Composite photosensitive structure and manufacturing method thereof

Abstract

To provide a method that forms a filtering film directly on a photosensitive element instead of a traditional filter assembly to reduce the size of the assembled product, where the filtering film can be further processed and shaped to have functions of micro-lens.SOLUTION: Provided are a composite photosensitive element and a method for preparing the composite photosensitive element. The composite photosensitive element includes a photosensitive element and a near-infrared absorption layer formed on the photosensitive element, wherein the near-infrared absorption layer includes a copper complex, and the copper complex is formed from a copper compound used for providing copper ions, phosphoric acid represented by formula 1 herein, and at least one phosphorus-containing compound represented by formulas 2 to 4 herein, wherein the OD value of the near-infrared absorption layer for the incident light wavelength from 930-950 nm is greater than 4.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present disclosure relates to a composite photosensitive structure, and more particularly to a composite photosensitive structure including a photosensitive element and a near-infrared absorbing layer formed thereon. [Background technology]

[0002] Known photosensitive elements generally include components such as microlenses, color filters, photoelectric conversion layers, and driving circuits. A photosensitive element array is fabricated on a wafer using several lithography processes, and then cut into photosensitive elements. The photoelectric conversion layer is sensitive to visible light and also to some near-infrared light. That is, the sensing wavelength range broadly encompasses visible light and some near-infrared light. However, since the electrical signals generated during sensing near-infrared light are considered interference signals and interfere with normal image display, it is desirable to effectively block infrared light entering the photoelectric conversion layer. Conventionally, when assembling photosensitive elements into optical lenses, the goal of blocking near-infrared light has typically been achieved by installing an independent external near-infrared filter on the light incident side.

[0003] However, as demand for higher image quality continues to grow, problems with using external near-infrared filters to block near-infrared rays are gradually becoming apparent. External near-infrared filters not only reduce the amount of light incident on the photoelectric conversion layer due to their insufficient visible light transmittance, but also require space for the external filter, resulting in the optical lens being too large. As a result, current smartphones generally have lenses that protrude outward, even in high-end smartphones, increasing the risk of scratches and damage. With the trend toward smaller and thinner components, the aforementioned limitations have made it difficult for optical lenses equipped with conventional external near-infrared filters to achieve significant progress.

[0004] In addition, in the manufacturing process of a near-infrared absorbing filter, an anti-reflective coating is generally applied after forming a near-infrared absorbing layer. However, the coating process for forming the anti-reflective layer is currently performed at a high temperature of 200 to 300°C, and the organic dye in the near-infrared absorbing layer is easily decomposed or deactivated by the high temperature. Therefore, there are significant limitations on the selection of organic dyes and the adjustment and control of parameters in the coating process. Summary of the Invention

[0005] In response to the above-mentioned problem, the present disclosure provides a composite photosensitive structure including a photosensitive element and a near-infrared absorbing layer formed on the photosensitive element, The near-infrared absorbing layer contains a copper complex, and the copper complex is formed from a copper compound used to supply copper ions, a phosphonic acid represented by the following formula 1, and at least one phosphorus-containing compound represented by the following formulas 2 to 4: TIFF0007827778000001.tif10667 (wherein R, R1, R2, and R3 each independently represent a substituted or unsubstituted C1 to C 12 Alkyl or C6-C 12 It is aryl. The composite photosensitive structure has an OD value of more than 4 for incident light wavelengths of 930 nm to 950 nm of the near-infrared absorbing layer.

[0006] In one embodiment, the photosensitive element is a photosensitive charged-couple device (CCD) or a complementary metal-oxide-semiconductor (CMOS) sensor.

[0007] In one embodiment, substituted or unsubstituted C1-C 12 Alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl, and is a substituted or unsubstituted C-C 12Aryl is selected from the group consisting of phenyl, naphthyl, and chlorophenyl.

[0008] In one embodiment, the haze of the near infrared absorbing layer is 0.4% or less.

[0009] In one embodiment, the X-ray photoelectron spectrum of the near-infrared absorbing layer has at least one main peak when the binding energy is 930 electron volts (eV) to 940 eV. In another embodiment, the X-ray photoelectron spectrum of the near-infrared absorbing layer has at least one main peak with a counts per second value of 4500 or more.

[0010] In one embodiment, the near-infrared absorbing layer has a thickness of 25 μm to 150 μm.

[0011] In one embodiment, the near-infrared absorbing layer further comprises an optical resin that is a thermoplastic resin and / or a photocurable resin. In another embodiment, the optical resin is selected from polycarbonates, polyesters, polycycloolefins, polyacrylic acids, siloxane resins, and polyimides. In another embodiment, the optical resin is methyl methacrylate.

