KR20180015639A - Solid-state imaging device, radiation-sensitive composition, colorant dispersion and color filter - Google Patents

Abstract

And a first pixel on which a color filter layer having a transmittance band in a visible light wavelength band is disposed on a light receiving surface of the first light receiving element, the color filter layer comprising a first compound which absorbs light in at least a part of a visible light wavelength band, And a second compound having a light absorption peak in an infrared wavelength band. It is possible to reduce the thickness of the optical filter by adding the function of absorbing the light in the infrared band band to the color filter layer selectively transmitting the light in the visible light band, thereby making it possible to miniaturize the solid-state image pickup device.

Description

Solid-state imaging device, radiation-sensitive composition, colorant dispersion and color filter

The present invention relates to a solid-state imaging device and a radiation-sensitive composition and a coloring agent dispersion liquid usable in the solid-state imaging device.

A solid-state imaging device used in an imaging device such as a camera is provided with a light-receiving element (a sensor for visible light detection) that detects visible light in the pixel portion. A light receiving element is provided in each pixel in the pixel portion. The light receiving element generates an electric signal in accordance with the intensity of the incident light, and the drive circuit and the image processing circuit process the electric signal to generate a picked-up image. The light receiving element is composed of a CCD sensor or a CMOS sensor. The pixel portion is provided with a color filter layer for spectroscopically receiving light in a wavelength band corresponding to each color. Since the light receiving element has optical sensitivity up to the infrared wavelength band, an infrared cut filter is provided in the pixel portion. The infrared cutoff filter is necessary to cut off light in the infrared wavelength band transmitted through the color filter layer. For example, Patent Document 1 discloses a solid-state image pickup device in which an infrared cut-off filter layer and a color filter layer are laminated on the light-receiving surface side of a light-receiving element.

The color filter layer contains a pigment, a dye or the like dispersed in a resin material in order to transmit light in a specific visible light band and to block visible light in another band. In the infrared cut filter, an infrared absorbent is used to absorb light in the infrared wavelength band. For example, Patent Document 2 discloses that at least one selected from metal oxides and diimmonium dyes is used as the infrared absorbing agent. Patent Document 3 discloses an infrared cut filter comprising a metal oxide and a dye as an infrared absorbing composition. Patent Document 4 discloses a curable resin composition containing a dye having a maximum absorption wavelength within a wavelength range of 600 to 850 nm and capable of being formed by a coating method.

Japanese Patent Application Laid-Open No. 2010-256633 Japanese Patent Application Laid-Open No. 2013-137337 Japanese Patent Application Laid-Open No. 2013-151675 Japanese Patent Application Laid-Open No. 2014-130343

Incidentally, a portable information device such as a smart phone or a tablet terminal has a built-in solid-state imaging device and an imaging function. BACKGROUND ART [0002] Electronic devices such as portable information devices are required to be downsized and thinned, and a sophisticated appearance is desired.

In the solid-state image pickup device disclosed in Patent Document 1, a color filter and an infrared cut filter are disposed on the light receiving surface of the light receiving element. That is, the conventional solid-state image pickup device has a structure in which a color filter layer and an infrared ray blocking filter layer are laminated on a semiconductor substrate on which a light receiving element is formed.

The color filter and the infrared cut filter require a thickness of at least several micrometers to several tens of micrometers in order to absorb the light of the wavelength band to be blocked. Therefore, miniaturization or thinning of the solid-state imaging device is naturally limited as long as a color filter and an infrared cut filter are required. Further, in the solid-state image pickup device, if the color filter and the infrared cut-off filter are provided as separate components, the number of parts increases and the cost becomes high.

One of the objects of the present invention is to reduce the size or thickness of the solid-state imaging device in view of such a problem.

According to an embodiment of the present invention, there is provided a light-emitting device including a first pixel on which a color filter layer having a transmission band in a visible light wavelength band is disposed on a light receiving surface of a first light receiving element, And a second compound having a light absorption peak in an infrared wavelength band.

In one embodiment of the present invention, the color filter layer may have a characteristic of transmitting light in one band selected from the red light wavelength band, the green light wavelength band and the blue light wavelength band. The color filter layer may be prepared using a curable composition containing a first compound and a second compound. The content ratio of the second compound may be 0.1 to 60% by mass in the color filter layer.

In one embodiment of the present invention, the second compound may be a metal atom-containing compound. The metal atom-containing compound may be at least one compound selected from a metal phthalocyanine compound, a metal porphyrin compound, a metal dithiol compound, a copper compound, a metal oxide, a metal boride, a noble metal, and a lake pigment.

In one embodiment of the present invention, the curable composition containing the first compound and the second compound may be a positive-tone radiation-sensitive composition further containing a photosensitizer and a curing agent. Further, the curable composition containing the first compound and the second compound may be a negative radiation-sensitive composition further containing a binder resin, a polymerizable compound and a photosensitizer.

In an embodiment of the present invention, a second pixel, which absorbs light in a visible light band and has a near-infrared ray pass filter layer having a transmission band in a near-infrared wavelength band, is disposed on the first pixel and the light receiving surface of the second light- And a first optical layer having at least one transmission band in each of a visible light wavelength band and an infrared wavelength band may be disposed on the light receiving surface of the first pixel and the second pixel.

According to one embodiment of the present invention, there is provided a positive type radiation sensitive composition containing a first compound that absorbs light in at least a part of a visible light wavelength band, a second compound that has a light absorption peak in an infrared wavelength band, A composition is provided.

According to one embodiment of the present invention, there is provided a liquid crystal composition comprising a first compound that absorbs light in at least a part of a visible light wavelength band, a second compound that has a light absorption peak in an infrared wavelength band, a binder resin, There is provided a negative radiation-sensitive composition containing an initiator.

According to one embodiment of the present invention, there is provided a colorant dispersion containing a first compound that absorbs light in at least some of the visible wavelength band, a second compound that has a light absorption peak in the infrared wavelength band, a dispersant, and a solvent .

According to one embodiment of the present invention, there is provided a color filter comprising a first compound that absorbs light in at least a part of a visible light wavelength band and a second compound that has a maximum absorption wavelength in an infrared wavelength band do.

According to the present invention, it is possible to reduce the thickness of the optical filter by adding the function of absorbing the light in the infrared band band to the color filter layer selectively transmitting the light in the visible light band, thereby reducing the size of the solid- .

1 is a schematic configuration diagram showing an example of a solid-state imaging device according to an embodiment of the present invention.
2 is a cross-sectional view showing the configuration of a pixel portion of a solid-state imaging device according to an embodiment of the present invention.
3 is a cross-sectional view showing the configuration of a pixel portion of a solid-state imaging device according to an embodiment of the present invention.
4 is a cross-sectional view showing a configuration of a pixel portion of a solid-state imaging device according to an embodiment of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention can be embodied in many different forms, and is not limited to the description of the embodiments described below. In order to make the description more clear, the widths, thicknesses, shapes, and the like of the respective parts are schematically shown in comparison with the actual form, but they are merely examples and do not limit the interpretation of the present invention. In the present specification and drawings, the same elements as those described above with respect to the drawing are denoted by the same reference numerals or similar symbols (numerals denoted by A, B, and the like after the numerals), and detailed descriptions may be appropriately omitted .

In the present specification, the term " phase " refers to a relative position with respect to the main surface (surface on which the solid-state image pickup elements are arranged) of the support substrate, and the direction away from the main surface of the support substrate is " up ". In the present drawing, the upper side toward the paper is " upper ". The " phase " includes the case of being in contact with an object (i.e., " on ") and the case of being located above the object (in the case of " over "). Conversely, " lower " refers to a relative position with respect to the main surface of the supporting substrate, and the direction toward the main surface of the supporting substrate is " lower ". In this drawing, the downward direction toward the paper is " lower ".

[First Embodiment]

<Structure of Solid-State Imaging Device>

Fig. 1 shows a schematic configuration diagram showing an example of the solid-state imaging device 100 according to the present embodiment. The vertical selection circuit 104, the horizontal selection circuit 106, the sample hold circuit 108, the amplification circuit 110, the A / D conversion circuit 112, and the A / D conversion circuit 110 are connected to the solid- A timing generating circuit 114, and the like. The various functional circuits attached to the pixel portion 102 and the pixel portion 102 may be provided on the same substrate (semiconductor chip). The pixel portion 102 includes a plurality of pixels 122 and is constituted by a CMOS type image sensor or a CCD type image sensor.

