signal. 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 a protective layer 48. A readout circuit 60 and a counter electrode voltage supply unit 62 are formed on the substrate 30.

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.

Formed inside the insulating layer 32 to use the readout circuit 60 and the opposite phase The pole voltage supply unit 62 is connected to a wiring layer 68 of a conductive material, for example, to the outside of the imaging element 20.

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 a circuit substrate 35. In addition, 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 the photoelectric conversion layer 52 is formed on the surface 50a of the electron blocking layer 50. 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, covering the photoelectric conversion Change 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. a metal nitride such as TiN, a metal such as gold (Au), platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni), or aluminum (Al), and further oxidizing the metal and the conductive metal. A mixture or laminate of the substance, an organic conductive compound such as polyaniline, polythiophene or polypyrrole, or a laminate with ITO. 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. another 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, which causes a dark current to rise. 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 on the substrate 30 corresponding to each of the plurality of pixel electrodes 34, and reads a signal corresponding to the electric charge captured by the corresponding pixel electrode 34.

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, tantalum nitride, 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, and antimony-doped Any material of zinc oxide (AZO) or gallium-doped zinc oxide (GZO). 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, a high-concentration n region surrounded by the p region is formed on the substrate 30, and the first connection 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 245 ° C or lower. The protective film 40 covers 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. Moreover, after the manufacture of the photographic element 20, the water molecules are prevented, The factor of deterioration of the organic photoelectric conversion material such as oxygen is immersed, 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 the same multilayer structure as the protective film 16. The protective film 40 has the same composition and density as the protective film 16, and forms two layers of ruthenium oxynitride represented by SiOxNy. The protective film 40 is a layer in which the first hafnium oxynitride layer 41a and the second hafnium oxynitride layer 41b are laminated. The protective film 40 is formed by a plasma CVD method at a temperature of 245 ° C or lower.

Further, for example, the total thickness of the protective film 40 is 50 nm to 500 nm.

When the total film thickness of the protective film 40 is less than 50 nm, the barrier property is lowered, or the resistance of the color filter to the developer is lowered. On the other hand, when the total film 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 total 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) inside becomes large, and the color mixture is caused. Therefore, it is preferable that the total film thickness of 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 spacer 44 is disposed between the color filters 42 on the protective film 40, It is used to improve the light transmission efficiency of the color filter 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. In the protective film 40, similarly to the protective film 16, a configuration in which another constituent layer is included between the first oxynitride layer 41a and the second oxynitride layer 41b may be employed.

The overcoat 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 protective 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 protective layer 48 can be patterned by photolithography, and thus it is easy to open the peripheral light shielding layer, the sealing layer, the insulating layer, and the like on the pad for soldering. When it is used as a photoresist, it is preferable to process the protective layer 48 itself into a microlens. On the other hand, the protective 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. And, in order In the pursuit of the function as a protective layer for the post-process, and the function as an anti-reflection layer, the protective 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 protective layer 48 may be formed to have the same composition and density as the protective film 16 in the same manner as the protective film 40 described above, and two layers of oxynitride layers represented by SiOxNy may be formed. In this case, as in the imaging element 20a shown in FIG. 2(b), the protective layer 48 may be a layer in which the first hafnium oxynitride layer 48a and the second hafnium oxynitride layer 48b are laminated. Further, the imaging element 20a shown in FIG. 2(b) differs from the imaging element 20 shown in FIG. 2(a) in that the protective layer 48 has a different configuration and is the same constituent, and therefore its description is omitted. Detailed description.

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.

Further, the refractive index difference of the protective film 40 is as small as 0.1 or less, preferably 0.05 or less, and generation of reflected light can be suppressed, and the loss of sensitivity in the imaging element 20 is also small. Thereby, the efficiency of the photographic element 20 can be improved.

