CN114047668A - Colored resin composition, method for producing the same, and method for producing resist structure - Google Patents
Colored resin composition, method for producing the same, and method for producing resist structure Download PDFInfo
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- CN114047668A CN114047668A CN202111295510.2A CN202111295510A CN114047668A CN 114047668 A CN114047668 A CN 114047668A CN 202111295510 A CN202111295510 A CN 202111295510A CN 114047668 A CN114047668 A CN 114047668A
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- 239000011342 resin composition Substances 0.000 title claims abstract 22
- 238000004519 manufacturing process Methods 0.000 title claims 7
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract 11
- 239000003999 initiator Substances 0.000 claims abstract 10
- 239000007787 solid Substances 0.000 claims abstract 10
- 238000010521 absorption reaction Methods 0.000 claims abstract 9
- 239000011347 resin Substances 0.000 claims abstract 8
- 229920005989 resin Polymers 0.000 claims abstract 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract 6
- 229910052753 mercury Inorganic materials 0.000 claims abstract 6
- 150000001875 compounds Chemical class 0.000 claims abstract 5
- 230000035515 penetration Effects 0.000 claims abstract 5
- 239000007858 starting material Substances 0.000 claims abstract 5
- 239000003086 colorant Substances 0.000 claims abstract 4
- 239000002904 solvent Substances 0.000 claims abstract 4
- 230000005540 biological transmission Effects 0.000 claims abstract 3
- 239000000758 substrate Substances 0.000 claims 7
- 239000011248 coating agent Substances 0.000 claims 3
- 238000000576 coating method Methods 0.000 claims 3
- 238000000034 method Methods 0.000 claims 2
- 239000000178 monomer Substances 0.000 claims 1
- 229920001187 thermosetting polymer Polymers 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract 1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Polymerisation Methods In General (AREA)
- Materials For Photolithography (AREA)
Abstract
The present disclosure provides a colored resin composition having a transmittance T%, which comprises an initiator, a colorant, an alkali-soluble resin, a polymerizable unsaturated compound, and a solvent. The solid content of the starter is S% and has an absorption value A%. The relationship between the absorption value, the solid content, the penetration value and the illuminance E% of the mercury lamp light source corresponds to the following formula: sigma(initiator){∫360‑460nm[ absorption value of initiator (A%) × transmission value of colored resin composition (T%) × illuminance of light source (E%)]Solid content (S%) of x initiator is ≧ 20, and illuminance E% of the light source is 100% when light with a wavelength of 365nm is emitted from the mercury lamp light source. According to the present disclosureThe color resin composition forms a photoresist structure having acceptable or good integrity of the overall and edge profiles.
Description
Technical Field
The present disclosure relates to a composition and a method for manufacturing the same, and more particularly, to a colored resin composition and a method for manufacturing the same, and a method for manufacturing a photoresist structure.
Background
Display devices have been commonly used in everyday life, including devices for various portable or non-portable electronic products, workplaces, smart appliances, or vehicles. Photoresists play an important role in display devices. Taking a color liquid crystal display device as an example, a color filter is one of the means for making the display device full-color and further improving its added value. The color filter generates three primary colors of red (R), green (G) and/or blue (B) by filtering, and mixes the three primary colors in different intensity ratios to present various colors. The colored resin composition is the main raw material of a Color Filter (Color Filter). The color filter is made by coating 3 colors of red, green and/or blue (RGB) on a glass substrate with a specific pattern.
In order to match various types of display applications, the composition of the colored resin composition can be adjusted and optimized to achieve the formation of various color filters with predetermined characteristics, including the formation of photoresist structures with less undercut and complete profile, which is also one of the goals of attention and efforts in the industry. However, the photoresist structure formed on the substrate by the current colored resin composition is still easy to have a large undercut or even a too deep undercut, thereby generating the problems of local peeling or incomplete profile.
Disclosure of Invention
Some embodiments of the present disclosure disclose a colored resin composition having a transmittance T% comprising an initiator, a colorant, an alkali-soluble resin, a polymerizable unsaturated compound, and a solvent. The solid content of the starter is S% and has an absorption value A%. The relationship between the absorption value, the solid content, the penetration value and the illuminance E% of the mercury lamp light source corresponds to the following formula:
Σ(initiator){∫360-460nm[ absorption value of initiator (A%) × transmission value of colored resin composition (T%) × illuminance of light source (E%)][ solid content of initiator ] } × 10000 ≧ 20,
wherein the illuminance E% of the light source is 100% when the mercury lamp light source emits light with a wavelength of 365 nm.
