JP2010085756A - Method of manufacturing color filter, and solid-state imaging device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reliably perform light shielding between color filters, and also to achieve microfabrication and film thinness. <P>SOLUTION: A color filter array including first and second colored layers 43 and 47 is formed on a support and then an aperture 59 for a black light shielding layer is formed by dry etching so that the first and second colored layers 43 and 47 may be left in a island shape. A black light shielding layer 60 is formed so as to fill the aperture 59 for the black light shielding layer. An aperture for a third colored layer is formed in the black light shielding layer 60 so as to form an island shape by dry etching. A third colored layer is formed so as to fill the aperture for the third colored layer and a color filter is formed so that the black light shielding layer 60 may be left in the boundaries between different colored layers. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is a color filter manufacturing method including a step of forming a black matrix at a boundary between different colored layers of a color filter array in which two or more colored layers are arranged on a support, and the manufacturing method. The present invention relates to a solid-state imaging device using a color filter.

  In recent years, in the solid-state imaging device, the number of imaging pixels has increased remarkably, and accordingly, the area per pixel has been reduced in the effective pixel region having the same size as the conventional one. In particular, a color filter provided in a solid-state imaging device is required to maintain color separation performance because color mixture between pixels becomes remarkable as the light receiving area decreases. As a method for producing a color filter, a photolithography method and a dry etching method are widely known.

  In the photolithography method, since the manufacturing process conforms to the photolithography process of semiconductor manufacturing, initial investment can be suppressed. Thus, conventionally, it has been widely used as a method for producing a color filter. In this color filter manufacturing method using the photolithographic method, a coating film formed by applying a radiation-sensitive composition such as a colored curable composition on a substrate and drying it is colored by pattern exposure, development and baking. Pixels are formed and this operation is repeated for each color to produce a color filter.

  On the other hand, a dry etching method is used as a method effective for forming a fine pattern with a thinner film than a color filter manufacturing method using a photolithography method. The dry etching method has been conventionally employed as a method for forming a pattern on a dye-deposited thin film (see, for example, Patent Document 1), and the thin film formation has a film thickness while maintaining the same spectral characteristics as compared to a photolithography system. However, it is possible to form a thin film having a thickness of 1/2 or less. In addition, a pattern forming method combining a photolithography method and a dry etching method has been proposed (see, for example, Patent Document 2).

  In addition, a color filter material (colorant-containing composition) different from the first color is applied on the first color filter (colored layer) patterned by the dry etching method, so that the second color filter (Colored layer) is formed, and the surface of the second color filter is flattened using the CMP (Chemical Mechanical Polishing) method or the etch-back method, and the second color is placed in the gap between the first color filters. A method for arranging color filters has been proposed (see, for example, Patent Document 3).

  Furthermore, since the performance of the color filter is related to maintaining the important characteristics of the solid-state imaging device, various performance improvements such as thinning and rectangularization, and prevention of color mixture between pixels (overlapping colors overlap each other) are required. Yes.

As a measure against the performance requirement of the color filter, in Patent Document 4, a filter separation layer for separating the color filters from each other is formed on a support, and then the color filter is formed on the filter separation layer by dry etching. There has been proposed a method of manufacturing a color filter by opening a region and embedding a colored layer, and removing a colored layer other than the region embedded in the opening by a planarization process such as CMP (Chemical Mechanical Polishing).
JP-A-55-146406 JP 2001-249218 A JP 2006-351786 A JP 2006-351775 A

  In the manufacturing method described in Patent Document 4, a filter separation layer is formed from a material having a refractive index different from that of the color filter layer, and incident light from an oblique direction is reflected by a difference in refractive index between the color filter and the filter separation layer. The purpose is to suppress color mixing. In this case, in the periphery of the screen of the image sensor, the angle of light from the exit pupil may be less than the critical angle at which light cannot be totally reflected, reflection efficiency is poor, and color mixing suppression effect cannot be obtained sufficiently There is.

  Therefore, in order to increase the color development effect and contrast of color filters in liquid crystal displays and plasma displays, a light-shielding black matrix (light-shielding wall) formed at the boundary between the three-color filters is used as the color filter of the solid-state imaging device. It is considered to apply. As a method for forming a light shielding wall applied to a liquid crystal display or the like, there are a chromium etching method in which metal chromium is vapor-deposited and etched, and a method in which a photoresist in which a black component such as a pigment is dispersed is photocured to form a pattern. is there. In particular, when the light-shielding wall is formed using a chromium etching method, the fine workability is excellent.

  When such a light shielding wall is provided in the color filter, the line width of 0.2 μm or less, which is narrower than the conventional manufacturing process, is used in order to satisfy the required performance while supporting further miniaturization and thickness reduction of the color filter. Must be formed. However, in each of the above methods, it is difficult to satisfy the required performance of the color filter and to make the line width of the light shielding wall smaller than the conventional one. That is, in the light shielding wall forming method using the chrome etching method, there is a problem that the reflectance is high and it is difficult to increase the contrast, so it is difficult to maintain the color separation performance of the color filter, and further, vacuum deposition process such as vapor deposition The cost is high. Further, when the pigment resist method is used, if the black component is increased in order to improve the light shielding property, the resolution of the photoresist is lowered. Therefore, it is difficult to improve the rectangularity and miniaturization of the light shielding wall.

  The present invention has been made in view of the above-described problems, and provides a color filter manufacturing method and a solid-state imaging device that can reliably perform light shielding between color filters and can be miniaturized and thinned. The purpose is to do.

  The method for producing a color filter of the present invention is a method for producing a color filter in which three colored layers are arranged on the surface of a substrate, and the coloration is performed during the step of forming the three colored layers. A region including a portion serving as a layer boundary is dry-etched to form a black light-shielding layer opening, and a black light-shielding layer containing a black colorant is formed in the black light-shielding layer opening. .

  A first color filter array forming step for forming the colored layer of at least one color and a region including a portion serving as a boundary with respect to the colored layer formed in the first color filter array forming step by dry etching; An etching process for forming a black light shielding layer, a black light shielding layer forming process for forming a black light shielding layer containing a black colorant so as to fill the opening for the black light shielding layer, The black light-shielding layer formed in the black light-shielding layer forming step is dry-etched so as to leave a portion that becomes the boundary of the colored layer to form a color filter array opening, and the color filter array opening It is preferable to have a second color filter array forming step for forming the remaining colored layers of three colors.

  The first or second color filter array forming step includes a color filter array etching step for forming the color filter array opening, and a colored layer for forming any of the colored layers in the color filter array opening. It is preferable that each of the forming steps is performed at least once.

  The width dimension of the color filter array opening is preferably smaller than the black light shielding layer opening. Also. The black light-shielding layer is preferably formed to have the same film thickness as the colored layer.

  After forming the colored layer in the color filter array opening, the black light shielding layer on the colored layer formed in the first color filter array forming step or the entire surface of the colored layer material is planarized. It is preferable to perform a flattening step for making the film thickness of the colored layer and the black light shielding layer uniform. Further, it is preferable that the planarization process uses either a CMP process or an etchback process. In the etch back process, it is preferable to use an etching gas containing at least one halogen gas such as fluorine, chlorine and bromine.

  In the color filter array etching step, a plurality of the color filter array openings are formed so as to be isolated by a part of the black light shielding layer, and between the colored layers formed in the colored layer forming step. The black light shielding layer is preferably formed as a light shielding wall.

  The light shielding wall preferably has a line width of 0.2 μm or less in a direction orthogonal to the film thickness direction of the black light shielding layer. The support is a semiconductor wafer having a bonding pad, a dicing line, and a light receiving portion formed for each pixel, and the black light shielding layer is formed at a place other than the light receiving portion, the bonding pad, and the dicing line. It preferably functions as a light-shielding film that absorbs obliquely incident light and blocks light passing between adjacent pixels.

  The black colorant preferably contains either a titanium black material or a carbon black material. Moreover, it is preferable that the said colored layer and the said black light shielding layer contain the thermosetting composition which does not have photosensitivity. During the first color filter array etching step in the first color filter array forming step, an alignment mark for an exposure machine is formed, and in the subsequent etching step, the mark is used as a reference. It is preferable to align the exposure machine.

  A solid-state imaging device according to the present invention includes a color filter manufactured by the color filter manufacturing method according to any one of claims 1 to 14.

  According to the present invention, between the process groups for forming the three colored layers, the region including the portion that becomes the boundary of the colored layer is dry-etched to form the opening for the black light shielding layer. Since the black light shielding layer containing the black colorant is formed in the opening, the light shielding between the color filters can be surely performed, and the line width is 0 without depending on the resolution of the photoresist. A black light-shielding layer having a thickness of 2 μm or less can be formed, and the color filter can be made finer and thinner.

  Hereinafter, the present invention will be specifically described with reference to the accompanying drawings. In FIG. 1, a solid-state imaging device 10 according to the present embodiment includes a semiconductor substrate 12 including photodiodes 11R, 11G, and 11B, and a color filter provided on the incident side of the semiconductor substrate 12 with respect to the photodiodes 11R, 11G, and 11B. 13R, 13G, 13B and the color filters 13R, 13G, 13B, which are formed at the boundaries between the respective color filters, isolate each other from each other, and the color filters 13R, 13G, 13B and the light shielding wall 14 are covered and flattened. And a microlens 16 provided on the planarization layer 15 so as to correspond to the formation regions of the color filters 13R, 13G, and 13B. The color filters 13R, 13G, and 13B transmit red, green, and blue light, respectively. Furthermore, the semiconductor substrate 12 is provided with a light shielding film (not shown) that is open only in the portions of the photodiodes 11R, 11G, and 11B, and this light shielding film is formed of tungsten or the like.

