JP2009111225A - Solid-state image sensor and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To suppress color mixing of a solid-state image sensor, to improve color reproducibility, and to improve shading characteristics. <P>SOLUTION: The solid-state image sensor 20 includes a semiconductor substrate 22 with photodiodes 26R, 26G and 26B, a device protective film 23 with a convex inner lens 28, and a color filter array with color filter layers 21R, 21G and 21B and separation walls 25 for separating the color filter layers. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a solid-state imaging device suitable for constituting a CCD, a MOS, and the like and a manufacturing method thereof.

  In recent years, the increase in the number of pixels of a solid-state imaging device has been remarkable, and the pixel size has been significantly reduced when compared with the conventional inch-size imaging device. In addition, as the pixel size is reduced, the performance requirements for color separation are stricter. To maintain device characteristics such as color shading characteristics and color mixing prevention, the performance required for color filters is reduced to thinner, rectangular, and the color between each filter. Performance such as the absence of overlapping regions that overlap each other has also been demanded.

Conventionally, a photolithography method has been often used as a method for producing a color filter. The photolitho method here is a method in which a radiation-sensitive composition such as a colored curable composition is applied onto a substrate and dried to form a coating, and the coating is subjected to pattern exposure / development / baking to form a colored pixel. This is a method of forming a color filter by repeating this operation for each color.
The photolithographic method can reduce initial investment because the manufacturing process conforms to the photolithographic process of semiconductor manufacturing. Also, the photolithographic process can be used to fabricate color filters with high-precision exposure and overlay accuracy of the photolithographic process. Widely used as a preferred method.

  Here, a general outline of a conventional method for producing a color filter by the photolithography method will be described with reference to FIGS.

As shown in FIG. 19, the first colored layer 2 is formed on the support 1 by applying, for example, a negative colored curable composition using a spin coater or the like. After pre-baking, as shown in FIG. 20, the first colored layer 2 is subjected to pattern exposure by ultraviolet irradiation through a photomask 3 (that is, the first colored pixel formation region in the first colored layer 2). 4 is exposed), and then the unnecessary non-exposed region 5 in the first colored layer 2 is removed by development processing, and further post-baking processing is performed, so that the first colored pattern 6 as shown in FIG. Form.
Thereafter, the same process as the formation of the first colored pattern 6 is repeated to form the second colored pattern 7 as shown in FIG. 22, and the third colored pattern 8 as shown in FIG. To form a color filter.

  The adjacent colored patterns are generally in contact with each other on the surface. For example, as shown in FIG. 24, the planarizing film 11 is formed on the blue color filter 9 and the green color filter 10, and the microlens 12 is formed thereon. ing. On the other hand, FIG. 24 shows a cross-sectional structure of a general color filter having a microlens. For example, in the structure shown in FIG. 24, when oblique light is incident between colored patterns, Problems such as inability to obtain separation performance may occur.

In the above-described color filter structure, for example, as shown in FIG. 24, when oblique light 13 is incident from the microlens side, the light passes through the microlens 12, the planarizing film 11, and the color filter 10 (9). At this time, the light 14 collected by the microlens 12 passes through the green color filter 10 and further passes through the protective film 16 and is collected by a photodiode (not shown). , There is light that leaks from the green color filter 10 to the blue color filter 9 like light 15. When leaking out, as shown in FIG. 24, the spectrum of the light 15 may be a mixture of blue and green, and may be incident on a blue photodiode.
In this case, although there is originally no incident light on the blue photodiode, the light 15 is incident on the blue photodiode by the light 15 and undergoes photoelectric conversion, and an output is generated in blue. appear. This thickness _{T 1} of the optical path green filter 10 of the light 15, when the thickness _{T 2} of the blue filter 9, a spectral transmission where an optical path _{= T 1/2 + T 2} /2 of the light 15. Specifically, as shown in the spectral characteristic of FIG. 25, the spectrum of the light 15 has a waveform spectral characteristic as shown by a solid line. The light 15 should originally be green light, but also has blue sensitivity, resulting in color mixing.

  Further, in the conventional method for producing a color filter, when a photolithographic method using a photosensitive composition is used, it is necessary to contain an alkali-soluble resin in a photosensitive curing component such as a photoinitiator or a monomer. There is a demerit that the content of the colorant in the solid content is relatively lowered, and as a result, the film thickness is increased. Moreover, since it has a photocurable component, the thickness of the composition affects the film thickness of the color filter, and it is difficult to realize a film thickness of 0.7 μm or less. As a result, color shading is deteriorated or color mixing caused by mixing optical paths as described above tends to occur.

  In order to overcome the above problems, a filter separation layer for separating the color filter is formed on the support, and then a region where the color filter is formed by dry etching is opened by etching and a colored layer is embedded, and flattened by CMP. There has been proposed a method of patterning by performing removal of the colored layer other than the embedded region and the embedded region (see, for example, Patent Document 1).

In addition, a solid-state imaging device having a separation layer formed of an air layer or a low refractive index material between color filters and having a condensing means on the upper portion and a manufacturing method thereof have also been proposed (for example, Patent Document 2). reference).
JP 2006-351775 A JP 2006-295125 A

  However, since the filter separation layer for separating the color filter is formed using another material other than the color filter, the cost and the number of processes increase, and it is not suitable for application to the manufacturing process. There's a problem.

  Moreover, in said patent document 2, after forming a separation layer between color filters, a flattening film is formed, a high-refractive sheet material is stuck on the upper part, and thermosetting is performed at a temperature of 180 ° C. to 250 ° C. Form a microlens. According to this method, when a flattened layer or a microlens is formed, an air layer is formed in a sealed space, and then heat treatment is performed at a high temperature. There is a concern that the frequency will increase.

  In each of the above patent documents, a light collecting means (a semicircular microlens in which resin is heat-flowed) is formed on the upper part of the color filter. Can only be obtained.

  The present invention has been made in view of the above, and an object of the present invention is to provide a solid-state imaging device having excellent color reproducibility by suppressing color mixing and excellent shading characteristics, and a method for manufacturing the same. Is an issue.

Specific means for achieving the above object are as follows.
<1> A color filter array having a semiconductor substrate, a color filter layer of two or more colors, and a separation wall that separates at least the different color filter layers, and is disposed between the semiconductor substrate and the color filter array. A solid-state imaging device.

  According to the solid-state imaging device according to <1>, since the color mixture of light is suppressed by forming a separation wall between a plurality of different color filter layers, photoelectric conversion or excellent color reproducibility or Imaging can be performed. Further, a condensing means such as a microlens is provided between the semiconductor substrate and the color filter layer, and a structure having no hemispherical microlens on the color filter layer on the semiconductor substrate is provided. The outermost surface is composed of a color filter layer and becomes flat, and oblique light from the exit pupil is introduced into a predetermined color filter layer, so that the light incident efficiency to the color filter in the peripheral pixel portion is reduced, and thus the light introduction efficiency is improved. As a result, it is possible to obtain excellent shading characteristics as compared with a conventional solid-state imaging device having an on-chip microlens.

  <2> The solid-state imaging device according to <1>, wherein the separation wall is formed of a layer formed of a material having a refractive index lower than that of the color filter layer.

  According to the solid-state imaging device described in <2>, since the refractive index of the separation wall provided between the color filter layers is lower than the refractive index of the color filter, the reflection efficiency of incident oblique light is increased, and color mixing is more effective. Can be prevented.

<3> The solid-state imaging device according to <1>, wherein the separation wall is formed of an air layer.
According to the solid-state imaging device described in <3>, since oblique light can be reflected by the air layer, color mixing of light can be effectively prevented while reducing the number of steps.

  <4> Any one of <1> to <3>, wherein a wall thickness of the separation wall in a direction orthogonal to a thickness direction of the color filter layer is 0.05 μm or more and 0.2 μm or less. It is a solid-state image sensor as described in one.

  According to the solid-state imaging device according to <4>, since the separation wall is configured to be thin, the transmission spectral characteristics are good and light is transmitted while suppressing color mixing due to incident oblique light. The area ratio of the color filter to the entire region can be ensured, and the color purity of each color filter layer (pixel) can be improved.

  <5> The above <1> to <4>, wherein the semiconductor substrate has a protective film, and the light collecting means is formed by processing at least a part of the protective film. It is a solid-state image sensor as described in any one.

  According to the solid-state imaging device according to the above <5>, an integrated type having both a protective function and a light collecting function by processing a protective film formed on a semiconductor substrate to have a thickness greater than a desired light collecting means. Since it is shape | molded, it can manufacture easily.

  <6> The semiconductor substrate has a protective film, and the light collecting unit is formed by providing a high refractive index material having a higher refractive index than the color filter layer on the protective layer. It is a solid-state image sensor as described in any one of <1>-<4>.