The pixel portion 102 has a configuration in which a plurality of pixels 122 are arranged in the row direction and the column direction, and the address lines are arranged in the row direction and the signal lines are arranged in the column direction, for example. The vertical selection circuit 104 applies a signal to the address lines, sequentially selects the pixels 122 in units of rows, outputs a detection signal from each pixel 122 of the selected row to the signal line, . The horizontal selection circuit 106 sequentially takes out the detection signals held in the sample hold circuit 108 and outputs them to the amplification circuit 110. The amplification circuit 110 amplifies the detection signal with an appropriate gain and outputs it to the A / D conversion circuit 112. The A / D conversion circuit 112 converts the detection signal, which is an analog signal, into a digital signal and outputs the digital signal. The timing generation circuit 114 controls the operation timings of the vertical selection circuit 104, the horizontal selection circuit 106, and the sample hold circuit 108.

1 shows an example in which the upper horizontal selection circuit 106a and the sample and hold circuit 108a are synchronized with the vertical selection circuit 104a with respect to the pixel portion 102 and the horizontal selection circuit 106b and sample hold And the circuit 108b is synchronized with the vertical selection circuit 104b. However, FIG. 1 is merely an example, and the solid-state imaging device 100 according to the present invention may be driven by one set of the vertical selection circuit, the horizontal selection circuit, and the sample-and-hold circuit. Alternatively, in the solid-state imaging device 100 according to the present invention, other circuit configurations may be applied to the circuit for driving the pixel portion 102. [

The enlarging unit 116 shown in Fig. 1 enlarges and shows a part of the pixel unit 102. Fig. In the pixel portion 102, the pixels 122 are arranged in the row direction and the column direction as described above. Fig. 2 shows a cross-sectional structure along the line A-B of the pixel portion 102a shown in the enlarged portion 116. Fig.

&Lt; Structure of pixel portion >

2 shows a sectional structure of the pixel portion 102a. A semiconductor layer 128, a wiring layer 130, an optical filter layer 132, and a microlens array 134 are laminated on the substrate 126 side of the pixel portion 102a. The pixel portion 102a has pixels 122 formed by stacking these layers. Fig. 2 shows a configuration in which the first pixels 122a to 122c are provided in the pixel portion 102a. The first pixels 122a to 122c detect light in different wavelength bands by the optical filter layer 132, respectively.

The substrate 126 is a semiconductor substrate, or a substrate having a semiconductor layer. As the semiconductor substrate, a silicon substrate is exemplified. As a substrate having a semiconductor layer, a substrate (SOI substrate) provided with a silicon layer on an insulating layer is exemplified. When the substrate 126 is a silicon substrate, the semiconductor substrate 128 is included in the silicon substrate. In the semiconductor layer 128, light receiving elements 136a to 136c are formed corresponding to the first pixels 122a to 122c.

The light receiving elements 136a to 136c are realized by an element having a function of generating a current or voltage by a photo-electromotive force effect. The light receiving elements 136a to 136c may be, for example, photodiodes. The semiconductor layer 128 and the wiring layer 130 in the region not shown in Fig. 2 (in the peripheral region of the pixel portion 102 shown in Fig. 1) output detection signals from the light receiving elements 136a to 136c A circuit for acquiring a signal is formed.

The wiring layer 130 includes wirings provided on the pixel portion 102a, such as an address line and a signal line. The wiring layer 130 may be divided into a plurality of layers by separating a plurality of wirings by an interlayer insulating film. In an ordinary case, since the address lines and the signal lines extend in the row direction and the column direction and intersect, the interlayer insulating film is provided in the other layer with the intervening layer therebetween.

The optical filter layer 132 includes a plurality of layers having different optical characteristics. In this embodiment, color filter layers 138a to 138c having a transmission band in the visible light wavelength region are provided on the wiring layer 130. [ The color filter layers 138a to 138c are provided so as to overlap the light receiving surfaces of the light receiving elements 136a to 163c, respectively. The color filter layers 138a to 138c have different transmission spectrums in the visible light wavelength band, respectively. That is, each of the color filter layers 138a to 138c has a colored layer having a different transmittance spectrum in the visible light wavelength band.

On the upper surfaces of the color filter layers 138a to 138c, a cured film 144 is provided. The cured film 144 has a flat upper surface by embedding a stepped portion by the color filter layers 138a to 138c. In other words, the cured film 144 has a function as a flattening film, and the bottom surface of the microlens array 134 is made flat.

The micro lens array 134 is provided on the upper surface of the cured film 144. The microlens array 134 is provided so that individual microlenses correspond to the first pixels 122a to 122c. The light condensed by each microlens enters the corresponding light receiving elements 136a to 136c, respectively. The microlens array 134 can be formed using a resin material. The microlens array 134 can be manufactured by processing a resin material coated on the cured film 144, for example.

The solid-state imaging device 100 according to the present embodiment has a semiconductor layer 128, a wiring layer 130, an optical filter layer 132, and a microlens array 134 stacked on a substrate 126, . Details of the optical filter layer 132 will be described below.

&Lt; Color filter layer &

The color filter layers 138a to 138c are pass filters that transmit visible light of different wavelength bands, respectively. For example, the color filter layer 138a transmits light in a wavelength band of red light (approximately 610 to 780 nm), the color filter layer 138b transmits light in a wavelength band of green light (approximately 500 to 570 nm) The color filter layer 138c is a pass filter capable of transmitting light in a wavelength band of blue light (approximately 430 to 460 nm). Transmitted light of the color filter layers 138a to 138c enters the light receiving elements 136a to 136c, respectively. Therefore, each pixel (first pixel) may be distinguished by a first pixel 122a for red light detection, a first pixel 122b for green light detection, and a first pixel 122c for blue light detection.

The color filter layers 138a to 138c include at least a first compound that absorbs light in at least a part of the visible light wavelength band and a second compound that has a light absorption peak in the infrared wavelength band. In this embodiment, at least one color filter layer of the color filter layer 138a, the color filter layer 138b, and the color filter layer 138c includes the first compound and the second compound. The color filter layer 138a, the color filter layer 138b, and the color filter layer 138c each contain different first compounds. At least one or more of the color filter layer 138a, the color filter layer 138b, and the color filter layer 138c includes the second compound. It is also preferable that the second compound is an infrared absorbing agent that absorbs light in a near infrared wavelength band (for example, 750 to 2,500 nm).

At least one of the color filter layers 138a to 138c includes a second compound together with a specific first compound so as to transmit light in a specific band of the visible light wavelength band and absorb light in the infrared wavelength band. That is, at least one of the color filter layers 138a to 138c has a function as a band-pass filter for transmitting a specific visible light band and a function as an infrared cut filter for blocking light in the infrared wavelength band.

The first compound may be a dye (pigment or dye) exhibiting light absorption in a specific wavelength band in the visible light band. The first compound is not limited to one kind of dye but may be composed of a plurality of dyes. In this case, the first compound may be regarded as a first compound group which is a group of a plurality of dyes or the like.

The color filter layers 138a to 138c each include a first compound having different light absorption characteristics. Thereby, each of the first pixels 122a to 122c becomes a pixel for detecting light corresponding to each color. For example, when the color filter layer 138a is a pass filter that transmits light in a wavelength band of red light, the first pixel 122a is used as a red detection pixel, and the color filter layer 138b is made to transmit light in a wavelength band of green light The first pixel 122b may be a green detection pixel and the color filter layer 138c may be a pass filter that transmits light in a wavelength band of blue light so that the first pixel 122c may be a blue detection pixel . This pixel configuration makes it possible to capture a color image.

Such a first compound can be used without particular limitation, and the color and the material can be appropriately selected depending on the use of the color filter. Specific examples thereof include pigments and dyes, which may be used alone or in combination of two or more.

As the pigment, for example, a compound classified as a pigment in the color index (published by CI. The Society of Dyers and Colourists), that is, a color index (C.I.) number is attached as follows.

C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Red pigments such as Pigment Red 264;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Green pigments such as Pigment Green 59;

C.I. Pigment Blue 15: 6, C.I. Pigment Blue 16, C.I. Pigment Blue 79, C.I. Blue pigments such as Pigment Blue 80;

C.I. Pigment Yellow 83, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 179, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 211, C.I. Yellow pigments such as Pigment Yellow 215;

C.I. An orange pigment such as Pigment Orange 38;

C.I. Pigment Violet 19, C.I. Purple pigment such as Pigment Violet 23.

In addition, the brominated diketopyrrolopyrrole pigment represented by the formula (Ic) in Japanese Patent Publication No. 2011-523433 may be used as a red pigment. Further, rake pigments described in JP 2001-081348 A and the like can be mentioned.