In some embodiments, the solid content of the starter can range between 1.0 and 10.0% by weight.
In some embodiments, the colored resin composition may further comprise a functional additive, wherein the content of the functional additive may be less than 1 wt% based on 100 wt% of the total weight of the colored resin composition.
In some embodiments, the alkali soluble resin may comprise a photocurable resin, a thermosetting resin, or a combination thereof.
In some embodiments, the alkali-soluble resin may be present in an amount ranging from 1 to 20 wt% based on 100 wt% of the total weight of the colored resin composition.
In some embodiments, the polymerizable unsaturated compound may comprise a photopolymerizable monomer.
In some embodiments, the content of the polymerizable unsaturated compound may be in a range of 10 to 30 wt% based on 100 wt% of the total weight of the colored resin composition.
Some embodiments of the present disclosure disclose a method for manufacturing a colored resin composition, comprising: preparing alkali soluble resin; and mixing the alkali-soluble resin with a colorant, a polymerizable unsaturated compound, a solvent, and an initiator to obtain the colored resin composition. The initiator has an absorption value A% and a solid content S%, the coloring resin composition has a penetration value T%, and the relationship between the absorption value, the solid content, the penetration value and the light source illuminance E% of the mercury lamp light source conforms to the following formula:
Σ(initiator){∫360-460nm[ absorption value of initiator (A%). times.transmittance value of colored resin composition (T%). times.illuminance of light source (E%)]The solid content (S%) of the x initiator is ≧ 20 × 10000,
wherein the illuminance E% of the light source is 100% when the mercury lamp light source emits light with a wavelength of 365 nm.
Some embodiments of the present disclosure disclose a method for fabricating a photoresist structure, comprising: providing a substrate; forming a coating on the substrate, wherein the coating comprises the colored resin composition; baking the coating layer at a temperature below 150 ℃ to form a photoresist layer; and performing exposure and development processes on the photoresist layer to form a photoresist structure.
In some embodiments, the photoresist structure is a protrusion having a bottom surface contacting the substrate, a top surface opposite to the bottom surface, and a side edge connecting the top surface and the bottom surface, wherein an angle between the side edge and the bottom surface is less than 95 ° when viewed from a cross-section of the protrusion.
In some embodiments, the photoresist structure is a protrusion having a bottom surface contacting the substrate and a top surface opposite the bottom surface, wherein the area of the top surface is less than the area of the bottom surface.
In some embodiments, the photoresist structure is a convex body having a bottom surface contacting the substrate and a top surface opposite to the bottom surface, a projection of the top surface on the substrate has a first projected edge and a projection of the bottom surface on the substrate has a second projected edge corresponding to the first projected edge, wherein the first projected edge and the second projected edge are separated by an undercut depth, and the undercut depth is less than or equal to 0 μm.
Compared with the prior art, the overall and edge profiles of the photoresist structure formed by the colored resin composition have acceptable or good integrity. Therefore, the display device with the photoresist structure can avoid the exposure defect generated by the pixel of the display device due to the local falling of the photoresist, and can also greatly improve the problem that the number of the photoresist defects is over high due to the uneven bright and dark lines generated by the defective photoresist.
Drawings
FIG. 1 is a cross-sectional view of a photoresist structure formed on a substrate by a conventional colored resin composition;
FIG. 2 is a flow chart illustrating a method of fabricating a photoresist structure according to an embodiment of the present disclosure;
FIGS. 3A-3D are schematic cross-sectional views illustrating stages in a method of fabricating a photoresist structure according to an embodiment of the disclosure;
FIGS. 4-13 are SEM images of photoresist structures according to examples and comparative examples of the present disclosure;
wherein, the notation:
10,20 substrate 13,23 photoresist structure
13t,23t top surface 13b,23b bottom surface
13s,23s lateral edges 13bs,23bs second projected edge
13ts,23ts first projected edge 21 coating
23' photoresist layer 200, manufacturing method
S201-S207 step d0 undercut depth.
Detailed Description
It will be further understood that the terms "comprises," "comprising," "includes" and/or "including," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, components, and/or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. When the singular forms "a" and "an" are used in this specification, the plural forms are intended to be included unless the context clearly dictates otherwise.
In addition, unless explicitly stated otherwise, numerical values associated with a particular component are to be construed as including a range of tolerances in the interpretation of the component.