  According to the solid-state imaging device described in <6>, since it is made of a high refractive index material having a higher refractive index than that of the color filter layer (n = 1.55 to 1.65), the light collection efficiency is further improved and color mixing is reduced. In addition, it is possible to display an image with good color reproducibility.

  <7> A flattening layer for flattening a region where the color filter array on the condensing unit side is formed at least partially between the condensing unit and the color filter array, The solid-state imaging device according to any one of <1> to <6>, wherein a separation wall is provided at least in an extending direction of the separation wall in the color filter array.

  According to the solid-state imaging device according to <7>, the separation wall is formed not only in the color filter array but also in the planarization layer provided between the light collecting unit and the semiconductor substrate. Since it can suppress, the image display excellent in color reproducibility can be performed.

  <8> A solid-state imaging device comprising a semiconductor substrate, a color filter array having two or more color filter layers and a separation wall separating at least the different color filter layers, wherein the color filter array Is a solid-state imaging device having no light collecting means other than the color filter array.

  According to the solid-state image pickup device according to <8>, since the color filter array has a light collecting effect as a light collecting portion, a solid-state image pickup device having a thin film structure can be easily obtained with a small number of steps. The light incident on the individual color filter layers separated by the separation walls of the color filter array is within the area of the individual color filter layers even when oblique light is generated, and a lens effect is obtained.

  <9> The solid-state imaging element according to any one of <1> to <8>, wherein the color filter layer is processed into a pattern by processing by a dry etching method. .

  According to the solid-state imaging device described in <9>, since a dry etching method (and CMP method if necessary) is used, the solid-state imaging device is manufactured using a colored composition (preferably a thermosetting composition) that does not use a photocurable component. In addition, a color filter layer made of a thin film and having a rectangular shape can be formed.

  <10> A step of forming a color filter array having two or more color filter layers on a semiconductor substrate, a step of forming a photosensitive resin layer on the color filter array on the semiconductor substrate, and The photosensitive resin layer is exposed and developed in a pattern, and patterned so that adjacent portions of adjacent color filter layers of different colors are exposed, and the patterned photosensitive resin layer is used as a mask for the color filter layer. And a step of forming a gap between at least different color filters by performing a dry etching process and removing the adjacent portion.

  According to the method for manufacturing a solid-state imaging device described in <10>, color mixture of light is suppressed at the separation wall, and the separation filter is formed by dry etching, so that each color filter layer is formed in a rectangular shape. Therefore, it is possible to manufacture a solid-state imaging device having excellent color reproducibility and excellent shading characteristics.

  <11> The method according to <10>, further including a step of forming a layer formed of a material having a refractive index lower than that of the color filter layer in the gap formed between different color filters. This is a method for manufacturing a solid-state imaging device.

  According to the method for manufacturing a solid-state imaging device according to <11>, a gap is provided between the color filter layer so that the refractive index is lower than that of the color filter, and the reflection efficiency of incident oblique light is increased. Therefore, it is possible to manufacture a solid-state imaging device that suppresses color mixing and has excellent color reproducibility.

  According to the present invention, it is possible to provide a solid-state imaging device that suppresses color mixing, has excellent color reproducibility, and has excellent shading characteristics, and a manufacturing method thereof.

  Hereinafter, embodiments of a solid-state imaging device and a method for manufacturing the same according to the present invention will be described in detail with reference to the drawings.

(First embodiment)
A first embodiment of a solid-state imaging device of the present invention will be described with reference to FIGS. In the solid-state imaging device of this embodiment, a separation wall having a refractive index lower than the refractive index of the color filter layer is provided between adjacent color filter layers, and a microlens (hereinafter referred to as a convex shape) convex on the upper side of the semiconductor substrate. , Referred to as a “convex inner lens”).

  As shown in FIG. 1, the solid-state imaging device 20 of the present embodiment is provided on a semiconductor substrate 22 provided with photodiodes 26R, 26G, and 26B and a photodiode non-formation surface of the semiconductor substrate 22, and a microlens portion (convex) Device protective film 23 having a mold inner lens), a color filter array having separation walls 25 separating the color filter layers 21R, 21G, and 21B and the color filter layers, and between the device protective film and the color filter array And a planarizing layer 24 provided.

  The light incident through the color filter array is condensed on each photodiode through a microlens portion that is a condenser lens at a position corresponding to each of the photodiodes 26R, 26G, and 26B that are light receiving elements. It is like that.

  On one side of the semiconductor substrate 22, a plurality of photodiodes 26R, 26G, and 26B that form a light receiving area of a solid-state imaging device (image sensor) and a transfer electrode 29 made of polysilicon or the like are formed. Furthermore, the semiconductor substrate 22 is provided with a light shielding film (not shown) in which only a photodiode (light receiving element) is opened, and this light shielding film is formed of tungsten or the like.

  The color filter array constituting the solid-state imaging device of the present embodiment has color filter layers 21R, 21G, and 21B, and a separation wall 25 that separates the color filter layer and the color filter layer. FIG. 1 is a schematic cross-sectional view showing the structure of the solid-state imaging device in the present embodiment.

  As shown in FIG. 1, the color filter array of this embodiment is provided between the color filter layers 21R, 21G, and 21B provided on the non-photodiode surface of the semiconductor substrate 22 and the color filter layers. A separation wall 25 that separates the filter layers from each other and a flattening layer 27 that covers and flattens the surface of the color filter layer of each color are provided.

The separation wall 25 is composed of a low refractive index layer formed of a low refractive index material having a refractive index lower than that of the color filter layer, and can reflect light when oblique light is incident. Yes. As will be described later, the separation wall 25 is processed and formed by a dry etching method so that the wall surface thereof is substantially parallel to the normal direction of the semiconductor substrate 22.
FIG. 2 is a plan view of the color filter array of the present embodiment as viewed from above the semiconductor substrate (in the normal direction), and the broken lines indicate the boundaries of the color filter layers.

  The color filter layer formed by coloring and curing has a refractive index of 1.55 to 1.65. As a low refractive index layer formed as a separation wall separating the color filter layers, a refractive index difference with the color filter can be provided by setting the refractive index n ≦ 1.5, thereby reflecting light. It can be an effective separation wall. The refractive index n of the separation wall is more preferably 1.45 or less, and most preferably 1.4 or less from the viewpoint of increasing the refractive index difference from the color filter layer.

As a low refractive material, glass (n = 1.52), porous layer of SiO ₂ film (silica; n = 1.3-1.35), fluorine-based polymer (n = 1.3-1.4) And siloxane polymer (n = 1.5). As a material for forming the “porous layer of SiO ₂ film”, a coating material for forming a porous layer matrix using a sol-gel method, and an opster low refractive index material JN series manufactured by JSR as a fluorine-based polymer Examples of the siloxane polymer include NR series manufactured by Toray Industries, Inc.

  The low-refractive material forms a separation wall and is further provided on the color filter layer, so that when the gap formed between the color filter layers is a hollow (air) layer, It can function as an antireflection layer between the color filter layers.

  The wall thickness of the separation wall in the direction orthogonal to the thickness direction of the color filter layer can be 0.05 μm or more and 0.2 μm or less. When the wall thickness of the separation wall is within the above range, the area ratio of the color filter to the entire region through which light is transmitted can be secured, and the color purity of each color filter layer (pixel) can be improved. The wall thickness is preferably 0.08 μm or more and 0.15 μm or less.

The color filter layers 21R, 21G, and 21B are formed of a colored composition (preferably a thermosetting composition) that does not perform photocuring in accordance with the processed shape of the separation wall 25.
For this reason, each color filter layer is formed in a thin film, and the device itself including the color filter layer on the light receiving element is made into a thin film, whereby the light collection efficiency of incident light is improved. Further, by reducing the thickness of the color filter layer, the color shading characteristics are improved and the device characteristics are improved. In addition, the color filter layer is not rounded at the corners, and a good rectangle is formed.

  The coloring composition can be selected from any known curable composition. As described above, a non-photosensitive coloring composition that does not use a photocurable component is used in order to produce a color filter composed of a plurality of colors by repeating the concave portion forming step and the filter forming step after the protective layer forming step. Preferably, it is a thermosetting composition. Details of the thermosetting composition will be described later.

As described above, the separation walls are provided between the color filter layers, so that obliquely incident light (oblique light) can be prevented from entering adjacent color layers (color filter layers).
That is, as shown in FIG. 3, when the oblique light 30 is incident, the incident light 30 passes through the color filter layer 21G through the planarization layer, but leaks from the color filter layer 21G to the color filter layer 21B. The light 31 to be emitted is totally reflected by the separation wall 25 located between the color filter layers when the light angle θ is greater than the critical angle, and light leakage to the color filter layer 21B is suppressed. Thereby, color mixing can be prevented.