The dye is not particularly limited, and known dyes can be used, for example, in addition to the compounds classified by the color index (CI., Published by The Society of Dyers and Colourists) as Dye.

Examples of such dyes include, in terms of the structure of the chromophore, xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, quinoline Dyes, nitro dyes, quinone imine dyes, phthalocyanine dyes, and squarylium dyes. It is also possible to use a dye multimer having a partial structure derived from a dye, for example, as described in JP-A-2013-029760.

The second compound is a compound having at least one light absorption peak in an infrared wavelength band of 650 to 2000 nm. Specifically, it is preferable to have a maximum absorption wavelength within a wavelength range of 650 to 2000 nm, more preferably to have a maximum absorption wavelength within a wavelength range of 700 to 1500 nm, and to have a maximum absorption wavelength within a wavelength range of 750 to 1300 nm It is particularly preferable to have a maximum absorption wavelength in the range of 800 to 1200 nm. As such a second compound, for example, a diamine compound, a squarylium compound, a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, a quaternary compound, an aminium compound, an iminium compound, Wherein the metal compound is selected from the group consisting of a quinone compound, a porphyrin compound, a pyrrolofirole compound, an oxolin compound, a chromium compound, a hexapyrin compound, a metal dithiol compound, a copper compound, a metal oxide, At least one kind of compound can be used. When the above-mentioned second compound is soluble in an organic solvent to be described later, it may be used as an infrared absorbent insoluble in an organic solvent by raising it. The rake can be performed by a known method, for example, Japanese Patent Application Laid-Open No. 2007-271745. These may be used alone or in combination of two or more.

Compounds which can be used as the second compound are exemplified below.

Specific examples of the diiminium (diimmonium) compound include, for example, JP-A-1-113482, JP-A-10-180922, WO-A-2003 / 48480, International Publication No. 2005/44782, International Publication No. 2006/120888, Japanese Patent Application Publication No. 2007-246464, International Publication No. 2007/148595, Japanese Patent Application Laid-Open No. 2011-038007, Compounds described in paragraphs [0118] and the like of 2011/118171 and the like. Examples of commercially available products include EPOLIGHT series such as EPOLIGHT1178 (manufactured by Epolin), CIR-108X series such as CIR-1085 and CIR-96X series (manufactured by Nippon Kagaku), IRG022, IRG023 and PDC-220 .

Specific examples of the squarylium-based compound include compounds described in Japanese Patent No. 3094037, Japanese Patent Application Laid-open No. 60-228448, Japanese Patent Application Laid-Open No. 1-146846, Japanese Patent Application Laid-Open No. 1-228960, A compound described in paragraph [0178] of the publication No. 2012-215806, and the like.

Specific examples of the cyanine-based compound include compounds described in paragraphs [0041] to [0042] of Japanese Patent Application Laid-Open No. 2007-271745, paragraphs [0016] to [0018] of Japanese Patent Application Publication No. 2007-334325, Japanese Patent Application Laid-Open Nos. 2009-108267, 2009-185161, 2009-191213, 2012-215806 [0160], Japanese Patent Laid-Open Publication No. 2013-155353 And compounds described in paragraphs [0047] to [0049] of the publication. Examples of commercially available products include NK series (such as Daito chmix 1371F (manufactured by Daitokemix), NK-3212 and NK-5060 (Hayashibara Seibutsugaku Kenkakusho), and the like.

Specific examples of the phthalocyanine-based compound include, for example, compounds described in Japanese Patent Application Laid-Open Nos. 60-224589, 2005-537319, 4-23868, 4-39361, Japanese Patent Application Laid-Open Nos. 5-78364, 5-222047, 5-222301, 5-222302, 5-345861, Japanese Patent Application Laid-Open Nos. 6-25548, 6-107663, 6-192584, 6-228533, 7-118551, Japanese Unexamined Patent Application Publication No. 7-118552, Japanese Unexamined Patent Publication No. 8-120186, Japanese Unexamined Patent Publication No. 8-225751, Japanese Unexamined Patent Publication No. 9-202860, Japanese Unexamined Patent Publication No. 10-120927, Japanese Patent Application Laid-Open No. 10-182995, Japanese Patent Application Laid-Open No. 11-35838, Japanese Patent Application Laid-Open Nos. 2000-26748, 2000-63691, 2001-106689, 2004-18561, 2005-220060, Japan The compounds described in paragraphs [0026] to [0027] of JP-A No. 2007-169343, JP-A No. 2013-195480, Table 1 of WO-A 2015/025779, and the like. Excolor series, Excolor TX-EX 720, 708K (manufactured by Nippon Shokubai), Lumogen IR788 (manufactured by BASF), ABS643 (manufactured by Nippon Shokubai), FB series (Manufactured by HWSANDS), TAP-15, IR-706 (manufactured by Yamagawa Chemical Industry Co., Ltd.) ) And the like.

Specific examples of the naphthalocyanine compound include, for example, those described in Japanese Patent Laid-Open Nos. 11-152413, 11-152414, 11-152415, and 2009-215542 And compounds described in the paragraphs [0046] to [0049] and the like.

Specific examples of the quaternary-based compound include compounds described in, for example, paragraph [0021] of JP-A No. 2008-009206 and the like. Commercially available products include, for example, Lumogen IR765 (manufactured by BASF).

Specific examples of the aminium compound include compounds described in paragraphs [0018] and 2007-039343 of JP-A 08-027371 and 2007-039343, for example. Commercially available products include, for example, IRG002 and IRG003 (manufactured by Nippon Kayaku Co., Ltd.).

Specific examples of the iminium compound include compounds described in, for example, paragraph [0116] of International Publication No. 2011/118171.

As specific examples of the azo-based compound, for example, compounds described in paragraphs [0114] to [0117] of Japanese Patent Application Laid-Open Publication No. 2012-215806 can be given.

Specific examples of the anthraquinone-based compound include, for example, the compounds described in paragraphs [0128] and [0129] of JP-A No. 2012-215806.

Specific examples of the porphyrin compound include compounds represented by the formula (1) in Japanese Patent No. 3834479, for example.

Specific examples of the pyrrolopyrrole compound include compounds described in paragraphs [0014] to [0027] of JP-A No. 2011-068731 and JP-A No. 2014-130343, for example.

Specific examples of the oxolin-based compound include compounds described in, for example, paragraph [0046] of JP-A 2007-271745.

Specific examples of the chromium compound include compounds described in paragraphs [0049], 2007-31644, 2007-169315, and the like of Japanese Patent Application Laid-Open No. 2007-271745 .

Specific examples of the hexapyrine compound include, for example, a compound represented by the formula (1) of International Publication No. 2002/016144 pamphlet.

Specific examples of the metal dithiol compound include, for example, those described in JP-A-1-114801, JP-A-64-74272, JP-A-62-39682, JP-A-61-80106 , JP-A-61-42585, JP-A-61-32003, JP-A-2010-516823 and the like. Commercially available products include, for example, ADS845MC, ADS870MC, ADS920MC (manufactured by American Dye Source, Inc).

Examples of the copper compound include metal copper, copper complex, and copper phosphate. Of these, copper complexes are preferable, and specific examples thereof include, for example, Japanese Patent Application Laid-Open Nos. 2013-253224, 2014-032380, 2014-026070, 2014- 026178, JP-A-2014-139616, JP-A-2014-139617, and the like. As the copper phosphate, KCuPO ₄ and the like can be mentioned. The metal copper can also be used as copper particles.

Examples of the metal oxide include zinc oxide, silicon oxide, aluminum oxide, zirconium dioxide, titanium oxide, cerium dioxide, tungsten oxide, yttrium oxide, indium oxide, tin oxide and compounds in which these metal oxides are doped with other metals. Among them, tungsten oxide is preferable, tungsten oxide and tungsten oxide are more preferable, and tungsten oxide is more preferable. The composition formula of tungsten oxide of cesium is Cs _{0 . 33} WO ₃ , and the composition formula of rubidium tungsten oxide is Rb _{0 . 33} WO ₃ , and the like. The tungsten oxide-based compound is also available as a dispersion of tungsten microparticles such as YMF-02A made by Sumitomo Heavy Industries.

Examples of the metal oxide doped with another metal include ITO (tin-doped indium oxide), ATO (antimony doped tin oxide), AZO (antimony doped zinc oxide) , And more preferably 1 to 100 nm.

