WO2014010432A1

WO2014010432A1 - Solid state imaging element and method for manufacturing solid state imaging element

Info

Publication number: WO2014010432A1
Application number: PCT/JP2013/067689
Authority: WO
Inventors: 俊博中谷
Original assignee: 富士フイルム株式会社
Priority date: 2012-07-09
Filing date: 2013-06-27
Publication date: 2014-01-16
Also published as: KR101671609B1; JP5806176B2; KR20150027175A; JP2014017374A

Abstract

Provided are a solid state imaging element and a method for manufacturing the same, which solid state imaging element uses an organic photoelectric conversion material, and with which, by forming a colour filter so as to exceed the formation range of an organic layer having a photoelectric conversion layer, the tearing of the film forming the element is prevented and the yield can be improved.

Description

Solid-state imaging device and method for manufacturing solid-state imaging device

The present invention relates to a solid-state imaging device including a photoelectric conversion layer containing an organic substance. In particular, the present invention relates to a solid-state imaging device capable of preventing film peeling of layers constituting the device, which occurs in the manufacturing process, and a manufacturing method thereof.

As an image sensor used in digital still cameras, digital video cameras, imaging modules for endoscopes, imaging modules for mobile phones, etc., pixels including photodiodes are arranged on a semiconductor substrate such as a silicon (Si) chip. Solid-state imaging devices (so-called CCD sensors and CMOS sensors) that acquire signal charges corresponding to photoelectrons generated in the photodiodes of each pixel with a CCD type or CMOS type readout circuit are widely known.
In addition, as shown in Patent Document 1, Patent Document 2, and the like, in recent years, an image sensor having an organic photoelectric conversion layer using an organic material that generates an electric charge in response to received light has been studied.

As shown in Patent Document 1, Patent Document 2, and the like, an imaging device having an organic photoelectric conversion layer includes a pixel electrode formed on a semiconductor substrate on which a signal readout circuit is formed, and an organic film formed on the pixel electrode. A photoelectric conversion layer, a transparent counter electrode (upper electrode) formed on the organic photoelectric conversion layer, a sealing layer formed on the counter electrode and protecting the counter electrode, and formed on the sealing layer And a color filter or the like.

JP 2008-252004 A JP 2008-227091 A

By the way, in the manufacture of semiconductor devices using not only solid-state imaging devices but also silicon wafers or the like, the back surface of the wafer (the surface opposite to the device formation surface) is polished and thinned for the purpose of reducing the size and weight of the semiconductor device. A so-called back grinding process is performed.
This back grinding process is performed after the formation of an element such as an integrated circuit is completed. Therefore, the back grinding process is performed by protecting a device by attaching a protective tape called a BG tape (back grind tape) to the surface on which the device is formed.
When the back grinding is finished, the protective tape is peeled off, and the wafer on which the element is formed is subjected to the next step.

However, according to the study of the present inventor, in the solid-state imaging device having the organic photoelectric conversion layer, when this back grinding process is performed, the protective tape is peeled between the layers constituting the device (film peeling). ) Often occurs, resulting in a decrease in yield.

An object of the present invention is to solve such problems of the prior art, in a solid-state imaging device having an organic photoelectric conversion layer made of an organic material that generates electric charge in response to received light, in a back grinding process. An object of the present invention is to provide a solid-state imaging device capable of preventing film peeling and improving yield, and a method for manufacturing the solid-state imaging device.

In order to achieve this object, a solid-state imaging device according to the present invention includes a plurality of pixel electrodes and a photoelectric conversion layer that is provided on the pixel electrodes and includes a photoelectric conversion layer made of an organic material that generates charges according to received light. A conversion unit, a counter electrode provided on the photoelectric conversion unit, common to the plurality of pixel electrodes, a sealing layer provided on the counter electrode so as to cover the counter electrode, and a sealing layer, A color filter provided so as to cover the entire surface of the photoelectric conversion unit, and a readout circuit that reads out a signal corresponding to the charge collected in the pixel electrode, and the color filter exceeds a range in which the photoelectric conversion layer is formed A solid-state imaging device is provided.

In such a solid-state imaging device of the present invention, it is preferable that the color filter formation range that exceeds the photoelectric conversion layer formation range is 0.05 μm or more.
The color filter preferably has a thickness of 0.1 μm or more.
Further, when the color filter is formed by arranging a red filter, a green filter, and a blue filter corresponding to the pixel electrode, the red filter and the green filter are formed beyond the formation range of the photoelectric conversion layer. Preferably it is at least one of the filters.
Moreover, it is preferable that a photoelectric conversion part has an electron blocking layer for suppressing injecting an electron from a pixel electrode to a photoelectric converting layer in the lower layer of a photoelectric converting layer.
The photoelectric conversion layer preferably has a bulk heterostructure formed by mixing a p-type organic semiconductor material and an n-type organic semiconductor material.
The n-type organic semiconductor material is preferably at least one of fullerene and fullerene derivatives.
In addition, the p-type semiconductor organic material is preferably a compound represented by the following general formula (1).

(In the general formula (1), Z ₁ represents a ring containing at least two carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. L ₁ , L ₂ and L ₃ each independently represents an unsubstituted methine group or a substituted methine group, D ₁ represents an atomic group, and n represents an integer of 0 or more.)
Further, the counter electrode is preferably indium tin oxide.

The solid-state imaging device manufacturing method of the present invention includes a plurality of pixel electrodes, a photoelectric conversion unit having a photoelectric conversion layer made of an organic material, a counter electrode, and a sealing layer covering the counter electrode on a substrate. Then, after laminating in this order, a color filter is formed on the sealing layer, including the entire surface of the photoelectric conversion portion, in a formation range exceeding the formation range of the photoelectric conversion layer, and a protective tape on the color filter formation surface side A solid-state imaging device manufacturing method is provided, in which a substrate is back-grinded, a back-grinding is performed, and then a protective tape is peeled off.

In such a method for producing a solid-state imaging device of the present invention, the formation range of the color filter that exceeds the formation range of the photoelectric conversion layer is preferably 0.05 μm or more.
The color filter preferably has a thickness of 0.1 μm or more.
In addition, when the color filter is a red filter, a green filter, and a blue filter arranged in correspondence with the pixel electrode, at least one of the red filter and the green filter exceeds the formation range of the photoelectric conversion layer. Preferably formed.
In the photoelectric conversion unit, an electron blocking layer for suppressing injection of electrons from the pixel electrode to the photoelectric conversion layer is preferably laminated as a lower layer of the photoelectric conversion layer.
The photoelectric conversion layer preferably has a bulk heterostructure formed by mixing a p-type organic semiconductor material and an n-type organic semiconductor material.
The n-type organic semiconductor material is preferably at least one of fullerene and fullerene derivatives.
In addition, the p-type semiconductor organic material is preferably a compound represented by the following general formula (1).

According to the present invention having the above configuration, in the solid-state imaging device using the organic photoelectric conversion layer made of an organic material that generates an electric charge according to the received light, the solid-state imaging device is used when the protective tape is peeled off in the back grinding process. Can be prevented from peeling off.
Therefore, according to the present invention, in a solid-state imaging device using an organic photoelectric conversion layer, defective products due to film peeling can be greatly reduced and a high yield can be obtained.

It is a figure which shows notionally an example of the solid-state image sensor of this invention manufactured by the manufacturing method of the solid-state image sensor of this invention. (A)-(c) is a conceptual diagram for demonstrating the manufacturing method of the solid-state image sensor of this invention. (A)-(c) is a conceptual diagram for demonstrating the manufacturing method of the solid-state image sensor of this invention.

Hereinafter, the solid-state imaging device of the present invention and the method for manufacturing the solid-state imaging device will be described in detail based on preferred embodiments shown in the accompanying drawings.

FIG. 1 conceptually shows an example of the solid-state image sensor of the present invention manufactured by the method for manufacturing a solid-state image sensor of the present invention.
As an example, this solid-state imaging device is used by being mounted on an imaging device such as a digital camera or a digital video camera, an imaging module of a mobile phone, an imaging module of an electronic endoscope, or the like.

A solid-state imaging device 10 (hereinafter, referred to as imaging device 10) illustrated in FIG. 1 includes a substrate 12, an insulating layer 14, a pixel electrode 16, a photoelectric conversion unit 18, a counter electrode 20, a sealing layer 22, And a color filter 26.
In the image sensor 10, a read circuit 40 and a counter electrode voltage supply unit 42 are formed on the substrate 12.

As the substrate 12, a semiconductor substrate such as an Si substrate is basically used. As the substrate 12, a glass substrate can also be used.
An insulating layer 14 made of a known insulating material is formed on the substrate 12.