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 compound (naphthalene derivative, anthracene derivative, phenanthrene derivative) , a thick tetraphenyl derivative, an anthracene derivative, an anthracene derivative, a fluoranthene derivative), 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, tetraazaindene, oxadiazole, imidazopyridine, pyrrolidine, pyrrolopyridine, thiadiazole pyridine, Benzodiazepine, tribenzoazepine, etc., poly-arylene compound, hydrazine compound, cyclopentadiene a compound, a decyl group compound, 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 dye, 4 nucleus cyanine dye, rhodamine pigment, miscellaneous cyanine pigment, staggered cyanine pigment, Aropole Alopolar dye, oxonium pigment, hemi-oxygen pigment, squalane salt, ketone oxime pigment, azamethine pigment, coumarin pigment, arylene pigment, anthraquinone pigment, triphenyl Methane pigment, azo dye, azo methine dye, spiro compound, metallocene pigment, anthrone dye, fulgide dye, anthraquinone, purple ketone, morphazine, phenothiazine, anthraquinone , diphenylmethane pigment, polyene pigment, acridine pigment, acridone pigment, diphenylamine pigment, quinacridone dye, quinophthalone dye, morphine dye, anthraquinone pigment, diketone Pyrrolopyrrole pigment, dioxane pigment, porphyrin pigment, chlorophyll pigment, phthalocyanine , Metal complex dye, a condensed aromatic carbocyclic ring dye (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene fused derivatives, pyrene derivatives, perylene 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 fullerene means fullerene C ₆₀ , fullerene C ₇₀ , fullerene C ₇₆ , fullerene C ₇₈ , fullerene C ₈₀ , fullerene C ₈₂ , fullerene C ₈₄ , Fuller Alkene C ₉₀ , fullerene C ₉₆ , fullerene C ₂₄₀ , fullerene C ₅₄₀ , mixed fullerenes, fullerene nanotubes, so-called fullerene derivatives are indicated on the fullerene A compound having a substituent.

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, morphine ring, phenothiazine ring, or The phenazine ring is 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, and particularly preferably a benzene ring, a naphthalene ring or a 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. When a path in which electrons are formed in a state in which molecules of a fullerene molecule or a fullerene derivative are connected to each other, electron transport properties are improved, and high-speed responsiveness of the photoelectric conversion element can be achieved. Therefore, it is preferred that The photoelectric conversion layer contains 40% by volume or more of fullerene or fullerene derivative. 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, anthracene derivative, Pyrazoline derivatives, tetrahydroimidazoles, polyarylalkanes, butadiene, 4,4',4"-tris(N-(3-methylphenyl)N-phenylamino)triphenylamine (m-MTDATA), porphyrin, tetraphenylporphyrin copper, phthalocyanine, copper phthalocyanine, titanium phthalocyanine oxide and other porphyrin compounds, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyaryl Alkane derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, annealing amine derivative, amine-substituted chalcone derivative, oxazole derivative, styryl group Anthracene derivatives, anthrone derivatives, anthracene derivatives, indole derivatives, carbazole derivatives, diterpene derivatives, etc., and phenylenevinylene, hydrazine, A polymer of carbazole, hydrazine, hydrazine, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof. 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. A schematic cross-sectional view of a method of manufacturing an imaging element according to an embodiment of the present invention shows a post-process of FIG. 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 the portion 66 is formed by a sputtering method to form the counter electrode 38 under a predetermined vacuum.

Next, the film is formed 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 is covered on the surface 32a of the insulating layer 32. For example, in the RF plasma CVD method, the first yttria layer 41a having a thickness of 100 nm and the second bismuth oxynitride layer 41b having a thickness of 100 nm are formed as a protective film 40.

In this case, the substrate layer (film formation temperature) is 245 ° C or lower, and the ruthenium oxynitride layer having the composition and the density is formed by the plasma CVD method as the protective film 40. With respect to the composition and density of the yttrium oxynitride layer, the yttrium oxynitride layer can be formed by changing the flow rate of the reaction gas or the like in advance, and the film formation conditions (film formation temperature, pressure at the time of film formation, and film formation) can be determined in advance. A high-frequency power, a gas type (SiH ₄ , NH ₃ , N ₂ O), a mixing ratio of gases, and the like are formed to form a ruthenium oxynitride layer in the range of the composition.