Specific examples of the metal boride include, for example, compounds described in paragraph [0049] and the like of Japanese Patent Application Laid-Open Publication No. 2012-068418. Among them, lanthanum boride is preferable.

Examples of the noble metal include gold, silver, platinum, palladium, rhodium, iridium, ruthenium, and osmium. Of these, gold, silver and palladium are preferable. These are preferably particulate or colloidal.

In addition to the infrared shielding materials exemplified above, compounds described in paragraph 0083 of Japanese Patent Application Laid-Open No. 2000-302972 may also be used.

Among them, the second compound preferably contains a metal atom-containing compound from the viewpoint of forming a color filter layer having excellent light-shielding performance and heat resistance in the infrared wavelength band. The metal atom-containing compound preferably contains at least one compound selected from a metal phthalocyanine compound, a metal porphyrin compound, a metal dithiol compound, a copper compound, a metal oxide, a metal boride, a noble metal and a rake pigment, , And a metal oxide.

As the second compound, a compound having a condensed ring is also preferable. By using such a compound, a color filter layer having excellent heat resistance can be formed. Among the compounds having a condensed ring, those containing at least one compound selected from a quaternary compound, an anthraquinone compound, a pyrrolofirole compound, a chromium compound, and a perylene compound are preferred.

When the color filter layers 138a to 138c include the second compound, the content ratio of the second compound per unit volume is preferably 0.1 to 60% by mass. When the color filter layers 138a to 138c include the first compound and the second compound, the content of the second compound is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, per 100 parts by mass of the first compound.

Color filter layers 138a through 138c are made using a curable composition comprising the first compound. Alternatively, the color filter layers 138a to 138c are manufactured using a curable composition comprising a first compound and a second compound. The curable composition for producing a color filter layer is based on a binder resin, a curing agent and the like, and the first compound is contained in the curable composition, or the first compound and the second compound are contained. By using such a curable composition, the color filter layers 138a to 138c can be provided above the light receiving elements 136a to 136c.

The curable composition for producing the color filter layers 138a to 138c may be a positive-tone radiation-sensitive composition further containing a photosensitizer and a curing agent in addition to the above composition. Alternatively, in addition to the above composition, a negative radiation-sensitive composition containing a binder resin, a polymerizable compound and a photosensitizer may be further used. Hereinafter, the positive radiation-sensitive composition and the negative radiation-sensitive composition will be described in detail.

- Negative radiation sensitive composition -

The negative-tone radiation-sensitive composition preferably contains a first compound, a binder resin, a polymerizable compound, and a photosensitizer, and may further include a second compound, a solvent, an additive, and the like, if necessary.

As the binder resin in the negative-tone radiation-sensitive composition, a (meth) acryl-based polymer having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group is preferable. Examples of the (meth) acrylic polymer having a carboxyl group (hereinafter also referred to as "carboxyl group-containing (meth) acrylic polymer") include an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter also referred to as "unsaturated monomer (Hereinafter also referred to as &quot; unsaturated monomer (2) &quot;) and other copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as &quot; unsaturated monomer (2) &quot;).

Examples of the unsaturated monomer (1) include unsaturated monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], omega -carboxylic polycaprolactone mono , p-vinylbenzoic acid, and the like.

Examples of the unsaturated monomer (2) include N-substituted maleimide, aromatic vinyl compound, (meth) acrylate, vinyl ether, macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain , And more specifically, monomers described in [0060] to [0062] of JP-A No. 2015-004968.

These unsaturated monomers (1) to (2) may be used singly or in combination of two or more.

As specific examples of the copolymer of the unsaturated monomer (1) and the unsaturated monomer (2), for example, JP-A-7-140654, JP-A-8-259876, JP-A-10-31308 , Japanese Patent Application Laid-Open Nos. 10-300922, 11-174224, 11-258415, 2000-56118, 2004-101728 And the like.

Further, for example, Japanese Unexamined Patent Publication Nos. 5-19467, 6-230212, 7-207211, 9-325494, 11 (Meth) acryl-based polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group on its side chain is used as a binder resin, as disclosed in JP-A-140144 and JP-A-2008-181095 It is possible.

The (meth) acrylic polymer in the present invention has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000 , Preferably from 3,000 to 50,000. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (meth) acrylic polymer in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0 to be. The term "Mn" as used herein refers to the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

The (meth) acrylic polymer in the present invention can be produced by a known method. For example, JP-A-2003-222717, JP-A-2006-259680, The structure, Mw, and Mw / Mn can also be controlled by a method disclosed in the publication pamphlet.

As the binder resin in the negative-tone radiation-sensitive composition, a siloxane polymer can also be preferably used. The siloxane polymer is not particularly limited, and a siloxane polymer having an aromatic hydrocarbon group is preferable. Herein, the term "aromatic hydrocarbon group" as used herein refers to a hydrocarbon group having an aromatic ring structure in its ring structure, and includes a monocyclic aromatic hydrocarbon group, a condensed aromatic hydrocarbon group in which benzene rings are condensed or condensed with a hydrocarbon ring other than a benzene ring, And a polycyclic aromatic hydrocarbon ring in which two or more of a benzene ring and a condensed ring are bonded by a single bond. The aromatic hydrocarbon group is not necessarily composed of only a ring structure, and a part of the ring structure may be substituted with a chain hydrocarbon group.

The number of carbon atoms of the aromatic hydrocarbon group is not particularly limited, but is preferably from 6 to 20, more preferably from 6 to 14, and even more preferably from 6 to 10.

Specific examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a styryl group, an indenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a pyrenyl group, A naphthyl group, a naphthyl group, a biphenyl group, a terphenyl group, and the like. Among them, an aromatic hydrocarbon group having 6 to 14 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and a phenyl group, a tolyl group and a naphthyl group are more preferable. Herein, in the present specification, the "aryl group" refers to a monocyclic to tricyclic aromatic hydrocarbon group.

The aromatic hydrocarbon group may have a substituent.

The content of the aromatic hydrocarbon group relative to the Si atom is preferably 5 mol% or more, more preferably 20 mol% or more, and more preferably 60 mol% or more, from the viewpoint of improving the crack resistance of the siloxane polymer in the present invention desirable. The content of the aromatic hydrocarbon group with respect to the Si atom may be 100 mol%, but it may be 95 mol% or less.

Such a siloxane polymer can be obtained by subjecting at least one selected from an aromatic hydrocarbon group and a silane compound having a hydrolyzable group and a partial hydrolyzate thereof to hydrolysis and condensation, and specifically, the siloxane polymer can be synthesized by a known method.

The siloxane polymer in the present invention has a weight average molecular weight (Mw) of preferably 500 to 10000, more preferably 700 to 5000. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

In the present invention, the binder resin may be used alone or in combination of two or more.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the first compound. The content of the polymerizable compound relative to 100 parts by mass of the binder resin is preferably 20 to 500, more preferably 50 to 200 parts by mass.

The polymerizable compound in the negative-tone radiation-sensitive composition means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenic unsaturated group, an oxiranyl group, an oxetanyl group, an N-alkoxymethylamino group, a silanol group, and a methylol group. In the present invention, as the polymerizable compound, a compound having two or more (meth) acryloyl groups, a compound having two or more N-alkoxymethylamino groups, a compound having two or more silanol groups, Group is preferable.

Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, a polyfunctional (meth) acrylate modified with caprolactone, A polyfunctional urethane (meth) acrylate obtained by reacting a (meth) acrylate modified with an alkylene oxide and a polyfunctional (meth) acrylate having a hydroxyl group and a polyfunctional isocyanate, a (meth) acrylate having a hydroxyl group and an acid anhydride And a polyfunctional (meth) acrylate having a carboxyl group obtained by the reaction. More specifically, a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound described in [0073] of JP-A No. 2015-004968 with (meth) acrylic acid, or a polyfunctional (meth) Polymerizable compounds described in [0074] to [0075] of -004968.

In the present invention, the polymerizable compounds may be used alone or in combination of two or more.

The content of the polymerizable compound in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, further preferably 30 to 300 parts by mass, per 100 parts by mass of the first compound.

The negative radiation sensitive composition of the present invention may contain a photosensitizer. Thereby, the negative radiation-sensitive composition can be imparted with radiation-sensitive properties. The photosensitizer used in the present invention is a compound that generates active species capable of initiating polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet light, deep ultraviolet light, electron beam, and X-ray.