  FIG. 2 is a plan view of the solid-state imaging device 10 as viewed from above the semiconductor substrate (normal direction), and broken lines indicate boundaries between the color filters 13R, 13G, and 13B. In the solid-state imaging device 10, the color filters 13R, 13G, and 13B constituting the pixels and the corresponding photodiodes 11R, 11G, and 11B are arranged in a Bayer array, that is, the odd lines are repeated of the color filters 13G and 13R, and the even lines are colored. The filters 13B and 13G are arranged repeatedly. Light that has entered the photodiodes 11R, 11G, and 11B through the microlens 16 and the color filters 13R, 13G, and 13B is generated and stored as signal charges corresponding to the light amounts of the respective colors by photoelectric conversion.

  The light shielding wall 14 isolates the color filters 13R, 13G, and 13B from each other, and therefore absorbs obliquely incident light among the light that has entered through the microlens 16 and the color filters 13R, 13G, and 13B. Light leakage (color mixing) is prevented from passing through the lens 16 and the planarization layer 15 to adjacent pixels.

That is, as shown in FIG. 1, when the oblique incident light L1 is incident, the incident light L1 passes through the color filter 13G through the planarization layer 15, but leaks from the color filter 13G to the color filter 13B. The light L2 to be absorbed is absorbed by the light shielding wall 14, and light leakage to the color filter 13B is suppressed. Thereby, color mixing can be prevented.
Furthermore, the semiconductor substrate 12 is provided with a transfer electrode (not shown), and the signal charges accumulated in the photodiodes 11R, 11G, and 11B are read and transferred.

  The light shielding wall 14 is made of a black colorant-containing composition that absorbs visible light, and absorbs light when oblique light is incident. As will be described later, the light shielding wall 14 is formed by dry etching so that the wall surface thereof is substantially parallel to the normal direction of the semiconductor substrate 12.

  In the light shielding wall 14 of the solid-state imaging device 10 to which the present invention is applied, the line width D in the direction orthogonal to the film thickness direction of the color filters 13R, 13G, and 13B can be set to 0.05 μm or more and 0.2 μm or less. When the line width D of the light shielding wall 14 is formed within the dimension range, the area ratio of the color filters 13R, 13G, and 13B to the total area of the light transmission region of the solid-state imaging device 10 can be secured, and each color filter 13R, The color purity of 13G and 13B (pixels) can be improved. The line width D is more preferably 0.08 μm or more and 0.15 μm or less.

  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 an MCP (microchannel plate) and an ITO (Indium Tin Oxide) film.

  Such a color filter constituting the solid-state imaging device 10 is particularly suitable when manufactured by applying a dry etching method. Hereinafter, the manufacturing method of the color filter concerning 1st Embodiment of this invention is demonstrated concretely.

  As shown in FIG. 3, the color filter manufacturing process 17 includes an etching stopper layer forming process 18, a first color filter array forming process 19, a black matrix forming process 20, and a second color filter array forming process 21. The first color filter array forming step 19 further includes first and second color filter forming steps 22 and 23, and the second color filter array forming step 21 includes a third color filter forming step 24. .

  The first to third color filter forming steps 22 to 24 include patterning steps 26 and 36, etching steps 27 and 37, photoresist removing steps 28 and 38, colored layer forming steps 25, 29, and 39, and flattening steps 30 and 40. Consists of. Note that the first color filter forming step 22 includes only the colored layer forming step 25 and does not include a patterning step, an etching step, a photoresist removing step, and a planarization step.

  On the other hand, the black matrix forming step 20 includes a patterning step 31, an etching step 32, a photoresist removing step 33, a black light shielding layer forming step 34, and a flattening step 35, as will be described in detail later.

  In the case of the solid-state imaging device 10, there is a step of forming a semiconductor substrate 12 or a semiconductor wafer as a support before these steps 18 to 21, and after these steps, a flat covering the color filters 13B and 13G. There is at least a step of forming the planarization layer 15 and the microlens 16 disposed on the planarization layer 15.

[Etching stopper layer forming process]
In the color filter manufacturing process 17, first, an etching stopper layer forming process 18 is performed. In the present embodiment, the configuration in which the etching stopper layer 42 is formed on the support 41 is illustrated, but the etching stopper layer 42 may or may not be formed. Accordingly, the etching stopper layer forming step 18 may not be appropriately performed, and the process may proceed to the next first color filter array forming step 19. As shown in FIG. 4, in this etching stopper layer forming step 18, an etching stopper layer 42 containing at least silicon oxide is formed on a support 41 by using, for example, VR1 (manufactured by Rasa Industrial Co., Ltd.) as a spin coater (SCWC80A large). Formed by Nippon Screen Co., Ltd. Next, using a hot plate, the heat treatment is performed at 200 to 250 ° C. for 5 to 10 minutes, and the coating film is dried and cured to form the etching stopper layer 42. Alternatively, a CVD method, a sputtering method, or a vapor deposition method may be used. From the viewpoint of not impairing the transparency of the colored layer, the etching stopper layer 42 is transparent in the visible region, and the film thickness is preferably 50 nm to 200 nm, more preferably 100 nm to 150 nm. The refractive index is preferably 1.45 to 1.7, more preferably 1.5 to 1.65. In addition, in order to form the etching stopper layer 42, in addition to the above, 4MS (manufactured by Lhasa Kogyo Co., Ltd.), OCD Type-12 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), CERAMATE-LNT (manufactured by Catalyst Kasei Kogyo Co., Ltd.) Also good. In addition, the etching stopper layer 42 may be configured to contain a halogen-based gas. In this case, TI 204 (made by Rasa Industrial Co., Ltd.) containing titanium oxide may be used.

  In the present embodiment, as the support body 41, a semiconductor wafer before being cut by a dicing machine is used. The support body 41 includes a bonding pad, a dicing line, and a light receiving portion formed for each pixel. The present invention is not limited to this, and the support 41 may be selected according to the application. For example, a semiconductor substrate is used when a solid-state imaging device is manufactured, and a glass substrate is used when a liquid crystal display device is manufactured. be able to.

[First color filter array forming step]
Following the etching stopper layer forming step 18, the first color filter array forming step 19 is performed as described below to form first and second colored layers 43 and 47 to be described later.

[First color filter forming process]
In the first color filter forming step 22, that is, the first colored layer forming step 25, as shown in FIG. 4, a spin coater (SCWC80A; manufactured by Dainippon Screen) is used on the etching stopper layer 42. A colorant-containing composition colored in one color (for example, blue (B)) is applied. Next, heat treatment is performed using a hot plate, the coating film is cured, and the first colored layer 43 is formed. This heat treatment may be performed simultaneously with the drying after the application of the composition, or a separate thermosetting step may be provided after the application and drying.

[Second color filter forming step]
Subsequent to the first color filter forming step 22 (first colored layer forming step 25), a second color filter forming step 23 is performed. In the second color filter forming step 25, first, a patterning step 26 for a photoresist is performed.

[I-line photoresist patterning]
Next, in FIG. 5A, a positive photoresist (FHi622BC: manufactured by Fuji Film Electronics Materials) is applied onto the first colored layer 43 using a spin coater. Pre-baking is performed for 60 seconds in the range of 80 to 100 ° C. with a hot plate to form the photoresist layer 44. Subsequently, ultraviolet rays of i-line (wavelength 365 nm) are applied from above the photoresist layer 44 to a region where the second colored layer (second color; for example, red (R)) 47 is formed using a photomask. Then, exposure is performed using a stepper. Next, post-baking is performed for 90 seconds at 100 to 120 ° C. using a hot plate. Thereafter, paddle development is performed with a developer, and post-baking is performed with a hot plate to remove the photoresist in the region where the second colored layer 47 is to be formed. FIG. 5B shows a state in which the photoresist in a region where a second colored layer 47 to be described later is formed in the patterning step 26 is removed, and reference numeral 45 denotes an opening from which the photoresist has been removed.

  In this patterning step 26, the photoresist in the region for forming the alignment mark of the exposure machine is removed in addition to the region in which the second colored layer 47 to be described later is to be formed.

  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. Any developer can be used as long as it does not affect the first colored layer 43 and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

[Etching process]
Next, an etching process 27 for dry etching the first colored layer 43 using the photoresist layer 44 as a mask will be described. As a dry etching apparatus, a reactive ion etching apparatus (RIE; U-621) manufactured by Hitachi High-Technologies Corporation is used. Using this RIE apparatus 45 (see FIG. 7), the etching step 27 is performed using the photoresist layer 42 as a mask and a mixed gas containing at least a halogen-based compound gas as an etching gas. Thus, the first colored layer 43 in the region where the second colored layer 47 is to be formed is removed. FIG. 6 shows a state where the first colored layer 43 is etched in the etching step 27, and reference numeral 46 denotes a second colored layer opening formed in the etching step 27.

  In the present embodiment, as will be described later, the first and second colored layers 43 and 47 formed in the first color filter array forming step 19 are formed in stripes, so that the first etching is performed in the etching step 27. The two colored layer openings 46 are in the form of stripes that are parallel to each other and have a uniform width.

  Further, in the etching step 27, in addition to the second colored layer opening 46, an alignment mark for the exposure machine is etched. In the subsequent patterning steps 31 and 36, alignment of the exposure machine is performed with reference to this mark.

  FIG. 7 shows a schematic configuration of the dry etching apparatus 48. The dry etching apparatus 48 includes a chamber 49, a planar electrode (cathode) 50, a counter electrode (anode) 51, an RF oscillator 52, a blocking capacitor 53, an etching gas supply unit 54, and a control unit for controlling them. 55.