As described above, since the separation wall that reflects light is formed between the color filters, the incident light can be prevented from leaking out of the wall even when oblique light is generated, and one color filter layer. Most of the incident light is captured in. Therefore, a lens effect is obtained in the area of each color filter layer of the color filter array, and the color filter layer can function as a light collecting means.
The solid-state imaging device generally has a form in which a microlens is provided in addition to the color filter. However, for example, a configuration in which a microlens is not provided by providing a photoelectric conversion layer as a lower layer of the color filter layer may be employed. In this case, examples of the photoelectric conversion layer include MCP (microchannel plate) and ITO film.

  The device protection film 23 is formed as a film for protecting the surface from external damage after completion of the wiring process of the semiconductor substrate, and the chip is protected from mechanical damage, chemical damage, and electrical damage. Play a role in protecting. The device protection film 23 is disposed on the side of the semiconductor substrate 22 where the photodiode is not formed, and the surface of the device protection film is made to correspond to the formation position of each color filter layer of the color filter array. The microlens portion (convex inner lens) 28 for improving the light collection efficiency is provided directly. The convex inner lens 28 is formed in a convex shape in the direction in which the color filter array of the semiconductor substrate is arranged (above the semiconductor substrate).

For example, the device protective film 23 can be configured by providing silicon nitride or the like by a CVD method or the like at a high temperature (for example, 500 to 800 ° C.) so that the entire light shielding film (not shown) on the semiconductor substrate is covered. Then, a device protective film is formed so as to have a film thickness equal to or greater than the height of the convex inner lens 28 to be formed, and a lens-shaped photoresist is provided, and the device protective film is shaped and transferred by etching or the like. Can be formed. The device protective film 23 shown in FIG. 1 is formed of silicon nitride with a thickness of 0.70 μm.
A known positive type photoresist can be used as the photoresist material. As the positive photoresist, a positive photosensitive resin composition that is sensitive to ultraviolet rays (g rays, i rays), far ultraviolet rays including excimer lasers such as KrF and ArF, and electron beams can be used.

  By forming the device protective film as thin as possible to ensure device reliability, the shading suppression can be further improved. Specifically, the film thickness of the thinnest film portion 23a after being processed by etching is preferably 0.10 μm or more. The film thickness of the thinnest part 23a is more preferably 0.15 μm or more, particularly preferably 0.20 μm or more, from the viewpoint of ensuring the function as a device protective film.

Examples of the device protective film include silicon oxide (SiO ₂ ), glass (PSG), polyimide, and the like in addition to silicon nitride (Si ₃ N ₄ ). In particular, silicon nitride suppresses diffusion of impurities, suppresses ingress of ions, Particularly preferred from the viewpoint of high moisture resistance.

  The initial film thickness before etching of the device protective film varies depending on the lens shape (including height) and etching conditions, but by setting the initial film thickness so as to control the film thickness of the thinnest film portion 23a, The film thickness of the device protective film after processing the convex inner lens can be controlled.

In addition to etching transfer with a photoresist as described above, the convex inner lens is (1) a desired positive photoresist is applied with a spin coater, exposed to a circular pattern of a desired size, and developed. After forming a circular pattern, it is heated and melted to be processed into a round lens shape, or (2) a high refractive index material for forming a microlens is provided on the protective film and etched. Can do.
The high refractive index material refers to a material having a refractive index higher than that of the color filter layer. For example, titanium oxide, zirconia, a mixture of titanium oxide and silicone oxide can be used.

The convex inner lens is formed by a method of etching with a circular pattern mask after depositing a protective film by the CVD method, a method of etching on the device protective film using a photoresist material for forming a microlens, etc. can do.
In the present embodiment, the microlens portion is provided, but a color filter array may be used as the light collecting means without providing the microlens.

  The planarization layer 24 is provided between the device protective film 23 and the color filter array, and reduces the light incident efficiency to the surrounding color filters to improve the light introduction efficiency. Thereby, compared with the conventional solid-state image sensor which has an on-chip microlens, the outstanding shading characteristic is acquired.

As described above, when a light collecting means such as a microlens is provided below the color filter layer, it is preferable to form a flattening layer and perform a flattening process. At this time, for the planarizing layer, a composition containing a polymer compound that can be cured by heat can be preferably used. As said high molecular compound, a polysiloxane type polymer and a polystyrene type polymer can be mentioned as a preferable thing, for example. Among them, materials known as spin-on-glass (SOG) material, an inorganic film such as SiO _2, may be mentioned a thermosetting composition whose main component is polystyrene derivative or a polyhydroxystyrene derivative as a more preferred it can. Among these, SiO ₂ is particularly preferable from the viewpoint of etching resistance to the fluorocarbon gas system used during dry etching.

  Further, after the convex inner lens is formed, the planarizing layer 24 is formed on the upper part of the lens (lower part of the color filter) on the semiconductor substrate, whereby the formed color filter can be formed into a flat layer.

The planarization layer preferably has a refractive index equivalent to that of the color filter layer and has a large difference from the refractive index of the convex inner lens material. Thereby, the condensing efficiency of a convex inner lens can be improved.
Specifically, the refractive index n of the color filter layer is n = 1.55 to 1.65, and the inner lens material is, for example, silicon nitride, n = 1.9 to 2.0. Accordingly, the refractive index of the planarizing layer is preferably 1.4 to 1.8, more preferably 1.5 to 1.7, most preferably 1.55 to 1.65, and the color filter layer. It is preferable that the refractive index is the same.

  In the present embodiment, the case where the convex inner lens is formed has been described. However, the shape of the inner lens is convex in the direction in which the color filter array of the semiconductor substrate is arranged (above the semiconductor substrate). Not only a convex type but also a downward convex shape opposite to the convex type, that is, a concave inner lens may be used. Specifically, it will be described in a second embodiment described later. Even in a form in which the inner lens is formed in a concave shape, the light collection efficiency can be improved by the refraction of light. In this case, the refractive index of the planarizing film is the same as that described above.

The above inner lens has been shown to be formed on the device protective film 23. From the viewpoint of stricter refractive index control, a transparent film for the inner lens is formed, and this is subjected to a dry etching process or the like. You may form by giving.

  On the exposed exposed surface of the color filter layer of the color filter array, a flattening layer 27 that covers and flattens each color filter layer is provided. The planarization layer 27 covers and planarizes the surface of each color filter layer of the color filter array. Thereby, a flatter surface property can be obtained and the light introduction efficiency can be further improved.

Next, the manufacturing method of the solid-state image sensor of this embodiment will be described.
The solid-state imaging device of the present embodiment is not particularly limited as long as it can be configured in the above-described structure, and can be manufactured by any method. However, in the present invention, a method having the following steps (solid-state imaging of the present invention) It can be suitably manufactured by a device manufacturing method).

  That is, the solid-state imaging device of the present invention includes a step of forming a color filter array having two or more color filter layers on a semiconductor substrate (hereinafter also referred to as “array formation step”), and a color on the semiconductor substrate. A process of forming a photosensitive resin layer on the filter array (hereinafter also referred to as “photosensitive layer forming process”), and exposing and developing the formed photosensitive resin layer in a pattern so that a different color filter is formed. A patterning process (hereinafter also referred to as a “patterning process”) so that adjacent adjacent parts are exposed, and the color filter layer is dry-etched using the patterned photosensitive resin layer as a mask to remove the adjacent parts. In this manner, a step of forming a gap between at least different color filters (hereinafter, also referred to as “gap formation step”) is provided. Door can be.

Hereinafter, a case where the solid-state imaging device of the present embodiment is manufactured will be specifically described for each process.
A desired semiconductor substrate is prepared. As shown in FIG. 1, on this semiconductor substrate, a plurality of photodiodes 26R, 26G, and 26B that form a light receiving area of the solid-state imaging device are formed on one side, and a transfer electrode 29 made of polysilicon or the like is further formed. And a light-shielding film (not shown) made of tungsten or the like in which only the photodiode (light receiving portion) is opened.

On the opposite side of the semiconductor substrate 22 from where the photodiodes 26R, 26G, and 26B are formed, a device protection film (passivation layer) made of silicon nitride so as to cover the entire light shielding film on the light shielding film of the semiconductor substrate. 23 is formed. The device protective layer 23 shown in FIG. 1 is formed of silicon nitride with a thickness of 0.70 μm.
Further, a device protective film is deposited and formed on the device protective film 23 so as to have a film thickness equal to or larger than the height of the microlens (light collecting means) to be formed by CVD. As shown in FIG. 1, the device protective film is processed and transferred by etching and the like, so that the color filter array on the semiconductor substrate 22 is formed in a convex shape. The mold inner lenses 28 are arranged in correspondence with the formation positions of the color filter layers. Further, the planarizing layer 24 is formed so as to cover the entire convex portions of the convex inner lens 28 and the device protective film.
The semiconductor substrate formed as described above is used as a photoelectric conversion substrate.