Examples of such photosensitizers include radical polymerization initiators and photoacid generators. Examples of the radical polymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, a benzophenone compound, Polynuclear quinone compounds, diazo compounds, imidosulfonate compounds and the like. More specifically, there may be mentioned the compounds described in [0081] to [0087] of JP-A No. 2015-004968. Among these radical polymerization initiators, at least one member selected from the group consisting of a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, and an O-acyloxime compound is preferable. Examples of the photoacid generator include those described in [0024] of Japanese Patent Laid-Open Publication No. 2011-068755.

In the present invention, the photosensitizer may be used alone or in combination of two or more.

In the present invention, the content of the photosensitizer is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, further preferably 5 to 50 parts by mass, per 100 parts by mass of the polymerizable compound.

The negative-tone radiation-sensitive composition is usually prepared as a liquid composition by blending a solvent. The solvent may be appropriately selected and used as long as it does not disperse or dissolve the components constituting the negative radiation sensitive composition and does not react with these components and has suitable volatility.

Examples of such a solvent include those described in [0090] to [0093] of JP-A No. 2015-004968. Among them, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl Acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, And organic solvents such as i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate.

In one embodiment of the present invention, the solvents may be used alone or in combination of two or more.

The content of the solvent is not particularly limited, but it is preferably such that the total concentration of each component except for the solvent of the negative-tone radiation sensitive composition is from 5 to 50 mass%, more preferably from 10 to 30 mass% desirable.

Additives such as a filler, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a residue remover, and a development improver may be added to the negative radiation sensitive composition. Examples of such an additive include those described in [0097] of Japanese Patent Laid-Open Publication No. 2015-004968.

- Positive radiation sensitive composition -

The positive-tone radiation-sensitive composition preferably includes a first compound, a photosensitizer, and a curing agent, and may further include a second compound, a binder resin, a solvent, an additive, and the like, if necessary.

Examples of the photosensitizer in the positive-tone radiation-sensitive composition include a compound having a naphthoquinone diazide group and a photo acid generator. As the compound having a naphthoquinone diazide group, for example, an ester of a phenol compound and a naphthoquinone diazidesulfonic acid compound can be used. Examples of the phenol compounds include 2- to 5-functional hydroxybenzophenones, and compounds represented by the following formulas (2) to (6) (wherein R in the formula (6) represents a hydrogen atom). Examples of the naphthoquinone diazidesulfonic acid compound include o-naphthoquinonediazide-5-sulfonic acid, o-naphthoquinonediazide-4-sulfonic acid, and the like. The photoacid generator may be the same as described above.

As the curing agent in the positive-tone radiation-sensitive composition, a compound having two or more N-alkoxymethylamino groups is preferable. N, N ', N'-tetra (alkoxymethyl) benzoguanamine, N, N', N'- N ', N'-tetra (alkoxymethyl) glycoluril and the like.

Examples of the binder resin, solvent and additive in the positive-tone radiation-sensitive composition include the same ones as the binder resin, solvent and additive in the negative-tone radiation-sensitive composition.

<Cured film>

In the solid-state imaging device of the present invention, the cured film 144 may be provided between the color filter layers 138a to 138c and the microlens array 134. [ It is preferable that the cured film 144 has transparency to light at least in the visible light wavelength region. Light incident through the microlens array 134 passes through the cured film 144 and light that has been separated by the color filter layers 138a to 138c enters the light receiving elements 136a to 136c.

It is preferable that the cured film 144 has insulating property so that parasitic capacitance is not generated between the cured film 144 and the wiring layer 130. Since the cured film 144 is provided on the front surface of the optical filter layer 132, if the cured film 144 is conductive, unintentional parasitic capacitance is generated between the cured film 144 and the wiring layer 130. When the parasitic capacitance occurs, the detection operation of the light receiving elements 136a to 136c is interrupted. Therefore, it is preferable that the cured film 144 has insulating property.

In addition, it is desired that the cured film 144 has excellent adhesion with the base layer. For example, if the adhesion between the cured film 144 and the color filter layers 138a to 138c is poor, peeling occurs and the optical filter layer 132 is damaged.

In addition, since the cured film 144 is filled with the color filter layers 138a to 138c and the microlens array 134 is provided thereon, it is preferable that the surface is planarized. That is, the cured film 144 is preferably used also as a planarizing film.

In order to satisfy such a characteristic, the cured film 144 preferably uses an organic film. When an organic film is used, it has transparency and insulation, and the surface can be planarized. That is, by using the curable composition for forming a planarizing film as the cured film 144, a flat surface can be formed even if the base surface contains unevenness by the leveling action after application of the composition.

As the composition for producing the cured film 144, a known curable composition may be used, and a method of forming a cured film may be adopted.

According to this embodiment, the bottom surface of the microlens array can be planarized by such a cured film which can protect the color filter layer by the cured film. In any case, according to the present embodiment, it is possible to reduce the thickness of the optical filter by adding the function of absorbing light in the infrared band to the color filter layer selectively transmitting the light in the visible light band, It is possible to achieve miniaturization.

[Second Embodiment]

3 shows a sectional structure of the pixel portion 102b of the solid-state imaging device according to the present embodiment. The pixel portion 102b is the same as the first embodiment in that it includes the semiconductor layer 128, the wiring layer 130, the optical filter layer 132, and the microlens array 134 in the layer structure. However, the pixel portion 102b of the solid-state imaging device according to the present embodiment has a back-illuminated configuration in which the wiring layer 130 is disposed on the lower surface side of the light-receiving elements 136a to 136c. The back-illuminated pixel portion is formed by forming light receiving elements 136a to 136c and a wiring layer 130 thereon on a semiconductor substrate, grinding and polishing the back surface of the semiconductor substrate to expose the light receiving elements 136a to 136c, It is. In this case, the substrate 126 is attached to the wiring layer 130 as a supporting substrate.

Since the backside illumination type pixel portion 102b has no wiring layer 130 on the light-receiving surface of the light-receiving elements 136a to 136c, the light aperture ratio is obtained, the loss of incident light is suppressed, There is an advantage that it can output.

In the present embodiment, the configurations of the optical filter layer 132 and the microlens array 134 are the same as those of the first embodiment. An organic film 146 is provided between the light receiving elements 136a to 136c and the color filter layers 138a to 138c. The organic film 146 covers the upper surfaces of the light receiving elements 136a to 136c and flattens the lower surface of the color filter layers 138a to 138c. It also serves as a protective film for the light receiving elements 136a to 136c.

The organic film 146 is produced using the same curable composition as the composition for producing the cured film 144 shown in the first embodiment. By using these materials, the upper surfaces of the light receiving elements 136a to 136c can be planarized.

According to the present embodiment, the pixel portion 102b is formed in a back surface irradiation type, thereby providing a solid-state imaging device with high light utilization efficiency and high sensitivity. In addition, since the optical filter layer 132 has the same configuration as that of the first embodiment, the optical filter layer is thinned, and the thickness of the solid-state imaging device can be reduced. That is, according to the present embodiment, it is possible to provide the solid-state imaging device having the back-illuminated type characteristics and exhibiting the same operational effects as those of the first embodiment.

[Third embodiment]

4 shows a sectional structure of the pixel portion 102c of the solid-state imaging device according to the present embodiment. This pixel portion 102c includes a pixel for infrared light detection by the second pixel 124 in addition to the pixel for visible light detection by the first pixels 122a to 122c. And has the same configuration as that of the pixel shown in the first embodiment except that the second pixel 124 is included. That is, the pixel portion 102c is formed by the semiconductor layer 128, the wiring layer 130, the optical filter layer 132, and the microlens array 134. [

In the second pixel 124, a near-infrared ray pass filter layer 140 is provided on the light-receiving surface side of the light-receiving element 136d. A microlens array 134 is provided above the near-infrared light path filter layer 140.

The near-infrared ray pass filter layer 140 is a pass filter that transmits light in at least a near-infrared wavelength region. The near-infrared ray pass filter layer 140 can be formed by adding a dye (pigment or dye) having absorption to a wavelength in the visible light wavelength region, such as a binder resin or a polymerizable compound. The near-infrared light path filter layer 140 absorbs (blocks) light having a wavelength of less than approximately 700 nm, preferably less than 750 nm, and more preferably less than 800 nm, and has a wavelength of 700 nm or more, preferably 750 nm or more, more preferably 800 nm or more And has a spectroscopic transmission characteristic.