In the formation of the protective film 40, after the first yttrium oxynitride layer 41a is formed in the same manner as the protective film 16, the second oxynitride layer 41b is formed by merely changing the high frequency power in the film formation conditions. Thereby, the value of x of the second hafnium oxynitride layer 41b can be made larger than the value of x of the first hafnium oxynitride layer 41a by 0.05 or more, and the composition can be changed. Further, the refractive index difference may be made 0.1 or less, or may be made 0.05 or less.

Further, by merely changing the high-frequency power in the film formation conditions, the first hafnium oxynitride layer 41a and the second hafnium oxynitride layer 41b can be continuously formed without stopping the film formation gas.

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. color 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 protective 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 protective layer 48 can be used by a person skilled in the art of organic solid-state imaging elements. The step of forming the protective layer 48 can be carried out under a prescribed vacuum or under a vacuum.

When the protective layer 48 is formed by a plurality of layers of oxynitride oxynitride (SiOxNy layer), 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 245 ° 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 is the same two-layer structure as the protective film 16, and has The same composition and density as the protective film 16. This protective film 80 can be 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 protective film 80 includes a first bismuth oxynitride layer 81a and a second bismuth oxynitride layer 81b. The protective film 80 can be configured as shown in FIGS. 1(b) and 1(c) in the same manner as the protective film 16.

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, the organic photoelectric conversion layer 76 can be protected for a long period of time in a high-temperature and high-humidity environment by providing the same protective film 80 as the protective film 16. 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 called 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 245 ° 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. On TFT 82, A power source 88 is connected to the cathode 84 and the transparent electrode 78. The protective film 80 has the same two-layer structure as the organic solar cell 70 shown in FIG. 5(a). In this case, the protective film 80 may be configured as shown in FIGS. 1(b) and 1(c) in the same manner as the protective film 16.

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 successively 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 having such a configuration, the organic EL layer 86 can be protected for a long period of time in a high-temperature and high-humidity environment by providing the same protective film 80 as the protective film 16. 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 245 ° C or less over a long period of time in a high-temperature and high-humidity environment, and the requirement is that the light is not incident on the organic functional layer and is derived from the organic The transparency of the light emission of the functional layer is suitably used.

Hereinafter, the film stress of the protective film 16 and the protective film 40, and the measuring method thereof will be described. Further, since the protective film 16 has the same configuration as the protective film 40, the protective film 16 will be described as an example. Further, the protective layer 48 may have the same configuration as that of the protective film 40. Therefore, the following description of the film stress and the method for measuring the same also includes the protective layer 48.

As shown in FIGS. 6(a) and 6(b), the substrate 100 on which the thin film 102 corresponding to the protective film 16 is formed is taken as an example, and the stress acting on the thin film 102 is used as a stress acting on the protective film 16. And explain it. The protective film 16 is a multilayer structure. When the multilayer structure is a single film and stress is measured, the film stress of the protective film 16 can be obtained. Further, the stress of each of the yttria layers of the protective film 16 can be measured in a single layer state, and the average value of each stress can be obtained, thereby measuring the film stress of the protective film 16.

Fig. 6(a) is a view showing the direction of the compressive stress σ _c acting on the film 102 when the substrate 100 on which the thin film 102 is formed is expanded by arrows. As shown in FIG. 6(a), when the side on which the thin film 102 is formed is protruded and the substrate 100 is warped, the film 102 formed on the substrate 100 is expanded, and the film 102 which is in close contact with the substrate 100 is subjected to a compressive force. . This force is the compressive stress σ _c .

Fig. 6(b) is a view showing the direction of the tensile stress σ _t acting on the film 102 when the substrate 100 on which the film 102 is formed is shrunk by arrows. As shown in FIG. 6(b), when the side on which the film 102 is formed is recessed and the substrate 100 is bent, the film 102 formed on the substrate 100 is shrunk, and the film 102 that is in close contact with the substrate 100 acts to extend the force. . This force is the tensile stress σ _t .

Here, the compressive stress σ _c and the tensile stress σ _t of the film 102 affect the amount of warpage of the substrate 100. Next, the stress can be measured using an optical lever method based on the amount of warpage of the substrate 100.