[0012] In one embodiment, the copper compound, the phosphonic acid represented by Formula 1, and at least one of the phosphorus-containing compounds represented by Formulas 2 to 4 are mixed with a solvent to form a dispersion containing a copper complex, and the dispersion is mixed with an optical resin in a mass ratio of 5:1 to 1:1 to form a near-infrared absorbing layer.

[0013] In one embodiment, the photosensitive element includes a plurality of photosensitive areas, and a near-infrared absorbing layer is formed on each of the photosensitive areas, with the boundary line of the near-infrared absorbing layer aligned with or extending beyond the boundary line of the photosensitive area.

[0014] In one embodiment, the near-infrared absorbing layer has opposing first and second surfaces, the second surface contacting the surface of the photosensitive area, and the first surface being flat, convex, or concave.

[0015] In one embodiment, the near-infrared absorbing layer is a microlens.

[0016] The present disclosure also provides a method for manufacturing a composite photosensitive structure, comprising: preparing a copper compound used to supply copper ions, a phosphonic acid represented by the following formula 1, and at least one phosphorus-containing compound represented by formulas 2 to 4, and forming a copper complex-containing coating liquid; TIFF0007827778000002.tif10667 (wherein R, R1, R2, and R3 are each independently substituted or unsubstituted C1 to C 12 Alkyl or C6-C 12 It is aryl. applying the coating solution onto a wafer including a photosensitive element array and curing the coating solution to form a near-infrared absorbing layer; and cutting the wafer to obtain a composite photosensitive structure; The present invention provides a method for producing a near-infrared absorbing layer having an OD value of more than 4 for incident light wavelengths of 930 nm to 950 nm.

[0017] In one embodiment, the photosensitive element is a photosensitive junction element or a complementary metal oxide semiconductor sensor.

[0018] In one embodiment, substituted or unsubstituted C1-C 12 Alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl, and is a substituted or unsubstituted C-C 12 Aryl is selected from the group consisting of phenyl, naphthyl, and chlorophenyl.

[0019] In one embodiment, the haze of the near infrared absorbing layer is 0.4% or less.

[0020] In one embodiment, the X-ray photoelectron spectrum of the near-infrared absorbing layer has at least one main peak when the binding energy is 930 electron volts (eV) to 940 eV. In another embodiment, the X-ray photoelectron spectrum of the near-infrared absorbing layer has at least one main peak with a counts per second value of 4500 or more.

[0021] In one embodiment, the near-infrared absorbing layer has a thickness of 25 μm to 150 μm.

[0022] In one embodiment, the step of forming the copper complex-containing coating liquid includes adding a copper compound, a phosphonic acid, and a phosphorus-containing compound to a solvent and mixing them to form a dispersion. In another embodiment, the mass ratio of the total of the copper compound, the phosphonic acid, and the phosphorus-containing compound to the solvent is 1:5 to 1:1. In another embodiment, the step of forming the copper complex-containing coating liquid further includes mixing the dispersion with an optical resin to form a coating liquid. In yet another embodiment, the mass ratio of the dispersion to the optical resin is 5:1 to 1:1.

[0023] In one embodiment, the optical resin is a thermoplastic resin and / or a photocurable resin. In another embodiment, the optical resin is selected from polycarbonates, polyesters, polycycloolefins, polyacrylic acids, siloxane resins, and polyimides. In another embodiment, the optical resin is methyl methacrylate.

[0024] In one embodiment, the curing step employs photocuring, and the solvent is removed by drying the coating liquid before curing.

[0025] In one embodiment, the method for fabricating the composite photosensitive structure of the present disclosure further comprises patterning the near-infrared absorbing layer by a lithography process.

[0026] The present disclosure first prepares a coating solution capable of forming a near-infrared absorbing layer that efficiently absorbs incident light with wavelengths of 800 nm to 1100 nm, particularly absorbing incident light with wavelengths of 940 nm, and exhibits very high transmittance for visible light. The coating solution is then directly applied to a photosensitive element to form a near-infrared absorbing layer, thereby producing a composite photosensitive structure. The use of an optical lens having the composite photosensitive structure of the present disclosure provides excellent near-infrared blocking effect without the need for a separate external near-infrared filter, significantly reducing the thickness of the optical lens. Furthermore, by performing a lithography process during the formation of the infrared absorbing layer, the near-infrared absorbing layer can be given a specific shape (e.g., a convex lens or a concave lens), allowing the near-infrared absorbing layer to be used as a microlens, further reducing the thickness of the optical lens. [Brief explanation of the drawings]