The near-infrared ray pass filter layer 140 shields light having a wavelength of less than a predetermined wavelength (for example, less than 750 nm) as described above and transmits near infrared rays in a predetermined wavelength region (750 nm or more, for example, 750 to 950 nm) So that near infrared rays are incident on the light receiving element 136d. Thus, the light receiving element 136d can detect infrared light with high accuracy without being affected by noise or the like caused by visible light. By providing the near-infrared ray pass filter layer 140, the second pixel 122d and the second pixel 124 can be used as infrared detection pixels. The near-infrared ray pass filter layer 140 can be formed using the photosensitive composition described in, for example, Japanese Patent Application Laid-Open No. 2014-130332.

On the other hand, the first pixels 122a to 122c have a characteristic in which the color filter layers 138a to 138c absorb light in the infrared wavelength band. Therefore, the solid-state image pickup device according to the present embodiment can juxtapose a pixel for detecting a visible light wavelength band and a pixel for detecting an infrared wavelength band without adding a new optical filter.

In the pixel portion 102c, it is preferable that the upper surfaces of the color filter layers 138a to 138c and the upper surface of the near-infrared ray pass filter layer 140 are provided so as to have substantially the same height. Thereby, the flatness of the bottom surface of the cured film 144 can be improved. The cured film 144 can function as a planarizing film itself. However, when the cured film 144 is formed by applying a known curable composition, the closer the flat surface is to the flat surface, the more the application of the curable composition The unevenness can be reduced and the upper surface flatness of the cured film 144 can be improved. Thereby, the micro lens array 134 formed on the upper surface of the cured film 144 can be molded with high precision, and the solid-state imaging device can acquire an image with less distortion.

The solid-state image pickup device according to the present embodiment may be provided with a two-band pass filter 148 on the microlens array 134 in addition to the above configuration. That is, on the upper surface of the microlens array 134, for example, an average transmittance in a wavelength range of 430 to 580 nm is 75% or more, an average transmittance in a wavelength range 720 to 750 nm is 15% Band pass filter 148 having an average transmittance in a range of 820 nm to 60% and an average transmittance in a range of 900 to 2000 nm of 15% or less may be provided. By adding the two-band pass filter 148, it is possible to further enhance the filtering ability in the visible light wavelength region and the infrared wavelength region.

The solid-state image pickup device 100 shown in Fig. 4 has a structure in which the light incident through the microlens array 134 is reflected by the color filter layers 138a to 138c in the first pixels 122a to 122c, The light in the infrared wavelength band is cut off and is incident on the light receiving elements 136a to 136c. On the other hand, the second pixel 124 is directly incident on the near-infrared ray pass filter layer 140.

In the first pixels 122a to 122c, the visible light beams filtered by the color filter layers 138a to 138c are incident on the light receiving elements 136a to 136c, respectively. In one or more of the color filter layers 138a to 138c, by having a characteristic of blocking infrared rays, visible light can be detected with high accuracy without being influenced by noise due to infrared rays. In the second pixel 124, light in the visible light wavelength region is blocked by the near-infrared light path filter layer 140, and light in the infrared wavelength region (particularly near-infrared wavelength region) enters the light receiving element 136d. As a result, the infrared ray can be detected with high accuracy without being affected by noise or the like caused by visible light.

The solid-state imaging device according to the present embodiment can realize the solid-state imaging device capable of measuring the distance by the TOF method by providing the visible light detection pixel and the infrared light detection pixel as one body. That is, it is possible to acquire the image data of the object from the pixel for visible light detection, and measure the distance from the pixel for infrared light detection to the object. Thereby, it becomes possible to acquire three-dimensional image data. In this case, in the pixel for visible light detection, light in the infrared wavelength range is blocked, and high-sensitivity imaging with less noise can be performed. In a pixel for infrared detection, light in a visible light wavelength range is blocked, and distance measurement with high accuracy can be performed.

In the solid-state image pickup device according to the present embodiment, the color filter layers 138a to 138c are provided with a function of blocking the light in the infrared wavelength band, so that the optical filter layer 132 is made thinner and the thickness of the solid- Lt; / RTI &gt; Thereby, it is possible to contribute to the thinning of the housing of the portable information device such as the smart phone or the tablet terminal.

The configuration of the pixel portion 102c according to the present embodiment includes a first pixel 122a to 122c for detecting light in the visible light band and a second pixel 124 for detecting light in the infrared wavelength band And is the same as that of the first embodiment. In other words, according to the present embodiment, in addition to the above features, it is possible to provide a solid-state imaging device that exhibits the same operational effects as those of the first embodiment.

Example

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

- Synthesis Example 1-

3 parts by mass of 2,2'-azobisisobutyronitrile and 100 parts by mass of propylene glycol monomethyl ether acetate (hereinafter also referred to as &quot; PGMEA &quot;) were charged into a flask equipped with a cooling tube and a stirrer, 12 parts by mass of phenylmaleimide, 10 parts by mass of styrene, 20 parts by mass of methacrylic acid, 15 parts by mass of 2-hydroxyethyl methacrylate, 29 parts by mass of 2-ethylhexyl methacrylate, 14 parts by mass of benzyl methacrylate, And 5 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SAKAI KAGAKU KOGYO CO., LTD.) Were charged and replaced with nitrogen. Thereafter, the mixture was gently stirred, the temperature of the reaction solution was raised to 80 캜, and the polymerization was maintained at this temperature for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 占 폚 and further polymerized for 1 hour to obtain a binder resin (B-1) solution (solid concentration of 40% by mass). The resulting binder resin (B-1) had Mw of 9,700 and Mn of 5,700.

- Synthesis Example 2-

With reference to Example 1 of the International Publication No. 2011/129078, an A block having a repeating unit derived from dimethylaminoethyl methacrylate, and an A block having a repeating unit derived from butyl methacrylate, PME-200 (manufactured by Nippon Kayaku Co., Ltd.) Block copolymer containing repeating units derived from methacrylic acid (the copolymerization ratio of the respective repeating units is selected from the group consisting of dimethylaminoethyl methacrylate / butyl methacrylate / PME-200 (methyl methacrylate / butyl methacrylate / / Methacrylic acid = 22/47/26/5, Mw = 10,000). This block copolymer is referred to as &quot; dispersant (X-1) &quot;.

- Preparation Example 1-

As a colorant, C.I. 7.5 parts by mass of Pigment Green 58, and 7.5 parts by mass of C.I. , 7.5 parts by mass of Pigment Yellow 139, 11.25 parts by mass of a dispersant (X-1) solution (solid content concentration of 40% by mass) as a dispersing agent, 13.75 parts by mass of a binder resin (B- And 60 parts by mass of PGMEA as a solvent were treated with a bead mill to prepare a pigment dispersion (A-1).

- Preparation 2-

As a colorant, C.I. 12 parts by mass of Pigment Blue 15: 6, and C.I. 3 parts by mass of Pigment Violet 23, 11.25 parts by mass of BYK-LPN21116 (trade name, a solid content concentration of 40% by mass) as a dispersant, 13.75 parts by mass of a binder resin (B-1) solution (solid content concentration of 40% by mass) And 60 parts by mass of PGMEA as a solvent were treated with a bead mill to prepare a pigment dispersion (A-2).

- Preparation 3-

After the inside of the flask was purged with nitrogen, 200 parts by mass of a methyl-3-methoxypropionate solution containing 0.6 parts by mass of 2,2'-azobisisobutyronitrile was added. Subsequently, 37.5 parts by mass of tert-butyl methacrylate and 62.5 parts by mass of glycidyl methacrylate were added, followed by stirring and heating at 70 ° C for 6 hours. After cooling, a resin solution containing a polymer was obtained.

Subsequently, 33.3 parts by mass (containing 10 parts of the polymer) of this resin solution, 31.9 parts by mass of methyl-3-methoxypropionate and 3.4 parts by mass of propylene glycol monomethyl ether, and then 0.3 parts by mass of trimellitic acid , 0.5 parts by mass of 3-glycidoxypropyltrimethoxysilane and 0.005 parts by mass of a trade name "FC-4432" (Sumitomo 3M Co., Ltd.) were dissolved to prepare a composition for forming a base film.