FIG. 7 is a schematic view showing a measuring device for measuring the amount of warpage of a substrate on which a thin film is formed. The measuring device 200 shown in FIG. 7 includes a laser irradiation unit 202 that irradiates laser light, and a separator 204 that reflects a part of light emitted from the laser irradiation unit 202 and transmits other light; the mirror 206, The light transmitted through the separator 204 is reflected. A film 102 as an object to be measured is formed on one surface of the substrate 100. The light reflected by the separator 204 is irradiated onto the thin film 102 of the substrate 100, and the first detecting portion 208 detects the reflection angle of the light reflected by the surface of the film 102 at this time. The light reflected by the mirror 206 is irradiated onto the film 102 of the substrate 100, and the second detecting unit 210 detects the angle of reflection of the light reflected by the surface of the film 102 at this time.

In addition, FIG. 7 shows an example of measuring the compressive stress that acts on the film 102 so that the surface on the side where the thin film 102 is formed on the substrate 100 protrudes and warps. Here, the thickness of the substrate 100 is h, and the thickness of the film 102 is t.

Next, the measurement procedure of the film stress of the measuring device 200 will be described.

As the apparatus used for the measurement, for example, a membrane pressure measuring device FLX-2320-S manufactured by Dongpeng Technology Co., Ltd. can be used. The measurement conditions in the case of using this device are shown below.

(Laser light (laser irradiation unit 202))

Use laser: KLA-Tencor-2320-S

Laser output power: 4mW

Laser wavelength: 670nm

Scanning speed: 30mm/s

(substrate)

Substrate material: 矽 (Si)

Direction: <100>

Type: P type (dopant: boron)

Thickness: 250μm±25μm or 280μm±25μm

(measurement order)

The amount of warpage of the substrate 100 on which the thin film 102 is formed is measured in advance, and the radius of curvature R1 of the substrate 100 is obtained. Then, a film 102 is formed on one surface of the substrate 100, and the amount of warpage of the substrate 100 is measured to obtain a radius of curvature R2. Here, as shown in FIG. 7, the amount of warpage is scanned by the surface of the substrate 100 on the side where the thin film 102 is formed by the laser, and the amount of warpage is calculated from the angle of reflection of the laser light reflected from the substrate 100, according to Calculate the radius of curvature R=R1 by the amount of warpage. R2/(R1-R2).

Thereafter, the stress of the film 102 was calculated according to the following calculation formula. The unit of stress of the film 102 is represented by Pa. If it is a compressive stress, it shows a negative value, and if it is a tensile stress, it shows a positive value. Further, the method of measuring the stress of the film 102 is not particularly limited, and a known method can be used.

(stress pressure calculation formula)

σ=E×h ² /6(1- v )Rt

Wherein E/(1- v ): two-axis elastic modulus (Pa) of the base substrate, v : Passon's ratio h: thickness (m) of the base substrate, t: film thickness (m) of the film, and R: base substrate Radius of curvature (m), σ: average stress (Pa) of the film.

The invention is basically constructed as described above. In the above, the organic-functional layer substrate and the method for producing the same according to the present invention are described in detail. However, the present invention is not limited to the embodiment, and various modifications and changes may 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 Example 1, Example 2, and Comparative Example 1 to Comparative Example 9 were produced, 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 two-layer structure of a ruthenium oxynitride layer represented by SiOxNy is used for the protective film. Niobium oxynitride layer

In the samples of Example 1, Example 2, and Comparative Example 1 to Comparative Example 9, an element unit of the same configuration, which will be described later, was used in addition to the configuration of the protective film.

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 by a sputtering method so as to cover the organic layer as a counter electrode.

Next, an aluminum oxide film (AlOx film) having a thickness of 30 nm was formed on the counter electrode by an atomic layer chemical vapor deposition method (AL-CVD method).

The sample of Example 1 can be produced as follows.