  The chamber 49 is provided with an introduction port 49a through which an etching gas is introduced from the side surface into the inside, and a planar electrode 50 and a counter electrode 51 are arranged inside. The planar electrode 50 and the counter electrode 51 are connected in series with the RF oscillator 52. Further, a blocking capacitor 53 is connected between the planar electrode 50 and the RF oscillator 52, and is connected to the ground 56 between the counter electrode 51 and the RF oscillator 52. The support 41 on which the color filter is formed is set on the planar electrode (cathode) 50.

[Anisotropic etching treatment]
When an anisotropic etching process is performed using the dry etching apparatus 48, an etching gas is introduced into the chamber 49 in which the support 41 is set on the planar electrode (cathode) 50. When a high frequency voltage is applied between the planar electrode 50 and the counter electrode 51 by the RF oscillator 52 with the etching gas introduced, plasma is generated between the planar electrode 50 and the counter electrode 51. . Electrons in the plasma are gathered at the planar electrode 50 and the counter electrode 51 immediately because the movement is lighter than the positive ions that are the active gas. Since the counter electrode 51 is connected to the ground 56, the potential of electrons collected at the counter electrode 51 does not change. However, in the planar electrode 50, a phenomenon called a cathode effect, that is, a direct current is blocked by the blocking capacitor 53. Therefore, electrons gather at the planar electrode 50 and become a negative potential. Due to this cathode effect, the first colored layer 43 is etched with anisotropy. That is, positive ions, which are active gases in the plasma, are attracted to the planar electrode 50, enter the wafer surface perpendicularly, collide with the first colored layer 43, and the first colored layer 43 is etched.

[Isotropic etching process]
When performing the etching process 27 using the dry etching apparatus 48, an isotropic etching process may be performed from a viewpoint of residue removal. A mixed gas (etching gas) containing at least oxygen gas is introduced into the chamber in which the semiconductor substrate is set on the planar electrode. When etching is performed with an etching gas containing oxygen gas, since the cathode effect does not occur, the first colored layer 43 is subjected to isotropic etching.

  In the etching step 27, the anisotropic etching process described above may be performed first, followed by the isotropic etching process. By alternately repeating the anisotropic etching process and the isotropic etching process, the deposit attached to the side wall of the opening from which the first colored layer 43 has been removed by the anisotropic etching process is isotropic. It is removed by an etching process. Therefore, the first colored layer 43 is etched with high accuracy against masking by the photoresist layer 44.

[Photoresist removal process]
Next, using a solvent or a photoresist stripping solution, a photoresist stripping process is performed to remove the photoresist layer 44 remaining on the first colored layer 43 (photoresist removal step 28). Thereafter, a dehydration bake treatment for solvent removal and dehydration treatment can be performed. As described above, the first colored layer 43 in the region where the second colored layer 47 is to be formed is removed by etching, and the photoresist layer 44 is peeled off. FIG. 8 shows the shape after stripping the photoresist. Alternatively, ashing treatment using at least oxygen gas may be performed.

[Second color filter forming step]
After the photoresist removing step 28, a second colored layer forming step 29 is subsequently performed.

[Second colored layer forming step]
In the second colored layer forming step 29, as shown in FIG. 9A, the entire first colored layer 43 is covered and embedded in the second colored layer opening 46 so that the second colored layer 43 is formed. A colored layer (second color; for example, red (R)) 47 is formed (second colored layer forming step 29). Similar to the method of forming the first colored layer 43, the color filter composition is applied using a spin coater. Next, the second colored layer 47 is formed by post-baking using a hot plate.

[Planarization process]
Next, as shown in FIGS. 9A and 9B, a flattening step 30 is performed in which the second colored layer 47 formed in the second colored layer forming step 29 is flattened. In the planarization step 30, anisotropic etching is performed using an etching gas containing at least one halogen gas such as fluorine, chlorine, and bromine, and the second colored layer is exposed until the first colored layer 43 is exposed. 47 is flattened by whole surface etching (flattening step 30). Thereby, the first color filter array forming step 19 is completed, and a color filter array composed of the first and second colored layers 43 and 47 is formed.

  In the present embodiment, when the first color filter array forming step 19 is completed and the first and second colored layers 43 and 47 are formed, as shown in FIG. The colored layers 43 and 47 are arranged in an alternating stripe pattern. Further, the first and second colored layers 43 and 47 are formed in a uniform width so as to be parallel to each other and to have a width dimension in pixel pitch units of the color filter. The present invention is not limited to this, and any one of the first and second colored layers 43 and 47 may be formed in an island shape arranged for each pixel. From the viewpoint of improvement, it is preferable to form the first and second colored layers 43 and 47 in stripes as in the present embodiment. The color of the first and second colored layers 43 and 47 is not limited to the above-described blue (B) and red (R), and green (G) may be used.

  In the first color filter array forming step 19 (color filter forming steps 22 and 23), the color filter array is formed using the dry etching method. However, the present invention is not limited to this, and the photolithographic method is used. May be. Specifically, Japanese Patent Application 2006-196622, Japanese Patent Application 2006-283454, Japanese Patent Application 2007-011291, Japanese Patent Application 2006-284363, Japanese Patent Application 2006-350428, Japanese Patent Application 2006-346108, Japanese Patent Application 2006-350429, Japanese Patent Application 2007. It is preferable to form from the photosensitive composition described in these prior patent documents, or a thermosetting composition using the method described in -033576.

[Black matrix formation process]
After the flattening step 30, a black matrix forming step 20 is subsequently performed. In the black matrix forming step 20, first, a photoresist layer 57 (see FIG. 11A) is formed so as to cover the entire first and second colored layers 43 and 47. The photoresist layer 57 is formed by using the same photoresist as that used in the first and second color filter forming steps 22 and 23 described above and using the same method.

[I-line photoresist patterning]
Next, using a photomask, the region where the black light shielding layer 60 is to be formed is exposed to ultraviolet rays of i-line (wavelength 365 nm) using a stepper. Next, a post baking process is performed with a hot plate. Thereafter, paddle development is performed with a developer, and post-baking is performed with a hot plate to remove the photoresist in the region where the second colored layer 47 is to be formed (patterning step 31). FIG. 11B shows a state in which the photoresist in the region where the black light shielding layer 60 is to be formed is removed, and reference numeral 58 denotes an opening from which the photoresist has been removed. The patterning step 31 is also performed by the same method as the patterning step 26 described above. The light source used for exposure is preferably a KrF line because the pattern formation of the black light shielding layer 60 only needs to have a resolving power of about 0.3 μm.

[Etching process]
Next, the etching process 32 for dry etching using the photoresist layer 57 as a mask will be described. As the dry etching apparatus to be used, it is preferable to use the RIE apparatus 48 described above or an ICP etcher apparatus (NE500: manufactured by ULVAC) using inductively coupled plasma (ICP). Then, an etching process is performed using the photoresist layer 57 as a mask and the photoresist layer 57 as a mask under etching conditions set in advance using plasma gas. Thereby, the region where the black light shielding layer 60 is to be formed is removed.

The plasma gas used in the etching step 32 is preferably a fluorine-based gas, an oxygen gas, or a mixed gas from the viewpoint of anisotropic processing. As the fluorine-based gas, SF6, CxFy (x = 1 to 5, y = 1 to 8), or CHF3 gas can be used. In terms of obtaining a fast and anisotropic processing of etching, for example, it is preferable to use a mixed gas of CF4 and O _2. The flow rate ratio is preferably 1/2 to 5/1.

From the standpoint of maintaining the partial pressure control stability of the etching plasma, in-plane uniformity, and the perpendicularity of the shape to be etched, the mixed gas is further mixed with helium (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 or the like), preferably at least one selected from the group of N ₂ , CO, and CO ₂ , and at least one selected from the group of Ar, He, Kr, N ₂ , and Xe More preferably, at least one selected from the group of He, Ar, and Xe is further included. However, if it is possible to maintain the partial pressure control stability of the etching plasma, the in-plane uniformity, and the perpendicularity of the shape to be etched, it may be composed of only a fluorine-based gas and an oxygen gas.

  The content of other gases that may be contained in addition to the mixed gas used in the etching step 32 is 25 or less in terms of the flow rate ratio when the total mixed gas flow rate is 1 in terms of the selectivity of the etching pattern. It is preferably 5 or more and 20 or less, more preferably 8 or more and 18 or less.

  In the present embodiment, after the black matrix forming step 20, the black light shielding layer 60 is etched in the second color filter array forming step 21 (third color filter forming step 24), and the third colored layer 64 is formed. Since the region to be formed is removed, the black light shielding layer opening 59 formed in the etching step 32 includes the region where the third colored layer 64 is to be formed. Thus, the state where the first and second colored layers 43 and 47 are etched in the etching step 32 is the state shown in FIGS. 11C and 12, and reference numeral 59 denotes the first step by the etching step 32. And the black light shielding layer opening 59 formed by removing the region including the boundary between the second colored layers 43 and 47 and the region where the third colored layer is to be formed. By forming the black light shielding layer opening 59 in this way, the first and second colored layers 43 and 47 are arranged in a checkered island-like arrangement in which each pixel is arranged. At this time, the first and second colored layers 43 and 47 are formed with the same width dimension W2, and the black light shielding layer opening 59 is formed with a width dimension W1 larger than these.

[Photoresist removal process]
Subsequent to the etching step 32, a photoresist removal step 33 is performed in which the remaining photoresist layer 61 is peeled off from the first and second colored layers 43 and 47 and removed. FIG. 13 shows a state in which the photoresist layer 61 has been removed. This photoresist removal step 33 can be performed using the same processing and method as the photoresist removal step 28 described above, the cleaning water used, the stripping solution or solvent, and the apparatus. In addition to the treatment similar to the photoresist removal step 28, the photoresist may be removed by ashing using an ozone ashing apparatus (UA-7200: manufactured by Hitachi High-Technologies Corporation). After the photoresist removing step 33, a black light shielding layer forming step 34 is subsequently performed.

