Transparent photoresist composition and preparation method therefor, pixel device, semiconductor device, and module device

Abstract

The present application discloses a transparent photoresist composition and a preparation method therefor, a semiconductor device structure, a pixel device structure, and an application of the transparent photoresist composition in automobiles and wearable devices. The materials for preparing the transparent photoresist composition comprise an acrylic resin, a photoinitiator, a photocurable monomer, an auxiliary agent, a solvent, and a film-forming resin, wherein the film-forming resin is formed by copolymerizing an enamine group (i) having an N-heterocyclic ring and an alkenyl chain (ii) containing an aromatic ring on a side chain.

Description

Transparent photoresist composition, preparation method thereof, pixel device, semiconductor device, and module device

[0001] Related applications

[0002] This application claims priority to Chinese Patent Application No. 202410856346.5, filed on June 28, 2024, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present application relates to the technical field of photoresist, in particular to a transparent photoresist composition, a preparation method thereof, a semiconductor device, a pixel device, and a module device. BACKGROUND

[0004] Micro LED (Micro Light Emitting Diode Display) is a display principle that designs red, green, and blue LED structures to be thin, small, and arrayed, with a size of only 1-10 microns or so; then the micron-level LEDs are transferred to a circuit substrate in batches, and a circuit and a transistor are installed under each micron LED to complete a simple Micro LED display. Each pixel of the Micro LED contains three LED sub-pixels that can self-illuminate and are independently controlled. Since the Micro LED uses self-illuminating micron-level LEDs, it is outstanding in color performance, with a half full width FWHM of the main wavelength of the micron LED light spectrum of only about 20 nm, which can provide a very high color saturation, usually more than 120% NTSC, which is almost the same as the color gamut provided by the top OLED display. At the same time, due to the stability of the inorganic LED, the color can remain consistent and stable no matter how long it is used, which is unmatched by OLED.

[0005] Micro LED also has the advantages of power saving and ultra-high brightness. In traditional LCD televisions, the display efficiency is about 3%, and the TFT in the LCD has very small loss because it is voltage-driven, but due to the energy loss in the color filter, polarizer, and LC material, the efficiency of the LCD is very low. Since the Micro LED has a simple structure and low energy consumption, it has higher photoelectric conversion efficiency, and the power consumption can be as low as 10% of the LCD and 50% of the OLED, which greatly reduces the unit power consumption and allows more energy to be used for direct light emission.

[0006] The transparent photoresist currently used for Micro LED, even the high-temperature cured transparent photoresist maturely applied on OGS, has a curing temperature of 230℃ and a dry film thickness of 1.5-2.5μm. Although the photoresist can achieve a higher film thickness by adjusting the solid content and viscosity, it cannot achieve low-temperature curing.

[0007] In addition, to achieve precise control of the process, automated technology is used to achieve precise control of key processes such as photoresist coating, baking, exposure, and development in the photoetching process. This includes strict control of parameters such as the speed of spin coating, baking temperature, exposure dose, and time to ensure the uniformity and consistency of the photoresist layer. Real-time development detection is used to monitor the development process and control the development time to control the groove shape. Spectral detection and pattern matching methods are used to achieve non-destructive testing of the groove parameters of the chrome-plated grating.

[0008] In order to more conveniently monitor and feedback in real time, sensors and monitoring systems are integrated to monitor key parameters such as the thickness and uniformity of the photoresist in real time during the photoetching process, and process parameters are adjusted in real time according to the monitoring results to optimize the performance of the photoresist.

[0009] On this basis, the formula is optimized, and feedback control rate technology is used to collect data feedback during the photoetching process to adjust the photoresist formula, thereby effectively screening out photoresist formulas with the best photosensitivity, resolution, and contrast.

[0010] The above content is only used to assist in understanding the technical solutions of the application and does not represent an acknowledgement that the above content is prior art. SUMMARY

[0011] The main purpose of the present application is to provide a transparent photoresist composition and a preparation method thereof, a semiconductor device, a pixel device, and a module device, aiming to improve the film thickness while achieving low-temperature curing.

[0012] To achieve the above-mentioned purpose, the transparent photoresist composition provided by the present application is prepared from materials including acrylic resin, photoinitiator, auxiliary agent, solvent photocuring monomer, and film-forming resin. The film-forming resin is copolymerized from an enamine (i) with an N-heterocycle and an enamine (ii) with an aromatic ring in the side chain.

[0013] In an embodiment, the enamine with an N-heterocycle has a structure as shown in formula (i):

[0014] In formula (i), R1 and R2 are methyl or hydrogen atoms.

[0015] Z is one of an N-containing aromatic heterocycle or an N-containing aliphatic heterocycle.

[0016] In one embodiment, the side chain contains an olefinic chain of aromatic ring structure as shown in formula (ii):

[0017] In formula (ii), R4 is a methyl group or a hydrogen atom;

[0018] R3 is H or a C2-C20 alkyl group;

[0019] Y is an unsaturated aromatic hydrocarbon group or a cyclic hydrocarbon structure.