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

The compositions of the protective films of the respective samples of Example 1, Example 2, and Comparative Example 1 to Comparative Example 9 are shown in Table 1 below. In addition, the film forming conditions (film forming temperature (substrate temperature), film forming temperature, film forming high-frequency power, gas type (SiH ₄ , NH ₃ , etc.) which are predetermined compositions and densities can be obtained in advance. N ₂ O) and a gas mixture ratio, etc., are formed under the production conditions. The flow rate of the fixed gas, the film formation temperature, the pressure at the time of film formation, and the frequency of the high-frequency wave at the time of film formation were changed, and only the high-frequency power was changed to prepare a protective film, and Example 1, Example 2, and Comparative Example 1 to Comparative Example 3 were produced, respectively. Protective film for each sample. In Comparative Example 4 and Comparative Example 5, a protective film of each sample was produced by changing both of the high frequency power and the film formation temperature.

In Example 1, Example 2, and Comparative Example 1 to Comparative Example 9, when the film formation temperature was not clearly described in Table 1 below, the film formation temperature was set to 154 °C. Unless otherwise specified, the same gas species as those of SiH ₄ , NH ₃ , and N ₂ O are used for film formation.

Further, the lower layer of Comparative Example 6 and the upper layer of Comparative Example 7 were formed by changing the film formation temperature to 350 ° C and changing the gas type to the gas type A. The lower layer of Comparative Example 8 and the upper layer of Comparative Example 9 were formed by changing the film formation temperature to 350 ° C and changing the gas type to the gas type B. In addition, the gas type A is a gas type in which the component amount of NH ₃ in the component is larger than the gas type used for film formation unless otherwise specified. The gas type B is a gas type having a larger amount of components of N ₂ O in the component than the gas type used in the film formation unless otherwise specified.

In the present Example, the film stress was measured on the protective films of the respective samples of Example 1, Example 2, and Comparative Example 1 to Comparative Example 9, and the wave was measured using an ellipsometer. The length is 550 nm. The results are shown in Table 1 below.

Further, each sample of Example 1, Example 2, and Comparative Example 1 to Comparative Example 9 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 until the value twice before the environment is placed. This measurement time was taken as the life. The results are shown in Table 1 below.

The film stress was measured using the method shown in Fig. 7 described above.

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 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.

In the dark current, an electric field of 2 × 10 ⁵ V/cm is applied to the counter electrode side in a state where the photoelectric conversion element body is shielded from light, and an electric current meter is used in this state (Ki Shili) The value of the current measured by (6430) manufactured by Keithley was used as the dark current.

Further, in Comparative Example 6 to Comparative Example 9, when the protective film was formed, the film formation temperature of any of the upper layer and the lower layer was as high as 350 ° C, and the protective film was formed, but the organic layer (photoelectric conversion layer) was damaged. Therefore, in the following Table 1, "85 ° C, 85% RH withstand time In the column of sex (relative time), it is marked as "NG".

As shown in the above Table 1, the overall film stress of the protective films of Examples 1 and 2 is 0 MPa to 220 MPa, which is a suitable region as a film stress. Further, even in the environment of a temperature of 85 ° C and a relative humidity of 85%, the time when the dark current is twice doubled is as long as 1000 hours in the first embodiment, and the durability can be improved. In the first embodiment and the second embodiment, the composition of the upper layer and the lower layer is changed by changing the high frequency power.

On the other hand, when Comparative Example 1 is the same composition of the upper layer and the lower layer of the protective film, when the overall film stress of the protective film is +5 MPa, the tensile stress acts, and the temperature The tolerance at 85 ° C and 85% relative humidity is also as low as 100 hours.

When Comparative Example 2 is the same composition of the upper layer and the lower layer of the protective film, when the overall film stress of the protective film is -120 MPa, the compressive stress acts, but the resistance at a temperature of 85 ° C and a relative humidity of 85% is as low as 350 hours.

When Comparative Example 3 is the same composition of the upper layer and the lower layer of the protective film, and the overall film stress of the protective film is -280 MPa, the compressive stress acts. The tolerance at a temperature of 85 ° C and a relative humidity of 85% was 1000 hours.

The lower layer of the protective film of Comparative Example 4 exceeded the upper limit of the value of x. Further, in Comparative Example 4, in order to form the upper layer and the lower layer of the protective film, it is necessary to change the film formation temperature when the lower layer is formed. Therefore, Comparative Example 4 cannot be produced by the production method of the present invention.