[Array formation process]
Next, an array forming step is provided to form a color filter array in which three color filter layers are provided on the photoelectric conversion substrate.

  As shown in FIG. 4, after applying the coloring composition for forming the first colored layer (first color; for example, green (G)) on the planarization layer of the photoelectric conversion substrate 31 with a spin coater. The first colored layer 32 is formed by heating for 5 minutes using a hot plate so that the temperature or atmospheric temperature of the coating film formed by coating is 220 ° C., and curing the coating film.

  Next, although not shown in the drawing, a positive photoresist is applied onto the first colored layer 32 by a spin coater and prebaked to form a photoresist layer 34. Subsequently, from above the photoresist layer 34 formed on the first colored layer 32, the photoresist layer in the region where the second colored layer (second color; for example, red (R)) is to be formed is i. Exposure is performed with a line stepper and PEB processing is performed. Thereafter, a paddle development process is performed with a developer, and a post-bake process is further performed to remove the photoresist in a region where the second colored layer is to be formed, and an opening 33 is formed as shown in FIG. .

As the photoresist, a known positive type photoresist can be used. As the positive photoresist, a positive photosensitive resin composition that is sensitive to ultraviolet rays (g rays, i rays), far ultraviolet rays including excimer lasers such as KrF and ArF, and electron beams can be used.
The light source used for exposure is preferably i-line because the formation of the color filter pattern only needs to have a resolving power of about 1.0 μm.

  Next, anisotropic etching is performed using the photoresist layer 34 as a mask under a desired etching condition using a mixed gas (plasma gas) in which a fluorocarbon gas and an oxygen gas are mixed in a dry etching apparatus, The colored layer 32 in the region where the colored layer is to be formed is etched. The etching conditions at this time mainly include a first etching process for processing the first colored layer (for example, green (G)) halfway with a mixed gas of fluorocarbon gas and oxygen, and nitrogen gas and oxygen gas. Etching conditions may be formed by providing a second etching step of etching up to the substrate using the second gas.

  As typical examples of the dry etching method, JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61- Examples include a method of depositing a colorant, applying a mask resist, patterning, and etching as described in Japanese Patent No. 41102.

  Next, using a solvent or a photoresist stripping solution, a photoresist stripping process is performed, and the photoresist remaining on the first colored layer 32 is removed. Thereafter, a dehydration bake treatment for solvent removal and dehydration treatment can be performed. In this way, as shown in FIG. 6, the colored layer 32 in the region where the second colored layer is to be formed is removed from the first colored layer 32 on the photoelectric conversion substrate, and the opening 35 is formed. . FIG. 6 shows the shape after stripping the photoresist.

  Subsequently, as shown in FIG. 7, the entire first colored layer 32 and the opening 35 are covered and embedded in the opening 35, and the second colored layer (second color; For example, after the coloring composition for forming red (R)) is applied, the coating film is post-baked using a hot plate to form the second colored layer 36.

  Next, as shown in FIG. 8, by polishing with a CMP apparatus until the surface of the first colored layer 32 is exposed, the second colored layer 37 is formed in a pattern. As the polishing agent, a slurry in which silica fine particles are dispersed is used. Slurry flow rate: 100 to 250 ml / min, wafer pressure: 0.2 to 5.0 psi, retainer ring pressure: 1.0 to 2.5 psi, from polishing cloth A polishing apparatus can be used. The polishing time is the time until the first colored layer 32 is exposed, the overpolishing rate is set to 20%, for example, and the polishing process is completed.

  The formation of the third colored layer (third color) can be performed by repeatedly performing the same operation as the formation of the second colored layer 37 described above. Specifically, a positive type photoresist is formed again on the colored layer 32, exposed and developed to remove the photoresist in the region where the third colored layer is to be formed, and the openings are patterned. Form. Then, anisotropic etching is performed using the photoresist layer as a mask, the colored layer 32 in the region where the third colored layer is to be formed is removed from the first colored layer 32 on the photoelectric conversion substrate, and the opening is further opened. Forming part. Subsequently, the first and second colored layers 32 and 37 and the entire opening are covered and embedded in the opening, and a third colored layer (third color; for example, blue (B After applying the coloring composition for forming)), the coating film is post-baked using a hot plate to form a third colored layer. Thereafter, polishing is performed by a CMP apparatus until the first and second colored layers 32 and 37 are exposed.

  After forming the first colored layer, coating and forming the second colored layer, curing, and then removing the second colored layer by the etch back method or CMP method until the first colored layer is exposed, The first and second colored layers can be formed in a pattern.

After the first colored layer is exposed, overetching and overpolishing for several seconds to several tens of seconds are performed. At this time, if the etching rates of the first colored layer and the second colored layer are different, A step is generated between the first colored layer and the second colored layer. There is no particular problem if it is in the range of 3σ / t ≦ 10%.
Further, when the first colored layer is thinned (processed and thinned) by the CMP process, it is patterned in advance with an initial set film thickness added with a thinning amount, and the set film thickness is adjusted after the CMP process. Control should be done.

  Regarding polishing by the CMP method, an example in which the second colored layer is formed after the formation of the first colored layer has been described. However, the third colored layer is formed on the substrate on which the first and second colored layers are formed. The present invention can also be applied when forming.

  As described above, a color filter array composed of RGB three colors as shown in FIG. 9 is formed. For example, when the first colored layer is a red pixel 40R, the second colored layer is a green pixel 40G, and the third colored layer is a blue pixel 40B, a color filter composed of three primary colors of red, green, and blue is produced. Can do. Similarly, when forming color filters of four or more colors, the second and subsequent colors can be easily manufactured in the form of islands.

[Photosensitive layer forming step]
Next, a positive photoresist is applied to the entire surface of the color filter array 40 formed on the photoelectric conversion substrate as described above to form a photoresist layer (photosensitive resin layer). The formed photoresist layer is preferably pre-baked.
As the positive photoresist, a known positive photoresist can be used. The known positive type photoresist is as described above.

[Patterning process]
Next, the formed photoresist layer is exposed in a pattern through a mask and developed to pattern the color filter layers of each color so that adjacent portions adjacent to each other are exposed. At this time, the mask pattern protects the area other than the area to be removed in the color filter, so that the separation wall can be formed at a desired position by a process described later.

Specifically, by exposing and developing a positive photoresist layer in a pattern by a photolithography method using i-line, KrF, and ArF, as shown in FIG. 10, a lattice-shaped space pattern 41 is formed. Form. Thereafter, PEB, alkali development, and post-baking are performed to obtain a desired mask pattern.
Note that the photolithography process is preferably performed by forming a pattern as a KrF or ArF light source, so that fine processing can be performed, and more preferably, the ArF process is performed from the viewpoint of miniaturization.

[Gap forming step]
Next, using the lattice-shaped space pattern 41 formed by patterning as a mask, the color filter layer is etched by plasma etching (dry etching treatment) mainly using a fluorocarbon-based gas until the planarizing layer 24 is exposed. The adjacent portions of the colored layers 40R, 40G, and 40B adjacent to each other are removed by a desired width. The etching stop is preferably a point where the photoelectric conversion substrate is exposed.

  As the dry etching method, as described above, JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102. Examples include a method of applying a mask resist, patterning, and etching after depositing a colorant as described in the publication.

  The etching process includes a first etching process in which a part of the colored layer is removed by a dry etching method using a first mixed gas containing a fluorine-based gas and an oxygen gas, and a coloring remaining after the first etching process. It is desirable to form a substrate exposed portion in a pattern by providing a second etching step in which the layer is removed by dry etching using a second gas containing nitrogen gas and oxygen gas. Here, by setting the second etching step to an etching condition using a second gas containing nitrogen gas and oxygen gas, the substrate can be prevented from being scraped, and as a result, the substrate scraping can be accurately controlled. Can be managed.

-First etching step-
The mixed gas used in the first etching step includes at least one fluorine-based gas and oxygen gas at least from the viewpoint that the colored layer portion (the portion to be etched) removed by the dry etching method can be processed into a rectangle. The containing composition is preferred.