The expression "a-b" as used herein to denote a particular numerical range is defined as ". gtoreq.a.ltoreq.b".
The photoresist composition is a radiation-sensitive compound mainly comprising a resin material as an adhesive (Binder), a solvent as a diluent liquid capable of dissolving other materials/compounds, an initiator and a photosensitizer, so that the photoresist composition is in a liquid form for convenient use. Generally, photoresist compositions can be classified into positive photoresist compositions and negative photoresist compositions. After the positive photoresist composition is irradiated with light, the exposed portions can be removed by dissolving with a chemical (a stripper or a developer), leaving the pattern of the unexposed portions. Negative photoresist compositions are the opposite of positive photoresist, and after the negative photoresist composition is irradiated with light, the unexposed portions can be dissolved away by a chemical (a stripper or a developer) to leave a pattern of exposed portions. The following description relates to negative photoresist compositions as photoresist materials in some embodiments of the present disclosure.
In the manufacturing method of the photoresist structure, in the conventional photoresist structure, in the photoresist process, especially in the low temperature photoresist process in which the process temperature is lower than the polymer glass transition temperature (Tg) after the photoresist is cured, the bottom sensitivity of the photoresist is insufficient along with the decrease of the light penetration, so that the bottom of the photoresist structure close to the substrate has insufficient cross-linking (Crosslink) and has a certain undercut (undercut) depth. FIG. 1 is a cross-sectional view of a photoresist structure 13 formed on a substrate 10 by a conventional colored resin composition. As shown in fig. 1, the photoresist structure 13 has a bottom surface 13b contacting the substrate 10, a top surface 13t opposite to the bottom surface 13b, and a side edge 13s connecting the top surface 13t and the bottom surface 13b, wherein the side edge 13s and the bottom surface 13b form an included angle α. As shown in fig. 1, the area of the top surface 13t > the area of the bottom surface 13b, and the included angle α > 90 °. Further, the projection of the top surface 13t on the substrate 10 has a first projected edge 13ts and the projection of the bottom surface 13b on the substrate 10 has a second projected edge 13 bs. The first projected edge 13ts is located at a distance from the second projected edge 13bs, which is defined as an undercut depth d 0. If the undercut depth d0 is too deep (too large), the photoresist may be peeled off during the developing process (Peeling), which may cause the pixels of the display device to be exposed, or the defect number of the photoresist may be determined by the inspection machine to be too high due to the uneven bright and dark lines.
In order to meet the above requirements, embodiments of the present disclosure provide a colored resin composition capable of improving the undercut problem after forming a photoresist structure by using a conventional colored resin composition in a photoresist process, particularly a low temperature photoresist process, a photoresist structure formed by using the colored resin composition, and a method for forming a photoresist structure.
One aspect of the present disclosure relates to a colored resin composition, which includes an initiator, a colorant, an alkali-soluble resin, a polymerizable unsaturated compound, and a solvent. The solid content of the starter is S% and has an absorption value A%. The relationship between the absorption value, the solid content, the penetration value and the illuminance E% of a mercury lamp light source corresponds to the following formula:
Σ(initiator){∫360-460nm[ absorption value of initiator (A%) [ transmission value of colored resin composition (T%) [ illuminance of light source (E%)]Solid content (S%) of the initiator > 10000 ≧ 20,
wherein the illuminance E% of the light source is 100% when the mercury lamp light source emits light with a wavelength of 365 nm.
The absorption value A% of the initiator is obtained by dissolving the initiator in 0.001 wt% of Propylene Glycol Monomethyl Ether Acetate (PGMEA), loading the initiator into a quartz cell (cell), and measuring with a UV/VIS UV/visible spectrometer, and the transmittance value T% of the colored resin composition is obtained by preparing the colored resin composition into a color chip and measuring with a UV/VIS UV/visible spectrometer. The illuminance (cumulative/per-second standard value) E% of the light source is obtained by measuring the spectrum of the mercury lamp light source by placing a spectrum spectrometer under the mercury lamp light source and normalizing (normalizing) the illuminance at 365nm of the light in the spectrum as 100%.