  The photoresist removing step 33 includes a step of applying a stripping solution or a solvent on the photoresist layer to make the photoresist layer removable, and a step of removing the photoresist layer using cleaning water. It is preferable to contain. As a process of applying a stripping solution or solvent on the photoresist layer to make it removable, for example, a paddle development process in which the stripping solution or solvent is applied on at least the photoresist layer and stagnated for a predetermined time. Can be mentioned. Although there is no restriction | limiting in particular as time to make stripping solution or a solvent stagnant, It is preferable that it is several dozen seconds to several minutes.

  The step of removing the photoresist layer using cleaning water includes, for example, a step of removing the photoresist layer by spraying cleaning water onto the photoresist layer from a spray type or shower type spray nozzle. Can do. As the washing water, pure water can be preferably used. Further, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support. When the spray nozzle is movable, the photoresist layer is more effectively removed by moving the support from the center of the support to the end of the support more than twice during the step of removing the photoresist layer and spraying the cleaning water. Can be removed.

  After completion of the etching treatment, the photoresist having a function as a mask (photosensitive resin layer after exposure) is removed with a stripping solution. The stripping solution generally contains an organic solvent, but may further contain an inorganic solvent. Examples of organic solvents include 1) hydrocarbon compounds, 2) halogenated hydrocarbon compounds, 3) alcohol compounds, 4) ether or acetal compounds, 5) ketones or aldehyde compounds, and 6) ester compounds. 7) polyhydric alcohol compounds, 8) carboxylic acids or acid anhydride compounds thereof, 9) phenol compounds, 10) nitrogen compounds, 11) sulfur compounds, and 12) fluorine compounds. The stripping solution in the present invention preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specifically, for example, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, O-nitroanisole, N-butylethanolamine, monoethanolamine, diethanolamine, triethanolamine, Examples include ethanolamine, and monoethanolamine, diethanolamine, and triethanolamine are preferable, and monoethanolamine (H ₂ NCH ₂ CH ₂ OH) is more preferable.

  Examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline, 2-pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, 2,6-lutidine and the like are preferable, N-methyl-2-pyrrolidone and N-ethylmorpholine are preferable, and N-methyl-2-pyrrolidone (NMP) is more preferable.

  The stripping solution in the present invention preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound, and among them, as the acyclic nitrogen-containing compound, at least one selected from monoethanolamine, diethanolamine and triethanolamine More preferably, the cyclic nitrogen-containing compound includes at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and further includes monoethanolamine and N-methyl-2-pyrrolidone. preferable.

  When removing with the above stripping solution, it is sufficient that the photoresist formed on the upper part of the color filter layer is removed, and even when a deposit as an etching product adheres to the side wall of the colored layer, the deposit is removed. The object may not be completely removed. Here, the deposit means an etching product deposited on the side wall of the colored layer.

  The content of the acyclic nitrogen-containing compound is 9 parts by mass or more and 11 parts by mass or less with respect to 100 parts by mass of the stripping solution, and the content of the cyclic nitrogen-containing compound is 65 parts by mass or more and 70 parts by mass or less. It is desirable. Moreover, it is preferable that the stripping solution in the present invention is obtained by diluting a mixture of a non-cyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

  In the present embodiment, as shown in FIG. 13, by peeling the photoresist, it is possible to form a shape in which the region where the black light shielding layer 60 is to be formed is formed in a concave shape. After the etching process is completed, the mask resist is removed with a special stripping solution or solvent. In the present invention, when the second etching process using the second gas mainly composed of oxygen gas is provided, the photoresist layer can be more easily peeled off by the stripping solution or solvent.

  In addition, after the photoresist layer removing step, a step of performing a dehydration bake treatment of solvent removal and dehydration treatment can be further provided.

[Black shading layer forming step]
The black light shielding layer forming step 34 covers the entire first and second colored layers 43 and 47 and is embedded in the black light shielding layer opening 59 so that the solvent containing the dispersion resin or the thermosetting resin is colored black. The coating liquid in which the agent is dispersed is applied using spin coating. After drying, using a hot plate, it is heated in the range of 200 to 250 ° C. for 5 to 10 minutes to cure the coating film to form the black light shielding layer 60 (state shown in FIG. 14A).

[Planarization process]
A flattening step of flattening the surface of the black light shielding layer 60 formed on the entire surface of the first and second colored layers 43 and 47 and on the black light shielding layer opening 59 by an entire surface etching (etch back) process. 35, the first and second colored layers 43 and 47 are exposed, and the film thicknesses of the first and second colored layers 43 and 47 and the black light shielding layer 60 are made uniform (FIG. 14B). The state shown in FIG. At this time, it is preferable that the thickness of the black light-shielding layer is set to the same set thickness as that of the first to third colored layers 43, 47, and 64.

[Etch back condition]
As a dry etching apparatus used in the planarization step 35, it is preferable to use the RIE apparatus 48 or the above-described ICP etcher apparatus. Further, the entire black light shielding layer 60 is etched (etched back) under the etching conditions set in advance using a mixed gas (plasma gas) containing either fluorocarbon gas or chlorine gas. Etchback is performed with the point where the surfaces of the first and second colored layers 43 and 47 are exposed and the film thicknesses of the first and second colored layers 43 and 47 and the black light-shielding layer 60 become uniform are the end points. Complete the process.

  The planarization step 35 is not limited to this, and a chemical mechanical polishing method (CMP method) may be used. A slurry in which silica fine particles are dispersed is used as an abrasive, and a slurry flow rate: 100 to 250 ml / min, a wafer pressure: 0.2 to 5.0 psi, a wafer and polishing pad rotational speed: 50 to 300 rpm. , Retainer ring pressure: 1.0 to 2.5 psi, an apparatus comprising an abrasive cloth can be used. After the polishing is completed, pure water cleaning and dehydration baking are performed, so that influences such as application failure and peeling in the next process can be eliminated.

[Third color filter forming step]
The second color filter array forming step 21 that follows the black matrix forming step 20, that is, the third color filter forming step 24, includes the patterning step 36, the etching step 37, and the second color filter forming step 23 described above. A photoresist removing step 38, a colored layer forming step 39, and a planarizing step 40 are performed. First, a photoresist layer 61 (see FIG. 16A) is formed over the black light shielding layer 60 and the first and second colored layers 43 and 47. Next, the photoresist is removed by patterning a region where the third colored layer 64 (third color; for example, green (G); see FIG. 13) is to be formed using a photomask (patterning step 36). ). FIG. 16A shows a state in which this patterning step 36 is performed, and reference numeral 62 denotes an opening of the photoresist layer 61 formed by patterning. In the patterning step 36, the aligner is positioned using the positioning marks formed on the first colored layer 43 in the first color filter array forming step 19. Accordingly, the position of the exposure device with respect to the first colored layer 43 can be positioned so as to be always the same position as in the first color filter array forming step 19.

[Etching process]
Then, as shown in FIG. 16B, an etching step 37 is performed to remove the region where the third colored layer 64 is to be formed. Reference numeral 63 in FIG. 16B denotes an opening of the black light shielding layer 60 removed by etching. The third colored layer opening 63 (color filter array opening) formed in the etching step 37 is formed to have the same width W2 as the first and second colored layers 43 and 47. Further, from the viewpoint of disposing the color filters finally formed in the color filter manufacturing process 17 at positions separated from each other and disposing the black light shielding layer 60 at a position serving as a boundary between the color filters, the black light shielding layer 60. The third colored layer opening 63 is formed with a width dimension W2 smaller than the width dimension W1. When there is an etching conversion difference between the opening 62 of the photoresist layer 61 and the third colored layer opening 63 formed in the etching step 37 using the photoresist layer 61 as a mask. The opening 62 of the photoresist layer 61 is formed in advance with a dimension including an etching conversion difference with respect to the dimension of the third colored layer opening 63.

In the etching step 37, it is preferable to use a chlorine-based gas or a fluorine-based gas. The chlorine gas may be a CL ₂ gas, BCl ₃ gas. Further, as the fluorine-based gas, for _{example, SF 6, C x F y} (X = 1~5, y = 1~8), it can be used CHF _3. Further, bromine gas may be used. As the etching step 37, an opening is formed in the photoresist layer by anisotropic etching, and then a surface-modified layer formed on the opening wall surface of the photoresist layer is used with a second gas containing oxygen gas. A form that is removed by an isotropic etching process is desirable. In this case, the etching amount of the device protective layer can be controlled by the anisotropic etching treatment, and the improvement of the peelability of the photoresist can be improved by the subsequent isotropic etching treatment.

[Anisotropic etching gas]
The mixed gas used in the anisotropic etching process of the etching step 37 is a case where a chlorine-based gas is used from the viewpoint that the black light shielding layer 60 (etched portion) removed by the dry etching method can be processed into a rectangle. It is preferable to use a mixed gas of chlorine CL ₂ and nitrogen N ₂ gas, or CL ₂ and C _x F _y , for example, C ₄ F ₆ gas. As the fluorine-based gas, it is preferable to use SF ₆ and C _x F _y , such as C ₄ F ₆ gas, CF ₄ and O ₂ gas.

  The content ratio of each mixed gas used in the anisotropic etching process of the etching step 37 is preferably set to 1/2 to 5/1 in flow rate ratio. By setting it within the above range, it is possible to ensure the rectangularity of etching of the black layer and the etching selectivity.