[0027] [Figure 1] FIG. 1 is a process schematic diagram of a method for fabricating a composite photosensitive structure of the present disclosure. [Figure 2] FIG. 2 is a process schematic diagram of a method for fabricating a composite photosensitive structure of the present disclosure. [Figure 3] FIG. 3 is a process schematic diagram of a method for fabricating a composite photosensitive structure of the present disclosure. [Figure 4] FIG. 4 is a process schematic diagram of a method for fabricating a composite photosensitive structure of the present disclosure. [Figure 5] FIG. 5 is a process schematic diagram of another method for fabricating a composite photosensitive structure of the present disclosure. [Figure 6] FIG. 6 is a process schematic diagram of another method for fabricating a composite photosensitive structure of the present disclosure. [Figure 7] FIG. 7 is a process schematic diagram of another method for fabricating a composite photosensitive structure of the present disclosure. [Figure 8] FIG. 8 shows an X-ray photoelectron spectrum of the near-infrared absorbing layer in Production Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0028] Hereinafter, the embodiments of the present disclosure will be described with reference to specific examples, and those skilled in the art can easily understand the scope and advantages of the present disclosure based on the contents of this specification.

[0029] However, the structures, ratios, sizes, etc. shown in the drawings attached to this specification are intended to facilitate understanding and reading by those skilled in the art in accordance with the contents of the specification and are not intended to limit the conditions for enabling the present disclosure, and therefore have no substantial technical significance. Any structural modifications, changes in ratios, or adjustments in size should be considered to be within the scope of the technical content disclosed in this disclosure, as long as they do not affect the effects and objectives achieved by the present disclosure. At the same time, the terms "upper," "first," "second," etc. used in this specification are used for convenience of explanation only and do not limit the scope of the present disclosure, and therefore, as long as there are no substantial changes in the technical content, any changes or adjustments to their relative relationships should be considered to be within the scope of the present disclosure.

[0030] In this specification, when a particular feature is described as "including," "comprising," or "having," unless otherwise specified, it may include other features such as parts, components, structures, areas, parts, devices, systems, steps, or connection relationships, and does not exclude such other features.

[0031] As used herein, the singular forms "a," "an," and "the" include the plural forms, and the terms "or" and "and / or" are used interchangeably, unless expressly stated otherwise.

[0032] The numerical ranges described herein are inclusive and combinable. Any numerical value included in a range described herein can be used as a minimum or maximum value to derive a further range. For example, a numerical range of "25 to 200" should be understood to include any further range between the endpoints of 25 and 200 (e.g., further ranges of 25 to 150, 30 to 200, 30 to 150, etc.). Furthermore, when a numerical value falls within each range described herein (e.g., between the maximum and minimum values), it should be considered to be within the scope of the present disclosure.

[0033] A first aspect of the present disclosure is a composite photosensitive structure including a photosensitive element and a near-infrared absorbing layer formed on the photosensitive element.

[0034] The photosensitive element is within the scope of the present disclosure as long as it can interact with incident light to generate a signal, including, but not limited to, a photosensitive coupled device (CCD) or a complementary metal oxide semiconductor sensor (CMOS).

[0035] The above-mentioned "formed on the photosensitive element" may specifically mean that the near-infrared absorbing layer is in direct contact with the photosensitive element. That is, all means by which the two can be brought into direct contact are included within the scope of the present disclosure, such as forming a near-infrared absorbing layer precursor on the surface of the photosensitive element and further treating the near-infrared absorbing layer precursor to form a near-infrared absorbing layer, or attaching the near-infrared absorbing layer to the surface of the photosensitive element with or without an adhesive using a pressure-sensitive adhesive, or attaching it to the surface of the photosensitive element without a pressure-sensitive adhesive, etc.

[0036] The near-infrared absorbing layer of the present disclosure includes a copper complex formed from a copper compound used to supply copper ions, a phosphonic acid represented by the following formula 1, and at least one phosphorus-containing compound represented by the following formulas 2 to 4: TIFF0007827778000003.tif10667In the formula, R, R1, R2, and R3 each independently represent a substituted or unsubstituted C1 to C 12 Alkyl or C6-C 12 It is aryl.

[0037] The copper complex has the chemical formula Cu 2+ X, where Cu 2+ is provided by a copper compound and X is provided by a phosphonic acid and / or phosphorus-containing compound.

[0038] The alkyl includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, etc. In addition, the substituted alkyl includes, but is not limited to, haloalkyl, hydroxyalkyl, nitroalkyl, alkoxyalkyl, etc. The aryl includes, but is not limited to, phenyl, naphthyl, etc. In addition, the substituted aryl includes, but is not limited to, haloaryl (e.g., chlorophenyl), nitroaryl, hydroxyaryl, alkoxyaryl, alkylaryl, haloalkylaryl, nitroalkylaryl, and hydroxyalkylaryl.