Examples of the initiator are not particularly limited as long as they conform to the above formula. By selecting the initiator according to the above formula, the colored resin composition can have less difference in the degree of crosslinking between the upper part (farther from the substrate) and the lower part (closer to the substrate) of the photoresist layer formed on the substrate, thereby reducing the difference in strength between the upper part and the lower part of the crosslinked composition. Therefore, the coloring resin composition disclosed by the invention can be coated on a substrate and has similar lateral erosion resistance on the upper part and the lower part of a photoresist layer formed after a photoetching process, and a photoresist structure with complete shape and no undercut over-depth defect is obtained after a developing process. Examples of the initiator may include, but are not limited to, oxime ester compounds, alkylthioxanthone compounds, alkylphenone compounds, bisimidazole compounds, triazine compounds, acylphosphine oxide (acyl phosphine oxide), benzoin compounds, diphenylketone compounds, quinone compounds, 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, acetophenone (acetophenone), cyclopentadienyl titanium (titanocene) compounds, and any combination thereof. In one embodiment, the initiator comprises at least one selected from the group consisting of: oxime ester compounds, alkylthioxanthone compounds, alkylphenone compounds, bisimidazole compounds, acetophenone compounds, triazine compounds, acylphosphine oxide compounds, bisimidazole compounds, and any combination thereof. In one embodiment, the initiator may be an oxime ester compound or an alkylthioxanthone compound. In some embodiments, the solid content S% of the starter ranges from 1.0 to 10.0%, from 1.5 to 8.0%, or from 1.94 to 5.71% by weight.
In an embodiment, the alkali soluble resin may comprise a photocurable resin, a thermosetting resin, or a combination thereof. In some embodiments, the alkali-soluble resin is a binder. By including one or more alkali-soluble resins, the colored resin composition of the present disclosure can be smoothly attached to the substrate surface after exposure and development, and effectively provide resistance against erosion by acids, alkalis, or plasmas.
In some embodiments, the content of the alkali-soluble resin can range from 1 to 20 wt%, from 5 to 15 wt%, or from 8 to 12 wt%, based on 100 wt% of the total weight of the colored resin composition.
According to some embodiments, the polymerizable unsaturated compound of the colored resin composition may be a monomer that is polymerized by a reactive radical and/or an acid generated from a photopolymerization initiator, including but not limited to an ethylenically unsaturated bond having polymerizability, such as a (meth) acrylate compound. Herein, the use of a compound described in parentheses is meant to include the presence and absence of the parenthetical letters, such as the case of (meth) acrylate compounds, the case of acrylate compounds, and methacrylate compounds. The polymerizable unsaturated compound may also be referred to as a polymerizable compound.
In some embodiments, the polymerizable unsaturated compound may comprise a photopolymerizable monomer, which may include, but is not limited to, at least one selected from the group consisting of: polymerizable compounds having one ethylenically unsaturated bond such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolone; polymerizable compounds having two ethylenically unsaturated bonds such as 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate; and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and mixtures thereof, Polymerizable compounds having three ethylenically unsaturated bonds such as caprolactone hexa (meth) acrylate-modified dipentaerythritol ester; and any combination thereof. In some embodiments, the polymerizable unsaturated compound is, for example, a compound having an ethylenically unsaturated double bond. In some embodiments, the polymerizable unsaturated compound comprises a polymerizable compound having three ethylenically unsaturated double bonds. In one embodiment, the polymerizable unsaturated compound may comprise dipentaerythritol hexa (meth) acrylate.
In some embodiments, the content of the polymerizable unsaturated compound may be in a range of 10 to 30 wt%, 15 to 25 wt%, or 18 to 22 wt% based on 100 wt% of the total weight of the colored resin composition.
In some embodiments, the solvent of the colored resin composition may include, but is not limited to, at least one selected from the group consisting of: an ester solvent (herein, it means a solvent containing-COO-but not-O-in the molecule), an ether solvent (herein, it means a solvent containing-O-but not-COO-in the molecule), an ether ester solvent (herein, it means a solvent containing-COO-and-O-in the molecule), a ketone solvent (herein, it means a solvent containing-CO-but not-COO-in the molecule), an alcohol solvent (herein, it means a solvent containing OH but not-O-, -CO-, and-COO-in the molecule), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, and any combination thereof.
Examples of ester solvents may include, but are not limited to, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ -butyrolactone. Examples of ether solvents may include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole. Examples of ketone solvents may include, but are not limited to, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, Cyclohexanone (CHN), and isophorone. Examples of alcoholic solvents may include, but are not limited to, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol. Examples of the aromatic hydrocarbon solvent may include, but are not limited to, benzene, toluene, xylene, 1,3, 5-trimethylbenzene, and the like. Examples of amide solvents may include, but are not limited to, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidinone.