The mixed gas used in the anisotropic etching process of the etching step 37 is not limited to the above gases, in order to maintain the partial pressure control stability of the etching plasma, in-plane uniformity, and the perpendicularity of the shape to be etched. Further, a noble gas such as helium (He), neon (Ne), argon (Ar), krypton (Kr), or xenon (Xe), or a halogen-based gas containing a halogen atom such as a chlorine atom, a fluorine atom, or a bromine atom ( For example, it is preferable to include at least one selected from the group consisting of CCl ₄ , CClF ₃ , AlF ₃ , AlCl _3, etc.), N ₂ , CO, and CO _2. Ar, He, Kr, N ₂ , and Xe More preferably, at least one selected from the group is included, and at least one selected from the group of He, Ar, and Xe is more preferable. Arbitrariness. However, if the etching plasma partial pressure control stability, in-plane uniformity, and perpendicularity of the shape to be etched can be maintained, the mixed gas used in the anisotropic etching process is fluorine gas and oxygen. It may consist of only gas.

  The content of other gases that may be included in addition to the mixed gas used in the anisotropic etching process of the etching step 37 is a flow rate when the total flow rate of the mixed gas is 1 in terms of the selectivity of the etching pattern. The ratio is preferably 25 or less, more preferably 5 or more and 20 or less, and particularly preferably 8 or more and 18 or less.

[Etching time]
In the etching step 37 in the present invention, it is preferable to obtain the etching processing time in advance by the following method. 1) The etching rate (nm / min.) When the black light shielding layer 60 is etched is calculated. 2) The processing time required to etch a desired thickness in the etching step 37 is calculated from the etching rate calculated above. The etching rate can be calculated, for example, by collecting data indicating the relationship between the etching time and the remaining film. In the present invention, the etching treatment time is preferably 10 minutes or less, more preferably 7 minutes or less.

In addition to managing the etching by time, a method of forming an end point detection layer under the black light shielding layer 60 and detecting the end point detection layer can also be used. In this case, as the end point detection layer, a layer transparent to light in the visible region, for example, SiO ₂ (silicon oxide, silicon oxide) is formed so as not to affect the optical characteristics of the color filter. The RIE apparatus 48 is provided with detection means for detecting the end point detection layer, for example, a detector for detecting plasma emission generated in the chamber 49. When the end point detection layer exposed by removing the black light shielding layer 60 is etched by the plasma gas, plasma emission of the reaction product generated by the etching occurs. By detecting the plasma emission by the detector, the end point of the black light shielding layer 60 can be detected without being influenced by the fluctuation of the etching rate.

  It is preferable that the etching process 37 further includes an overetching process. The overetching process step is preferably performed by setting an overetching ratio. The overetching ratio is preferably calculated from the processing time of the etching step 37. The overetching ratio can be arbitrarily set, but is preferably 30% or less of the etching processing time in the etching step 37 in terms of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched, and is 5 to 25%. More preferably, it is 10 to 20%.

  Following the etching step 37 is a step of removing the photoresist layer 61 (photoresist removing step 38), and FIG. 17 shows a state where the photoresist layer 61 has been removed. Next to the photoresist removal step 38, as shown in FIG. 18A, the first and second colored layers 43 and 47 and the black light shielding layer 60 are entirely covered and a third colored layer opening is formed. A third colored layer (third color; for example, green (G)) 64 is formed so as to be embedded in the portion 63 (colored layer forming step 39). Next, as shown in FIG. 18B, the first and second colored layers 43 and 47 and the black light shielding layer 60 are exposed, and the first and second colored layers 43 and 47 and the black light shielding layer are exposed. The third colored layer 64 is flattened by an etch-back process until the layer 60 and the third colored layer have the same film thickness (flattening step 40). In addition, this planarization process 40 is performed on the conditions similar to the planarization process 30 mentioned above. FIG. 19 shows a state in which the color filter manufacturing process 17 has been completed after the third colored layer 64 is etched back to the same thickness as the black light-shielding layer 60 and the first and second colored layers 43 and 47. Show. As described above, the third coloring layer opening 63 is formed with the width dimension W2 smaller than the width dimension W1 of the black light shielding layer 60, and the third coloring layer is filled so as to fill the third coloring layer opening 63. A layer is formed.

  As described above, in the color filter manufacturing process 17, the black light shielding layer opening 59 is formed between the first to third color filter forming processes 22 to 24 to fill the black light shielding layer opening. The black colored light shielding layer 60 is formed on the black colored light shielding layer 60, the third colored layer opening 63 is formed with a width W2 smaller than the width W1 of the black light shielding layer 60, and the third colored layer opening 63 is filled. Thus, since the process of forming the colored layer 64 is performed, the color filter array including the first to third colored layers 43, 47, 64 and the first to third colored layers 43, 47, 64 are formed. A black light shielding layer 60 (light shielding wall) having a thin line width located at the boundary is formed. Specifically, in the conventional color filter manufacturing process, the line width of the light shielding wall depends on the resolution of the photoresist, and the line width dimension is limited to 0.2 μm, but in the present invention, the black light shielding layer 60 is used. Since the black light shielding layer 60 is formed as a light shielding wall by removing the colored layer opening 6 having a smaller width dimension, the black having a thin line width, for example, a line width of 0.1 mm, does not depend on the resolution of the photoresist. The light shielding layer 60 (light shielding wall) can be formed. Therefore, it is possible to meet further performance requirements of the color filter, and it is possible to cope with the miniaturization and thinning of the color filter. In addition, the light shielding wall of the black light shielding layer 60 formed in the color filter manufacturing process 17 in this way is formed at a place other than the light receiving portion, the bonding pad, and the dicing line of the support (semiconductor wafer) 41, and is oblique. It absorbs incident light and blocks light passing between adjacent pixels.

  In the first embodiment, in the first color filter array forming step 19, the first and second color filter forming steps are performed. After the black matrix forming step 20, in the second color filter array forming step 21, Although the third color filter forming step is performed, the present invention is not limited to this, and in the second embodiment of the present invention described below, the first color filter forming step is performed in the first color filter array forming step. After the black matrix forming step, the second and third color filter forming steps are performed in the second color filter array forming step 21. The color filter manufacturing process to which this manufacturing method is applied is shown in FIG. As shown in FIG. 15, the color filter manufacturing process 70 includes an etching stopper layer forming process 18, a first color filter array forming process 71, a black matrix forming process 72, and a second color filter array forming process 73. The first color filter array forming step 71 includes a first color filter forming step 74, and the second color filter array forming step 73 includes second and third color filter forming steps 75 and 76. In addition, about the process of performing the process similar to the said 1st Embodiment, and the same material, a same sign is attached | subjected and description is abbreviate | omitted.

[First color filter array forming step]
In the color filter manufacturing process 70, the etching stopper layer forming process 18 is performed in the same manner as in the above embodiment, and the first color filter array forming process 71 is only the first colored layer forming process 25. It carries out similarly to embodiment. FIG. 21 shows a state in which a first colored layer 43 (first color; for example, green (G)) is formed on the support 41 and the etching stopper layer 42. Subsequently, a black matrix forming step 72 is performed.

[Black matrix formation process]
In the black matrix forming step 72, the patterning step 77 and the etching step 78 are performed in the same manner as in the first embodiment. In the present embodiment, after the black matrix forming step 72, the second color filter array forming step 73 ( In the second and third color filter forming steps 75 and 76), the black light shielding layer 60 is etched to remove regions where the second and third colored layers 47 and 64 are to be formed. The black light-shielding layer opening 91 formed in (1) includes a region where the second and third colored layers 47 and 64 are to be formed. Thus, the state where the first colored layer 43 is etched in the etching step 78 and the photoresist layer on the first colored layer 43 is peeled off (photoresist removal step 79) is shown in FIGS. Thus, the black light shielding layer opening 91 is formed. By forming the black light shielding layer openings 91 in this way, the first colored layer 43 is arranged in a checkered island-like arrangement in which each pixel is arranged.

  Further, the black light shielding layer 60 is formed so as to fill the entire upper surface of the first colored layer 43 and the black light shielding layer opening 91 (black light shielding layer forming step 80), and the same film thickness as the first colored layer 43 is formed. Is planarized (planarization step 81). FIG. 24 shows a state in which the black light shielding layer 60 is flattened to the same thickness as the first colored layer 43 in the flattening step 81. In addition, about the processes 77-81, the same process is performed using the same apparatus and material as the processes 31-35 of the said 1st Embodiment.

[Second color filter array forming step]
Subsequently, in the second color filter array forming step 73, a second color filter forming step 75 is performed. As in the first embodiment, the patterning step 82, the etching step 83, and the photoresist removal step 84 are performed. In this embodiment, the black light shielding layer 60 is already formed. The layer 60 is etched to remove the region where the second colored layer 47 is to be formed. The reference numeral 92 in FIGS. 25 and 26 is an opening of the black light shielding layer 60 removed in the etching step 83. The second colored layer opening 92 formed in the etching step 83 is arranged in a checkered island shape and has the same width W2 as the first colored layer 43. Further, a second colored layer 47 (second color; for example, blue (B)) is formed so as to fill the entire upper surface of the first colored layer 43 and the black light shielding layer 60 and the second colored layer opening 92. It is formed (colored layer forming step 85) and flattened to the same film thickness as the first colored layer 43 (flattened step 86). FIG. 27 shows a state in which the second colored layer 47 is planarized to the same film thickness as the first colored layer 43 in the planarization step 86. In addition, about the processes 82-86, the same process is performed using the same apparatus and material as the processes 36-40 of the said 1st Embodiment.