[0039] In one embodiment, the phosphonic acid is butylphosphonic acid.

[0040] The copper compound used to supply the copper ions is primarily used as a source of copper ions, and any known copper compound capable of supplying copper ions, such as a copper salt, can be used. Examples include copper acetate or copper acetate hydrate, as well as anhydrous or hydrated copper chloride, copper formate, copper stearate, copper benzoate, copper pyrophosphate, copper naphthenate, and copper citrate. In one embodiment, the copper compound used to supply copper ions is copper acetate.

[0041] The phosphorus-containing compound may have a dispersing function, allowing the components in the composition (including the formed copper complex) to be uniformly dispersed without agglomeration. One effect of this function is that the crystallite size in the composition is 100 nm or less, or even between 5 nm and 80 nm, or between 20 nm and 60 nm, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 nm. When the crystallite size is 5 nm or more, sufficient near-infrared absorption properties are exhibited, while when the crystallite size is 100 nm or less, the average particle number of agglomerated particles is small, resulting in low haze in the manufactured product.

[0042] The copper complex of the present disclosure can be produced using a near-infrared absorbing composition. The near-infrared absorbing composition includes the copper compound, phosphonic acid, and phosphorus-containing compound described above, and the components interact and react with each other to form a copper complex. In the present disclosure, the ratio of each component can be adjusted as needed. For example, the amount of copper compound used to provide copper ions in the near-infrared absorbing composition may be 150 parts by mass, examples of which include 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or 150 parts by mass, and the amount of phosphonic acid is 100 parts by mass. The total amount of the phosphorus-containing compounds may be 1 to 90 parts by mass, examples of which include 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 parts by mass, and the total amount of the phosphorus-containing compounds may be 1 to 90 parts by mass, examples of which include 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 parts by mass.

[0043] In one embodiment, the near infrared absorbing composition contains all of the phosphorus-containing compounds represented by Formulas 2 to 4, and the ratio thereof can be adjusted as necessary. For example, in the near infrared absorbing composition, the amount of the phosphorus-containing compound represented by Formula 2 may be 1 to 90 parts by mass, the amount of the phosphorus-containing compound represented by Formula 3 may be 1 to 90 parts by mass, and the amount of the phosphorus-containing compound represented by Formula 4 may be 1 to 90 parts by mass, and among them, the amount of each of the phosphorus-containing compounds represented by Formulas 2 to 4 may be 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 parts by mass. In another embodiment, the ratio of the phosphorus-containing compound represented by Formula 2:the phosphorus-containing compound represented by Formula 3:the phosphorus-containing compound represented by Formula 4 is 20:20:50.

[0044] In one embodiment, the near infrared absorbing composition may be in the form of a dispersion, i.e., further contains a solvent in addition to the copper compound, phosphonic acid, and phosphorus-containing compound. During preparation, the copper compound, phosphonic acid, and phosphorus-containing compound may be added to and mixed in a solvent, and the ratio of these components to the solvent is 1:5 to 1:1, for example, but is not limited to, 1:3.

[0045] The solvent may be selected from known solvents, including, but not limited to, water, alcohols, ketones, ethers, esters, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, etc. Specific examples of the alcohols include methanol, ethanol, and propanol. Examples of the esters include alkyl formates, alkyl acetates, alkyl propionates, alkyl butyrates, alkyl lactates, alkyl alkoxyacetates, 3-alkoxyalkyl propionates, 2-alkoxyalkyl propionates, alkyl 2-alkoxy-2-methylpropionates, alkyl pyruvates, alkyl acetoacetates, and alkyl 2-oxobutyrates. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene and xylene.

[0046] The mixing may be performed by thoroughly stirring at room temperature (for example, 25° C.), for example, but is not limited to, 4 hours or more, 6 hours or more, or 8 hours or more.

[0047] In the present disclosure, a near-infrared absorbing composition in the form of a dispersion is mixed with an optical resin to form a near-infrared absorbing composition in the form of a coating liquid, which is then formed into a near-infrared absorbing layer. The ratio of the dispersion to the optical resin is 5:1 to 1:1 or 3:1 to 1:1, and may be, for example, 0.65:0.35, but is not limited thereto. When a near-infrared absorbing composition in the form of a coating liquid is used, it is applied on a substrate and dried and cured to form a near-infrared absorbing layer.

[0048] The optical resin may be a thermoplastic resin and / or a photocurable resin. In one embodiment, the optical resin is selected from polycarbonates, polyesters, cycloolefin polymers, polyacrylic acids, siloxane resins, and polyimides. In another embodiment, the optical resin is a siloxane resin. In another embodiment, the optical resin is methyl methacrylate.