In some embodiments, the solvent may be selected from the group consisting of Propylene Glycol Monomethyl Ether Acetate (PGMEA), ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone, N-dimethylformamide, and any combination thereof, from the viewpoint of coatability, drying property, and the like. In one embodiment, the solvent may comprise propylene glycol monomethyl ether acetate.
In some embodiments, the content of the solvent may be in a range of 3 to 95 wt%, 40 to 60 wt%, or 43 to 50 wt% based on 100 wt% of the total weight of the colored resin composition. When the content of the solvent is within the above range, the flatness at the time of coating can be improved, thereby improving the display characteristics.
In some embodiments, the colorant of the colored resin composition may comprise a pigment and a dye.
According to some embodiments, The pigment is not particularly limited, and an organic pigment or any known pigment, such as a compound classified as a pigment (pigment) in The Society of Dyers and Colourists publication, may be used. Examples of pigments may include, but are not limited to, c.i. pigment red R9, R97, R105, R122, R123, R144, R149, R166, R168, R175, R176, R177, R179, R180, R192, R209, R215, R216, R224, R242, R254, R255, R264, R265; c.i. pigment yellow Y3, Y12, Y13, Y14, Y15, Y16, Y17, Y20, Y24, Y31, Y53, Y83, Y86, Y93, Y94, Y109, Y110, Y117, Y125, Y128, Y137, Y138, Y139, Y147, Y148, Y150, Y153, Y154, Y166, Y173, Y194, Y214; c.i. pigment blue B15, B15: 3. b15: 4. b15: 6. b60, B80, B16; c.i. pigment orange O13, O31, O36, O38, O40, O42, O43, O51, O55, O59, O61, O64, O65, O71, O73; c.i. pigment violet P1, P19, P23, P29, P32, P36, P38; c.i. pigment green G1, G2, G4, G7, G8, G10, G13, G14, G15, G17, G18, G19, G26, G36, G45, G48, G50, G51, G54, G55, G58, G59; or any combination thereof.
According to some embodiments, The dye of The colorant is not particularly limited, and any known dye may be used, such as solvent dyes, acid dyes, direct dyes, mordant dyes, compounds classified as substances having a hue other than pigments in The color index (published by The Society of Dyers and Colourists), and/or known dyes described in dyeing notes (Dyers). Examples of dyes may include, but are not limited to, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squaraine dyes, acridine dyes, styryl dyes, coumarin dyes, cyanine dyes, anthraquinone dyes, azo dyes, squaraine dyes, dipyrromethene dyes, quinoline dyes, porphyrin dyes, quinoline dyes, nitro dyes, or any combination thereof.
In some embodiments, the colorant can be present in an amount ranging from 15 to 55 wt%, from 20 to 55 wt%, or from 22 to 53 wt%, based on 100 wt% of the total colored resin composition.
In one embodiment, the colored resin composition may further comprise a functional additive. Examples of functional additives may include, but are not limited to, antioxidants, surfactants, leveling agents, fillers, photostabilizers, and chain transfer agents. When the coloring resin composition contains the functional additive, the content of the functional additive is less than 1 wt% based on 100 wt% of the total weight of the coloring resin composition.
Another aspect of the present disclosure relates to a photoresist structure and a method for fabricating the same. The photoresist structure of the present disclosure can be formed by the above-mentioned colored resin composition by the manufacturing method of the photoresist structure of the present disclosure. The photoresist structure and the method for fabricating the same according to the present disclosure are further described with reference to fig. 2 to 3D.
FIG. 2 is a flow chart illustrating a method 200 of fabricating a photoresist structure according to an embodiment of the present disclosure. Fig. 3A-3D are schematic cross-sectional views illustrating stages of a method 200 for fabricating a photoresist structure according to an embodiment of the disclosure.
Referring to fig. 2 and fig. 3A together, the manufacturing method 200 provides the substrate 20 in step S201. The material used to form the substrate 20 is not particularly limited. Examples of substrates may include, but are not limited to, silicon substrates, metal substrates, glass substrates, polyimide substrates, or sapphire substrates. Step S201 may include performing a cleaning process on the substrate 20 to remove impurities on the substrate 20, thereby increasing adhesion between the substrate 20 and a coating layer subsequently formed thereon, and avoiding defects or peeling of the finally obtained photoresist structure.