As the fluorine-based gas, a known fluorine-based gas can be used, but a fluorine-based compound gas represented by the following formula (I) is preferable.
C _n H _m F _l Formula (I)
[In formula, n represents 1-6, m represents 0-13, and l represents 1-14. ]

Examples of the fluorine-based gas represented by the formula (I) include CF ₄ , C ₂ F ₆ , C ₃ F ₈ , C ₂ F ₄ , C ₄ F ₈ , C ₄ F ₆ , C ₅ F ₈ , And at least one selected from the group of CHF ₃ . As the fluorine-based gas in the present invention, one kind of gas can be selected from the above group, and two or more kinds of gases can be used in combination.
Among these, the fluorine-based gas is preferably at least one selected from the group of CF ₄ , C ₂ F ₆ , C ₄ F ₈ , and CHF ₃ from the viewpoint of maintaining the rectangularity of the etched portion, and CF ₄ And / or C ₂ F ₆ is more preferable, and CF ₄ is particularly preferable.

  As the mixed gas used in the first etching step, the content ratio of the fluorine-based gas and the oxygen gas (fluorine-based gas / oxygen gas) is preferably 2/1 to 8/1 in terms of a flow rate ratio. By setting it within the above range, it is possible to prevent the etching product from adhering to the sidewall of the photoresist layer during the etching process, and the photoresist layer can be easily peeled off in the photoresist layer removing step described later. In particular, the content ratio of the fluorine-based gas and the oxygen gas is 2/1 to 6/1 in terms of preventing the re-deposition of the etching product to the photoresist sidewall while maintaining the rectangularity of the etched portion. It is preferable that the ratio is 3/1 to 5/1.

The mixed gas used in the first etching step is helium as another gas in addition to the fluorine-based gas and the oxygen gas, from the viewpoint of maintaining the partial pressure control stability of the etching plasma and maintaining the perpendicularity of the shape to be etched. (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe) and other rare gases, and halogen gases containing halogen atoms such as chlorine atoms, fluorine atoms, bromine atoms (for example, CCl ₄ , CClF ₃ , AlF ₃ , AlCl _3, etc.), N ₂ , CO, and CO ₂ , preferably at least one selected from the group of Ar, He, Kr, N ₂ , and Xe More preferably, it contains at least one, and more preferably contains at least one selected from the group consisting of He, Ar, and Xe.
However, if it is possible to maintain the partial pressure control stability of the etching plasma and the perpendicularity of the shape to be etched, the mixed gas used in the first etching step consists of only a fluorine-based gas and an oxygen gas. It may be.

  In the mixed gas used in the first etching step, the content of other gases that may be contained in addition to the fluorine-based gas and the oxygen gas is that when the oxygen gas is set to 1 in terms of the rectangularity of the etching pattern. The flow rate ratio is preferably 25 or less, more preferably 10 or more and 20 or less, and particularly preferably 14 or more and 18 or less.

Here, a method for calculating the etching processing time will be described.
In the first etching step, it is preferable to obtain the etching processing time in advance by the following method.
(1) The device protection film etching rate [nm / min] in the first etching step is calculated.
(2) The processing time required to etch a desired thickness in the first etching step is calculated from the etching rate calculated in (1) above.

The etching rate can be calculated, for example, by collecting the relationship between the etching time and the remaining film.
In the present invention, the etching time is preferably 10 minutes or less, and more preferably 7 minutes or less.

-Second etching step-
In the second etching step, the second mixed gas contains nitrogen gas and oxygen gas, but may contain a fluorine-based gas as long as the effects of the present invention are not impaired. The content ratio of the fluorine-based gas to the oxygen gas (fluorine-based gas / oxygen gas) is preferably 5% or less by flow rate ratio, and particularly preferably does not contain the fluorine-based gas. When the content of the fluorine-based gas is within the above range, damage to the support can be more effectively suppressed.

  The content ratio of nitrogen gas and oxygen gas (nitrogen gas / oxygen gas) in the second mixed gas is preferably 10/1 to 3/1 in terms of a flow rate ratio. By making it within the above range, it is possible to more effectively suppress the adhesion of the etching product to the side wall of the photoresist layer during the etching process, and the peeling of the photoresist layer in the photoresist layer removing step described later can be further suppressed. Can be easily. The content ratio is preferably 20/1 to 3/1 from the viewpoint of maintaining the rectangularity of the portion to be etched and preventing the redeposition of the etching product to the side wall of the photoresist layer, and 15/1 to 4 / 1 is more preferable, and 10/1 to 5/1 is particularly preferable.

From the viewpoint of maintaining the partial pressure control stability of the etching plasma and the verticality of the shape to be etched, the second mixed gas includes helium (He) and neon as other gases in addition to the nitrogen gas and the oxygen gas. (Ne), argon (Ar), krypton (Kr), at least one gas selected from the group of xenon (Xe) is preferably contained, and at least one selected from the group of He, Ar, and Xe More preferably, the gas is contained.
However, when it is possible to maintain the partial pressure control stability of the etching plasma and the perpendicularity of the shape to be etched, the second mixed gas can be composed of only nitrogen gas and oxygen gas.
In the second mixed gas, in addition to the nitrogen gas and the oxygen gas, the content of other gases that may be further contained is preferably 25 or less in terms of a flow rate ratio when the oxygen gas is 1. It is preferably 20 or more and particularly preferably 8 or more and 12 or less.

In the second etching step, for example, the dry etching process is terminated after elapse of the processing time calculated in the same manner as the “calculation method of the etching processing time” from the start of the dry etching processing for removing the colored layer removing portion. be able to. Moreover, you may manage the dry etching processing time which removes a colored layer removal part by endpoint detection. In the second etching process in the present invention, it is preferable to manage the dry etching process time for removing the colored layer removal portion by detecting the end point.
The etching processing time is preferably within 10 minutes, more preferably within 7 minutes.

  It is preferable that the second etching step further includes an overetching treatment step. After removing the colored layer removal portion by dry etching using the second mixed gas and forming the support exposed portion, the remaining etching residue is further removed by over-etching using the second mixed gas. Further, it can be efficiently removed while maintaining the rectangularity of the pattern, and the occurrence of damage to the support can be more effectively suppressed.

The overetching process is preferably performed by setting an overetching time. Although the over-etching time can be set arbitrarily, the etching process time (t ₁ ) in the first etching step and the colored layer in the second etching step are the points of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched. The total processing time (t ₁ + t ₂ ) with the etching processing time (t ₂ ) for removing the removed portion is preferably 30% or less, more preferably 5 to 25%, and more preferably 15 to 20%. It is particularly preferred.

After the dry etching is completed, the photoresist is dissolved and removed with an organic solvent or the like to obtain a color filter array in which a gap is formed between the color filters as shown in FIG. After the etching is completed, the mask resist (photosensitive resin layer after curing) is removed with a dedicated stripping solution or an organic solvent.
In the case of performing the second etching process using the second gas containing nitrogen gas and oxygen gas, the photoresist layer can be more easily removed with a remover or an organic solvent.

  Thereafter, a material having a lower refractive index than the colored layers 40R, 40G, and 40B (for example, a fluorine-based coating material) is applied on the color filter layer so that the gap between the color filter layers is embedded, and is baked at 200 ° C. for 10 minutes, for example. By performing the treatment, as shown in FIG. 12, a low refractive index separation wall 43 is formed between the color filter layers, and a low refractive index flattening layer 44 is formed on the color filter.

[Coloring composition]
The colored composition can reduce or eliminate the use of the photocurable component by patterning by dry etching as described above. In a colored pattern with little or preferably no photocurable component, the concentration of the colorant can be increased. Therefore, it is possible to form a pattern thinner than before, which has been considered difficult, while maintaining transmission spectroscopy. Therefore, a non-photosensitive curable composition containing no photocurable component is preferable, and a thermosetting composition is more preferable.
Hereinafter, the thermosetting composition will be described in detail.

(Thermosetting composition)
The thermosetting composition comprises a colorant and a thermosetting compound, and the colorant concentration in the total solid content is preferably 30% by mass or more and less than 100% by mass. By increasing the colorant concentration, a thinner color filter can be formed.

~ Colorant ~
The colorant is not particularly limited, and various conventionally known dyes and pigments can be used alone or in combination.

  Examples of the pigment include conventionally known various inorganic pigments or organic pigments. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having an average particle size as small as possible, and considering the handling properties, the average particle size of the pigment is 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable.

  The following are mentioned as a preferable pigment in this invention. However, the present invention is not limited to these.

C. I. Pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185;
C. I. Pigment orange 36, 71;
C. I. Pigment red 122,150,171,175,177,209,224,242,254,255,264;
C. I. Pigment violet 19, 23, 32;
C. I. Pigment blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment Black 1

  In the present invention, when the colorant is a dye, it can be uniformly dissolved in the composition to obtain a non-photosensitive thermosetting colored resin composition.