[0049] In one embodiment, the near-infrared absorbing composition may further include a polymerization initiator, such as a photopolymerization initiator, to polymerize the optical resin upon irradiation with light. Known polymerization initiators may be used, including but not limited to azobisisobutyronitrile. In one embodiment, a solvent may be added to facilitate uniform mixing. Known solvents include, but are not limited to, those described herein. In one embodiment, a curing agent, such as a photocuring agent, may be added to accelerate the curing process, allowing the composition to be cured upon irradiation with light to form a film.

[0050] In one embodiment, an absorbing dye may be included to further improve the optical properties of the near-infrared absorbing layer, for example, to further improve blocking of near-infrared and ultraviolet rays. In one embodiment, the absorbing dye includes a near-infrared absorbing dye and / or an ultraviolet absorbing dye.

[0051] The near-infrared absorbing dyes, such as azo compounds, diimine compounds, dithiophene metal complexes, squaraine compounds, cyanine compounds, and phthalocyanine compounds, can have a maximum absorption wavelength adjusted to 650 to 1100 nm, more specifically, 650 to 750 nm. The ultraviolet absorbing dyes include, for example, azomethine compounds, indole compounds, ketone compounds, benzimidazole compounds, and triazine compounds.

[0052] In one embodiment, in order to maintain better light transmittance, the haze of the near infrared absorbing layer is 0.4% or less, 0.3% or 0.2% or less, for example, 0.4%, 0.35%, 0.3%, 0.25%, 0.2%, 0.19%, 0.18%, 0.17%, 0.16%, 0.15%, 0.14%, 0.13%, 0.12%, 0.11%, or 0.1%.

[0053] The thickness of the near-infrared absorbing layer also affects the near-infrared absorbing properties. Generally, as the thickness of the near-infrared absorbing layer increases, the near-infrared blocking ability also increases, but this does not satisfy the requirement for thinning. On the other hand, as the thickness of the near-infrared absorbing layer decreases, the near-infrared blocking ability also decreases. In an embodiment, the near-infrared absorbing layer of the present disclosure can achieve excellent near-infrared blocking ability even when it has a small thickness. Specifically, the thickness of the near-infrared absorbing layer is between 25 μm and 150 μm, between 50 μm and 150 μm, or between 100 μm and 150 μm, for example, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 146 μm, 147 μm, or 150 μm.

[0054] In one embodiment, the X-ray photoelectron spectrum of the near-infrared absorbing layer of the present disclosure has at least one main peak when the binding energy is 930 eV to 940 eV. In one embodiment, the counts per second of the at least one main peak are 4500 or more, 4600 or more, 4700 or more, 4800 or more, 4900 or more, or 5000 or more.

[0055] In one embodiment, the near-infrared absorbing layer of the present disclosure has a maximum transmittance for incident light in a wavelength range of 930 nm to 950 nm (including 940 nm incident light) of 0.1% or less, less than 0.1%, 0.05% or less, less than 0.05%, 0.01% or less, less than 0.01%, 0.0005% or less, or less than 0.005%, for example, 0.1%, 0.09%, 0.08%, 0.07%, 0.06%, 0.05%, 0.04%, 0.03%, 0.02%, 0.01%, 0.009%, 0.008%, 0.007%, 0.006%, 0.005%, 0.004%, 0.003%, 0.002%, or 0.001%. On the other hand, the OD value of the near-infrared absorbing layer for incident light wavelengths of 930 nm to 950 nm (including 940 nm incident light) is 3 or more, more than 3, 3.5 or more, more than 3.5, 4 or more, more than 4, 4.5 or more, or more than 4.5, for example, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9. In one embodiment, the minimum transmittance of the near-infrared absorbing layer of the present disclosure for incident light wavelengths in the range of 460 nm to 560 nm is 80% or more or 85% or more, for example, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90%.

[0056] In one embodiment, the near-infrared absorbing layer has a pass band overlapping with a wavelength range of 300 nm to 850 nm, 300 nm to 800 nm, or 350 nm to 750 nm, and the center wavelength of the pass band is within a wavelength range of 300 nm to 850 nm, 300 nm to 800 nm, 350 nm to 750 nm, 400 nm to 700 nm, 450 nm to 650 nm, 500 nm to 600 nm, or 500 nm to 550 nm. In this specification, the term "pass band" refers to a domain in which the transmittance of incident light within a wavelength range is 50% or more, and the term "center wavelength of the pass band" refers to the average value of two wavelengths of incident light when the transmittance of the incident light is 50%.