[0020] In one embodiment, the film-forming resin has a structure as shown in formula (1):

[0021] In formula (1), n = 60-180;

[0022] R1, R2 and R4 are methyl groups or hydrogen atoms;

[0023] R3 is H or a C2-C20 alkyl group;

[0024] Y is an unsaturated aromatic hydrocarbon group or a cyclic hydrocarbon structure.

[0025] Z is one of an N-containing aromatic heterocycle or an N-containing aliphatic heterocycle.

[0026] In one embodiment, the group of Z includes one of In one embodiment, the group of Z includes one of

[0027] In one embodiment, the group of Y includes one of a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, an isopropylphenyl group, a butylphenyl group, a hydroxyphenyl group, a methoxyphenyl group, an acetoxyphenyl group, a butoxyphenyl group, a chlorophenyl group, a bromophenyl group, a dichlorophenyl group, a chloromethylphenyl group.

[0028] In one embodiment, the preparation materials of the transparent photoresist composition include, by weight fraction:

[0029] an acrylic resin 5-40 parts;

[0030] a photoinitiator 0.5-10 parts;

[0031] a photocurable monomer 5-50 parts;

[0032] a film-forming resin 5-50 parts;

[0033] an auxiliary agent 0.2-5 parts;

[0034] a solvent 10-200 parts.

[0035] In an embodiment, the acrylic resin comprises one or more of a methyl methacrylate and methyl methacrylate copolymer, a methyl methacrylate and methyl methacrylate cyclohexyl ester copolymer, a methyl methacrylate and methyl methacrylate glycidyl ester copolymer, a methyl methacrylate and methyl methacrylate-2-hydroxyethyl ester copolymer, a methyl methacrylate and methyl methacrylate cyclohexyl ester copolymer, and a methyl methacrylate-2-hydroxyethyl ester and styrene copolymer; and / or,

[0036] The photoinitiator comprises an oxime ester type initiator and an imidazole type initiator; and / or,

[0037] The photo-curing monomer comprises an oligomer crosslinking agent containing an olefinic double bond; and / or,

[0038] The auxiliary agent comprises one or more of a coupling agent, a leveling agent, a defoaming agent, an ultraviolet absorber, a stabilizer; and / or,

[0039] The solvent comprises one or more of N,N'-dimethylformamide, N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethyl urea, 1,3-dimethyl-2-imidazoline, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether.

[0040] In an embodiment, the average acid value of the acrylic resin is 75-140 mgKOH / g; and / or,

[0041] The amount ratio of the oxime ester type initiator and the imidazole type initiator is 1:1-1:3; and / or,

[0042] The amount ratio of the photoinitiator and the photo-curing monomer is 1:6-1:100;

[0043] The photo-curing monomer comprises one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, 3-hydroxymethyl pentaerythritol triacrylate, 3-hydroxyethyl pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate.

[0044] The present application also proposes a preparation method of a transparent photoresist composition, for preparing the transparent photoresist composition described above, comprising an N heterocyclic intermediate, the N heterocyclic intermediate comprising one of the N-heterocyclic enamine is prepared by Stork synthesis reaction; wherein, the preparation material of the transparent photoresist composition comprises acrylic resin, photoinitiator, auxiliary agent, solvent photocuring monomer and film-forming resin, and the film-forming resin is copolymerized by the N-heterocyclic enamine (i) and the ene chain (ii) containing aromatic ring in the side chain.

[0045] In an embodiment, the film-forming resin is copolymerized by the radical solution of the N-heterocyclic enamine group (i) and the radical solution of the ene chain (ii) containing aromatic ring in the side chain.

[0046] The application also provides a pixel device, comprising a substrate and a dry film layer arranged on the substrate, wherein the dry film layer is cured by the transparent photoresist composition described above; the substrate is a glass substrate, a Si substrate, a PET substrate, a CPI substrate, a COP substrate or a PEN substrate; the transparent photoresist composition is cured into the dry film layer by the processes of spin coating (Spin), pre-baking, exposure, middle baking, development, post-UV and post-baking; the preparation material of the transparent photoresist composition comprises acrylic resin, photoinitiator, auxiliary agent, solvent photocuring monomer and film-forming resin, and the film-forming resin is copolymerized by the N-heterocyclic enamine (i) and the ene chain (ii) containing aromatic ring in the side chain.

[0047] The application also provides a semiconductor device, which comprises a carrier board pixel device of a micro light emitting diode (Micro-LED) display and / or a radio frequency chip, and the carrier board pixel device comprises the pixel device described above, and the pixel device comprises a micro light emitting diode display having an upper layer, a lower layer or a double-layer structure of the dry film layer, wherein the dry film layer is prepared by a black photoresist composition; one of the black photoresist compositions comprises, by weight, 2-20 parts of bisphenol fluorene acrylic resin, 1-10 parts of tertiary amine resin containing β-H atom, 0.1-2 parts of perfluorinated ethylene monomer auxiliary agent A, 0.2-5 parts of aromatic peroxide auxiliary agent B, 0.5-2 parts of photoinitiator, 5-10 parts of photocuring resin monomer, 10-50 parts of black colorant and 50-500 parts of polar organic solvent.