A plurality of pixel electrodes 16 are formed on the surface of the insulating layer 14. The pixel electrodes 16 are arranged in a one-dimensional or two-dimensional manner, for example.
Examples of the material of the pixel electrode 16 include metals, metal oxides, metal nitrides, metal borides, organic conductive compounds, and mixtures thereof. Specifically, 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, titanium nitride (TiN) Metal nitrides such as gold (Au), platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni), aluminum (Al), etc., and these metals and conductive metal oxides A mixture or laminate of the above, an organic conductive compound such as polyaniline, polythiophene, and polypyrrole, a laminate of these with ITO, and the like. A particularly preferable material for the pixel electrode 16 is any one of titanium nitride, molybdenum nitride, tantalum nitride, and tungsten nitride.

In addition, a first connection portion 44 that connects the pixel electrode 16 and the readout circuit 40 is formed in the insulating layer 14.
Furthermore, a second connection portion 46 that connects the counter electrode 20 and the counter electrode voltage supply unit 42 is formed in the insulating layer 14. The second connection portion 46 is formed at a position not connected to the pixel electrode 16 and the photoelectric conversion portion 18. Both the first connection portion 44 and the second connection portion 46 are made of a conductive material.

A wiring layer 48 for connecting the readout circuit 40 and the counter electrode voltage supply unit 42 to, for example, the outside of the imaging device 10 is formed inside the insulating layer 14. The wiring layer 48 is made of a conductive material.
Hereinafter, the circuit board 11 is formed by forming the pixel electrodes 16 connected to the first connection portions 44 on the surface of the insulating layer 14 formed on the substrate 12 as described above. The circuit board 11 is also called a CMOS substrate.

The photoelectric conversion unit 18 is formed so as to cover the plurality of pixel electrodes 16 and to avoid the second connection unit 46. The photoelectric conversion unit 18 includes an organic photoelectric conversion layer 50 containing an organic photoelectric conversion material and an electron blocking layer 52. In the photoelectric conversion unit 18, the electron blocking layer 52 is formed on the pixel electrode 16 side (lower layer side), and the photoelectric conversion layer 50 is formed on the electron blocking layer 52.

The electron blocking layer 52 is a layer for preventing electrons from being injected from the pixel electrode 16 into the photoelectric conversion layer 50, and is composed of a single layer or a plurality of layers. The electron blocking layer 52 includes an organic material, an inorganic material, or both.
The electron blocking layer 52 may be composed of a single organic material film, or may be composed of a mixed film of a plurality of different organic materials. The electron blocking layer 52 is preferably formed of a material having a high electron injection barrier from the adjacent pixel electrode 16 and high hole transportability. As an electron injection barrier, the electron affinity of the electron blocking layer 52 is preferably 1 eV or less, more preferably 1.3 eV or less, and particularly preferably 1.5 eV or more than the work function of the adjacent electrode.
The material for forming the electron blocking layer 52 will be described in detail later.

The electron blocking layer 52 preferably has a thickness of 20 nm or more in order to sufficiently suppress the contact between the pixel electrode 16 and the photoelectric conversion layer 50 and to avoid the influence of defects and dust existing on the surface of the pixel electrode 16. . The thickness of the electron blocking layer 52 is more preferably 40 nm or more, and particularly preferably 60 nm or more.
If the electron blocking layer 52 is too thick, the problem of increasing the supply voltage necessary for applying an appropriate electric field strength to the photoelectric conversion layer 50 and the carrier transporting process in the electron blocking layer 52 are due to photoelectric conversion. There may be a problem that the performance of the element is adversely affected. Therefore, the total film thickness of the electron blocking layer 52 is preferably 300 nm or less. The total film thickness of the electron blocking layer 52 is more preferably 200 nm or less, and still more preferably 100 nm or less.

The photoelectric conversion layer 50 generates electric charge according to the amount of light L received such as incident light, and is made of an organic photoelectric conversion material (mainly composed of an organic photoelectric conversion material).
Preferably, the photoelectric conversion layer 50 made of an organic photoelectric conversion material is a layer containing a p-type organic semiconductor material or an n-type organic semiconductor material. The photoelectric conversion layer 50 is more preferably a bulk hetero layer in which a p-type organic semiconductor material and an n-type organic semiconductor material are mixed. More preferably, the photoelectric conversion layer 50 is a bulk hetero layer in which a p-type organic semiconductor material and a fullerene (fullerene derivative) as an n-type organic semiconductor material are mixed.
By using a bulk hetero layer as the photoelectric conversion layer 50, the disadvantage that the carrier diffusion length of the organic layer is short can be compensated and the photoelectric conversion efficiency can be improved. By producing a bulk hetero layer with an optimal mixing ratio, the electron mobility and hole mobility of the photoelectric conversion layer 50 can be increased, and the photoresponse speed of the photoelectric conversion element can be sufficiently increased. . The proportion of fullerene in the bulk hetero layer is preferably 40% to 85% (volume ratio). The bulk hetero layer (bulk hetero junction structure) is described in detail in Japanese Patent Application Laid-Open No. 2005-303266.
The material for forming the photoelectric conversion layer 50 will be described in detail later.

The thickness of the photoelectric conversion layer 50 is preferably 10 to 1000 nm or less, more preferably 50 to 800 nm or less, and particularly preferably 100 to 500 nm or less.
By setting the thickness of the photoelectric conversion layer 50 to 10 nm or more, a suitable dark current suppressing effect can be obtained. Moreover, suitable photoelectric conversion efficiency is obtained by making the thickness of the photoelectric conversion layer 50 1000 nm or less.
Note that the photoelectric conversion layer 50 and the electron blocking layer 52 may have other film thicknesses as long as the film thickness is constant on the pixel electrode 16.

The photoelectric conversion layer 50 is preferably formed by a vacuum evaporation method. When vapor-depositing the photoelectric conversion layer 50, it is preferable that all steps be performed in a vacuum. Basically, the compound is not directly in contact with oxygen and moisture in the outside air. Further, when vapor-depositing the photoelectric conversion layer 50, it is preferable to perform PI control or PID control of the vapor deposition rate using a film thickness monitor such as a crystal resonator or an interferometer. When two or more kinds of compounds are vapor-deposited simultaneously, a co-evaporation method, a flash vapor deposition method, or the like can be preferably used.
Or the coating material containing the organic photoelectric converting material (especially p-type organic-semiconductor material and n-type organic-semiconductor material) which comprises the photoelectric converting layer 50 is prepared, this coating material is apply | coated and dried, Furthermore, as needed The photoelectric conversion layer 50 may be formed by a coating method that performs heat treatment.

The counter electrode (upper electrode) 20 is an electrode that faces the pixel electrode 16 and is provided so as to cover the entire surface of the photoelectric conversion layer 50 (further, the electron blocking layer 52) including side surfaces (end portions in the surface direction described later). It has been. Therefore, the photoelectric conversion layer 50 is provided between the pixel electrode 16 and the counter electrode 20. In the illustrated example, the counter electrode 20 is common to all the pixel electrodes 16.
Further, the counter electrode 20 is electrically connected to the second connection portion 46 disposed outside the photoelectric conversion layer 50, and is connected to the counter electrode voltage supply portion 42 through the second connection portion 46. Has been.

The counter electrode 20 is preferably made of a transparent conductive oxide in order to increase the absolute amount of light incident on the photoelectric conversion layer and increase the external quantum efficiency.
_{Specifically, ITO, IZO, SnO 2,} ATO ( antimony-doped tin oxide), ZnO, AZO (Al-doped zinc oxide), GZO (gallium-doped zinc oxide), TiO _2, FTO (fluorine-doped tin oxide) or the like Preferably exemplified.
Various methods can be used to form the counter electrode 20 depending on the material, but a sputtering method is preferably exemplified.

The light transmittance of the counter electrode 20 is preferably 60% or more, more preferably 80% or more, more preferably 90% or more, and more preferably 95% or more in the visible light wavelength.
The counter electrode 20 preferably has a thickness of 5 to 20 nm. By making the counter electrode 20 have a thickness of 5 nm or more, the lower layer can be sufficiently covered, and uniform performance can be obtained. On the other hand, if the thickness of the counter electrode 20 exceeds 20 nm, the counter electrode 20 and the pixel electrode 16 may be locally short-circuited, resulting in an increase in dark current. Moreover, generation | occurrence | production of a local short circuit can be suppressed by making the counter electrode 20 into a film thickness of 20 nm or less.

The counter electrode voltage supply unit 42 applies a predetermined voltage to the counter electrode 20 via the second connection unit 46. When the voltage to be applied to the counter electrode 20 is higher than the power supply voltage of the image sensor 10, the power supply voltage is boosted by a booster circuit such as a charge pump to supply the predetermined voltage.

The pixel electrode 16 is a charge collecting electrode for collecting charges generated in the photoelectric conversion layer 50 between the pixel electrode 16 and the counter electrode 20 facing the pixel electrode 16. The pixel electrode 16 is connected to the readout circuit 40 via the first connection portion 44. The readout circuit 40 is provided on the substrate 12 corresponding to each of the plurality of pixel electrodes 16, and reads out a signal corresponding to the charge collected by the corresponding pixel electrode 16.
The pixel electrode 16 can be made of the same material as the pixel electrode 16 described above. Therefore, a detailed description of the material of the pixel electrode 16 is omitted.