[0057] In one embodiment, when incident light is incident on the near-infrared absorbing layer of the present disclosure at incident angles of 0 degree and 30 degree, respectively, the center wavelength of the pass band shifts by 1.4 nm or less, for example, 1.4 nm, 1.3 nm, 1.2 nm, or 1.1 nm. In one embodiment, when incident light is incident on the near-infrared absorbing layer of the present disclosure at incident angles of 0 degree and 35 degree, respectively, the center wavelength of the pass band shifts by 1.9 nm or less, for example, 1.9 nm, 1.8 nm, or 1.7 nm.

[0058] In the composite photosensitive structure of the present disclosure, the photosensitive element may include multiple photosensitive areas, and a near-infrared absorbing layer may be formed on each photosensitive area. For example, if the photosensitive element is an uncut wafer having multiple photosensitive units, the photosensitive units refer to the photosensitive areas described herein, and the near-infrared absorbing layer may be formed on the entire wafer surface and further processed. More specifically, the near-infrared absorbing layer may contact multiple photosensitive units. In one embodiment, the boundaries of the near-infrared absorbing layer are aligned with or extend beyond the boundaries of the photosensitive areas, so that infrared light is blocked by the near-infrared absorbing layer and does not leak into the underlying photosensitive areas.

[0059] In one embodiment, the near-infrared absorbing layer of the composite photosensitive structure of the present disclosure has opposing first and second surfaces, the second surface of the near-infrared absorbing layer contacting the surface of the photosensitive area, and the first surface of the near-infrared absorbing layer being flat, convex, or concave. The first surface of the near-infrared absorbing layer may be processed, for example, by etching, laser cutting, grinding, or a photolithography process, and the processing may be performed before, during, or after the near-infrared absorbing layer is formed on the photosensitive area. The term "convex" refers to the first surface protruding outward relative to the second surface. The term "concave" refers to the first surface inwardly recessed relative to the second surface. In one embodiment, the first surface of the near-infrared absorbing layer is the light incident surface, and the near-infrared absorbing layer functions as a microlens by converging or diverging light through the first surface.

[0060] A second aspect of the present disclosure is a method for manufacturing a composite photosensitive structure, comprising: preparing a copper compound used to supply copper ions, a phosphonic acid represented by Formula 1, and at least one phosphorus-containing compound represented by the following Formulas 2 to 4, and forming a copper complex-containing coating liquid; TIFF0007827778000004.tif10667 (wherein R, R1, R2, and R3 are each independently substituted or unsubstituted C1 to C 12 Alkyl or C6-C 12 It is aryl. applying the coating solution onto a wafer including a photosensitive element array and curing the solution to form a near-infrared absorbing layer; and and cutting the wafer to obtain a composite photosensitive structure.

[0061] Specific implementation means are shown in Figures 1 to 4. First, a copper compound, phosphonic acid, and phosphorus-containing compound used to supply copper ions are prepared, and then these are mixed with a solvent to form a dispersion. For example, the mixing here can be performed by first mixing the copper compound with a solvent to form a first mixture, separately mixing the phosphorus-containing compound with a solvent to form a second mixture, and then mixing the first and second mixtures, followed by further mixing with phosphonic acid to form a dispersion. Here, a copper complex is formed in the dispersion due to the reaction and interaction of the components.

[0062] To form a coating solution, the dispersion is further mixed with an optical resin, said optical resin being as described in the first aspect herein.

[0063] In one embodiment, the dispersion is first dried to a powder, and then the powder is added to a second solvent to form a dispersion, which is then mixed with an optical resin. The second solvent may be selected from the solvents described in the first aspect of this specification.

[0064] When an absorbing dye is added, the absorbing dye is added to the dispersion liquid or coating liquid as needed. For example, the absorbing dye is added to the dispersion liquid before mixing with the optical resin, mixed with the optical resin together with the dispersion liquid, or added to the coating liquid after mixing the dispersion liquid and the optical resin.

[0065] As shown in FIG. 1, the coating liquid 20 is applied onto a wafer 10 including a photosensitive element array (including a plurality of photosensitive areas 11). If necessary, before or after application, air bubbles may be removed from the coating liquid by, for example, ultrasonic vibration, placing the wafer in a negative pressure environment, or both. The method for applying the coating is not limited herein, and the coating may be performed by, for example, spin coating, spray coating, blade coating, roller coating, dipping, or the like.

[0066] Next, the coating liquid is cured to form a near-infrared absorbing layer. As shown in Fig. 2, photocuring can be used for curing, and the coating liquid is irradiated from a light source L to form a near-infrared absorbing layer 21 on the entire surface of the wafer 10.