  The dye that can be used as the colorant is not particularly limited, and conventionally known dyes for color filters can be used.

  The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

  Although it does not specifically limit as a coloring agent content rate in the total solid of a thermosetting composition, Preferably it is 30 to 100 mass%, More preferably, it is 50 to 80 mass%. . By setting the colorant content to 30% by mass or more, an appropriate chromaticity as a color filter can be obtained. Moreover, photocuring can fully be advanced by setting it as less than 100 mass%, and the strength reduction as a film | membrane can be suppressed.

-Thermosetting compound-
The thermosetting compound is not particularly limited as long as the film can be cured by heating. For example, a compound having a thermosetting functional group can be used. As the thermosetting compound, for example, those having at least one group selected from an epoxy group, a methylol group, an alkoxymethyl group, and an acyloxymethyl group are preferable.

  More preferable thermosetting compounds include (a) an epoxy compound, (b) a melamine compound, a guanamine compound, and a glycoluril substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Examples thereof include a compound or a urea compound, (c) a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group. Among these, a polyfunctional epoxy compound is particularly preferable as the thermosetting compound.

  The epoxy compound (a) may be any epoxy compound as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. Divalent glycidyl group-containing low molecular weight compounds such as hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline, and the like; Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc .; similarly, pentaerythritol tetraglycidyl ether, tetramethylol Tetravalent glycidyl group-containing low molecular weight compounds typified by Sphenol A tetraglycidyl ether; similarly, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether; (Meth) acrylate, glycidyl group-containing polymer represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like It is done.

  Commercially available products include alicyclic epoxy compounds: “CEL-2021”, etc., alicyclic solid epoxy resins: “EHPE-3150”, etc., epoxidized polybutadiene: “PB3600”, etc. Ring epoxy compound: etc. "CEL-2081", lactone modified epoxy resin: "PCL-G" etc. are mentioned (all are Daicel Chemical Industries Ltd. make). Other examples include “Celoxide 2000”, “Epolide GT-3000”, “GT-4000” (all manufactured by Daicel Chemical Industries, Ltd.), and the like. Among these, the alicyclic solid epoxy resin has the best curability, and “EHPE-3150” has the best curability. These compounds may be used alone or in combination of two or more, and combinations with other types shown below are also possible.

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups contained in (b) that are substituted for each compound is 2 to 6 for melamine compounds, glycoluril compounds, guanamine compounds, and urea compounds. Although it is 2-4, Preferably it is 5-6 in the case of a melamine compound, and 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) in (b).

  The methylol group-containing compound in (b) can be obtained by heating the alkoxymethyl group-containing compound in (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound in (b) can be obtained by mixing and stirring the methylol group-containing compound in (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound in (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexakis (methoxymethyl) melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexakis (methoxyethyl) melamine, hexakis (acyloxy) Methyl) melamine, a compound in which 1 to 5 methylol groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof.

  Examples of the guanamine compound include tetramethylolguanamine, tetrakis (methoxymethyl) guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolguanamine, or a mixture thereof, tetrakis (methoxyethyl) guanamine, tetrakis (acyloxy) Methyl) guanamine, a compound obtained by acyloxymethylating 1 to 3 methylol groups of tetramethylolguanamine, or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetrakis (methoxymethyl) glycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril or a mixture thereof, and tetramethylolglycoluril methylol. Examples thereof include compounds in which 1 to 3 groups are acyloxymethylated, or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetrakis (methoxymethyl) urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolurea or a mixture thereof, tetrakis (methoxyethyl) urea, and the like. .
These compounds in (b) may be used alone or in combination.

  The compound in the above (c), that is, a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is a compound in the above (b). As in the case of, the intermixing with the overcoated photoresist is suppressed and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) in (c).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the compound in (c) is at least 2 per molecule, and from the viewpoints of thermosetting and storage stability, a phenolic compound that becomes a skeleton A compound in which all of the 2- and 4-positions are substituted is preferred. In addition, the naphthol compound and hydroxyanthracene compound serving as the skeleton are also preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

The methylol group-containing compound in (c) is a compound in which the phenolic OH group has a hydrogen atom at the 2nd or 4th position, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide, etc. Obtained by reacting with formalin in the presence of a basic catalyst.
The alkoxymethyl group-containing compound in (c) can be obtained by heating the methylol group-containing compound in (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound in (c) can be obtained by reacting the methylol group-containing compound in (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in (c) include phenol compounds, naphthols, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. For example, phenol, cresol isomers, 2, 3 -Bisphenols such as xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol and bisphenol A; 4,4'-dihydroxybiphenyl, TrisP-PA (Honshu Chemical Industry Co., Ltd.) Manufactured), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, and the like.

  Specific examples of (c) include, as a phenol compound, for example, trimethylolphenol, tris (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol-3- Compound obtained by methoxymethylating one or two methylol groups of cresol, tris (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, tetramethylol Bisphenol A, tetrakis (methoxymethyl) bisphenol A, compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolbisphenol A, tetramethylol-4,4′-dihydroxybiphenyl, tetrakis (methoxymethyl) -4,4′-dihydroxybiphenyl, a hexamethylol form of TrisP-PA, a hexakis (methoxymethyl) form of TrisP-PA, a compound obtained by methoxymethylating 1 to 5 methylol groups of the hexamethylol form of TrisP-PA, And bis (hydroxymethyl) naphthalenediol.

  In addition, examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include a part of the methylol group of the methylol group-containing compound, or Examples include compounds that are all acyloxymethylated.

Among these compounds, preferred are trimethylolphenol, bis (hydroxymethyl) -p-cresol, tetramethylolbisphenol A, hexamethylol bodies of TrisP-PA (Honshu Chemical Co., Ltd.) or their methylols. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds in (c) may be used alone or in combination.

  The total content of the thermosetting compound in the thermosetting composition is preferably 0.1 to 50% by mass with respect to the total solid content (mass) of the curable composition, although it varies depending on the material. 0.2-40 mass% is more preferable, and 1-35 mass% is especially preferable.

~ Various additives ~
In the thermosetting composition, various additives such as a binder, a curing agent, a curing catalyst, a solvent, a filler, a polymer compound other than the above, and an interface are added as necessary as long as the effects of the present invention are not impaired. An activator, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a dispersant, and the like can be blended.

~~binder~~
The binder is often added at the time of preparing the pigment dispersion, does not require alkali solubility, and may be soluble in an organic solvent.

  The binder is preferably a linear organic polymer that is soluble in an organic solvent. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  Among these various binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.

As the acrylic resin, a copolymer comprising monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, for example, benzyl methacrylate / methacrylic acid, Each copolymer such as benzyl methacrylate / benzylmethacrylamide, KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.
By dispersing the colorant in these binders at a high concentration, it is possible to impart adhesion to the lower layer and the like, which also contributes to the coated surface shape during spin coating and slit coating.

~~ Hardener ~~
When an epoxy resin is used as the thermosetting compound, it is preferable to add a curing agent. There are many types of curing agents for epoxy resins, and their properties, pot life with resin and curing agent mixture, viscosity, curing temperature, curing time, heat generation, etc. vary greatly depending on the type of curing agent used. An appropriate curing agent must be selected according to the purpose of use, use conditions, working conditions, and the like. The curing agent is described in detail in Chapter 5 of Hiroshi Kakiuchi “Epoxy resin (Shojodo)”. Examples of the curing agent are as follows.
Those that act catalytically include tertiary amines, boron trifluoride-amine complexes, those that react stoichiometrically with functional groups of epoxy resins, polyamines, acid anhydrides, etc .; Examples include diethylenetriamine, polyamide resin, and medium temperature curing examples such as diethylaminopropylamine and tris (dimethylaminomethyl) phenol; examples of high temperature curing include phthalic anhydride and metaphenylenediamine. In terms of chemical structure, in the case of amines, diethylenetriamine as an aliphatic polyamine; metaphenylenediamine as an aromatic polyamine; tris (dimethylaminomethyl) phenol as a tertiary amine; phthalic anhydride as an acid anhydride; polyamide resin Polysulfide resin, boron trifluoride-monoethylamine complex; Synthetic resin initial condensate includes phenol resin, dicyandiamide and the like.

  These curing agents react with an epoxy group by heating and polymerize to increase the crosslinking density and cure. For thinning, both the binder and the curing agent are preferably as small as possible. In particular, the curing agent is 35% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less with respect to the thermosetting compound. It is preferable that

~~ Curing catalyst ~~
In order to realize a high colorant concentration, curing by reaction between epoxy groups is effective in addition to curing by reaction with the curing agent. For this reason, a curing catalyst can be used without using a curing agent. The addition amount of the curing catalyst is about 1/10 to 1/1000, preferably about 1/20 to 1/500, more preferably 1/30, based on the mass of the epoxy resin having an epoxy equivalent of about 150 to 200. It can be cured with a slight amount of about 1/250.