[Example 1]

40.54 parts by mass of YMF-02A (a dispersion of 18.5 mass% of cesium tungsten oxide (Cs _0.33 WO ₃ , average dispersed particle size of 800 nm or less) manufactured by Sumitomo Mining Holdings, Inc.) and 33.33 parts by mass of a pigment dispersion (A-1) Mass part were mixed to prepare a colorant dispersion. 9.17 parts by mass of a binder resin (B-1) solution (solid content concentration of 40% by mass) was added as a binder resin to this coloring dispersion, and 10 parts by mass of a polymerizable compound such as Kayarad DPEA-12 (manufactured by Nippon Kayaku Kabushiki Kaisha, 4.0 parts by mass of an epoxy-modified dipentaerythritol hexaacrylate), 0.98 parts by mass of adeka aques NCI-930 (manufactured by Adeka Corp.) as a radical polymerization initiator, 0.02 part by mass of Gent FTX-218 (manufactured by Neos Co., Ltd.) and 11.96 parts by mass of PGMEA were mixed to prepare a negative radiation-sensitive composition (S-1). The solid concentration in the negative-tone radiation-sensitive composition (S-1) is 24.5% by mass, and the content of the polymerizable compound with respect to 100 parts by mass of the binder resin is 73 parts by mass. The content ratio of the infrared shielding material and the colorant is 7.5 / 5.0 (mass ratio).

The above base film forming composition was applied by spin coating using an automatic coating and developing apparatus (Cleantrack, trade name "MARK-Vz" manufactured by Tokyo Electron Limited) on a 6-inch silicon wafer, Followed by baking for 2 seconds to form a foundation film having a thickness of 0.6 mu m.

The negative-tone radiation-sensitive composition (S-1) was applied on the base film by spin coating and then prebaked at 100 ° C for 120 seconds to form a coating film having a thickness of 2.0 탆. Thereafter, the obtained substrate was cooled to room temperature, and a film of 365 nm (i-line) was formed on the coating film on the substrate through a photomask by using a reduction projection exposure apparatus (NSR-2205i12D manufactured by Nikon Corporation, lens numerical aperture = At an exposure dose of 300 mJ / cm &lt; 2 &gt;. Subsequently, a 30 second puddle (liquid sticking) phenomenon with a 0.3% tetramethylammonium hydroxide aqueous solution was performed twice in the automatic coating and developing apparatus. After spin drying, post-baking was performed on a hot plate at 220 캜 for 300 seconds to form a green cured film pattern.

The green cured film pattern had a maximum transmittance wavelength in a wavelength range of 500 to 600 nm and a transmittance at a maximum transmittance wavelength of 60% or more. The maximum transmittance in the wavelength range of 750 to 800 nm was more than 10% and 30% or less, and the maximum transmittance in the wavelength range of 800 to 1200 nm was more than 10% and 30% or less. Further, even after further post-baking for 10 minutes at 230 占 폚 with respect to this green cured film pattern, the minimum transmittance was 30% or less in a part of the wavelength range of 750 to 1200 nm. Therefore, the color filter layer having the green cured film pattern as a green pixel can be said to have an excellent transmittance in the green region and a reduced transmittance in the infrared wavelength band. Therefore, in the solid-state image pickup device having such a color filter layer, It is possible to make the thickness of the optical filter thinner, and therefore, the solid-state image pickup device can be miniaturized.

[Example 2]

A negative-tone radiation-sensitive composition (S-2) was prepared in the same manner as in Example 1 except that the pigment dispersion (A-2) was used instead of the pigment dispersion (A-1) in Example 1.

Subsequently, a blue cured film pattern was formed in the same manner as in Example 1, except that the negative-tone radiation-sensitive composition (S-2) was used instead of the negative-tone radiation-sensitive composition (S-1) Respectively.

The blue cured film pattern had a maximum transmittance wavelength in a wavelength region of 400 to 500 nm and a transmittance at a maximum transmittance wavelength of 60% or more. The maximum transmittance in the wavelength range of 750 to 800 nm was more than 10% and 30% or less, and the maximum transmittance in the wavelength range of 800 to 1200 nm was more than 10% and 30% or less. The blue cured film pattern had a minimum transmittance of 30% or less in a part of the wavelength region of 750 to 1200 nm even after further post-baking at 230 캜 for 10 minutes. Therefore, the color filter layer having the blue cured film pattern as a blue pixel can be said to have an excellent transmittance in the blue region and a reduced transmittance in the infrared wavelength band. Therefore, the solid- It is possible to make the thickness of the optical filter thinner, and therefore, the solid-state image pickup device can be miniaturized.

[Comparative Example 1]

, 33.33 parts by mass of the pigment dispersion (A-1), 19.0 parts by mass of a binder resin (B-1) solution (solid content concentration of 40% by mass) as a binder resin, 19.0 parts by mass of a cyanide DPEA-12 (Nippon Kayaku Kabushiki , 6.86 parts by mass of ethylene oxide-modified dipentaerythritol hexaacrylate), 1.68 parts by mass of Adeka AQUAZ NCI-930 (manufactured by Adeka Co., Ltd.) as a polymerization initiator, (S-3) was prepared by mixing 0.03 parts by mass of an active agent, Fotogen FTX-218 (manufactured by NEOS Corporation) and 39.1 parts by mass of PGMEA. The solid content concentration in the negative-tone radiation-sensitive composition (S-3) was 24.5% by mass, and the content of the polymerizable compound relative to 100 parts by mass of the binder resin was 73 parts by mass.

Subsequently, a green cured film pattern was formed in the same manner as in Example 1 except that the negative radiation-sensitive composition (S-3) was used instead of the negative-tone radiation-sensitive composition (S-1) Respectively. This green cured film pattern had a maximum transmittance wavelength in a wavelength range of 500 to 600 nm and a transmittance at a maximum transmittance wavelength of 60% or more. However, the maximum transmittance in the wavelength region of 750 to 800 nm was 30% or more and 50% or less, and the maximum transmittance in the wavelength region of 800 to 1200 nm was 50% or more. Therefore, the color filter layer having the green cured film pattern as green pixels has excellent transmittance in the green region, but it can not be said that the transmittance in the infrared wavelength band is reduced, so that it is difficult to miniaturize the solid-state image pickup device .

[Comparative Example 2]

A negative-tone radiation-sensitive composition (S-4) was prepared in the same manner as in Comparative Example 1 except that the pigment dispersion (A-2) was used instead of the pigment dispersion (A-1) in Comparative Example 1.

Subsequently, a blue cured film pattern was formed in the same manner as in Example 1, except that the negative-tone radiation-sensitive composition (S-4) was used instead of the negative-tone radiation-sensitive composition (S-1) Respectively. This blue cured film pattern had a maximum transmittance wavelength in a wavelength range of 400 to 500 nm and a transmittance at a maximum transmittance wavelength of 60% or more. However, the maximum transmittance in the wavelength region of 750 to 800 nm was 30% or more and 50% or less, and the maximum transmittance in the wavelength region of 800 to 1200 nm was 50% or more. Therefore, the color filter layer having the blue cured film pattern as a blue pixel has an excellent transmittance in the blue region, but it can not be said that the transmittance in the infrared wavelength band is reduced, so that it is difficult to miniaturize the solid state image pickup device .

[Example 3]

In Example 1, instead of 40.54 parts by mass of YMF-02A, 39.20 parts by mass of a 5 mass% cyclohexanone solution of the compound (a-12) (phthalocyanine compound having a center metal of vanadium) in International Publication No. 2015/025779 pamphlet A negative-tone radiation-sensitive composition (S-5) was prepared in the same manner as in Example 1 except that the composition was used.

A green cured film pattern was formed in the same manner as in Example 1, except that the negative radiation-sensitive composition (S-5) was used instead of the negative-tone radiation-sensitive composition (S-1) Respectively.

The green cured film pattern had a maximum transmittance wavelength in a wavelength range of 500 to 600 nm and a transmittance at a maximum transmittance wavelength of 60% or more. The maximum transmittance in the wavelength range of 750 to 800 nm was more than 10% but not more than 30%, but the maximum transmittance in the wavelength range of 800 to 1200 nm was more than 50%. Further, even after further post-baking at 230 占 폚 for 10 minutes, the green cured film pattern had a minimum transmittance of 30% or less in a part of the wavelength region of 750 to 800 nm. Therefore, the color filter layer having the green cured film pattern as a green pixel can be said to have a high transmittance in the green region and a reduced transmittance in the infrared wavelength band in the range of 750 to 800 nm. Therefore, The imaging device can reduce the thickness of the optical filter, and therefore, the solid-state imaging device can be miniaturized.

[Example 4]

According to Production Example 2, CI Pigment Blue 15: 6 12 parts by weight, and CI Pigment Violet in place of 233 parts by mass of Japan "Dye-E" described in the publication No. 2011-225761 [Patent Publication ₆ and K (P ₂ MoW ₁₇ O ₆₂ ) was prepared in the same manner as in Production Example 2 except that 15 parts by mass of a salt-forming compound (a lake pigment obtained by raising a cyanine-based compound, a salt of a cationic cyanine chromophore and an anion having a molybdenum atom and a tungsten atom) To thereby prepare a pigment dispersion (A-3). Subsequently, a negative-tone radiation-sensitive composition (S-6) was produced in the same manner as in Example 1 except that the pigment dispersion (A-3) was used instead of 40.54 parts by mass of YMF- .