[0067] Also, as shown in Figures 3 and 4, the wafer 10 is cut with a cutting tool C such as a laser or a diamond knife to obtain a composite photosensitive structure 1 having a photosensitive element 12 and a near-infrared absorbing layer 21 formed thereon.

[0068] 5 to 7 show another specific embodiment of the method for manufacturing a photosensitive structure. Compared with FIGS. 1 to 4, a process of patterning the near-infrared absorbing layer is further implemented. The processes shown in FIGS. 5 to 7 follow on from FIG. 1 and correspond to FIGS. 2 to 4, respectively. FIG. 5 differs from FIG. 2 in that a lithography process is further implemented. Specifically, a photomask M, such as a grayscale mask, is placed and the coating liquid underneath is selectively exposed to obtain near-infrared absorbing layers 21', 21" having a specific pattern or a specific shape. The "specific pattern or specific shape" can refer to a protrusion or depression of the first surface of the near-infrared absorbing layer, as shown in FIGS. 6 and 7.

[0069] In one embodiment, the coating solution on the entire surface of the wafer forms independent patterned near-infrared absorbing layers on positions corresponding to the photosensitive areas 11, such as near-infrared absorbing layers 21′ and 21″ shown in FIGS. 6 and 7. Here, the term “independent” specifically refers to the absence of contact between any two adjacent infrared absorbing layers, which can be achieved by the lithography process.

[0070] In one embodiment, the coating is dried (eg, dried at 120° C.) to remove the solvent before curing.

[0071] The present disclosure will be further described in detail with reference to the following specific examples, which are not intended to limit the scope of the disclosure. (Example)

[0072] Manufacturing Example 1 - Near-infrared absorbing layer 150 parts by weight of copper acetate and 15,000 parts by weight of ethanol were mixed and stirred at room temperature for 1.5 hours to form a first mixture. Separately, 20 parts by weight of a phosphorus-containing compound represented by Formula 2 (Plysurf A242G, purchased from Nippon Daiichi Kogyo Seiyaku Co., Ltd.), 20 parts by weight of a phosphorus-containing compound represented by Formula 3 (Plysurf W542C, purchased from Nippon Daiichi Kogyo Seiyaku Co., Ltd.), and 50 parts by weight of a compound represented by Formula 4 (Plysurf A285C, purchased from Nippon Daiichi Kogyo Seiyaku Co., Ltd.) were mixed with 1,500 parts by weight of ethanol to form a second mixture. The first mixture and the second mixture were mixed and stirred at room temperature for 1 hour. Subsequently, 100 parts by weight of butylphosphonic acid was added and the mixture was stirred at room temperature for 3 hours to allow the mixture to react. The mixture was then placed in an oven at 85°C and left for 12 hours to obtain a powder. The powder and xylene were mixed in a mass ratio of 1:3 to form a dispersion, and the dispersion and methyl methacrylate (MMA) were mixed in a mass ratio of 0.65:0.35 to form a coating liquid, which was then applied to a substrate and baked at 70°C for 30 minutes to obtain a near-infrared absorbing layer.

[0073] The near-infrared absorbing layer was analyzed by X-ray photoelectron spectroscopy (ESCA / XPS). The X-ray photoelectron spectrum is shown in FIG. 5. When the binding energy is 930 eV to 940 eV, a characteristic peak associated with a copper complex (Cu(PO x ) y , CuO, Cu2O, Cu(OH)2) have been observed. Note that the peak that appears when the binding energy is 940 eV or higher is a satellite peak.

[0074] Example 1 A dispersion and coating solution were prepared according to the method of Preparation Example 1, but 0.5 g of azobisisobutyronitrile (AIBN) as a photopolymerization initiator and an appropriate amount of propylene glycol monomethyl ether (PGME) as a solvent were further added to the coating solution. Next, air bubbles were removed by ultrasonic vibration under a negative pressure environment, and the solution was then spin-coated onto a wafer with a photosensitive element array. The solvent was removed by baking at 120°C, and the coating layer was irradiated with ultraviolet light to form a near-infrared absorbing layer on the surface of the photosensitive element array. Finally, the wafer was cut with a laser to obtain a composite photosensitive structure.

[0075] Example 2 A near-infrared absorbing layer was formed on the wafer having the photosensitive element array in the same manner as in Example 1, except that after the spin coating process and before UV irradiation, a grayscale mask was placed on the wafer and the coating solution was selectively exposed to the mask. This formed a patterned near-infrared absorbing layer on the surface of the photosensitive element array, resulting in a composite photosensitive structure.