  The third color filter forming process 76 performed following the second color filter forming process 75 is the same patterning process 36, etching process 37, and photoresist removal as the third color filter forming process 24 of the first embodiment. Step 38, colored layer forming step 39, and planarization step 40 are performed. That is, the region where the third colored layer 64 is to be formed is etched in the patterning step 36 and the etching step 37, thereby forming the third colored layer opening 63 in the black light shielding layer 60. Similarly to the first embodiment, the third colored layer opening 63 (color filter array opening) is arranged in a checkered island shape, and the first and second colored layers 43 and 47 are arranged. And the width dimension W2 smaller than the width dimension W1 of the black light shielding layer 60. A third colored layer 64 (third color; for example, red (R) so as to fill the entire upper surface of the first and second colored layers 43 and 47 and the black light shielding layer 60 and the third colored layer opening 63. ))) Is formed (colored layer forming step 39), and flattened to the same film thickness as the first and second colored layers 43 and 47 (flattened step 40). As a result, as shown in FIG. 28, the color filter array composed of the first to third colored layers 43, 47, 64 and the black light shielding located at the boundary between the first to third colored layers 43, 47, 64. A layer 60 (light shielding wall) is formed.

  In the said embodiment, although the planarization process is performed after the 2nd colored layer formation process, the black light shielding layer formation process, and the 3rd colored layer formation process, it is not restricted to this, 2nd colored layer The flattening step after the forming step and the black light shielding layer forming step is omitted, and the second colored layer, the black light shielding layer, and the first flattening step after the third color layer forming step are performed. The three colored layers may be simultaneously planarized by etching to form the same thickness as the first colored layer.

[Composition of colored layer]
The composition of the colored layer used in the present invention will be described below. Since the composition of the colored layer forms a pattern by dry etching as described above, a photocurable component is unnecessary. In the composition of the colored layer that contains a small amount of the photocurable component and more preferably does not contain the photocurable component, the concentration of the colorant can be increased. Therefore, it is possible to form a pattern that is thinner than before 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 used in the present invention comprises a colorant and a thermosetting compound, and the concentration of the colorant in the total solid content is preferably 50% 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 that can be used in the present invention is not particularly limited, and various conventionally known dyes and pigments can be used alone or in combination.

[Pigment]
Examples of the pigment that can be used in the present invention 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.

Examples of pigments that can be preferably used in the present invention include the following. It is preferable to select an inorganic pigment having high light resistance. In the following, CI 15: 3 is a representative example.
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

[dye]
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 constituting the composition in the present invention is not particularly limited, and conventionally known dyes for color filters can be used. The chemical structure includes 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.

[Colorant concentration]
The colorant content in the total solid content of the thermosetting composition (colored layer composition) in the present invention is not particularly limited, but is preferably 30% by mass or more and less than 60% by mass. By setting the 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 60 mass%, and the strength reduction as a film | membrane can be suppressed.

[Thermosetting compound]
The thermosetting compound that can be used in the present invention 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.

  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) is 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 body of TrisP-PA (Honshu Chemical Co., Ltd.) or their methylol. 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.

[Curing agent]
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 kinds of compounds are used. For example, a phthalocyanine derivative (commercial product 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 Nihon 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.

  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 addition to the color filter composed of RGB three colors, the desired hue can be obtained by providing the number of groups corresponding to the desired number of hues, including the recess forming process after the black layer formation, the filter forming process, and the flattening process. The color filter which consists of can be obtained.

[Adjustment of blue pigment dispersion]
The following blue pigment dispersion was prepared.
B pigment dispersion, Pigment Blue 15: 6 125 parts by mass, Pigment Violet 25 parts by mass, Dispersant PLADDED211 (manufactured by Enomoto Kasei Co., Ltd.) 40 parts by mass, benzyl methacrylate / glycidyl methacrylate copolymer 15 parts by mass, PGMEA 755 parts by mass Each of the above materials was agitated with a homogenizer, and then finely dispersed with a disperser using 0.3 mm zirconia beads (Dispermat, manufactured by GETZMANN) for 5 hours.

[Adjustment of blue coloring composition]
A non-photosensitive coloring composition was prepared by further adding a thermosetting resin to the B pigment dispersion.
-EHPE-3150 0.8 parts by mass (based on the blue pigment dispersion)
Furthermore, PGMEA was added to the blue pigment dispersion and the thermosetting resin, and the solid content of the composition was diluted to 13.0%.

[Adjustment of red pigment dispersion]
The following red pigment dispersion was prepared.
Pigment Red 254 80 parts by mass Pigment Yellow 139 20 parts by mass Dispersant EDAPLAN472 (manufactured by Enomoto Kasei Co., Ltd.) 30 parts by mass 10 parts by mass of benzyl methacrylate / glycidyl methacrylate copolymer PGMEA 700 Mass parts Each of the above materials was stirred with a homogenizer, and then finely dispersed for 5 hours with a disperser (Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads.

[Adjustment of red coloring composition]
A non-tourist coloring composition was prepared by further adding a thermosetting resin to the R pigment dispersion.
EHPE-3150 0.5 part by mass (based on the red pigment dispersion)
Furthermore, PGMEA was added to the red pigment dispersion and the thermosetting resin, and the solid content of the composition was diluted to 15.0%.

[Adjustment of green pigment dispersion]
The following green pigment dispersion was prepared.
G pigment dispersion, Pigment Green 36, 90 parts by mass, Pigment Green 7, 25 parts by mass, Pigment Yellow 139, 40 parts by mass, Dispersant PLADDED151 (manufactured by Enomoto Kasei Co., Ltd.), 20 parts by mass, benzyl methacrylate / glycidyl methacrylate copolymer Combined 10 parts by mass / PGMEA 630 parts by mass The above materials were stirred with a homogenizer, and then finely dispersed with a disperser using 0.3 mm zirconia beads (Dispermat, manufactured by GETZMANN) for 5 hours. .

[Adjustment of green coloring composition]
A non-photosensitive coloring composition was prepared by further adding a thermosetting resin to the G pigment dispersion.
-EHPE-3150 0.8 part by mass (based on the green pigment dispersion)
Furthermore, PGMEA was added to the blue pigment dispersion and the thermosetting resin, and the solid content of the composition was diluted to 13.0%.

[Black colorant-containing composition]
(1) Composition The composition of the present invention is a colorant containing (A) a colorant, (B) a thermosetting compound, and (C) an organic solvent. The black colorant-containing composition of the present invention may contain other components as additives in addition to the above (A) to (C).

Examples of the colorant (A) include the following colorants.
(A) Titanium black The black colorant-containing composition of the present invention contains titanium black as a black colorant.
Titanium black has a higher light shielding ability in the infrared region than conventional pigments and dyes dispersed and dissolved in photosensitive resin compositions, particularly photosensitive resin compositions for light shielding films. The infrared light region can be surely shielded, which cannot be shielded by combination. In particular, the light-shielding film obtained by curing the black colorant-containing composition of the present invention has a high light-shielding property in the infrared region, and can suppress noise due to dark current of a solid-state imaging device including the light-shielding film. Titanium black can be cured with a small amount of exposure because it absorbs less i-rays for pattern formation than carbon black commonly used as a black colorant. It can contribute to improvement.

  Titanium black is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of the titanium black particles can be chemically modified as necessary for the purpose of improving dispersibility and suppressing aggregation. Specifically, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and as disclosed in Japanese Patent Application Laid-Open No. 2007-302836. Surface treatment with a water repellent material is also possible. In addition, the titanium black is a composite oxide such as Cu, Fe, Mn, V, and Ni, and a black pigment such as cobalt oxide, iron oxide, carbon black, and aniline black for the purpose of adjusting dispersibility, colorability, and the like. You may contain 1 type or in combination of 2 or more types. In addition, for the purpose of controlling the light-shielding property of a desired wavelength, it is also possible to add existing colorants such as pigments such as red, blue, green, yellow, cyan, magenta, violet, orange, or dyes. .

  Examples of commercially available titanium black products include Gemco Corporation (sold by Mitsubishi Materials Corporation) Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, and Ako Kasei Co., Ltd. Tilac D etc. are mentioned.

  The titanium black can be produced by heating a mixture of titanium dioxide and titanium metal in a reducing atmosphere for reduction (Japanese Patent Laid-Open No. 49-5432), ultrafine obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not a thing.

  The particle size of the titanium black particles is not particularly limited, but the average particle size (average primary particle size) is 10 to 150 nm from the viewpoints of dispersibility and colorability and the influence on the yield in a solid-state imaging device. It is preferable that it is, and it is more preferable that it is 15-100 nm, and it is especially preferable that it is 20-80 nm. The average particle diameter can be measured by applying titanium black to a suitable substrate and observing with a scanning electron microscope. The specific surface area of the titanium black is not particularly limited. However, since the water repellency after the surface treatment of the titanium black with a water repellent agent has a predetermined performance, the value measured by the BET method is about 5 to 150 m @ 2. / G, more preferably about 20 to 100 m <2> / g.

(B) Carbon black Carbon black is black fine particles including carbon fine particles, and preferred particles include carbon fine particles having a diameter of about 3 to 1,000 nm. In addition, the surface of the fine particles can have functional groups containing various carbon atoms, hydrogen atoms, oxygen atoms, sulfur atoms, nitrogen atoms, halogens, inorganic atoms, and the like. Carbon black can be changed in its properties by changing the particle diameter (particle size), structure (particle connection), and surface properties (functional group) according to the intended application. It is also possible to change the blackness and affinity with the resin, or to provide conductivity.