Next, referring to fig. 2 and 3B, a coating layer 21 including the above-described colored resin composition is formed on the substrate 20 in step S203. Any method may be used to form the coating 21 on the substrate 20. The method for forming the coating layer 21 is not particularly limited, and examples thereof may include, but are not limited to, an inkjet process, a coating process, a transfer process, or a screen printing process.
Referring to fig. 2 and 3C, in step S205, the coating layer 21 is baked at a temperature of less than 150 ℃ to form a photoresist layer 23'. In some embodiments, the polymer glass transition temperature (Tg) of the photoresist layer 23 'is greater than or equal to 150 ℃, and in one embodiment, the polymer glass transition temperature (Tg) of the photoresist layer 23' is in a range of 150 to 200 ℃, but the disclosure is not limited thereto.
Referring to fig. 2 and 3D, in step S207, an exposure and development process is performed to form a photoresist structure 23. As shown in fig. 3D, the photoresist structure 23 has a bottom surface 23b contacting the substrate 20, a top surface 23t opposite to the bottom surface 23b, and a side edge 23s connecting the top surface 23t and the bottom surface 23b, wherein the side edge 23s is an arc line segment. In some embodiments, the area of top surface 23t ≦ the area of bottom surface 23 b. In some embodiments, the side edge 23s is at an angle α to the bottom surface 23b, in some embodiments α < 95 °, and in further embodiments α ≦ 90 °.
The projection of the top surface 23t on the substrate 20 has a first projected edge 23ts and the projection of the bottom surface 23b on the substrate 20 has a second projected edge 23 bs. The first projected edge 23ts is subtracted from the second projected edge 23bs to obtain a distance, which is defined as the undercut depth d 0. When the value of the first projected edge 23ts is less than or equal to the value of the second projected edge 23bs, i.e. the value of the first projected edge 23ts minus the second projected edge 23tb is less than or equal to 0 μm, as shown in fig. 3D, it is determined that the undercut depth D0 does not exist.
In order to make the above and other objects, features and advantages of the present disclosure more comprehensible, several examples and comparative examples are illustrated below, and after forming a photoresist structure using the colored resin compositions in these examples, several inspection analyses and evaluations were performed to observe the characteristics of the photoresist structure manufactured by the colored resin compositions according to the examples of the present disclosure.
Commercially available products such as NCI-730 (manufactured by ADEKA corporation), PBG-345, PBG-346, PBG-327 (manufactured by Changzhou powerful new electronic materials Co., Ltd.), DETX (manufactured by Nippon Kagaku Co., Ltd.) and the like are used as initiators; propylene Glycol Monomethyl Ether Acetate (PGMEA) as solvent; dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by japan chemicals (stock)), as a polymerizable unsaturated compound; 4,4' -butylidene bis (6-tert-butyl-m-cresol) (BBM-S) as an antioxidant; the experiments were carried out with alkali-soluble resin a, alkali-soluble resin B, alkali-soluble resin C, or a combination thereof, and a colorant described below. These experimental contents can specifically explain the effects that can be achieved by the colored resin compositions according to the embodiments of the present disclosure. However, the following examples and comparative examples are illustrative only and should not be construed as limiting the practice of the present disclosure.
1. Preparation of alkali-soluble resin A
(1) Preparation of alkali-soluble resin A
After 213.6g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, the temperature of the propylene glycol monomethyl ether acetate was raised to 90 ℃ while stirring the propylene glycol monomethyl ether acetate while introducing nitrogen gas through the gas inlet tube to replace the air in the flask. Next, 4.0g of t-butylperoxy-2-ethylhexanoate was added to a monomer mixture comprising 70.0g (0.70 mole) of methyl methacrylate, 11.0g (0.05 mole) of tricyclodecanyl methacrylate and 18.1g (0.25 mole) of methacrylic acid to form a mixture. The mixture was dropped into the flask via a funnel. After completion of the dropping, the mixture was stirred at 95 ℃ for about 1 hour to effect copolymerization. Subsequently, 28.5g (0.20 mol) of glycidyl methacrylate, 0.6g of triphenylphosphine (catalyst) and 0.6g of hydroquinone (polymerization inhibitor) were added thereto, and ring-opening addition reaction was carried out at 120 ℃ for 8 hours, thereby producing a copolymer. Finally, 221.3g of propylene glycol monomethyl ether was added to this reaction solution to obtain a copolymer solution (weight-average molecular weight 6,500) having a solid concentration of 30% by mass as an alkali-soluble resin A.