The pixel electrode 16 has a steep step corresponding to the film thickness of the pixel electrode 16 at the end, significant unevenness on the surface of the pixel electrode 16, and minute dust (particles) adheres to the pixel electrode 16. As a result, the layer on the pixel electrode 16 becomes thinner than a desired film thickness or a crack occurs. When the counter electrode 20 is formed on the layer in such a state, a pixel defect such as an increase in dark current or a short circuit occurs due to contact or electric field concentration between the pixel electrode 16 and the counter electrode 20 in the defective portion. Furthermore, the above-described defects may reduce the adhesion between the pixel electrode 16 and the layer thereon and the heat resistance of the organic photoelectric conversion material.

In order to prevent this defect and improve the reliability of the element, the surface roughness Ra of the pixel electrode 16 is preferably 0.6 nm or less. The smaller the surface roughness Ra of the pixel electrode 16, the smaller the surface unevenness, and the better the surface flatness.
In order to remove particles on the pixel electrode 16, it is particularly preferable to clean the pixel electrode 16 and the like before forming the electron blocking layer 52. This cleaning may be performed using a general cleaning technique used in a semiconductor manufacturing process.

The readout circuit 40 is constituted by, for example, a CCD, a MOS circuit, or a TFT circuit. The read circuit 40 is shielded from light by a light shielding layer (not shown) provided in the insulating layer 14. The readout circuit 40 is preferably a CCD or CMOS circuit for general image sensor applications, and is preferably a CMOS circuit from the viewpoint of noise and high speed.
Although not shown, for example, a high-concentration n region surrounded by a p region is formed on the substrate 12, and the first connection portion 44 is connected to the n region. A read circuit 40 is provided in the p region. The n region functions as a charge storage unit that stores the charge of the photoelectric conversion layer 50. The signal charge accumulated in the n region is converted into a signal corresponding to the amount of charge by the readout circuit 40 and output to the outside of the image sensor 10 via the wiring layer 48, for example.

The sealing layer (protective layer) 22 is for protecting the photoelectric conversion layer 50 containing an organic photoelectric conversion material from deterioration factors, such as a water molecule. The sealing layer 22 is formed to cover the entire surface of the counter electrode 20 including the side surfaces.
The following conditions are required for the sealing layer 22.
First, it is possible to protect the photoelectric conversion layer by preventing intrusion of factors that degrade the organic photoelectric conversion material contained in the solution, plasma, and the like in each manufacturing process of the device.
Secondly, after the device is manufactured, the intrusion of factors such as water molecules that degrade the organic photoelectric conversion material is prevented, and deterioration of the photoelectric conversion layer 50 is prevented over a long period of storage / use.
Third, when the sealing layer 22 is formed, the already formed photoelectric conversion layer is not deteriorated.
Fourth, since incident light reaches the photoelectric conversion layer 50 through the sealing layer 22, the sealing layer 22 must be transparent to light having a wavelength detected by the photoelectric conversion layer 50.

The sealing layer 22 can also be composed of a thin film made of a single material. However, by forming the sealing layer 22 in a multi-layer configuration and providing each layer with a different function, stress relaxation of the entire sealing layer 22, cracking due to dust generation during the manufacturing process, suppression of defects such as pinholes, etc. In addition, the effects such as easy optimization of material development can be expected.
For example, the sealing layer 22 is formed by laminating a “sealing auxiliary layer” having a function that is difficult to achieve on the layer that serves the original purpose of preventing the penetration of deterioration factors such as water molecules. A two-layer structure can be formed. Three or more layers are possible, but considering the manufacturing cost, it is preferable that the number of layers is as small as possible.

Moreover, what is necessary is just to form the sealing layer 22 as follows, for example.
The performance of organic photoelectric conversion materials is significantly deteriorated due to the presence of deterioration factors such as water molecules. Therefore, it is necessary to cover and seal the entire photoelectric conversion layer with a dense metal oxide film, metal nitride film, metal oxynitride film, or the like that does not allow water molecules to permeate. Conventionally, aluminum oxide, silicon oxide, silicon nitride, silicon nitride oxide, a laminated structure thereof, a laminated structure of them and an organic polymer, or the like is used as a sealing layer by various vacuum film forming techniques. The conventional sealing layer is a film compared to the flat part because the growth of the thin film is difficult (because the step becomes a shadow) at the step due to structures on the substrate surface, minute defects on the substrate surface, particles adhering to the substrate surface, etc. The thickness is significantly reduced. For this reason, the step portion becomes a path through which the deterioration factor penetrates. In order to completely cover this step with the sealing layer 22, it is necessary to form the film so as to have a film thickness of 1 μm or more in the flat portion, thereby increasing the thickness of the entire sealing layer 22.

In the image sensor 10 having a pixel size of less than 2 μm, particularly about 1 μm, if the distance between the color filter 26 and the photoelectric conversion layer 50, that is, the film thickness of the sealing layer 22 is large, incident light is diffracted in the sealing layer 22. Or it diverges and color mixing occurs. For this reason, the imaging element 10 having a pixel size of about 1 μm requires a sealing layer material and a manufacturing method thereof that do not deteriorate the element performance even when the film thickness of the entire sealing layer 22 is reduced.

The ALD (atomic layer deposition) method is a kind of CVD method, and adsorption / reaction of organometallic compound molecules, metal halide molecules, and metal hydride molecules, which are thin film materials, onto the substrate surface and unreacted groups contained in them. Is a technique for forming a thin film by alternately repeating decomposition.
Since the ALD method is in a low molecular state when the thin film material reaches the substrate surface (deposition surface), the thin film can be grown in a very small space in which the low molecule can enter. For this reason, the step portion, which was difficult with the conventional thin film formation method, is completely covered (the thickness of the thin film grown on the step portion is the same as the thickness of the thin film grown on the flat portion), that is, the step coverage is very high. Excellent. For this reason, steps due to structures on the substrate surface, minute defects on the substrate surface, particles adhering to the substrate surface, and the like can be completely covered, and such a step portion does not become an intrusion path for a deterioration factor of the photoelectric conversion material. That is, when the sealing layer 22 is formed by the ALD method, the required sealing layer thickness can be reduced more effectively than in the prior art.

In the case of forming the sealing layer 22 by the ALD method, a material that exhibits the function required for the above-described sealing layer can be appropriately selected. However, it is limited to a material capable of growing a thin film at a relatively low temperature so that the organic photoelectric conversion material does not deteriorate.
According to the ALD method using alkyl aluminum or aluminum halide as a material, a dense aluminum oxide thin film can be formed at less than 200 ° C. at which the organic photoelectric conversion material does not deteriorate. In particular, when trimethylaluminum is used, an aluminum oxide thin film can be formed even at about 100 ° C., which is preferable. Silicon oxide and titanium oxide are also preferable because a dense thin film can be formed as the sealing layer 22 at a temperature lower than 200 ° C. similarly to aluminum oxide by appropriately selecting materials.

The thin film formed by the ALD method can achieve a high-quality thin film formation at a low temperature that is unmatched from the viewpoint of step coverage and denseness. However, the thin film may be deteriorated by chemicals used in the photolithography process. For example, since an aluminum oxide thin film formed by the ALD method is amorphous, the surface is eroded by an alkaline solution such as a developer or a stripping solution. In such a case, a thin film having excellent chemical resistance is required on the aluminum oxide thin film formed by the ALD method. That is, a sealing auxiliary layer that becomes a functional layer for protecting the sealing layer 22 is necessary.

In particular, the sealing layer 22 has a two-layer structure, and includes any one of aluminum oxide, silicon oxide, silicon nitride, and silicon nitride oxide formed on the first sealing layer by plasma CVD or sputtering. A configuration having a second sealing layer is preferable. In this case, the first sealing layer preferably contains any of aluminum oxide, silicon oxide, and titanium oxide.
What is necessary is just to set suitably the thickness of a 1st sealing layer and a 2nd sealing layer according to the formation material, formation method, etc. of each layer. As an example, the first sealing layer has a high barrier property with a high stress of 200 MPa or more, for example, an aluminum oxide film by ALD method, and the second sealing layer has a low stress of 100 MPa or less, for example, nitriding by plasma CVD method In the case of a silicon oxide film, the thickness of the first sealing layer is preferably 1 to 40 nm and the thickness of the second sealing layer is preferably 75 nm or more.