[0048] The application also provides a module device, which comprises a vehicle-mounted display screen, a wearable device display screen or a chip packaging device, and the vehicle-mounted display screen, the wearable device display screen or the chip packaging device comprises the semiconductor device described above.

[0049] The film-forming resin of the technical scheme of the present application includes copolymerization of an enamine with an N-heterocycle and an enchain with an aromatic ring in the side chain, and the double bond of the enamine with an N-heterocycle participates in a stereoscopic cross-linking reaction, thereby increasing the thickness of the transparent photoresist composition, so that the dry film layer after curing does not collapse, and the thickness of the dry film layer is improved; at the same time, the transparent photoresist composition can be cured at low temperature, and the problem of low heat resistance limit of quantum dot materials is solved. The transparent photoresist composition of the present application can resist the erosion of acid, alkali, solvent, stripping liquid and copper etching liquid after being cured into a dry film layer, and can resist 25-200℃ metal plating film, and its surface resistivity is stable at 5.0E×10 16 ohms or more. BRIEF DESCRIPTION OF DRAWINGS

[0050] In order to more clearly illustrate the technical schemes in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor on the basis of the drawings shown.

[0051] Fig. 1 is a schematic diagram of the molecular general formula of the film-forming resin of the present application;

[0052] Fig. 2 is a schematic diagram of the Micro-LED device structure in which the photoresist of the present application is located;

[0053] Fig. 3 is a microscope picture after the photoresist of the present application is located in the carrier plate and "hollowed out" and developed;

[0054] Fig. 4 is a microscope picture after the photoresist of the present application is located in the carrier plate and lines are made. DETAILED DESCRIPTION

[0055] The technical schemes in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only some embodiments of the present application, not all embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0056] It should be noted that the meaning of "and / or" appearing throughout the text is that it includes three parallel schemes. Taking "A and / or B" as an example, it includes A scheme, or B scheme, or A and B schemes. In addition, the technical schemes of each embodiment can be combined with each other, but it must be based on the fact that those skilled in the art can realize it. When the combination of technical schemes appears contradictory or unachievable, it should be considered that the combination of technical schemes does not exist and is not within the scope of protection claimed by the present application.

[0057] "comprising," "containing," "including," "having," or other variations thereof, are to be construed in an open-ended manner, that is, they are to be construed to leave out other steps and elements. The term "comprising" is used to mean "consisting essentially of, but also "consisting of." The compositions and methods / processes of the present application comprise, consist essentially of, and consist of the essential elements and limitations described herein, in any of the various combinations described herein, as well as any additional or optional ingredients, components, steps, or limitations described herein. All numerical values or expressions relating to quantities of components, process conditions, and the like, as used in the specification and claims, are to be construed in all instances as "about" the value or expression. All ranges are inclusive of the endpoints, unless otherwise indicated. Since these ranges are continuous, they include every value within that range. It is also understood that any numerical range recited in this application is intended to include all sub-ranges of the same entire range. As used herein, "parts by weight," "parts," "mass parts," or "mass parts" are used interchangeably, and the parts referred to can be any one of a fixed weight expressed in milligrams, grams, or kilograms (e.g., 1 mg, 1 g, 2 g, 5 g, or 1 kg, etc.). For example, a composition consisting of 1 part of component a and 9 parts of component b can be a composition consisting of 1 g of component a + 9 g of component b, or 10 g of component a + 90 g of component b, etc.

[0058] In the related art, the transparent photoresist for Micro LED needs high-temperature curing, and the curing temperature is generally above 200°C, and the dry film thickness after curing is only 1.5-2.5 μm; and the heat resistance limit of quantum dot material is small.

[0059] To this end, the present application provides a transparent photoresist composition.

[0060] In the embodiments of the present application, the preparation materials of the transparent photoresist composition include acrylic resin, photoinitiator, photocuring monomer, and film-forming resin, and the film-forming resin is copolymerized from enamine (i) with N-heterocycle and enchain (ii) with side chain containing aromatic ring.

[0061] The transparent photoresist composition is polymerized from enamine with N-heterocycle and enchain with side chain containing aromatic ring into a new type of film-forming resin, and the dry film layer thickness after curing of the transparent photoresist composition is large, and low-temperature curing can be realized at the same time, the deformation amount of the dry film layer is small, and the low-temperature curing operation also reduces the influence of quantum dot material.

[0062] The film-forming resin of the technical solution of the present application is copolymerized by an enamine with N-heterocycle and an ene chain with an aromatic ring in the side chain, the double bond of the enamine with N-heterocycle participates in a stereoscopic cross-linking reaction, thereby increasing the thickness of the transparent photoresist composition, so that the dry film layer after curing does not collapse, and the thickness of the dry film layer is improved; meanwhile, the transparent photoresist composition can be cured at low temperature, and the problem of low heat resistance limit of quantum dot materials is solved. The transparent photoresist composition of the present application can be cured into a dry film layer, can resist the erosion of acid, alkali, solvent, stripping liquid and copper etching liquid, can resist metal plating at 25-200℃, and the surface resistivity thereof is stable at 5.0E×10 16 ohms or more.