  Specific examples of the carbon black include, for example, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850 manufactured by Mitsubishi Chemical Corporation. , MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diab N339, diamond black SH, diamond black SHA, diamond black LH, diamond black H, diamond black HA, diamond black SF, diamond black N550M, diamond black E, diamond black G, diamond black R, diamond black N760M, diamond Black LP. Carbon black thermax N990, N991, N907, N908, N990, N991, N908 made by Cancarb. Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2, ColorBlack Fw1, ColorBlack 170, BlackBlack, BlackBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, Printex140V, etc. It can be mentioned.

The carbon black may preferably have an insulating property.
The carbon black having an insulating property is a carbon black exhibiting an insulating property when the volume resistance as a powder is measured by the following method. This insulating property is based on the fact that an organic compound is present on the surface of the carbon black particle, for example, an organic substance is adsorbed, coated or chemically bonded (grafted) on the surface of the carbon black particle. That is, carbon black is dispersed in propylene glycol monomethyl ether so that the molar ratio of benzyl methacrylate and methacrylic acid is a 70:30 copolymer (weight average molecular weight 30,000) and 20:80 weight ratio. Was applied to a chrome substrate having a thickness of 1.1 mm and 10 cm × 10 cm to prepare a coating film having a dry film thickness of 3 μm, and the coating film was further heated in a hot plate at 220 ° C. for about 5 minutes. Later, a high resistivity meter manufactured by Mitsubishi Chemical Corporation conforming to JISK6911, Hirestar UP (MCP-HT450) is applied, and the volume resistance value is measured in an environment of 23 ° C. and 65% relative humidity. Carbon black having a volume resistance value of 10 5 Ω · cm or more, more preferably 10 6 Ω · cm or more, and particularly preferably 10 7 Ω · cm or more is preferred.

  As the carbon black as described above, for example, JP-A-11-60988, JP-A-11-60989, JP-A-10-330634, JP-A-11-80583, JP-A-11-80584, Resin-coated carbon black disclosed in JP-A-9-124969 and JP-A-9-95625 can be used.

  The average particle size (average primary particle size) of the black colorant used in combination with titanium black is preferably small from the viewpoint of foreign matter generation and the influence on the yield in the production of a solid-state imaging device. . The average primary particle size is preferably 50 to 100 nm, more preferably 50 nm or less, and preferably 30 nm or less. The average particle diameter can be measured by applying a black colorant to a suitable substrate and observing with a scanning electron microscope.

  The content of titanium black in the thermosetting resin composition is not particularly limited, but the average transmittance in the visible region to infrared region (400 to 1,600 nm) of the formed light-shielding filter is 1. % Or less is preferable. It is preferable that an optical density of 2.0 or more is obtained with substantially the same film thickness as a color separation filter such as RGB. The blending amount of titanium black in the solid content of the black colorant-containing composition is preferably 10 to 95% by weight, and more preferably 20 to 80% by weight.

  In the present invention, titanium black and carbon black may be used in combination, and one black coloring agent other than titanium black and carbon black may be used in combination.

  As the black colorant that can be used in combination, various known black pigments and black dyes can be used, and iron oxide, manganese oxide, graphite and the like are particularly preferable from the viewpoint of realizing a high optical density with a small amount.

  As the other composition, the compound used in the above-described coloring composition can be applied.

[Preparation of colored thermosetting composition]
Three types of colored thermosetting compositions as shown in Table 1 were prepared. All were adjusted with the mass%.
(Colored thermosetting composition 1)
Colorant) Titanium black, solid content ratio: 58.8% by mass
Solid content) 20.0% by mass
Curing component) 12.0% by mass
(Colored thermosetting composition 2)
Colorant) Titanium black and carbon black, mixing ratio = 6: 5
Ratio in solid content: 66.0% by mass
Solid content) 20.0% by mass
Curing component) 12.0%
(Colored thermosetting composition 3)
Colorant) Carbon black, solid content ratio: 62.5% by mass
Solid content) 20.0% by mass
Curing component) 12.0%

  Examples of the present invention and comparative examples will be shown below to specifically describe the present invention. However, the present invention is not limited to these examples and comparative examples.

[Example 1]
In the color filter manufacturing process of the first embodiment, a first colored layer (blue) is formed on a support, patterned using an i-line photoresist (FHi622BC: manufactured by Fuji Film Electronics Materials), The region where the colored layer 2 is formed is dry-etched in stripes. At this time, the first colored layer was formed with a width dimension of 1.0 μm. The dry etching is performed by performing anisotropic etching using a mixture of CF ₄ gas, O ₂ gas, and Ar gas, and subsequently performing isotropic etching using a mixed gas of N ₂ gas and O ₂ gas. Was processed using. Next, a second colored layer (red) is formed in the stripe-shaped opening, and the second colored layer formed on the first colored layer is removed by CMP or etch back processing. Similar to the first colored layer, the width of the second colored layer was 1.0 μm. In the case of CMP treatment, a slurry in which silica fine particles were dispersed in an abrasive was used, and polishing was performed at a slurry flow rate of 150 ml / min, a wafer pressure of 1 psi, a rotation speed of 150 rpm, and a retainer ring pressure of 2 psi. In the case of the etch-back process, a mixed gas of N ₂ gas, O ₂ gas, and Ar gas was used under the output conditions of pressure 1.0 Pa, source power 600 W, and wafer bias 500 W.

[Black matrix formation process]
Next, patterning is performed using an i-line photoresist (FHi622BC: manufactured by FUJIFILM Electronics Materials Co., Ltd.), and dry etching is performed so as to leave the first and second colored layers in a checkered island shape. At this time, the black light shielding layer opening formed by dry etching was larger than the image cell size, and the width dimension was 1.2 μm. The dry etching was performed by performing anisotropic etching using a mixture of CF ₄ gas, O ₂ gas, and Ar gas. As a black light-shielding layer, the colorant-curable composition 1 shown in Table 1 is applied to fill the black light-shielding layer opening, thereby forming a black light-shielding layer. Here, the excess black light shielding layer remaining on the first and second color filter layers is removed by CMP or etch back processing.

[Second color filter array forming step]
Next, patterning is performed using an i-line photoresist (FHi622BC: manufactured by FUJIFILM Electronics Materials Co., Ltd.), and dry etching is performed so as to open a checkered island shape. The dry etching was performed using a mixed gas of chlorine gas and nitrogen gas. At this time, the third colored layer opening formed by dry etching was formed at 1.0 μm. On the side surfaces of the third colored layer opening, a light shielding wall made of a black light shielding layer is left on both sides with a width of 0.1 μm. A third colored layer (green) is formed so as to fill the third colored layer opening. Here, the excess third colored layer remaining on the first and second color filter layers is removed by CMP or etchback processing. Through the above steps, a color filter having a black matrix (black light shielding wall) with an image cell size of 1.0 μm and a size of 0.1 μm is formed.

[Example 2]
In the color filter manufacturing process of the first embodiment, after forming a stripe-shaped color filter array having a width of 1.0 μm and comprising a first colored layer (blue) and a second colored layer (red), Ichimatsu Etching so as to leave the first and second colored layers in the pattern island shape, and forming a black light-shielding layer to fill the openings for the black light-shielding layer formed by this etching, the colorant-curable composition of Table 1 2 is applied to form a black light shielding layer. Then, the black light-shielding layer is etched so as to open in a checkered island shape, and a third colored layer (green) is formed so as to fill the third colored layer opening formed by this etching. Conditions other than these are the same as in Example 1 above, and a color filter layer having an image cell size of 1.0 μm and a black matrix (black light shielding wall) of 0.1 μm in size is formed.

[Example 3]
In the color filter manufacturing process of the first embodiment, after forming a stripe-shaped color filter array having a width of 1.0 μm and comprising a first colored layer (blue) and a second colored layer (red), Ichimatsu Etching so as to leave the first and second colored layers in the pattern island shape, and forming a black light-shielding layer to fill the openings for the black light-shielding layer formed by this etching, the colorant-curable composition of Table 1 3 is applied to form a black light shielding layer.

[Second color filter array forming step]
Next, patterning is performed using an i-line photoresist (FHi622BC: manufactured by FUJIFILM Electronics Materials Co., Ltd.), and dry etching is performed so as to open a checkered island shape. The dry etching was performed using a mixed gas of CF ₄ gas and O ₂ gas . At this time, the third colored layer opening formed by dry etching was formed at 1.0 μm. On the side surfaces of the third colored layer opening, a light shielding wall made of a black light shielding layer is left on both sides with a width of 0.1 μm. A third colored layer (green) is formed so as to fill the third colored layer opening. Here, the excess third colored layer remaining on the first and second color filter layers is removed by CMP or etchback processing. Conditions other than these are the same as those in the first embodiment. Through the above steps, a color filter having a black matrix (black light shielding wall) with an image cell size of 1.0 μm and a size of 0.1 μm is formed.

[Example 4]
In the color filter manufacturing process of the second embodiment, a first colored layer (green) is formed on a support and patterned using an i-line photoresist (FHi622BC: manufactured by Fuji Film Electronics Materials). The region where the colored layer 2 is formed is dry-etched so as to remain in a checkered island shape. At this time, the black light shielding layer opening formed by dry etching was larger than the image cell size, and the width dimension was 1.2 μm. The dry etching is performed by performing anisotropic etching using a mixture of CF ₄ gas, O ₂ gas, and Ar gas, and subsequently performing isotropic etching using a mixed gas of N ₂ gas and O ₂ gas. Was processed using. As a black light-shielding layer, the colorant-curable composition 1 shown in Table 1 is applied to fill the black light-shielding layer opening, thereby forming a black light-shielding layer.