A color filter 26 is formed on the sealing layer 22.
The color filter 26 divides incident light into, for example, R (red), G (green), and B (blue), and makes the incident light enter the region corresponding to each pixel electrode 16 of the photoelectric conversion layer 50. It is. In the illustrated example, the color filter 26 corresponds to the color filters of the R filter 26R, the G filter 26G, and the B filter 26B corresponding to the position and arrangement of the pixel electrodes 16 in the same manner as the color filter of a normal solid-state imaging device. It has sequentially and repeatedly.
In other words, in the image sensor 10, the pixel electrode 16 and one pixel electrode 16 on which the photoelectric conversion unit 18, the counter electrode 20, and the color filter are provided are pixels (unit pixels).
In the present invention, the color filter is not limited to the three primary color filters of R, G, and B, and various color filters (combination of color filters) used in the solid-state imaging device can be used. . For example, C (cyan), M (magenta), Y (yellow), or even G complementary color filters may be used.

In the image pickup device 10 of the present invention, the color filter 26 may basically be formed by a method used in the manufacture of a known color solid-state image pickup device such as photolithography.
As an example, a known color resist material having negative photosensitivity (for example, a photocurable composition described in paragraph Nos. [0017] to [0064] of Japanese Patent No. 4717370) is formed on the surface on which the color filter 26 is formed. Apply to the entire surface and pre-bake. Next, using a mask having a pattern for exposing the color filter forming portion, exposure is made with ultraviolet light or the like to make it developable. Thereafter, the light-shielding part is removed with a developing solution, washed with water and dried, and further post-baked on the part not removed by development. A method of forming the color filter 26 in which the R, G, and B color filters are arranged by performing this operation three times according to the R filter 26R, the G filter 26G, and the B filter 26B is exemplified. .

Here, in the image sensor 10 of the present invention, the color filter 26 exceeds the formation range of the photoelectric conversion layer 50 in the arrangement direction of the pixel electrodes 16 (hereinafter also referred to as a plane direction), as shown in FIG. Formed to the extent. That is, the color filter 26 is formed in the surface direction up to a range exceeding the end portion of the photoelectric conversion layer 50 in the surface direction.
In other words, the color filter 26 covers the entire surface of the formation region of the photoelectric conversion layer 50 in the surface direction on the sealing layer 22 and extends to a range wider than the formation range of the photoelectric conversion layer 50 in the surface direction. It is formed (out of the formation range of the photoelectric conversion layer 50).
By having such a configuration, the imaging element 10 of the present invention can prevent the film separation between the photoelectric conversion layer 50 and the counter electrode 20 in the back grinding process, and can improve the yield.

As is well known, in the manufacturing process of a semiconductor device using a silicon wafer or the like, after the formation of elements on the wafer is completed, the back surface of the wafer (element forming surface and A back grinding process for polishing the reverse surface) is performed.
This back grinding process is performed using a polishing apparatus called a BG wheel, for example, by attaching a protective tape (so-called BG tape) for protecting the element to the element forming surface. When the polishing of the back surface of the wafer is completed, the protective tape is peeled off and the wafer is supplied to the next process or the like.

Here, in the solid-state imaging device having a photoelectric conversion layer made of an organic photoelectric conversion material, the present inventor peels off a layer (film) of a layer (film) constituting the element at the time of peeling of the protective tape in the background process. It was found that this film peeling contributed to a decrease in product yield.
As a result of further investigation, the present inventor has a low adhesion between the photoelectric conversion layer 50 made of an organic photoelectric conversion material and the counter electrode 20, and peeling of the film is a photoelectric conversion layer 50 made of an organic photoelectric conversion material and the counter electrode. It was found that it is likely to occur between 20 and 20.

The inventor conducted extensive studies in order to prevent film peeling between the photoelectric conversion layer 50 and the counter electrode 20. In the following description, unless otherwise specified, “film peeling” indicates film peeling between the photoelectric conversion layer 50 and the counter electrode 20.
As a result, as described above, the formation range of the color filter 26 is made wider than the formation range of the photoelectric conversion layer 50, that is, the color filter 26 is extended to the range exceeding the end of the photoelectric conversion layer 50 in the plane direction. It was found that film peeling can be prevented by forming.
In addition, the present inventor indicated that the film peeling between the photoelectric conversion layer 50 and the counter electrode 20 has a bulk heterostructure in which the photoelectric conversion layer 50 is a mixture of a p-type organic semiconductor material and an n-type organic semiconductor material. It has been found that the effects of the present invention are prominent because it is likely to occur when it is included. In particular, when the n-type organic semiconductor material is fullerene (fullerene derivative), the effect of the present invention becomes more remarkable. Among them, the p-type organic semiconductor material is a compound represented by the general formula (1) described later. The case was found to be particularly noticeable.
In addition, the film peeling between the photoelectric conversion layer 50 and the counter electrode 20 is more likely to occur when the counter electrode 20 formed of ITO is combined with the photoelectric conversion layer 50 having the bulk heterostructure. It was found that the effect becomes even more remarkable.

By forming the color filter 26 up to a region exceeding the end of the photoelectric conversion layer 50 in the surface direction, the color filter 26 becomes a buffer material that suppresses the force to peel the counter electrode 52 from the photoelectric conversion layer 50. And can prevent film peeling.
Here, the thickness of the color filter 26 is preferably 0.1 μm or more, more preferably 0.2 μm or more, and particularly preferably 0.3 μm or more. By setting the thickness of the color filter 26 to this thickness, the effect of preventing film peeling can be obtained more suitably. On the other hand, from the viewpoint of reducing development residue, the thickness of the color filter 26 is preferably 2.0 μm or less, more preferably 1.5 μm or less, and particularly preferably 1.0 μm or less.
The thickness of the color filter 26 may be the same for all color filters. Alternatively, the thickness of the color filter 26 may vary depending on the color and the formation region.

Therefore, according to the present invention, it is possible to obtain the imaging device 10 with a high yield by suppressing a decrease in yield due to film peeling between the photoelectric conversion layer 50 and the counter electrode 20.

If the formation range of the color filter 26 slightly exceeds the formation range of the photoelectric conversion layer 50 in the surface direction, film peeling can be prevented.
According to the study of the present inventor, the color filter 26 is formed in a range of 0.05 μm or more in the plane direction and beyond the end portion of the photoelectric conversion layer 50, thereby obtaining the effect of preventing film peeling more suitably. be able to. That is, the distance a between the end of the photoelectric conversion layer 50 and the end of the color filter 26 shown in FIG. 1 (the extra distance of the color filter 26 from the end of the photoelectric conversion layer 50) is 0.05 μm or more. Is preferred. More preferably, the distance a between the end of the photoelectric conversion layer 50 shown in FIG. 1 and the end of the color filter 26 is 0.1 μm or more, and particularly preferably 0.3 μm or more.

On the other hand, if the distance a is too large, film peeling (of the counter electrode 20 and the photoelectric conversion layer 50) can be prevented. However, when the protective tape is peeled off in the back grinding process, 26 and the sealing layer 22 are likely to be peeled off.
The distance a between the end of the photoelectric conversion layer 50 and the end of the color filter 26 is preferably 1.5 mm or less, and more preferably 1.0 mm or less. By setting the distance a to 1.5 mm or less, such damage to the color filter 26 can be suitably prevented.

The distance a between the end portion of the photoelectric conversion layer 50 and the end portion of the color filter 26 does not need to be uniform over the entire circumference in the surface direction of the photoelectric conversion layer 50.
That is, when the shape of the photoelectric conversion layer 50 in the surface direction is a square according to the configuration of the imaging element 10 or the like, one or more of the four sides may have a different distance a from the other sides.

The color filter 26 formed in the region beyond the photoelectric conversion layer 50, that is, the color filter corresponding to the outermost unit pixel in the surface direction is preferably an R filter 26R or a G filter 26G.
At this time, the color filters of the outermost unit pixels in the surface direction may or may not be unified.

As described above, the color filter 26 is formed, for example, by forming each color filter of the R filter 26R, the G filter 26G, and the B filter 26B by exposing and developing using a photosensitive material. The
Here, in many cases, exposure is performed by irradiating ultraviolet rays (UV light). Therefore, the B filter 26B that absorbs the largest amount of ultraviolet rays is hard to be cured. As a result, the B filter 26 </ b> B is insufficiently cured in the vicinity of the lower portion, and easily becomes brittle. For this reason, the B filter 26B is more likely to be damaged or peeled off from the sealing layer 22 than other colors.
On the other hand, the lower part of the R filter 26R and the G filter 26G is sufficiently cured even when irradiated with ultraviolet light. The effect can be expressed more suitably.

In the image sensor 10 of the present invention, the color filter 26 may have a light-shielding partition wall between the color filters in order to prevent crosstalk (color mixing) of the colors. The partition walls can also be formed in the same manner as the color filters described above.
The imaging device 10 prevents light from entering the photoelectric conversion layer 50 formed outside the effective pixel region other than the region (effective pixel region) where the color filter 26 is provided on the sealing layer 22. You may have a light shielding layer.