[0063] The structure of the enamine with N-heterocycle is various, in an embodiment, the structure of the enamine with N-heterocycle is shown as formula (i):

[0064] In formula (i), R1 and R2 are methyl or hydrogen atoms; Z is one of an N-containing aromatic heterocycle or an N-containing aliphatic heterocycle.

[0065] Similarly, the structure of the ene chain with an aromatic ring in the side chain is various, in an embodiment, the structure of the ene chain with an aromatic ring in the side chain is shown as formula (ii):

[0066] In formula (ii), R4 is methyl or a hydrogen atom; R3 is H or an alkyl group of C2-C20; Y is an unsaturated aromatic hydrocarbon group or a cyclic hydrocarbon structure.

[0067] The structure of the film-forming resin copolymerized by the enamine with N-heterocycle and the ene chain with an aromatic ring in the side chain is various, in an embodiment, the structure of the film-forming resin is shown as formula (1):

[0068] In formula (1), n=60-180; R1, R2 and R4 are methyl or hydrogen atoms; R3 is H or an alkyl group of C2-C20; Y is an unsaturated aromatic hydrocarbon group or a cyclic hydrocarbon structure; Z is one of an N-containing aromatic heterocycle or an N-containing aliphatic heterocycle.

[0069] In an embodiment, the group of Z is selected from one of the following structures:

[0070] In an embodiment, the group of Y includes one of a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, an isopropylphenyl group, a butylphenyl group, a hydroxyphenyl group, a methoxyphenyl group, an acetoxyphenyl group, a butoxyphenyl group, a chlorophenyl group, a bromophenyl group, a dichlorophenyl group, a chloromethylphenyl group.

[0071] In an embodiment, the preparation material of the transparent photoresist composition includes, by weight parts, 5-40 parts of an acrylic resin, 0.5-10 parts of a photoinitiator, 5-50 parts of a photocuring monomer, 5-50 parts of a film-forming resin, 0.2-5 parts of an auxiliary agent, and 10-200 parts of a solvent.

[0072] The transparent photoresist composition can be prepared by mixing, uniformly dispersing, and filtering, by weight parts, the acrylic resin, the photoinitiator, the photocuring monomer, the film-forming resin, the auxiliary agent, and the solvent to obtain a photosensitive solution of the transparent photoresist composition. In the operation, unsolved particles and impurities can be removed by filtering.

[0073] In an embodiment, the acrylic resin includes one or more of a methyl methacrylate-methyl methacrylate copolymer, a methyl methacrylate-cyclohexyl methacrylate copolymer, a methyl methacrylate-glycidyl methacrylate copolymer, a methyl methacrylate-2-hydroxyethyl methacrylate copolymer, a methyl methacrylate-cyclohexyl methacrylate-styrene-2-hydroxyethyl methacrylate copolymer.

[0074] The average acid value of the acrylic resin cannot be too high or too low. If the average acid value is too high, overdevelopment is easy to occur, leading to poor patterning. If the average acid value is too low, development is difficult to achieve graphic accuracy, also leading to poor patterning. In an embodiment, the average acid value of the acrylic resin is 75-140 mgKOH / g.

[0075] In an embodiment, the photocuring monomer includes an oligomer crosslinking agent containing an olefinic double bond. In an embodiment, the photocuring monomer includes one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, 3-hydroxymethyl pentaerythritol triacrylate, 3-hydroxyethyl pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0076] In an embodiment, the photoinitiator includes an oxime ester type initiator and an imidazole type initiator. The oxime ester type initiator functions as a photo-initiator to achieve a photocuring effect, and the imidazole type initiator functions as a photo-initiator and a thermal initiator in the pre-baking and post-baking stages. In an embodiment, the amount ratio of the oxime ester type initiator to the imidazole type initiator is 1:1-1:3.

[0077] The amount of the photoinitiator is too much, not only increasing the cost, but also easily leading to photoinitiator residue, causing overexposure and affecting reliability; and the amount of the photoinitiator is too little, leading to incomplete curing. Therefore, in an embodiment, the amount ratio of the photoinitiator to the photocuring monomer is 1:6-1:100. In an embodiment, the amount ratio of the photoinitiator to the photocuring monomer is 1:15-1:100. In an embodiment, the amount ratio of the photoinitiator to the photocuring monomer is 1:10-1:50. Further, in an embodiment, the amount ratio of the photoinitiator to the photocuring monomer is 1:6-1:20.

[0078] In an embodiment, the auxiliary agent includes one or more of coupling agent, leveling agent, defoaming agent, ultraviolet absorber, stabilizer. The low-temperature crosslinking curing is increased by the auxiliary agent, further improving the low-temperature curing effect of the transparent photoresist composition.