[Second color filter array forming step]
Next, patterning is performed using an i-line photoresist (FHi622BC: manufactured by FUJIFILM Electronics Materials Co., Ltd.), and dry etching is performed so as to open a checkered island shape. The dry etching was performed using a mixed gas of chlorine gas and nitrogen gas. At this time, the second colored layer opening formed by dry etching was formed with a width of 1.0 μm. A second colored layer (blue) is formed so as to fill the second colored layer opening. Further, in the same process, the third colored layer opening is formed by dry etching with a width of 1.0 μm, and the third colored layer (red) is formed so as to fill the third colored layer opening. To do. Conditions other than these are the same as those in the first embodiment. Through the above steps, a color filter having a black matrix (black light shielding wall) with an image cell size of 1.0 μm and a size of 0.1 μm is formed.
[Comparative Example 1]
Conventional color filter manufacturing process, that is, after first forming a green, blue, red color filter layer, a KrF line photoresist (GKR5303: manufactured by Fuji Film Electronics Materials) is applied on the color filter layer, Patterning is performed so as to open the color filter layer boundary. The opening is a portion where a black light shielding layer (black matrix) is formed. The line width of the opening is 0.1 μm.

Anisotropic etching is performed using the patterned photoresist as a mask. As an etching gas introduced in the anisotropic etching process, a mixed gas of CF ₄ gas (flow rate 200 ml / min) and O ₂ gas (flow rate 50 ml / min) was used. A subsequent isotropic etching process was performed using O ₂ gas (flow rate: 25 ml / min). It took 5 seconds for the etching process time until the opening of the color filter layer was completely removed. Next, using a developer (MS230C: manufactured by FUJIFILM Electronics Materials), paddle development processing was performed to remove the photoresist.

  The black colorant composition is applied to cover the color filter layer and fill the opening formed in the color filter layer to form a black light-shielding layer. Then, the black light shielding layer on the color filter layer is polished and removed by a CMP apparatus. The polishing conditions are the same as in Example 1, and a color filter having a black matrix (black light shielding wall) formed through all the steps is formed.

  Table 2 below shows the evaluation of the color filter manufactured under the above conditions. In addition, as an evaluation method, the line width dimension of the light-shielding wall was measured by length measurement SEM (S-9380II by Hitachi High-Technologies). In addition, the rectangularity was measured using a cross-section SEM (S-4800 manufactured by Hitachi High-Technologies). As evaluation criteria, the light shielding wall was evaluated as ◯ if the light shielding wall had a shape of 80 ° or more and 90 ° or less with respect to the substrate, Δ if it was 70 ° or more and 80 ° or less, and × if it was less than 70 °. The overall evaluation was as follows: ○: Good, Δ: Usable, × Unusable.

  With respect to the black light shielding layer (black matrix) of the color filter manufactured under the above conditions, as shown in Table 2 above, all of the line widths of Examples 1 to 4 can be 0.1 μm, and rectangularity is also practical. Since it is within the possible range, the overall evaluation is good or usable. Therefore, in Examples 1 to 4, it is possible to form a black light shielding layer having a line width of 0.2 μm or less without depending on the resolution of the photoresist, and it is possible to cope with further miniaturization and thinning of the color filter. . On the other hand, in Comparative Example 1, it is difficult to form a line width of 0.2 μm or less depending on the resolution of the photoresist material, and the rectangularity is also poor. In addition, since there is no end point detection layer in the CMP process, the end point margin for stopping polishing is reduced, which affects the yield. Therefore, it cannot be used even in comprehensive evaluation.

It is principal part sectional drawing of a solid-state imaging device. It is a top view which shows the arrangement | sequence of a color filter and a black matrix. It is process drawing explaining a color filter manufacturing process. It is sectional drawing which shows the state in which the 1st colored layer and the photoresist layer were formed. It is sectional drawing which shows the state which patterned the 1st colored layer. It is explanatory drawing which shows the state in which the etching process of the area | region which forms a 2nd colored layer in a 1st colored layer was performed. It is the schematic of a dry etching apparatus. It is sectional drawing which shows the state from which the photoresist layer was peeled after the 2nd colored layer opening part was etched. It is explanatory drawing which shows the state in which the planarization process was performed after forming the 2nd colored layer. It is the top view which looked at the color filter array in which the 1st and 2nd colored layer was formed from the normal line direction. It is explanatory drawing which shows a state when the etching process of the area | region which forms a black light shielding layer is performed. It is the top view which looked at the color filter array in which the etching process of the area | region which forms a black light shielding layer was performed from the normal line direction. It is sectional drawing which shows the state from which the photoresist layer was peeled after the opening part for black light shielding layers was etched. It is explanatory drawing which shows the state by which the planarization process was performed after forming a black light shielding layer. It is a top view which shows the state in which the black light shielding layer was formed so that the opening part for black light shielding layers might be filled. It is sectional drawing when the etching process of the area | region in which a 3rd colored layer is formed is performed. It is sectional drawing which shows the state from which the photoresist layer was peeled after the 3rd colored layer opening part was etched. It is explanatory drawing which shows the state in which the planarization process was performed after forming the 3rd colored layer. It is a top view which shows the state by which the 3rd colored layer was formed so that the opening part for 3rd colored layers might be filled, and the color filter of the 1st-3rd color was formed. It is process drawing explaining the color filter manufacturing process of 2nd Embodiment. It is sectional drawing which shows the state in which the 1st colored layer was formed in 2nd Embodiment. It is sectional drawing which shows the state by which the opening part for black light shielding layers was etched in 2nd Embodiment. It is the top view which looked at the state by which the opening part for black light shielding layers was etched in 2nd Embodiment from the normal line direction. It is sectional drawing which shows the state in which the black light shielding layer was formed in 2nd Embodiment. It is sectional drawing which shows the state by which the opening part for 2nd colored layers was etched in 2nd Embodiment. It is the top view which looked at the state by which the opening part for 2nd colored layers was etched in 2nd Embodiment from the normal line direction. It is sectional drawing which shows the state in which the 2nd colored layer was formed in 2nd Embodiment. It is a top view which shows the state in which the 3rd colored layer was formed in 2nd Embodiment, and the 1st-3rd color filter was formed.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Solid-state imaging device 13B B color filter 13G G color filter 13R R color filter 14 Black matrix 41 Support body 43 1st colored layer 47 2nd colored layer 59,91 Black light shielding layer opening 60 Black light shielding layer 63 Third colored layer opening 64 Third colored layer

Claims (15)

A method for producing a color filter in which three colored layers are arranged on the surface of a substrate,
During the step of forming the three colored layers, the region including the boundary of the colored layer is dry-etched to form a black light shielding layer opening, and the black light shielding layer opening is black. A method for producing a color filter, comprising forming a black light-shielding layer containing a colorant. A first color filter array forming step of forming the colored layer of at least one color;
A black light-shielding layer etching step for dry etching a region including a portion serving as a boundary with respect to the colored layer formed in the first color filter array forming step to form a black light-shielding layer opening;
A black light shielding layer forming step of forming the black light shielding layer containing a black colorant so as to fill the opening for the black light shielding layer;
A color filter array opening is formed by dry etching the black light shielding layer formed in the black light shielding layer forming step so as to leave a portion that becomes a boundary of the colored layer. The method for producing a color filter according to claim 1, further comprising: a second color filter array forming step of forming the remaining three color layers in the portion.   The first or second color filter array forming step includes a color filter array etching step for forming the color filter array opening, and a colored layer for forming any of the colored layers in the color filter array opening. The method for producing a color filter according to claim 2, wherein each of the forming steps is performed at least once.   4. The method for manufacturing a color filter according to claim 2, wherein the width dimension of the color filter array opening is formed smaller than that of the black light shielding layer opening.   5. The method for producing a color filter according to claim 1, wherein the film thickness of the black light-shielding layer is formed to be the same as a set film thickness of the colored layer.   After forming the colored layer in the color filter array opening, the black light shielding layer on the colored layer formed in the first color filter array forming step or the entire surface of the colored layer material is planarized. The method for producing a color filter according to claim 2, wherein a flattening step for uniformizing the thicknesses of the colored layer and the black light shielding layer is performed.   The method for manufacturing a color filter according to claim 6, wherein the planarization step uses a planarization process of either a CMP process or an etch-back process.   8. The method of manufacturing a color filter according to claim 7, wherein the etch back process uses an etching gas containing at least one halogen gas such as fluorine, chlorine and bromine.   In the color filter array etching step, a plurality of the color filter array openings are formed so as to be isolated by a part of the black light shielding layer, and between the colored layers formed in the colored layer forming step. The method for manufacturing a color filter according to claim 1, wherein the black light shielding layer is formed as a light shielding wall.   The method for manufacturing a color filter according to claim 9, wherein the light shielding wall has a line width of 0.2 μm or less in a direction orthogonal to the film thickness direction of the black light shielding layer.   The support is a semiconductor wafer having a bonding pad, a dicing line, and a light receiving portion formed for each pixel, and the black light shielding layer is formed at a place other than the light receiving portion, the bonding pad, and the dicing line. The method for manufacturing a color filter according to claim 1, wherein the color filter functions as a light shielding film that absorbs obliquely incident light and blocks light passing between adjacent pixels.   The method for producing a color filter according to any one of claims 1 to 11, wherein the black colorant includes a titanium black material or a carbon black material.   The method for producing a color filter according to claim 1, wherein the colored layer and the black light-shielding layer contain a thermosetting composition having no photosensitivity.   During the first color filter array etching step in the first color filter array forming step, an alignment mark for an exposure machine is formed, and in the subsequent etching step, the mark is used as a reference. 14. The method for producing a color filter according to claim 3, wherein alignment of the exposure device is performed.   15. A solid-state imaging device comprising a color filter manufactured by the color filter manufacturing method according to claim 1.

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