Furthermore, the image sensor 10 may have a protective layer (overcoat layer) for protecting the color filter 26 and the like on the color filter 26 (covering the entire upper surface).
For the protective layer, a polymer material such as an acrylic resin, a polysiloxane resin, a polystyrene resin, or a fluorine resin, or an inorganic material such as silicon oxide or silicon nitride can be used as appropriate.
When a photosensitive resin such as polystyrene is used, the protective layer can be patterned by a photolithography method. Therefore, it becomes easy to use the protective layer as a photoresist when opening the peripheral light shielding layer, sealing layer, insulating layer, etc. on the bonding pad, or to process the protective layer itself as a microlens, preferable.
On the other hand, the protective layer can be used as an antireflection layer, and it is also preferable to form various low refractive index materials used as the partition walls of the color filter 26. In addition, in order to pursue a function as a protective layer and a function as an antireflection layer with respect to a subsequent process, the protective layer may have a structure of two or more layers combining the above materials.

In the illustrated example, the pixel electrode 16 is formed on the surface of the insulating layer 14. However, the configuration is not limited thereto, and the pixel electrode 16 may be embedded in the surface portion of the insulating layer 14.
Moreover, although the structure which provides the 2nd connection part 46 and the counter electrode voltage supply part 42 was made, it may be plural. For example, a voltage drop at the counter electrode 20 can be suppressed by supplying a voltage from both ends of the counter electrode 20 to the counter electrode 20. The number of sets of the second connection unit 46 and the counter electrode voltage supply unit 42 may be appropriately increased or decreased in consideration of the chip area of the element.

Hereinafter, the manufacturing method of the solid-state imaging device of the present invention will be described in detail by explaining the manufacturing method of the imaging device 10.
In the following manufacturing of the image sensor 10, the film forming conditions of each layer (film) may be set as appropriate according to the layer forming material and the like.

When manufacturing the image sensor 10, as an example, as conceptually shown in FIG. 2A, the first connection is formed on the substrate 12 on which the readout circuit 40 and the counter electrode voltage supply unit 42 are formed. The insulating layer 14 provided with the portion 44, the second connecting portion 46, and the wiring layer 48 is formed. Further, the pixel electrode 16 connected to each first connecting portion 44 is formed on the surface 14a of the insulating layer 14. A formed circuit board 11 (CMOS substrate) is prepared.
In this case, as described above, the first connection unit 44 and the readout circuit 40 are connected, and the second connection unit 46 and the counter electrode voltage supply unit 42 are connected. The pixel electrode 16 is made of, for example, TiN.

Next, in the film forming chamber for the electron blocking layer 52, as conceptually shown in FIG. 2B, the electron blocking material is formed so as to cover all the pixel electrodes 16 except on the second connection portion 46. Is deposited by, for example, vacuum deposition to form the electron blocking layer 52.
As will be described later, examples of the electron blocking material include carbazole derivatives, and more preferably bifluorene derivatives.

Next, in the film formation chamber of the photoelectric conversion layer 50, the photoelectric conversion layer 50 is formed on the surface 52a of the electron blocking layer 52 as conceptually shown in FIG.
The photoelectric conversion part 18 is formed by forming the photoelectric conversion layer 50.

Next, in the film formation chamber of the counter electrode 20, as conceptually shown in FIG. 3A, a pattern that covers the photoelectric conversion layer 18 and is formed on the second connection portion 46, for example, a sputtering method. The counter electrode 20 is formed by depositing ITO.

Next, in the film forming chamber for the sealing layer 22, as shown in FIG. 3B, an aluminum oxide film, for example, is formed as a sealing layer 22 on the surface 14 a of the insulating layer 14 so as to cover the counter electrode 20. Then, a laminated film made of a silicon nitride oxide film is formed.
In this case, as described above, for the aluminum oxide film, aluminum oxide is formed on the surface 14a of the insulating layer 14 by using the ALD method, and silicon nitride oxide is formed on the aluminum oxide film by plasma CVD or sputtering. It is preferable to form a silicon nitride oxide film by using the film.
The sealing layer 22 may be a single layer film as described above.

After forming the sealing layer 22, the color filter 26 is formed.
As described above, the color filter 26 is formed as follows as an example. That is, first, a color resist material to be a filter is applied to the surface 22a of the sealing layer 22 and prebaked. Next, exposure is performed with ultraviolet light or the like using a mask corresponding to the formation pattern of the color filter, and thereafter development is performed to remove the light shielding portion. Further, after washing and drying, post baking is performed to form a color filter.
This operation is performed three times corresponding to the color filters of the R filter 26R, the G filter 26G, and the B filter 26B, thereby forming the color filter 26 in which the color filters are arranged.

Here, in the present invention, the color filter 26 is applied up to the region exceeding the end of the photoelectric conversion layer 50 by applying a coating material for forming a color filter to the region exceeding the end of the photoelectric conversion layer 50 in the surface direction. Such a color filter 26 is formed using a mask for forming (corresponding color filter). That is, in this example, the mask that forms the unit pixel at the end in the surface direction has a pattern that exposes the area exceeding the end of the photoelectric conversion layer 50 in the corresponding unit pixel.
As a result, as shown in FIG. 1, the color filter 26 having a formation range that exceeds the formation range of the photoelectric conversion layer 50 in the plane direction, that is, the region in the plane direction that extends beyond the end of the photoelectric conversion layer 50 in the plane direction. The color filter 26 to be formed is formed.

The coating method for coating is not particularly limited, and various known methods such as spin coating and bar coating can be used.
Further, the color filter existing up to the region beyond the edge in the surface direction of the photoelectric conversion layer 50 is preferably the R filter 26R or the G filter 26G, and the edge of the photoelectric conversion layer 50 and the color filter 26 The distance a to the end is preferably 0.05 μm or more, more preferably 1.5 mm or less, and the film thickness of the color filter is preferably 0.1 μm or more as described above. It is.

In the image sensor 10, the color filter 26 may have a partition between the color filters.
Further, if necessary, a light shielding layer as described above may be formed on the sealing layer 22 other than the region where the color filter 26 is provided, and a protective layer (overcoat layer) is formed on the uppermost layer. It may be formed.

When the color filter 26 is formed in this way, a back grinding process is performed. First, as shown in FIG. 3C, a protective tape T is attached to the surface on which the color filter 26 is formed so as to cover the color filter 26 (a protective layer when a protective layer is formed).
Next, the back surface of the substrate 12 (circuit substrate 11 (wafer)) is polished. The back surface of the substrate 12 may be polished by a known method used in the manufacture of semiconductor devices, such as polishing using a BG wheel.

When the polishing of the back surface of the substrate 12 is completed, the protective tape T is peeled off.
Here, in the present invention, since the color filter 26 is formed in the plane direction up to a range exceeding the formation range of the photoelectric conversion layer 50, even if the protective tape T is peeled off in such a back grinding process, The film peeling between the conversion layer 50 and the counter electrode 20 can be suitably prevented.

Hereinafter, materials for forming the photoelectric conversion layer 50 and the blocking layer 52 will be described.
As described above, the imaging element 10 of the present invention has the photoelectric conversion layer 50 made of an organic material. Preferably, the photoelectric conversion layer 50 is a layer having a bulk heterostructure formed by mixing an n-type organic semiconductor material and a p-type organic semiconductor material.

Exciton dissociation efficiency can be increased by joining a p-type organic semiconductor material and an n-type organic semiconductor material to form a donor-acceptor interface. For this reason, the photoelectric conversion layer of the structure which joined the p-type organic-semiconductor material and the n-type organic-semiconductor material expresses high photoelectric conversion efficiency. In particular, a photoelectric conversion layer in which a p-type organic semiconductor material and an n-type organic semiconductor material are mixed is preferable because the junction interface is increased and the photoelectric conversion efficiency is improved.

The p-type organic semiconductor material (compound) is a donor-type organic semiconductor material (compound), which is mainly represented by a hole-transporting organic compound and refers to an organic compound having a property of easily donating electrons. More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound. For example, triarylamine compound, benzidine compound, pyrazoline compound, styrylamine compound, hydrazone compound, triphenylmethane compound, carbazole compound, polysilane compound, thiophene compound, phthalocyanine compound, cyanine compound, merocyanine compound, oxonol compound, polyamine compound, indole Compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), nitrogen-containing heterocyclic compounds The metal complex etc. which it has as can be used.
Not limited to this, as described above, any organic compound having an ionization potential smaller than that of the organic compound used as the n-type (acceptor property) compound may be used as the 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 means an organic compound having a property of easily accepting electrons. More specifically, an n-type organic semiconductor refers to an organic compound having a larger electron affinity when two organic compounds are used in contact with each other. Therefore, as the acceptor organic compound, any organic compound can be used as long as it is an electron-accepting organic compound. For example, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), 5- to 7-membered heterocyclic compounds containing nitrogen atoms, oxygen atoms, and sulfur atoms (E.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole , Benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, oxy Diazole, imidazopyridine, pyralidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine, etc.), polyarylene compounds, fluorene compounds, cyclopentadiene compounds, silyl compounds, nitrogen-containing heterocyclic compounds as ligands Etc. Not limited to this, as described above, any organic compound having an electron affinity higher than that of the organic compound used as the p-type (donor property) compound may be used as the acceptor organic semiconductor.