[0079] The solvent is used for dissolving and dispersing the resin uniformly, and is beneficial to the photopolymerization reaction and the thermal polymerization reaction. In an embodiment, the solvent includes one or more of N,N'-dimethylformamide, N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethyl urea, 1,3-dimethyl-2-imidazoline, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether.

[0080] The present application also proposes a preparation method of the transparent photoresist composition, for preparing the transparent photoresist composition described above, and the preparation method of the film-forming resin includes the following steps:

[0081] S1, obtaining the enamine with N-heterocycle by using N-heterocycle intermediate;

[0082] S2, synthesizing the film-forming resin by using the enamine monomer (i) with N-heterocycle and the monomer (ii) containing Y group under the condition of initiator free radical solution copolymerization.

[0083] In the step S1, a preparation method of the enamine is proposed, and the group of the N-heterocycle intermediate Z can be selected from one of the following structures:

[0084] The enamine with N-heterocycle is synthesized by Stork synthesis reaction route.

[0085] The reaction characteristics are:

[0086] (1) prepared from aldehyde ketone and one equivalent of N-heterocycle intermediate under the condition of dehydrating agent;

[0087] (2) During the preparation of the reaction process, an aminal is usually generated, which can be converted into an enamine by azeotropic distillation;

[0088] (3) Allyl-, benzyl-, propargyl-, or active alkyl halide such as active aryl halide is used as;

[0089] (4) The reaction rate is slow when a large steric hindrance ketone or a large steric hindrance amine forms an enamine;

[0090] (5) The reaction is selectively performed on the side with less substituent of the ketone in the reaction region.

[0091] In an embodiment, the film-forming resin is prepared by free radical solution copolymerization of the above-mentioned enamine monomer (i) with N-heterocycle and the monomer (ii) with Y group under the condition of an initiator. The molecular weight of the copolymer is controlled between 20 and 200, preferably between 40 and 180, and more preferably between 80 and 150.

[0092] In an embodiment, the enamine monomer (i) with N-heterocycle includes but is not limited to the following compounds:

[0093] In an embodiment, the monomer (ii) with Y group includes but is not limited to the following compounds:

[0094] The initiator includes but is not limited to one or a combination of the following compounds: azobisisobutyronitrile, azobisisoheptyl nitrile, dimethyl azobisisobutyrate, benzoyl peroxide, t-butyl benzoyl peroxide, methyl ethyl ketone peroxide, dodecanoyl peroxide.

[0095] The free radical reaction is performed in a solvent of the same type as the photoresist composition, which is not listed one by one. The reaction starting temperature is 90°C, and after 5Hr, the temperature is increased to 105°C for continuous reaction for 3Hr. The degree of polymerization can be controlled by adjusting the amount and type of initiator.

[0096] The application also provides a pixel device, which comprises a substrate and a dry film layer provided on the substrate, and the dry film layer is cured from the above-mentioned transparent photoresist composition. The specific parameters of the pixel device refer to the above-mentioned embodiments. Since the transparent photoresist composition adopts all the technical solutions of the above-mentioned embodiments, it at least has all the beneficial effects brought by the technical solutions of the above-mentioned embodiments, which are not listed one by one.

[0097] In one embodiment, the substrate is a glass substrate, a Si substrate, a PET substrate, a CPI substrate, a COP substrate, or a PEN substrate. The transparent photoresist composition can be coated on the substrate using a slit process, and a dry film layer can be formed by baking at 120-140°C after vacuum-1 atm / 30s. It can be understood that the dry film layer can be an insulating protective layer. The transparent photoresist composition can be cured into a dry film layer by a spin coating (Spin), pre-baking, exposure, post-exposure baking, development, post-UV, and post-baking process.

[0098] The present application also provides a semiconductor device, which includes a micro-LED display and / or a carrier substrate pixel device of a radio frequency chip, the carrier substrate pixel device including the pixel device described above, the pixel device including a micro-LED display having an upper layer, a lower layer, or a double-layer structure including the dry film layer prepared from the black photoresist composition;

[0099] The black photoresist composition includes, by weight parts, 2-20 parts of a bisphenol fluorene-based acrylic resin, 1-10 parts of a tertiary amine-based resin containing β-H atoms, 0.1-2 parts of a perfluorosubstituted ethylene-based monomer aid A, 0.2-5 parts of an aromatic peroxide aid B, 0.5-2 parts of a photoinitiator, 5-10 parts of a photocurable resin monomer, 10-50 parts of a black colorant, and 50-500 parts of a polar organic solvent.

[0100] In one embodiment, the method for preparing the black photoresist dry film layer includes the following steps:

[0101] coating: coating the transparent photoresist composition on the upper layer, the lower layer, or the double-layer structure of the transparent photoresist dry film layer;

[0102] pre-baking: baking the coated substrate at a temperature of 85-120°C for 110-240s;

[0103] exposure: exposure at an exposure energy of 50-300 mj / cm2;

[0104] post-baking: baking at 130-180°C for 30-60 min.