A green cured film pattern was formed in the same manner as in Example 1 except that the negative radiation-sensitive composition (S-6) was used instead of the negative-tone radiation-sensitive composition (S-1) Respectively.

The green cured film pattern had a maximum transmittance wavelength in a wavelength range of 500 to 600 nm and a transmittance at a maximum transmittance wavelength of 60% or more. The maximum transmittance in the wavelength range of 750 to 800 nm was more than 10% but not more than 30%, but the maximum transmittance in the wavelength range of 800 to 1200 nm was more than 50%. Further, even after further post-baking at 230 占 폚 for 10 minutes, the green cured film pattern had a minimum transmittance of 30% or less in a part of the wavelength region of 750 to 800 nm. Therefore, the color filter layer having the green cured film pattern as a green pixel can be said to have excellent transmittance in the green region and transmittance in the infrared wavelength band in the range of 750 to 800 nm is reduced. Therefore, The solid-state imaging device can reduce the thickness of the optical filter, and therefore, the solid-state imaging device can be miniaturized.

[Example 5]

Except that 46.55 parts by mass of a 10% by mass cyclohexanone solution of ADS870MC (manufactured by American Dye Source), which is a nickel dithiol compound, was used instead of 40.54 parts by mass of YMF-02A in Example 1, To thereby prepare a radiation-sensitive composition (S-7).

A green cured film pattern was formed in the same manner as in Example 1, except that the negative radiation-sensitive composition (S-7) was used instead of the negative-tone radiation-sensitive composition (S-1) Respectively.

The green cured film pattern had a maximum transmittance wavelength in a wavelength range of 500 to 600 nm and a transmittance at a maximum transmittance wavelength of 60% or more. The maximum transmittance in the wavelength range of 750 to 800 nm was more than 10% but not more than 30%, but the maximum transmittance in the wavelength range of 800 to 1200 nm was more than 50%. Further, even after further post-baking at 230 占 폚 for 10 minutes, the green cured film pattern had a minimum transmittance of 30% or less in a part of the wavelength region of 750 to 800 nm. Therefore, the color filter layer having the green cured film pattern as a green pixel can be said to have a high transmittance in the green region and a reduced transmittance in the infrared wavelength band in the range of 750 to 800 nm. Therefore, The imaging device can reduce the thickness of the optical filter, and therefore, the solid-state imaging device can be miniaturized.

[Example 6]

Except that 12.25 parts by mass of a 5 mass% cyclohexanone solution of the compound (a-12) (a phthalocyanine compound having a central metal of vanadium) in the pamphlet of International Publication No. 2015/025779 was further added as an infrared shielding material in Example 1 A negative-tone radiation-sensitive composition (S-8) was prepared in the same manner as in Example 1.

A green cured film pattern was formed in the same manner as in Example 1, except that the negative-tone radiation-sensitive composition (S-8) was used instead of the negative-tone radiation-sensitive composition (S-1) Respectively.

The green cured film pattern had a maximum transmittance wavelength in a wavelength range of 500 to 600 nm and a transmittance at a maximum transmittance wavelength of 60% or more. The maximum transmittance in the wavelength region of 750 to 800 nm was 10% or less, and the maximum transmittance in the wavelength region of 800 to 1200 nm was 10% or less. Further, even after further post-baking for 10 minutes at 230 占 폚 with respect to this green cured film pattern, the minimum transmittance was 30% or less in a part of the wavelength range of 750 to 1200 nm. Therefore, the color filter layer having the green cured film pattern as a green pixel can be said to have an excellent transmittance in the green region and a very low transmittance in the infrared wavelength band. Therefore, the solid-state image pickup device having such a color filter layer , It is possible to reduce the thickness of the optical filter, and therefore, it is possible to reduce the size of the solid-state imaging device.

[Comparative Example 3]

Except that 40.54 parts by mass of YMF-02A in Example 1 was replaced by 24.50 parts by mass of a 2% by mass cyclohexanone solution in the squarylium compound represented by the following formula (a-3) , And a negative radiation-sensitive composition (S-9).

A green cured film pattern was formed in the same manner as in Example 1, except that the negative-tone radiation-sensitive composition (S-9) was used instead of the negative-tone radiation-sensitive composition (S-1) Respectively. This green cured film pattern had a maximum transmittance wavelength in a wavelength range of 500 to 600 nm and a transmittance at a maximum transmittance wavelength of 60% or more. The maximum transmittance in the wavelength region of 750 to 800 nm was more than 10% but not more than 30%, but the maximum transmittance in the wavelength region of 800 to 1200 nm was more than 50%. Further, the green cured film pattern was further subjected to post-baking at 230 캜 for 10 minutes, and the minimum transmittance in the wavelength region of 750 to 800 nm was more than 30%. Therefore, the color filter layer having the green cured film pattern as green pixels has excellent transmittance in the green region, but it can not be said that the transmittance in the infrared wavelength band is reduced, so that it is difficult to miniaturize the solid-state image pickup device .

100 ... Solid state imaging device, 102 ... A pixel portion 104, Vertical selection circuit, 106 ... Horizontal selection circuit, 108 ... Sample hold circuit, 110 ... Amplification circuit, 112 ... A / D conversion circuit, 114 ... Timing generating circuit, 116 ... The enlargement unit 122 ... The first pixel, 124 ... The second pixel 126, Substrate, 128 ... Semiconductor layer, 130 ... Wiring layer, 132 ... Optical filter layer, 134 ... Micro lens array, 136 ... Photodiode, 138 ... Color filter layer, 140 ... Near-infrared path filter layer 144, Cured film, 146 ... Organic film, 148 ... 2 bandpass filter

Claims (14)

And a first pixel on which a color filter layer having a transmission band in a visible light wavelength band is disposed on the light receiving surface of the first light receiving element,
Wherein the color filter layer comprises a first compound that absorbs light in at least a part of a visible light wavelength band and a second compound that has a maximum absorption wavelength in an infrared wavelength band. The solid-state imaging device according to claim 1, wherein the color filter layer transmits light in one band selected from a red light wavelength band, a green light wavelength band, and a blue light wavelength band. The solid-state imaging device according to claim 1, wherein the second compound comprises a metal atom-containing compound. The metal-containing compound according to claim 3, wherein the metal atom-containing compound comprises at least one compound selected from a metal phthalocyanine compound, a metal porphyrin compound, a metal dithiol compound, a copper compound, a metal oxide, a metal boride, a noble metal, The solid-state image pickup device. The solid-state imaging device according to any one of claims 1 to 4, wherein the color filter layer is formed using a curable composition containing the first compound and the second compound. The solid-state imaging device according to claim 5, wherein the curable composition is a positive-tone radiation sensitive composition further comprising a photosensitizer and a curing agent. The solid-state imaging device according to claim 5, wherein the curable composition is further a negative radiation-sensitive composition containing a binder resin, a polymerizable compound and a photosensitizer. The solid-state imaging device according to any one of claims 1 to 4, wherein the content ratio of the second compound in the color filter layer is 0.1 to 60 mass%. The solid-state imaging device according to any one of claims 1 to 4, wherein the wavelength of the infrared rays is 750 to 2500 nm. The liquid crystal display device according to any one of claims 1 to 4,
And a second pixel on the light receiving surface of the second light receiving element, the near infrared ray pass filter layer absorbing light in the visible light band and having a transmission band in the near infrared band,
Wherein a first optical layer having at least one transmission band in each of a visible light wavelength band and an infrared light wavelength band is disposed on the light receiving surface of the first pixel and the second pixel. 1. A positive radiation-sensitive composition comprising a first compound that absorbs light in at least a portion of a visible light wavelength band, a second compound that has a light absorption peak in the infrared wavelength band, a photosensitizer, and a curing agent. A negative radiation-sensitive composition comprising a first compound that absorbs light in at least some of the visible wavelength band, a second compound that has a light absorption peak in the infrared wavelength band, a binder resin, a polymerizable compound, and a photosensitizer. A dispersion of a colorant comprising a first compound that absorbs light in at least some of the visible wavelength band, a second compound that has a light absorption peak in the infrared wavelength band, a dispersant, and a solvent. A first compound which absorbs light in at least a part of the visible light wavelength band and a second compound which has a maximum absorption wavelength in the infrared wavelength band.

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