Any organic dye may be used as the p-type organic semiconductor material or the n-type organic semiconductor material, but preferably a cyanine dye, a styryl dye, a hemicyanine dye, and a merocyanine dye (including zero methine merocyanine (simple merocyanine)). 3-nuclear merocyanine dye, 4-nuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye , Triphenylmethane dye, azo dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, perinone dye, phenazine dye, phenazine dye Thiazine dye, quinone dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, phenoxazine dye, phthaloperylene dye, diketopyrrolopyrrole dye, dioxane dye, porphyrin dye, chlorophyll dye, phthalocyanine And dyes, metal complex dyes, and condensed aromatic carbocyclic dyes (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives).

As the n-type organic semiconductor material, it is particularly preferable to use fullerene and / or fullerene derivatives having excellent electron transport properties. The fullerene, 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 Fullerene and fullerene nanotube. Moreover, a fullerene derivative represents the compound which added the substituent to these.
In addition, as an n-type organic semiconductor material, only fullerene may be used, only a fullerene derivative may be used, and fullerene and a fullerene derivative may be used together.

The substituent for the fullerene derivative is preferably an alkyl group, an aryl group, or a heterocyclic group. The alkyl group is more preferably an alkyl group having 1 to 12 carbon atoms, and the aryl group and the heterocyclic group are preferably a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring. , Biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran Ring, benzimidazole ring, imidazopyridine ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroli Ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, or phenazine ring, more preferably a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyridine ring, imidazole ring, oxazole ring, Or a thiazole ring, particularly preferably a benzene ring, a naphthalene ring, or a pyridine ring. These may further have a substituent, and the substituents may be bonded as much as possible to form a ring. In addition, you may have a some substituent and they may be the same or different. A plurality of substituents may be combined as much as possible to form a ring.

When the photoelectric conversion layer 50 contains fullerene and / or fullerene derivative, electrons generated by photoelectric conversion can be quickly transported to the pixel electrode 16 or the counter electrode 20 via the fullerene molecule or fullerene derivative molecule. When fullerene molecules or fullerene derivative molecules are connected to form an electron path, the electron transport property is improved, and high-speed response of the photoelectric conversion element can be realized. For this purpose, it is preferable that fullerene and / or fullerene derivatives are contained in the photoelectric conversion layer 50 by 40% (volume ratio) or more. However, when there are too many fullerenes and / or fullerene derivatives, the p-type organic semiconductor is reduced, the junction interface is reduced, and the exciton dissociation efficiency is lowered.

When the triarylamine compound described in Japanese Patent No. 4213832 is used as a p-type organic semiconductor material mixed with fullerene and / or fullerene derivatives in the photoelectric conversion layer 50, a high SN ratio of the photoelectric conversion element can be expressed. It is particularly preferable. If the ratio of fullerene or fullerene derivative in the photoelectric conversion layer is too large, the amount of triarylamine compounds decreases and the amount of incident light absorbed decreases. As a result, the photoelectric conversion efficiency is reduced. Therefore, the fullerene and / or fullerene derivative contained in the photoelectric conversion layer preferably has a composition of 85% (volume ratio) or less.

The p-type semiconductor organic material used for the photoelectric conversion layer 50 is particularly preferably a compound represented by the following general formula (1).

In the general formula (1), Z ₁ represents a ring containing at least two carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. . L ₁ , L ₂ , and L ₃ each independently represent an unsubstituted methine group or a substituted methine group. D ₁ represents an atomic group. n represents an integer of 0 or more.

Z ₁ is a ring containing at least two carbon atoms, and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. As the condensed ring containing at least one of a 5-membered ring, a 6-membered ring, and a 5-membered ring and a 6-membered ring, those usually used as an acidic nucleus in a merocyanine dye are preferable.
Specific examples thereof include the following.

(A) 1,3-dicarbonyl nucleus: for example, 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6- Zeon etc.
(B) pyrazolinone nucleus: for example 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazoyl) -3-methyl-2 -Pyrazolin-5-one and the like.
(C) isoxazolinone nucleus: for example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one, etc.
(D) Oxindole nucleus: For example, 1-alkyl-2,3-dihydro-2-oxindole and the like.
(E) 2,4,6-triketohexahydropyrimidine nucleus: for example, barbituric acid or 2-thiobarbituric acid and its derivatives. Examples of the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl, 1,3-diphenyl, 1,3-diaryl compounds such as 1,3-di (p-chlorophenyl) and 1,3-di (p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, Examples include 1,3-di (2-pyridyl) 1,3-diheterocyclic substituents and the like.
(F) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and its derivatives. Examples of the derivatives include 3-alkylrhodanine such as 3-methylrhodanine, 3-ethylrhodanine and 3-allylrhodanine, 3-arylrhodanine such as 3-phenylrhodanine, and 3- (2-pyridyl) rhodanine. And the like.

(G) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazoledione nucleus: for example, 3-ethyl-2-thio-2,4-oxazolidinedione and the like.
(H) Tianaphthenone nucleus: For example, 3 (2H) -thianaphthenone-1,1-dioxide and the like.
(I) 2-thio-2,5-thiazolidinedione nucleus: for example, 3-ethyl-2-thio-2,5-thiazolidinedione and the like.
(J) 2,4-thiazolidinedione nucleus: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione and the like.
(K) Thiazolin-4-one nucleus: for example, 4-thiazolinone, 2-ethyl-4-thiazolinone and the like.
(L) 2,4-imidazolidinedione (hydantoin) nucleus: for example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, etc.
(M) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione etc.
(N) Imidazolin-5-one nucleus: for example, 2-propylmercapto-2-imidazolin-5-one and the like.
(O) 3,5-pyrazolidinedione nucleus: for example, 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione and the like.
(P) Benzothiophen-3-one nucleus: for example, benzothiophen-3-one, oxobenzothiophen-3-one, dioxobenzothiophen-3-one and the like.
(Q) Indanone nucleus: for example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, 3,3-dimethyl-1-indanone, etc.

The ring formed by Z ₁ is preferably a 1,3-dicarbonyl nucleus, a pyrazolinone nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body, for example, a barbituric acid nucleus, 2-thiobarbitur tool) Acid nucleus), 2-thio-2,4-thiazolidinedione nucleus, 2-thio-2,4-oxazolidinedione nucleus, 2-thio-2,5-thiazolidinedione nucleus, 2,4-thiazolidinedione nucleus, 2, In 4-imidazolidinedione nucleus, 2-thio-2,4-imidazolidinedione nucleus, 2-imidazolin-5-one nucleus, 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus, indanone nucleus More preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine nucleus (including thioketones, such as barbituric acid nucleus, Tool acid nucleus), 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus, indanone nucleus, more preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine Nuclei (including thioketone bodies, such as barbituric acid nuclei, 2-thiobarbituric acid nuclei), particularly preferably 1,3-indandione nuclei, barbituric acid nuclei, 2-thiobarbituric acid nuclei and their derivatives. is there.

L ₁ , L ₂ , and L ₃ each independently represent an unsubstituted methine group or a substituted methine group. The substituted methine groups may be bonded to each other to form a ring (eg, a 6-membered ring such as a benzene ring). Although the substituent W of the substituted methine group includes the substituent W, it is preferable that all of L ₁ , L ₂ and L ₃ are unsubstituted methine groups.
L ₁ to L ₃ may be connected to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

N represents an integer of 0 or more, preferably 0 or more and 3 or less, more preferably 0. When n is increased, the absorption wavelength region can be made longer, or the thermal decomposition temperature is lowered. N = 0 is preferable in that it has appropriate absorption in the visible region and suppresses thermal decomposition during vapor deposition.

D ₁ represents an atomic group. D ₁ is preferably a group containing —NR ^a (R ^b ), more preferably —NR ^a (R ^b ) represents a substituted arylene group. R ^a and R ^b each independently represent a hydrogen atom or a substituent.

The arylene group represented by D ₁ is preferably an arylene group having 6 to 30 carbon atoms, and more preferably an arylene group having 6 to 18 carbon atoms. The arylene group may have a substituent W described later, and is preferably an arylene group having 6 to 18 carbon atoms which may have an alkyl group having 1 to 4 carbon atoms. Examples thereof include a phenylene group, a naphthylene group, an anthracenylene group, a pyrenylene group, a phenanthrenylene group, a methylphenylene group, and a dimethylphenylene group, and a phenylene group or a naphthylene group is preferable.