[0105] In the coating operation, Slit or Slit+Spin method can be used, vacuum-1 atm / 30 s. The pre-baking operation removes the solvent in the photoresist, enhances adhesion, releases the stress in the photoresist film, and prevents the photoresist from polluting the equipment. In the exposure operation, direct exposure can be used, parallel light can be used for exposure; visible light, ultraviolet, electron beam and X-ray radiation energy can be used for exposure. The post-baking operation is used to cure the transparent photoresist composition into a dry film layer, and the temperature of post-baking is 130-180°C and below, so as to realize low-temperature curing and avoid the influence of high temperature on quantum dot materials.

[0106] The dry film layer can be a thin layer: 0.5-2 μm; or a thick layer: 4-40 μm.

[0107] The dry film layer can be a thin layer or a thick layer, in an embodiment, the layer thickness of the dry film layer is 10-200 μm. In an embodiment, the layer thickness of the dry film layer is 0.5-2.0 μm. Alternatively, in an embodiment, the layer thickness of the dry film layer is 4-40 μm. Through the thick layer of the dry film layer, not only the gap between the quantum dots is filled, but also the height of the quantum dot pixel layer is greater than the height of the quantum dot pixel layer, so as to planarize and insulate the quantum dot pixel layer.

[0108] The application also proposes a module device, which comprises a vehicle-mounted display screen, a wearable device display screen or a chip packaging device, and the vehicle-mounted display screen, the wearable device display screen or the chip packaging device comprises the above-mentioned semiconductor device. Taking the wearable device as an example, the wearable device comprises a main body and the above-mentioned pixel device, and the pixel device is installed on the main body to improve the display information such as images; in an embodiment, the wearable device comprises VR, AR or MR.

[0109] The embodiments of the application will be described in detail below with specific examples, but those skilled in the art will understand that the following examples are only used to illustrate the application and should not be regarded as limiting the scope of the application. If the specific conditions are not specified in the examples, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0110] Example 1

[0111] A transparent photoresist composition, by weight fraction, acrylic resin 5 parts, photoinitiator 1 part, photocuring monomer 8 parts, film-forming resin 8 parts, auxiliary agent 0.5 parts, solvent 20 parts.

[0112] Dry film layer preparation method:

[0113] Coating: the transparent photoresist composition is coated on the substrate to form a coating on the surface of the substrate;

[0114] Pre-bake: the coating-formed substrate is baked at 90℃ for 120s;

[0115] Exposure: exposure is carried out at 100 mj / cm2;

[0116] Post-bake: 90℃, baked for 30-60min, solidified into dry film layer.

[0117] Example 2

[0118] A transparent photoresist composition, by weight parts, acrylic resin 5 parts, photoinitiator 1.2 parts, photocuring monomer 8 parts, film-forming resin 10 parts, auxiliary agent 0.5 parts, solvent 25 parts.

[0119] Dry film layer preparation method is the same as example 1.

[0120] Example 3

[0121] A transparent photoresist composition, by weight parts, acrylic resin 8 parts, photoinitiator 1.5 parts, photocuring monomer 8 parts, film-forming resin 6 parts, auxiliary agent 0.5 parts, solvent 20 parts.

[0122] Dry film layer preparation method is the same as example 1.

[0123] Example 4

[0124] A transparent photoresist composition, by weight parts, acrylic resin 5 parts, photoinitiator 1 part, photocuring monomer 10 parts, film-forming resin 15 parts, auxiliary agent 0.5 parts, solvent 20 parts.

[0125] Dry film layer preparation method is the same as example 1.

[0126] Example 5

[0127] A transparent photoresist composition, by weight parts, acrylic resin 5 parts, photoinitiator 1 part, photocuring monomer 6 parts, film-forming resin 8 parts, auxiliary agent 1 part, solvent 20 parts.

[0128] Dry film layer preparation method is the same as example 1.

[0129] Example 6

[0130] A transparent photoresist composition, by weight parts, acrylic resin 6 parts, photoinitiator 1 part, photocuring monomer 9 parts, film-forming resin 15 parts, auxiliary agent 0.5 parts, solvent 25 parts.

[0131] Dry film layer preparation method is the same as example 1.

[0132] Example 7

[0133] A transparent photoresist composition, by weight parts, acrylic resin 6 parts, photoinitiator 1 part, photocuring monomer 9 parts, film-forming resin 13 parts, auxiliary agent 0.5 parts, solvent 25 parts.

[0134] The dry film layer is prepared in the same way as in Example 1.

[0135] Example 8

[0136] A transparent photoresist composition, by weight parts, acrylic resin 6 parts, photoinitiator 1.2 parts, photocuring monomer 10 parts, film-forming resin 14 parts, auxiliary agent 0.5 parts, solvent 25 parts.

[0137] The dry film layer is prepared in the same way as in Example 1.

[0138] Example 9

[0139] A transparent photoresist composition, by weight parts, acrylic resin 6 parts, photoinitiator 1.2 parts, photocuring monomer 9 parts, film-forming resin 15 parts, auxiliary agent 0.5 parts, solvent 25 parts.

[0140] The dry film layer is prepared in the same way as in Example 1.