(2) Preparation of alkali-soluble resin B
After 213.6g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, the temperature of the propylene glycol monomethyl ether acetate was raised to 90 ℃ while stirring the propylene glycol monomethyl ether acetate while introducing nitrogen gas through the gas inlet tube to replace the air in the flask. Next, 4.0g of t-butylperoxy-2-ethylhexanoate was added to a monomer mixture containing 15.0g (0.10 mole) of benzyl methacrylate, 93.0g (0.55 mole) of cyclohexyl methacrylate, and 25.3g (0.35 mole) of methacrylic acid to form a mixture. The mixture was dropped into the flask via a funnel. After completion of the dropping, the mixture was stirred at 95 ℃ for about 2 hours to effect copolymerization. Subsequently, 28.5g (0.20 mol) of glycidyl methacrylate, 0.6g of triphenylphosphine (catalyst) and 0.6g of hydroquinone (polymerization inhibitor) were added thereto, and ring-opening addition reaction was carried out at 120 ℃ for about 7 hours, thereby producing a copolymer. Finally, 221.3g of propylene glycol monomethyl ether was added to this reaction solution to obtain a copolymer solution having a solid concentration of 33% by mass (weight-average molecular weight of 17,000) as an alkali-soluble resin B.
(3) Preparation of alkali-soluble resin C
100 parts by weight of propylene glycol monomethyl ether acetate was placed in a flask equipped with a reflux condenser, a dropping funnel and a stirrer under a nitrogen atmosphere by flowing an appropriate amount of nitrogen gas, and the propylene glycol monomethyl ether acetate was heated to 85 ℃ while stirring. Subsequently, a solution containing 19 parts by weight of methacrylic acid and 171 parts by weight of 3, 4-epoxytricyclo [5.2.1.02,6] decan-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.02,6] decan-9-yl acrylate dissolved in 40 parts by weight of propylene glycol monomethyl ether acetate (containing a molar ratio of 50: 50) (trade name "E-DCPA", manufactured by Dacellosolve Co., Ltd.) was dripped into the flask using a dripping pump for about 5 hours. On the other hand, a solution containing 26 parts by weight of the polymerization initiator 2,2' -azobis (2, 4-dimethylvaleronitrile) dissolved in 120 parts by weight of propylene glycol monomethyl ether acetate was dropped into the flask using another dropping pump for about 5 hours. After the end of dropping of the solution containing the polymerization initiator, the same temperature was maintained for about 3 hours, and thereafter it was cooled to room temperature, to obtain a copolymer (weight average molecular weight 11000) having a solid concentration of 30% by weight as an alkali-soluble resin C.
2. Preparation of colored resin composition
The colored resin compositions of examples 1 to 6 and comparative examples 1 to 4 were prepared in the compositions and weight percentages shown in tables 1 to 3 below.
TABLE 1
TABLE 2
TABLE 3
3. Evaluation of colored resin composition
(1) The initiators used in examples 1 to 6 and comparative examples 1 to 4 were dissolved in Propylene Glycol Monomethyl Ether Acetate (PGMEA) to prepare 0.001 wt%, and the solution was placed in a quartz cell and placed in a UV/VIS UV/visible spectrophotometer (model: UV-2600shimadzu) to obtain the absorption values (A%) of the initiators used in examples 1 to 6 and comparative examples 1 to 4, respectively.
(2) After the colored resin compositions of examples 1 to 6 and comparative examples 1 to 4 were prepared into color chips, the transmittance T% of the colored resin compositions of examples 1 to 6 and comparative examples 1 to 4 was measured by an ultraviolet-visible spectrometer (model: uv-2600 shimadzu). The illuminance E% of the light source was measured by an optical spectrum spectrometer (model: Ocean Optics USB2000+) and normalized with 100% as the illuminance at 365 nm.
(3) Integrating the measured absorption value A% of the initiator, the penetration value T% of the colored resin composition and the illumination E% of the light source, and calculating the X value of the colored resin compositions of examples 1-6 and comparative examples 1-4 by substituting the solid content by weight of the initiator used in each example and comparative example into the following formula:
Σ(initiator){∫360-460nm[ absorption value of initiator (A%) [ transmission value of colored resin composition (T%) [ illuminance of light source (E%)]Solid content of starter (S%) } 10000 ═ X
The solid contents of the initiators of examples 1 to 6 and comparative examples 1 to 4, the integrals calculated from the above results, and the X values are shown in tables 4 to 6 and 4
TABLE 5
TABLE 6
4. Manufacture of photoresist structure
(1) The colored resin compositions of examples 1 to 6 and comparative examples 1 to 4 were coated on glass substrates having a thickness of about 0.4mm to about 0.7mm, respectively, by spin coating.