[0076] The above-described embodiments and specific examples do not limit the present disclosure, and the described technical features and approaches can be combined with each other. The present disclosure can also be implemented or applied in other different embodiments. Various changes and modifications can be made to the details described in this specification according to different viewpoints and applications without departing from the present disclosure. [Explanation of symbols]

[0077] 1,1': Composite photosensitive structure 10: Wafer 11: Photosensitive area 12: Photosensitive element 20: Coating liquid 21, 21', 21": near-infrared absorbing layer C: Cutting device L:Light source M: Photomask

Claims

1. A composite photosensitive structure including a photosensitive element and a near-infrared absorbing layer formed on the photosensitive element, The near-infrared absorbing layer includes a copper complex, and the copper complex is formed from a copper compound used to supply copper ions, a phosphonic acid represented by the following formula 1, and at least one phosphorus-containing compound represented by the following formulas 2 to 4: (In the formula, R, R １ , R ２ , R ３ are each independently a substituted or unsubstituted C １ ~C １２ Alkyl or C ６ ~C １２ It is aryl. the near-infrared absorbing layer has an OD value of greater than 4 for incident light wavelengths of 930 nm to 950 nm;

2. 2. The composite photosensitive structure according to claim 1, wherein the photosensitive element is a photosensitive junction element or a complementary metal oxide semiconductor sensor.

3. The substituted or unsubstituted C １ ~C １２ The alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl, and the substituted or unsubstituted C ６ ~C １２ 2. The composite photosensitive structure of claim 1, wherein aryl is selected from the group consisting of phenyl, naphthyl, and chlorophenyl.

4. 2. The composite photosensitive structure of claim 1, wherein the near-infrared absorbing layer has a haze of 0.4% or less.

5. 2. The composite photosensitive structure of claim 1, wherein the X-ray photoelectron spectrum of the near-infrared absorbing layer has at least one main peak when the binding energy is between 930 electron volts (eV) and 940 eV.

6. 6. The composite photosensitive structure of claim 5, wherein the value of the counts per second of the at least one main peak is 4500 or more.

7. 2. The composite photosensitive structure of claim 1, wherein the near-infrared absorbing layer has a thickness of 25 μm to 150 μm.

8. 2. The composite photosensitive structure of claim 1, wherein the photosensitive element includes a plurality of photosensitive areas, the near-infrared absorbing layer is formed on each of the photosensitive areas, and a boundary line of the near-infrared absorbing layer is aligned with or exceeds a boundary line of the photosensitive area.

9. 2. The composite photosensitive structure of claim 1, wherein the near-infrared absorbing layer has a first surface and a second surface opposite to each other, the second surface contacting the surface of the photosensitive area, and the first surface being a flat surface, a convex surface, or a concave surface.

10. 10. The composite photosensitive structure according to claim 9, wherein the near-infrared absorbing layer is a microlens.

11. A method for manufacturing the composite photosensitive structure according to any one of claims 1 to 10, comprising the steps of: preparing a copper compound used to supply copper ions, a phosphonic acid represented by Formula 1, and at least one phosphorus-containing compound represented by Formula 2 to Formula 4, and forming a copper complex-containing coating liquid; (In the formula, R, R １ , R ２ , R ３ are each independently substituted or unsubstituted C １ ~C １２ Alkyl or C ６ ~C １２ It is aryl. applying the copper complex-containing coating solution onto a wafer including a photosensitive element array and curing the solution to form a near-infrared absorbing layer; and cutting the wafer to obtain a composite photosensitive structure; The near-infrared absorbing layer has an OD value of more than 4 for incident light wavelengths of 930 nm to 950 nm.

12. The method of claim 11 , wherein the photosensitive element is a photosensitive junction element or a complementary metal oxide semiconductor sensor.

13. The substituted or unsubstituted C1 to C １２ The alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl, and the substituted or unsubstituted C ６ ~C １２ The process according to claim 11, wherein aryl is selected from the group consisting of phenyl, naphthyl, and chlorophenyl.

14. The method according to claim 11 , wherein the near-infrared absorbing layer has a haze of 0.4% or less.

15. The method according to claim 11, wherein the X-ray photoelectron spectrum of the near-infrared absorbing layer has at least one main peak when the binding energy is 930 electron volts (eV) to 940 eV.

16. The method of claim 15, wherein the value of the number of counts per second of the at least one main peak is 4500 or more.

17. The method according to claim 16, wherein the near-infrared absorbing layer has a thickness of 25 μm to 150 μm.

18. The method according to claim 11 , wherein the curing is photocuring, and the solvent is removed by drying the copper complex-containing coating liquid before curing.

19. The method of claim 11 , further comprising patterning the near-infrared absorbing layer by a lithography process.

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