[0141] Example 10

[0142] A transparent photoresist composition, by weight parts, acrylic resin 5 parts, photoinitiator 1.2 parts, photocuring monomer 10 parts, film-forming resin 14 parts, auxiliary agent 0.5 parts, solvent 25 parts.

[0143] The dry film layer is prepared in the same way as in Example 1.

[0144] Example 11

[0145] A transparent photoresist composition, by weight parts, acrylic resin 5 parts, photoinitiator 1.2 parts, photocuring monomer 9 parts, film-forming resin 14 parts, auxiliary agent 0.5 parts, solvent 25 parts.

[0146] The dry film layer is prepared in the same way as in Example 1.

[0147] Example 12

[0148] A transparent photoresist composition, by weight parts, acrylic resin 6 parts, photoinitiator 1.2 parts, photocuring monomer 10 parts, film-forming resin 14 parts, auxiliary agent 0.8 parts, solvent 25 parts.

[0149] The dry film layer is prepared in the same way as in Example 1.

[0150] Comparative Example 1

[0151] A transparent photoresist composition, by weight parts, acrylic resin 3 parts, photoinitiator 0.2 parts, photocuring monomer 2 parts, film-forming resin 1 part, auxiliary agent 0.1 part, solvent 200 parts.

[0152] The dry film layer is prepared according to the method of Example 1.

[0153] Comparative Example 2

[0154] A transparent photoresist composition, by weight parts, acrylic resin 30 parts, photoinitiator 2 parts, photocuring monomer 20 parts, film-forming resin 10 parts, auxiliary agent 10 parts, solvent 20 parts.

[0155] The dry film layer is prepared according to the method of Example 1.

[0156] Comparative Example 3

[0157] A transparent photoresist composition, by weight parts, acrylic resin 3 parts, photoinitiator 1.2 parts, photocuring monomer 30 parts, film-forming resin 1 part, auxiliary agent 0.5 parts, solvent 25 parts.

[0158] The dry film layer is prepared according to the method of Example 1.

[0159] Comparative Example 4

[0160] A transparent photoresist composition, by weight parts, acrylic resin 30 parts, photoinitiator 1.2 parts, photocuring monomer 3 parts, film-forming resin 10 parts, auxiliary agent 0.5 parts, solvent 25 parts.

[0161] The dry film layer is prepared according to the method of Example 1.

[0162] The above Examples 1 to 12, Comparative Examples 1 to 4, according to the component ratio, are mixed and filtered into a uniform transparent photoresist composition photosensitive solution. And according to the above dry film layer preparation method, a dry film layer is formed. The components and specific gravity are referred to Table 1 below:

[0163] Table 1: Component ratio table of each sample

[0164] And, two conventional transparent photoresists are purchased from the market as Comparative Examples 3 and 4. In order to verify the various properties of the transparent photoresist composition and dry film layer of the present application, the above 5 examples and 4 comparative examples are subjected to physical and chemical property tests and weather resistance tests.

[0165] I. Physical and chemical property tests

[0166] (1) Viscosity: The above transparent photoresist is measured using a viscometer, 1 mL of transparent photoresist is placed in a rotational viscometer constant temperature 25°C for measurement.

[0167] (2)Specific gravity: More than 100 mL of transparent photoresist was injected into a 100 mL specific gravity cup. The specific gravity was calculated according to the weight after weighing according to the use method.

[0168] (3) Film uniformity: 1 mL of transparent photoresist was spin-coated, and then 9 points were selected by a step film thickness meter (Japan small plate ET200A-3D step meter) or a probe film thickness meter after yellow light process, and the film thickness was measured to calculate the film uniformity.

[0169] (4) Water absorption rate: About 1 gram of transparent photoresist was placed in aluminum foil and weighed to record the actual weight. The water loss weight was recorded after 100°C oven baking for 2 hours, and the weight loss ratio was calculated.

[0170] (5) Surface resistivity: High resistance meter SM7120 was used according to the method of national standard QJ 2220.2-1992.

[0171] (6) Tg value: The transfer temperature of the sample was measured using a DSC thermal analyzer with a temperature program of 100°C-400°C (10°C / min).

[0172] (7) Crosshatch test: A crosshatch knife was used to draw a 10x10 (1mm*1mm) grid on the surface, and 3M tape was used to stick the test grid vertically at 90°. The tape was quickly pulled off to see the peeling condition.

[0173] (8) Film thickness: 1 mL of transparent photoresist was spin-coated, and then the film thickness was measured by a step film thickness meter (Japan small plate ET200A-3D step meter) or a probe film thickness meter after yellow light process. The thickness of the dry film layer was measured by a probe film thickness meter.

[0174] The results are shown in Table 2.

[0175] Table 2 Test results of physical and chemical properties

[0176] According to Table 2, the viscosity of the photosensitive liquid of Examples 1 to 12 is about 100 times that of Comparative Examples 1, 3 to 4, and its viscosity is much higher than that of the comparative examples. Although the viscosity of Comparative Example 2 is not much different from that of the examples, its film uniformity and water absorption rate are high, the tg value is low, and the crosshatch test is 4B.