Examples of the substituent represented by R ^a and R ^b include the substituent W described later, and preferably an aliphatic hydrocarbon group (preferably an alkyl group or alkenyl group which may be substituted) or an aryl group (preferably substituted). A phenyl group which may be substituted), or a heterocyclic group.

The aryl groups represented by R ^a and R ^b are each independently preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 18 carbon atoms. The aryl group may have a substituent, and is preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 18 carbon atoms which may have an aryl group having 6 to 18 carbon atoms. . Examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a phenanthrenyl group, a methylphenyl group, a dimethylphenyl group, and a biphenyl group, and a phenyl group or a naphthyl group is preferable.

The heterocyclic groups represented by R ^a and R ^b are each independently preferably a heterocyclic group having 3 to 30 carbon atoms, more preferably a heterocyclic group having 3 to 18 carbon atoms. The heterocyclic group may have a substituent, and preferably a C 3-18 heterocyclic group which may have an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 18 carbon atoms. It is. The heterocyclic group represented by R ^a and R ^b is preferably a condensed ring structure, and is a furan ring, thiophene ring, selenophene ring, silole ring, pyridine ring, pyrazine ring, pyrimidine ring, oxazole ring, thiazole ring, triazole. A condensed ring structure of a ring combination selected from a ring, an oxadiazole ring, and a thiadiazole ring (which may be the same) is preferable. A quinoline ring, an isoquinoline ring, a benzothiophene ring, a dibenzothiophene ring, a thienothiophene ring, and a bithienobenzene ring A bithienothiophene ring is preferred.

The arylene group and aryl group represented by D ₁ , R ^a , and R ^b are preferably a benzene ring or a condensed ring structure, more preferably a condensed ring structure containing a benzene ring, a naphthalene ring, an anthracene ring, pyrene A benzene ring, a naphthalene ring or an anthracene ring, more preferably a benzene ring or a naphthalene ring.

As the substituent W, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, and a heterocyclic group (May be referred to as a heterocyclic group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyl group, aryl Oxycarbonyl group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercap Group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic ring Azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ), phosphato group (-OPO (OH) ₂ ), sulfato group (-OSO ₃ H), and other known substituents.

When R ^a and R ^b represent a substituent (preferably an alkyl group or an alkenyl group), the substituent is an aromatic ring (preferably benzene ring) skeleton of an aryl group substituted by —NR ^a (R ^b ). It may combine with a hydrogen atom or a substituent to form a ring (preferably a 6-membered ring).
R ^a and R ^b may be bonded to each other to form a ring (preferably a 5- or 6-membered ring, more preferably a 6-membered ring), and R ^a and R ^b are each L A ring (preferably a 5-membered or 6-membered ring, more preferably a 6-membered ring) may be formed by combining with a substituent in (represents any one of L ₁ , L ₂ , and L ₃ ).

The compound represented by the general formula (1) is a compound described in Japanese Patent Application Laid-Open No. 2000-297068, and a compound not described in the above publication can be produced according to the synthesis method described in the above publication. it can. Moreover, it is preferable that the compound represented by General formula (1) is a compound represented by General formula (2).

In the general formula (2), Z ₂ , L ₂₁ , L ₂₂ , L ₂₃ , and n are synonymous with Z ₁ , L ₁ , L ₂ , L ₃ , and n in the general formula (1), and preferred The example is similar. D ₂₁ represents a substituted or unsubstituted arylene group. D ₂₂ and D ₂₃ each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

The arylene group represented by D ₂₁ has the same meaning as the arylene ring group represented by D ₁ , and preferred examples thereof are also the same. The aryl group represented by D ₂₂ and D ₂₃ is independently the same as the heterocyclic group represented by R ^a and R ^b , and preferred examples thereof are also the same.

Hereinafter, preferred specific examples of the compound represented by the general formula (1) are shown using the general formula (3), but the present invention is not limited to these.

In the general formula (3), Z ₃ represents any one of A-1 to A-12 in Chemical Formula 4 shown below. L ₃₁ represents methylene and n represents 0. D ₃₁ represents any one of B-1 to B-9, and D ₃₂ and D ₃₃ represent any one of C-1 to C-16. Z ₃ is preferably A-2, D ₃₂ and D ₃₃ are preferably selected from C-1, C-2, C-15, and C-16, and D ₃₁ is B-1 or B- 9 is preferred.

Particularly preferred p-type organic materials include dyes or materials having no 5 or more condensed ring structures (materials having 0 to 4, preferably 1 to 3 condensed ring structures). When using a pigment-based p-type material generally used in organic thin-film solar cells, the dark current tends to increase at the pn interface, and the light response is slow due to trapping at the crystalline grain boundary. Since it tends to be, it is difficult to use for an image sensor. For this reason, a dye-based p-type material that is difficult to crystallize, or a material that does not have five or more condensed ring structures can be preferably used for the imaging element.

More preferred specific examples of the compound represented by the general formula (1) are combinations of the substituents, linking groups and partial structures shown below in the general formula (3), but the present invention is not limited to these. Absent.

In the chemical formula 7, A-1 to A-12, B-1 to B-9, and C-1 to C-16 have the same meanings as shown in the chemical formula 4.
Although the especially preferable specific example of a compound represented by General formula (1) below is shown, this invention is not limited to these.

(Molecular weight)
The compound represented by the general formula (1) preferably has a molecular weight of 300 to 1500, more preferably 350 to 1200, and still more preferably 400 to 900, from the viewpoint of film forming suitability. When the molecular weight is too small, the film thickness of the formed photoelectric conversion film decreases due to volatilization. Conversely, when the molecular weight is too large, vapor deposition cannot be performed, and a photoelectric conversion element cannot be manufactured.

(Melting point)
The compound represented by the general formula (1) has a melting point of preferably 200 ° C. or higher, more preferably 220 ° C. or higher, and further preferably 240 ° C. or higher from the viewpoint of vapor deposition stability. If the melting point is low, it melts before vapor deposition, and in addition to being unable to form a stable film, the decomposition product of the compound increases, so the photoelectric conversion performance deteriorates.

(Absorption spectrum)
The peak wavelength of the absorption spectrum of the compound represented by the general formula (1) is preferably 400 nm to 700 nm from the viewpoint of absorbing a wide range of light in the visible region.

(Molar extinction coefficient of peak wavelength)
The higher the molar extinction coefficient is, the better the compound represented by the general formula (1) is from the viewpoint of efficiently using light. Absorption spectrum (chloroform solution), in the visible region of the wavelength 400nm to 700 nm, the molar absorption coefficient preferably 20000 ^-1 cm ^-1 or more, more preferably 30000 m ^-1 cm ^-1 or more, 40000M ^{^-1} cm ^-1 or more Is more preferable.

An electron donating organic material can be used for the electron blocking layer 52 which comprises the photoelectric conversion part 18 with the photoelectric converting layer 50 which consists of such an organic photoelectric converting material.
Specifically, for low molecular weight materials, N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine (TPD) or 4,4′-bis [N Aromatic diamine compounds such as-(naphthyl) -N-phenyl-amino] biphenyl (α-NPD), oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene derivative, pyrazoline derivative, tetrahydroimidazole, polyarylalkane, butadiene 4,4 ′, 4 ″ -tris (N- (3-methylphenyl) N-phenylamino) triphenylamine (m-MTDATA), porphine, tetraphenylporphine copper, phthalocyanine, copper phthalocyanine, titanium phthalocyanine oxide, etc. Porphyrin compounds, triazole derivatives, oxazizazo Derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, annealed amine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, silazane derivatives, carbazole derivatives, bifluorenes Derivatives and the like can be used. As the polymer material, polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, and derivatives thereof can be used.
Even if it is not an electron-donating compound, it can be used as long as it has a sufficient hole transporting property.

An inorganic material can also be used for the electron blocking layer 52.
In general, since an inorganic material has a dielectric constant larger than that of an organic material, when it is used for the electron blocking layer 52, a large voltage is applied to the photoelectric conversion layer, and the photoelectric conversion efficiency can be increased. Materials that can be the electron blocking layer 52 include calcium oxide, chromium oxide, chromium oxide copper, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, Examples include indium silver oxide and iridium oxide.

As described above, the solid-state imaging device and the method for manufacturing the solid-state imaging device of the present invention have been described in detail. However, the present invention is not limited to the above-described examples, and various improvements and modifications can be made without departing from the gist of the present invention. Of course, you may do this.

Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention.

[Examples (Examples 1 to 4, Comparative Examples 1 to 4)]
As the substrate, a CMOS calling circuit, a wiring layer, an insulating layer, and a pixel electrode formed on a Si substrate by a standard CMOS image sensor process was used.
This substrate was transported to the organic vapor deposition chamber, the organic vapor deposition chamber was closed, and the interior was depressurized to 1 × 10 ⁻⁴ Pa. The following compound 1 was vacuum deposited on the pixel electrode at a deposition rate of 0.1 to 0.12 nm / sec to form an electron blocking layer having a thickness of 100 nm.