The lower layer of the protective film of Comparative Example 5 satisfies the value of x and the formula of y, and the upper layer exceeds the upper limit of the value of x. Therefore, the barrier property was lowered, and the resistance at a temperature of 85 ° C and a relative humidity of 85% was 10 hours.

In Comparative Example 6 to Comparative Example 9, although the film formation temperature was as high as 350 ° C as described above, a protective film could be formed, but the organic layer (photoelectric conversion layer) was damaged.

Further, in Comparative Example 6 and Comparative Example 7, since the refractive index difference was 0.12 and was outside the range of the present invention, reflection of incident light could not be suppressed, reflectance increased, and sensitivity of the photoelectric conversion element body was lowered.

The lower layer of Comparative Example 8 failed to satisfy the formula of y, and the upper layer satisfies the value of x and the expression of y. The film stress of the entire protective film of Comparative Example 8 was as large as -350 MPa, and film peeling occurred.

The lower layer of Comparative Example 9 satisfies the value of x and the expression of y, and the upper layer does not satisfy y. formula. The film stress of the entire protective film of Comparative Example 9 was as large as -350 MPa, and film peeling occurred.

10‧‧‧With organic layer substrate

10a, 10b‧‧‧ with organic functional layer substrate

12‧‧‧Substrate

14‧‧‧Organic functional layer

16‧‧‧Protective film

16a‧‧‧1st bismuth oxynitride layer

16b‧‧‧2nd bismuth oxynitride layer

17‧‧‧3rd bismuth oxynitride layer

19‧‧‧Other constituent layers

Claims (10)

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 comprising a plurality of oxynitride represented by SiOxNy In the ruthenium layer, the absolute value of the refractive index difference of each of the ruthenium oxynitride layers is 0.1 or less, and the x and y satisfy 0.5 ≦ x ≦ 1.0, and -2.2 y + 2.1 ≦ x ≦ - 2.2 y + 2.41. In the protective film, among the plurality of the ruthenium oxynitride layers, the value of x of the ruthenium oxynitride layer farther from the organic functional layer is larger than the value of nitrogen oxidized at a position closest to the organic functional layer. The value of x in the enamel layer is 0.05 or more. The organic functional layer substrate according to claim 1, wherein the protective film has a total thickness of 50 nm or more. The organic functional layer substrate according to claim 1, wherein the protective film contains other layers between the respective ruthenium oxynitride layers. The organic functional layer substrate according to claim 2, wherein the protective film contains another layer between the respective ruthenium oxynitride layers. The organic functional layer substrate according to any one of claims 1 to 4, wherein the organic functional layer is an organic photoelectric conversion layer that generates a charge when irradiated with light, and the organic photoelectric conversion layer is a lower electrode is disposed on the substrate side, and a transparent upper electrode is disposed on an opposite side of the substrate. The protective film is disposed on the upper electrode. The organic functional layer substrate according to any one of claims 1 to 4, wherein the organic functional layer is a color filter layer containing an organic substance on the color filter layer. The protective film is disposed. The organic functional layer substrate according to any one of claims 1 to 4, wherein the x, y satisfy 0.5≦x≦1.0, and -2.2y+2.1≦x≦-2.2y +2.32. The organic functional layer substrate according to any one of claims 5, wherein the 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 6 to 6, wherein the x, y satisfy 0.5 ≦ x ≦ 1.0, and -2.2 y + 2.1 ≦ x ≦ - 2.2 y + 2.32. A manufacturing method of an organic functional layer substrate, comprising: a protective film forming step of forming a plurality of bismuth oxynitride represented by SiOxNy by plasma chemical vapor deposition on an organic functional layer disposed on a substrate a layer as a protective film; in the protective film forming step, only the high frequency power in the film forming conditions in the plasma chemical vapor deposition method is changed, and the value ratio of x is formed closest to the organic The value of x of the yttrium oxynitride layer at the position of the functional layer is 0.05 or more, and a ruthenium oxynitride layer farther from the organic functional layer is formed.