(2) The glass substrate coated with the colored resin composition was placed on a Hot plate (Hot plate) at about 80 to 90 ℃ and prebaked for about 120 seconds.
(3) After the glass substrate is cooled, an exposure machine is used to perform an exposure step, and then the glass substrate is moved to a developing machine to perform a developing step, so as to form the photoresist structures of examples 1 to 6 and comparative examples 1 to 4 on the glass substrate.
5. Evaluation of resist Structure
The photoresist structures of the examples and comparative examples were photographed by a Scanning Electron Microscope (SEM) (model: Hitachi SU3500), and the cross-sectional shapes of the photoresist structures, undercut depth (undercut depth) and the angles between the side edges and the bottom surface were observed. SEM images of the photoresist structures of examples 1-6 and comparative examples 1-4 are shown in FIGS. 4-13, respectively.
Fig. 4 to 13 are SEM images of photoresist structures according to the embodiments and comparative examples of the present disclosure. FIG. 4 is an SEM image of a photoresist structure of example 1; FIG. 5 is an SEM image of the photoresist structure of comparative example 1; FIG. 6 is an SEM image of the photoresist structure of comparative example 2; FIG. 7 is an SEM image of a photoresist structure of comparative example 3; FIG. 8 is an SEM image of a photoresist structure of example 2; FIG. 9 is an SEM image of a photoresist structure of example 3; FIG. 10 is an SEM image of a photoresist structure of example 4; FIG. 11 is an SEM image of the photoresist structure of comparative example 4; FIG. 12 is an SEM image of a photoresist structure of example 5; and FIG. 13 is an SEM image of the photoresist structure of example 6.
The thickness of the photoresist structures, the included angles between the side edges and the bottom surface, and the undercut depth were measured according to the SEM images of the photoresist structures of examples 1 to 6 and comparative examples 1 to 4, and the photoresist structures of examples 1 to 6 and comparative examples 1 to 4 were evaluated according to the measured undercut depth and the included angles between the side edges and the bottom surface.
X is rated when the undercut depth d0 > 0 μm and excellent when the angle between the side edge and the bottom surface is ≦ 90 deg. The undercut depth is defined with reference to the undercut depth D0 of the photoresist structures 13 and 23 shown in fig. 1 and 3D, and the included angle between the side edge and the bottom surface is defined with reference to the included angle α shown in fig. 1 and 3D. The thickness, undercut depth, X value and evaluation of the photoresist structures of examples 1-6 and comparative examples 1-4 are shown in tables 7-9 below.
TABLE 7
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Thickness (μm) | 2.2 | 2.4 | 2.4 | 2.4 |
| Value of X | 26.70 | 4.89 | 0.00 | 0.00 |
| Undercut depth | -1.4μm | 2.1μm | 1.5μm | 5.6μm |
| Determination | ◎ | X | X | X |
TABLE 8
TABLE 9
| Example 5 | Example 6 | |
| Thickness (μm) | 2.4 | 2.2 |
| Value of X | 48.02 | 21.12 |
| Undercut depth | 0μm | -11.3μm |
| Determination | ◎ | ◎ |
From the results shown in tables 7 to 9, it can be seen that when the colored resin composition has an X value ≧ 20 as calculated by the above formula, the photoresist structure formed therefrom has defects of complete shape and no undercut-too-deep defects. Therefore, the photoresist structure formed by the colored resin composition according to the embodiments of the present disclosure has acceptable or good integrity of the whole and the edge profile. Therefore, the display device with the photoresist structure of the embodiment of the disclosure can avoid the exposure defect generated by the pixel of the display device due to the local falling of the photoresist, and can also greatly improve the problem that the number of the photoresist defects is over high due to the uneven bright and dark lines generated by the defective photoresist.
The embodiments described above are merely exemplary and do not limit the scope of the disclosure, which is defined by the claims, and the disclosure may be practiced with other features, elements, methods, and parameters. The embodiments are provided only for illustrating the technical features of the present disclosure, and not for limiting the claims of the present disclosure. Those skilled in the art will recognize that various modifications and changes may be made in the embodiments without departing from the scope of the present disclosure.
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