On this electron blocking layer, the following compound 2 and fullerene C60 were vacuum deposited (co-evaporated) at a deposition rate of 0.16 to 0.18 nm / sec and 0.25 to 0.25 nm / sec, respectively, A 400 nm photoelectric conversion layer was formed.

The substrate on which the photoelectric conversion layer was formed was taken out from the organic vapor deposition chamber and transferred to the sputtering chamber. In the sputtering chamber, an ITO film was formed on the photoelectric conversion layer by RF magnetron sputtering to form a counter electrode having a thickness of 10 nm.
The substrate on which the counter electrode was formed was taken out of the sputtering chamber and transferred to the ALD chamber. In the ALD chamber, an aluminum oxide film was formed by ALD on the counter electrode to form a first sealing layer having a thickness of 30 nm.
The substrate on which the first sealing layer was formed was taken out of the ALD chamber and transferred to the plasma CVD chamber. In the plasma CVD chamber, a SiON film was formed on the first sealing layer, a second sealing layer having a thickness of 300 nm was formed, and the sealing layer was completed.

On the sealing layer, COLOR MOSAIC-EXIS SR-4000L manufactured by FUJIFILM Electromaterials Co., Ltd. was uniformly applied as an R filter color resist, and prebaked.
Next, the portion corresponding to the R filter is subjected to pattern exposure using an i-line stepper (NSR-2205i12D manufactured by Nikon Corporation), and further developed with a developer (CD-2060 manufactured by Fuji Film Electromaterials Co., Ltd.). Then, the light shielding part was removed, then washed with water and dried, and then post-baked to form an R filter.
Further, the same processing is performed for the G filter and the B filter, and a color filter formed by arranging an R filter, a G filter, and a B filter corresponding to the pixel electrode on the sealing layer is formed. A plurality of types of solid-state imaging devices as shown in FIG. 1 were produced.

The color filter was controlled to have a thickness of 0.1 μm or 0.3 μm.
The color filter was formed by changing the distance from the end (formation range) of the photoelectric conversion layer in the plane direction within a range of −200 to 1500 μm. The sign of the color filter formation range is positive when the color filter formation range exceeds the photoelectric conversion layer formation state (the state shown in FIG. 1), and does not exceed (from the end of the photoelectric conversion layer) Was also negative.
In addition, it was B filter that exceeded the formation range of a photoelectric converting layer.
A total of eight types of solid-state imaging devices (Examples 1 to 4 and Comparative Examples 1 to 4) were produced by combining the thickness of the color filter and the distance from the end of the photoelectric conversion layer of the color filter.

Adhesive tape (BGE-194U, manufactured by Denki Kagaku Kogyo Co., Ltd.) was attached to the color filters of the eight types of solid-state imaging devices that were produced. The adhesive tape was attached using a wafer mounter (UT-114 manufactured by Technovision).
Next, the adhesive tape was peeled off by pulling in the 180 ° direction.

After peeling off the adhesive tape, the color filter forming surface of the image sensor was confirmed with an optical microscope (Nikon Corporation ECRIPSE LV100D).
“Excellent” when the film peeling was not confirmed, “Good” when the probability of film peeling (number of film peeling elements / number of test elements) was less than 1%, and the probability of film peeling of 1% or more Rated as “impossible”.
The film thickness of the color filter, the distance from the end of the photoelectric conversion layer, the probability of film peeling, and the evaluation are summarized in the following table.

As shown in the above table, in Comparative Examples 1 to 4 in which the color filter formation range does not exceed the photoelectric conversion layer formation range, a large amount of film peeling occurs between the photoelectric conversion layer having weak adhesion and the counter electrode. Has occurred.
On the other hand, in the solid-state imaging device of the present invention (Examples 1 to 4) in which the color filter is formed beyond the formation range of the photoelectric conversion layer, the occurrence of film peeling between the photoelectric conversion layer and the counter electrode is 1 %.
From the above results, the effects of the present invention are clear.

DESCRIPTION OF SYMBOLS 10 (Solid) image pick-up element 12 Board | substrate 14 Insulating layer 16 Pixel electrode 18 Photoelectric conversion part 20 Counter electrode 22 Sealing layer 26 Color filter

26R R filter

26G G filter

26B B filter 40 Reading circuit 42 Counter electrode voltage supply part 44 1st Connection unit 46 Second connection unit 50 Photoelectric conversion layer 52 Electron blocking layer

Claims

A plurality of pixel electrodes;
A photoelectric conversion unit including a photoelectric conversion layer made of an organic material that generates charges according to received light, provided on the pixel electrode;
A counter electrode provided on the photoelectric conversion portion and common to the plurality of pixel electrodes;
A sealing layer provided on the counter electrode so as to cover the counter electrode;
A color filter provided on the sealing layer so as to cover the entire surface of the photoelectric conversion unit;
A readout circuit that reads out a signal corresponding to the charge collected by the pixel electrode;
And the said color filter is formed to the range exceeding the formation range of the said photoelectric converting layer, The solid-state image sensor characterized by the above-mentioned.
The solid-state imaging device according to claim 1, wherein a formation range of the color filter exceeding a formation range of the photoelectric conversion layer is 0.05 μm or more.
The solid-state imaging device according to claim 1 or 2, wherein the color filter has a thickness of 0.1 µm or more.
When the color filter is formed by arranging a red filter, a green filter, and a blue filter corresponding to the pixel electrode,
The solid-state imaging device according to any one of claims 1 to 3, wherein at least one of a red filter and a green filter is formed beyond a formation range of the photoelectric conversion layer.
5. The photoelectric conversion unit according to claim 1, further comprising an electron blocking layer for suppressing electrons from being injected into the photoelectric conversion layer from the pixel electrode under the photoelectric conversion layer. Solid-state image sensor.
The solid-state imaging device according to any one of claims 1 to 5, wherein the photoelectric conversion layer has a bulk heterostructure formed by mixing a p-type organic semiconductor material and an n-type organic semiconductor material.
The solid-state imaging device according to claim 6, wherein the n-type organic semiconductor material is at least one of fullerene and a fullerene derivative.
The solid-state imaging device according to claim 6 or 7, wherein the p-type semiconductor organic material is a compound represented by the following general formula (1).

(In the general formula (1), Z 1 represents a ring containing at least two carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. L 1 , L 2 and L 3 each independently represents an unsubstituted methine group or a substituted methine group, D 1 represents an atomic group, and n represents an integer of 0 or more.)
The solid-state imaging device according to any one of claims 1 to 8, wherein the counter electrode is indium tin oxide.
After laminating a plurality of pixel electrodes, a photoelectric conversion part having a photoelectric conversion layer made of an organic material, a counter electrode, and a sealing layer covering the counter electrode in this order on the substrate,
On the sealing layer, including the entire surface of the photoelectric conversion part, forming a color filter in a formation range exceeding the formation range of the photoelectric conversion layer,
A method for producing a solid-state imaging device, comprising: attaching a protective tape to the color filter forming surface side, performing back grinding of the substrate, performing back grinding, and then peeling the protective tape.
The method for manufacturing a solid-state imaging device according to claim 10, wherein a formation range of the color filter exceeding a formation range of the photoelectric conversion layer is 0.05 μm or more.
The method for manufacturing a solid-state imaging device according to claim 10 or 11, wherein the color filter has a thickness of 0.1 µm or more.
When the color filter is formed by arranging a red filter, a green filter, and a blue filter corresponding to the pixel electrode,
The method for manufacturing a solid-state imaging device according to any one of claims 10 to 12, wherein at least one of the red filter and the green filter is formed beyond a formation range of the photoelectric conversion layer.
14. The photoelectric conversion unit according to claim 10, wherein an electron blocking layer for suppressing injection of electrons from the pixel electrode to the photoelectric conversion layer is laminated as a lower layer of the photoelectric conversion layer. Manufacturing method of solid-state image sensor.
15. The method for manufacturing a solid-state imaging device according to claim 10, wherein the photoelectric conversion layer has a bulk heterostructure formed by mixing a p-type organic semiconductor material and an n-type organic semiconductor material.
The method for manufacturing a solid-state imaging device according to claim 15, wherein the n-type organic semiconductor material is at least one of fullerene and a fullerene derivative.
The method for producing a solid-state imaging device according to claim 15 or 16, wherein the p-type semiconductor organic material is a compound represented by the following general formula (1).

(In the general formula (1), Z 1 represents a ring containing at least two carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. L 1 , L 2 and L 3 each independently represents an unsubstituted methine group or a substituted methine group, D 1 represents an atomic group, and n represents an integer of 0 or more.)
The method for manufacturing a solid-state imaging device according to any one of claims 10 to 17, wherein the counter electrode is indium tin oxide.