~~solvent~~
The thermosetting composition can be used as a solution dissolved in various solvents. Each solvent used in the thermosetting composition is basically not particularly limited as long as the solubility of each component and the applicability of the thermosetting composition are satisfied.

~~ dispersant ~~
A dispersant can be added to improve the dispersibility of the pigment. As the dispersant, known ones can be appropriately selected and used, and examples thereof include a cationic surfactant, a fluorosurfactant, and a polymer dispersant.

  As these dispersants, many types of compounds are used. For example, phthalocyanine derivatives (commercially available products EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Nippon Lubrizol); organosiloxane polymer KP341 (Shin-Etsu) Chemical Industry Co., Ltd.), (Meth) acrylic acid type (co) polymer polyflow No.75, No.90, No.95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) ) And other cationic surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate , Sorbita Nonionic surfactants such as fatty acid esters; Anionic surfactants such as W004, W005, W017 (manufactured by Yusho Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400 , EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by San Nopco) Various Solsperse dispersants (manufactured by Nippon Lubrizol) such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F 8, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co.) and Isonetto S-20 (manufactured by Sanyo Chemical Co.) and the like

  The dispersants may be used alone or in combination of two or more. The amount of the dispersant added in the thermosetting composition of the present invention is usually preferably about 0.1 to 50 parts by mass with respect to 100 parts by mass of the pigment.

~~ Other additives ~~
Various additives can be further added to the non-photosensitive colored curable composition as necessary. Specific examples of the various additives include the various additives described in the above colored photocurable composition.

(Second Embodiment)
A second embodiment of the solid-state imaging device of the present invention will be described with reference to FIG. In this embodiment, the device protective film in the first embodiment is not formed by heating at a high temperature, but by heating at a relatively low temperature, and a convex concave inner lens is provided on the substrate side. .
In addition, the same referential mark is attached | subjected to the component similar to 1st Embodiment, and the detailed description is abbreviate | omitted.

  As shown in FIG. 13, the solid-state imaging device 50 of the present embodiment is provided with silicon nitride while being kept at a relatively low temperature (for example, 300 to 500 ° C.), so that the device protective film has a concave shape according to the unevenness on the semiconductor substrate 51 is formed. The device protection film 51 is formed of silicon nitride with a thickness of 0.70 μm.

By forming the device protective film as thin as possible to ensure device reliability, shading suppression can be further improved. Specifically, this is the same as in the first embodiment. In addition to silicon nitride (Si ₃ N ₄ ), examples of the device protective film include silicon oxide (SiO ₂ ), glass (PSG), polyimide, and the like. In particular, silicon nitride suppresses impurity diffusion and prevents ions from entering. Particularly preferred from the viewpoint of suppression and high moisture resistance.

  A planarization layer 52 is formed so as to cover the entire surface of the device protection film 51, and a concave inner lens 52L is integrally formed on the planarization layer 52. The concave inner lens 52L is formed in a convex shape in the opposite direction (opposite side) to the direction (upper side of the semiconductor substrate) in which the color filter array of the semiconductor substrate is arranged. The concave shape as described above can also collect light on the photodiode.

  The planarization layer 52 is provided between the device protection film 51 and the color filter array, and reduces the light incident efficiency to the surrounding color filters to improve the light introduction efficiency. Thereby, compared with the conventional solid-state image sensor which has an on-chip microlens, the outstanding shading characteristic is acquired. As described above, when a light collecting means such as a microlens is provided below the color filter layer, it is preferable to form a flattening layer and perform a flattening process.

As the planarizing layer, a composition containing a polymer compound that can be cured by heat can be preferably used. As said high molecular compound, a polysiloxane type polymer and a polystyrene type polymer can be mentioned as a preferable thing, for example. Among them, materials known as spin-on-glass (SOG) material, an inorganic film such as SiO _2, may be mentioned a thermosetting composition whose main component is polystyrene derivative or a polyhydroxystyrene derivative as a more preferred it can. Among these, SiO ₂ is particularly preferable from the viewpoint of etching resistance to the fluorocarbon gas system used during dry etching.

  It is desirable that the planarizing layer has a refractive index equivalent to that of the color filter and has a large difference from the refractive index of the convex inner lens material. Thereby, the condensing efficiency of a concave inner lens can be improved. Specifically, this is the same as in the first embodiment.

  The details of the coloring composition (thermosetting composition) and the like are the same as in the first embodiment.

(Third embodiment)
A third embodiment of the solid-state imaging device of the present invention will be described with reference to FIG. In the present embodiment, a separation wall is further formed on the planarization layer in the first embodiment at a position on the extension of the separation wall of the color filter array.
In addition, the same referential mark is attached | subjected to the component similar to 1st Embodiment, and the detailed description is abbreviate | omitted.

  In the solid-state imaging device of the present embodiment, as shown in FIG. 14, the separation wall 61 is formed in a continuous line from the color filter array to the planarization layer, and the separation wall 61 is a convex inner of the planarization layer 24. The lens 28 is disposed so as to correspond to the formation position of the color filter layer constituting the color filter array.

The separation wall 61 is composed of a low refractive index layer formed of a low refractive material having a refractive index lower than that of the color filter layer, and can reflect light when oblique light is incident. It has become. Similar to the first embodiment, the separation wall 61 is formed by dry etching so that the wall surface thereof is substantially parallel to the normal direction of the semiconductor substrate 22.
The details of the refractive index of the color filter layer, the low refractive index layer formed as the separation wall, the low refractive material, the wall thickness of the separation wall, and the like are as described in the first embodiment.

  Since the separation wall 61 is also present in the planarization layer, color mixing is difficult to occur when oblique light is incident, and a solid-state imaging device with better color reproducibility can be obtained.

The separation wall 61 can be formed by performing dry etching with the fluorocarbon gas that forms the separation wall in the first embodiment until the device protective film is exposed. Other forms can be implemented according to the first embodiment.
In this embodiment, when a microlens that is a condensing unit is provided below the color filter layer viewed from the semiconductor substrate and a planarizing layer is formed on the microlens, all of light in a region that does not include the condensing unit is used. The light can be reflected, and light can be efficiently collected on the photodiode. Further, by forming the gap of the light collecting means (here, the convex inner lens) narrower than the width of the separation wall, it is possible to further enhance the color mixing suppression effect.

(Fourth embodiment)
A fourth embodiment of the solid-state imaging device of the present invention will be described with reference to FIGS. In the present embodiment, the separation wall in the third embodiment is configured by a hollow air layer.
In addition, the same referential mark is attached | subjected to the component similar to 1st, 3rd embodiment, and the detailed description is abbreviate | omitted.

  In the solid-state imaging device of the present embodiment, as shown in FIG. 15, the separation wall 65 is an air layer formed in an internal hollow. Also by providing an air layer as a separation wall between the color filter layers, as shown in FIG. 16, the light can be reflected when the oblique light 30 is incident, and light leakage to the color filter layer 21B is suppressed. . Thereby, color mixing of light can be prevented.

  The separation wall 65 is formed by forming a gap in the color filter array of the third embodiment by dry etching, and ending the process when the photoresist is removed, thereby forming the separation wall 65 as an air layer between the color filter layers. it can. About another structure and manufacturing process, it is the same as 3rd Embodiment.

(Fifth embodiment)
A fifth embodiment of the solid-state imaging device of the present invention will be described with reference to FIG. In this embodiment, a separation wall is further formed on the planarization layer in the second embodiment at a position on the extension of the separation wall of the color filter array.
In addition, the same referential mark is attached | subjected to the component similar to 1st, 2nd embodiment, and the detailed description is abbreviate | omitted.

  In the solid-state imaging device of the present embodiment, as shown in FIG. 17, the separation wall 71 is continuously formed from the color filter array to the planarization layer, and the separation wall 71 is a concave inner lens of the planarization layer 52. 52L is arranged so as to correspond to the formation position of the color filter layer constituting the color filter array. In addition, the device protective film 51 is formed in a concave shape according to the unevenness on the semiconductor substrate by providing silicon nitride while being kept at a relatively low temperature (for example, 300 to 500 ° C.). The device protection film 51 is formed of silicon nitride with a thickness of 0.70 μm.

The separation wall 71 is composed of a low refractive index layer formed of a low refractive index material having a refractive index lower than that of the color filter layer, and can reflect light when oblique light is incident. It has become. As in the first embodiment, the separation wall 71 is processed and formed by dry etching so that the wall surface is substantially parallel to the normal direction of the semiconductor substrate 22.
The details of the refractive index of the color filter layer, the low refractive index layer formed as the separation wall, the low refractive material, the wall thickness of the separation wall, and the like are as described in the first embodiment.

  Since the separation wall 71 is also present in the planarization layer, color mixing is difficult to occur when oblique light is incident, and a solid-state imaging device with better color reproducibility can be obtained. Further, since the inner lens is concave, the light collection efficiency can be further improved.

  The separation wall 71 can be formed by performing dry etching with the fluorocarbon gas that forms the separation wall in the first embodiment until the device protective film 51 is exposed. Other forms can be implemented according to the first embodiment.

  It is desirable that the planarization layer 52 has a refractive index equivalent to that of the color filter and has a large difference from the refractive index of the convex inner lens material. Thereby, the condensing efficiency of a concave inner lens can be improved. Specifically, this is the same as in the first and second embodiments.

  Details of the device protective film, the planarization layer, the concave inner lens, and the coloring composition (thermosetting composition) are the same as those in the first and second embodiments.

(Sixth embodiment)
A sixth embodiment of the solid-state imaging device of the present invention will be described with reference to FIG. In the present embodiment, the separation wall in the fifth embodiment is configured by a hollow air layer.
In addition, the same referential mark is attached | subjected to the component similar to 1st, 5th embodiment, and the detailed description is abbreviate | omitted.

  In the solid-state imaging device of the present embodiment, as shown in FIG. 18, the separation wall 75 is an air layer formed in a hollow interior. By providing an air layer, light can be reflected when oblique light is incident, and light color mixing can be prevented.

  The separation wall 75 is formed by forming a gap in the color filter array of the fifth embodiment by dry etching, and ending the process when the photoresist is removed, thereby forming the separation wall 75 as an air layer between the color filter layers. it can. Other configurations and manufacturing processes are the same as those of the fifth embodiment.

In each of the above-described embodiments, the case where primary color filters using red (R), green (G), and blue (B) are created has been described as an example. However, cyan, magenta, yellow, and (green) are used. This is also useful when a complementary color filter is produced.
In each embodiment, the microlens unit is provided. However, the color filter array may be configured as a light collecting unit without providing the microlens.

  Each of the above embodiments has been described with respect to the case where a convex or concave inner lens is used as the light condensing means. However, the present invention can also be applied to a case where a light condensing means using a diffraction grating and a prism is provided.

  The present invention can be applied not only to a front-illuminated solid-state image sensor but also to a back-illuminated solid-state image sensor that has been developed in recent years. The back-illuminated solid-state image sensor is obtained by cutting the image sensor thinly to a dozen μm and receiving light from the back surface of the image sensor, and is a high-sensitivity image sensor due to high quantum efficiency. When the color filter of the present invention in which color mixing is suppressed as described above is applied to a back-illuminated image sensor, it is possible to provide an image sensor with little color mixing and excellent color reproducibility and high sensitivity.

  As described above, the solid-state imaging device manufactured according to the present invention can suppress color mixing of light and has good color reproducibility. Further, a light collecting means such as a microlens is formed between the semiconductor substrate and the color filter layer, and the color filter layer forms the outermost layer farthest from the semiconductor substrate to obtain flatness. Compared with a conventional configuration in which a microlens or the like is formed on a solid-state imaging device, the color shading characteristics are improved and the device characteristics are good.

  In addition to the device structure described in each of the above embodiments, the present invention further includes a sensor for amplifying a signal by installing an MCP on the entire surface of the light receiving surface, and a photoelectric conversion layer by installing a photoelectric conversion layer below the color filter. It can also be applied to devices having a structure in which photons are converted into electrons and then electrons are sent to the device.

It is a schematic sectional drawing which shows the structure of the solid-state image sensor which concerns on 1st Embodiment of this invention. It is the top view which looked at the color filter array of a 1st embodiment from the upper part (normal line direction) of a semiconductor substrate. It is a conceptual diagram for demonstrating a mode that the light which injected in the separation wall using a low refractive material reflects. It is the schematic which shows the state in which the 1st colored layer is formed. It is the schematic which shows the state in which the opening part is formed in the photoresist on a 1st colored layer. It is the schematic which shows the state by which the opening part is formed in the area | region which is going to form the 2nd colored layer in the 1st colored layer. It is the schematic which shows the state in which the 2nd colored layer 36 was formed covering the 1st colored layer and opening part. It is the schematic which shows the place where the 1st and 2nd colored layer is formed in pattern shape. It is the schematic which shows the color filter array which consists of RGB 3 colors. It is sectional drawing which shows the state in which the grid | lattice-like space pattern was formed on the color filter array. It is sectional drawing which shows the state in which the gap | interval was formed between the color filter layers. It is sectional drawing which shows the color filter array in which the separation wall of the low refractive index was formed between the color filter layers. It is a schematic sectional drawing which shows the structure of the solid-state image sensor which concerns on 2nd Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the solid-state image sensor which concerns on 3rd Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the solid-state image sensor which concerns on 4th Embodiment of this invention. It is a conceptual diagram for demonstrating a mode that the light which injected in the hollow separation wall reflects. It is a schematic sectional drawing which shows the structure of the solid-state image sensor which concerns on 5th Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the solid-state image sensor which concerns on 6th Embodiment of this invention. It is a figure for demonstrating the place which forms the 1st colored layer 2 in the manufacturing method of the conventional color filter. It is the schematic for demonstrating the exposure process in the manufacturing method of the conventional color filter. It is a schematic sectional drawing which shows the place where the 1st coloring pattern is formed. It is a schematic sectional drawing which shows the place where the 1st-2nd coloring pattern is formed. It is a schematic sectional drawing which shows the place where the 1st-3rd coloring pattern is formed. It is a schematic sectional drawing for demonstrating the structure of the conventional solid-state image sensor. It is a graph which shows the spectral characteristic of the transmitted light.

Explanation of symbols

20, 50 ... solid-state image pickup devices 21R, 21G, 21B ... color filter layers 23, 51 ... device protective films 25, 43, 61, 65, 71, 75 ... separation walls 24, 27, 52 ... flattening layer 28 ... convex type Inner lens (micro lens)
40 ... color filter array 42 ... gap 52L ... concave inner lens (microlens)

Claims (11)

A semiconductor substrate;
A color filter array having a color filter layer of two or more colors and a separation wall separating at least the color filter layers of different colors;
Light condensing means disposed between the semiconductor substrate and the color filter array;
A solid-state imaging device.   The solid-state imaging device according to claim 1, wherein the separation wall is formed of a layer formed of a material having a refractive index lower than that of the color filter layer.   The solid-state imaging device according to claim 1, wherein the separation wall is formed of an air layer.   4. The wall thickness of the separation wall in a direction orthogonal to the thickness direction of the color filter layer is 0.05 μm or more and 0.2 μm or less. 5. Solid-state image sensor.   5. The method according to claim 1, further comprising a protective film on the semiconductor substrate, wherein the light collecting unit is formed by processing at least a part of the protective film. The solid-state imaging device described.   The protective substrate is provided on the semiconductor substrate, and the light collecting means is formed by providing a high refractive index material having a higher refractive index than the color filter layer on the protective layer. The solid-state image sensor of any one of Claim 4.   A flattening layer for flattening a region where the color filter array on the condensing means side is formed is at least partially between the condensing means and the color filter array, and the flattening layer includes the color filter. The solid-state imaging device according to claim 1, wherein a separation wall is provided at least in an extending direction of the separation wall in the filter array.   A solid-state imaging device comprising a semiconductor substrate, a color filter array having two or more color filter layers and a separation wall separating at least the different color filter layers, wherein the color filter array collects light A solid-state imaging device that is a means and has no light collecting means other than a color filter array.   The solid-state imaging device according to any one of claims 1 to 8, wherein the color filter layer is processed into a pattern by a dry etching method. Forming a color filter array having a color filter layer of two or more colors on a semiconductor substrate;
Forming a photosensitive resin layer on the color filter array on the semiconductor substrate;
Exposing and developing the formed photosensitive resin layer in a pattern, and patterning so that adjacent portions adjacent to different color filter layers are exposed; and
Forming a gap between at least different color filters by performing dry etching on the color filter layer using the patterned photosensitive resin layer as a mask, and removing the adjacent portion;
A method for manufacturing a solid-state imaging device.   The solid-state imaging device according to claim 10, further comprising a step of forming a layer made of a material having a refractive index lower than that of the color filter layer in the gap formed between different color filters. Manufacturing method.

Images