[0177] The surface resistivity of the Examples 1 to 12 and Comparative Examples 1 to 4 were all tested, and the film forming uniformity, water absorption, tg value and crosshatch test of Examples 1 to 12 were all passed, meeting the requirements, indicating that the transparent photoresist composition of the present application has good physical and chemical properties. Moreover, the thickness of Examples 1 to 12 is at least 30 μm, while the thickness of Comparative Examples 1, 3 to 4 is only 1.45-1.50 μm, which is small and cannot form a dry film layer with a relatively large thickness. That is, the transparent photoresist composition of the present application can realize thick film, and its physical and chemical properties meet the requirements.

[0178] II. Weather resistance test

[0179] (1) Acid and alkali resistance: the photosensitive liquid coating was immersed in 2.38% TMAH, propylene glycol methyl ether acetate, and ethanol at room temperature 25°C for 10 min, respectively.

[0180] (2) High temperature and high humidity test ①: the photosensitive liquid coating was placed in a constant temperature and humidity test chamber at 65°C / 90% RH for 240 hrs, and then taken out and recovered for 2 hrs at room temperature.

[0181] (3) High temperature and high humidity test ②: the photosensitive liquid coating was placed in a constant temperature and humidity test chamber at 85°C / 85% RH for 240 hrs, and then taken out and recovered for 2 hrs at room temperature.

[0182] (4) Water boiling test: the photosensitive liquid coating was tested using a water bath, and was placed in a constant temperature water bath at 90°C for 1 hour.

[0183] After the above (1) to (4) operations were completed, crosshatch test was performed, and the peeling was observed. The results are shown in Table 3.

[0184] Table 3 Weather resistance test results

[0185] Note:

[0186] 5B represents the highest level of adhesion, which means that the edges of the cutouts are completely smooth and there is no peeling at the edges of the grid;

[0187] 4B represents a high level of adhesion, which means that there is a small amount of peeling at the intersection of the cutouts, and the total peeling area is less than 5%;

[0188] 3B represents that there is a small amount of peeling at the edges and intersection of the cutouts, and the total peeling area is between 5% and 15%;

[0189] 2B represents that there is a large amount of peeling at the edges and intersection of the cutouts, and the total peeling area is between 15% and 35%;

[0190] 1B represents that there are pieces of peeling at the edges and intersections of the cuts, and the total area of the peeling is between 35%-65%;

[0191] 0B represents that there are pieces of peeling at the edges and intersections of the cuts, and the total area of the peeling is greater than 65%.

[0192] As can be seen from Table 3, the acid and alkali resistance, high temperature and high humidity test and boiling test results of Examples 1 to 12 are all 5B, the adhesion level of the dry film layer is high, the edges of the cuts are completely smooth, and there is no peeling at the edges of the grid, which shows that the examples of the present application pass the weather resistance test. The cross-hatch test results of Comparative Examples 1 to 2 are 0B, which do not pass the weather resistance test; the cross-hatch test results of Comparative Examples 3 to 4 are also 1-4B, some of which are even 0B, but the dry film layer is relatively thin, while the dry film layer of the examples of the present application is thick and achieves the weather resistance performance effect of a thin dry film layer.

[0193] Therefore, the transparent photoresist composition of the present application can be formed into a dry film layer, can resist 2.38% TMAH, propylene glycol methyl ether acetate, ethanol erosion, can resist 25-200℃ metal plating film, and its surface resistivity is stable at 5.0E×10 16 ohm or more. The film-forming resin of the present application participates in the stereoscopic cross-linking reaction through the double bond of the N-heterocyclic enamine, increases the thickness of the transparent photoresist composition, makes the dry film layer after curing not collapse, and further improves the thickness of the dry film layer; and the photosensitive liquid is low-temperature cured, which solves the problem of low heat resistance limit of quantum dot materials.

[0194] The raw materials and equipment used in the present application are all common raw materials and equipment in the art unless otherwise specified; the methods used in the present application are all conventional methods in the art unless otherwise specified. Unless otherwise specified, the meanings of the terms in the specification are the same as those generally understood by those skilled in the art, but if there is a conflict, the definitions in the specification shall prevail.

[0195] The foregoing examples are merely illustrative for explaining some features of the method described in the present application. The appended claims are intended to claim as broad a scope as can be conceived, and the examples presented herein are merely illustrative of selected implementations according to all possible combinations of the embodiments. Therefore, it is the intention of the applicant that the appended claims not be limited by the selection of examples of features of the present application. Some numerical ranges used in the claims also include sub-ranges within them, and variations in these ranges should also be interpreted as covered by the appended claims, if possible.

Claims

1. A transparent photoresist composition, wherein, The preparation material of the transparent photoresist composition includes acrylic resin, photoinitiator, photocuring monomer, auxiliary agent, solvent and film forming resin, and the film forming resin is copolymerized by enamine (i) with N-heterocycle and enchain (ii) with side chain containing aromatic ring.

2. The transparent photoresist composition of claim 1, wherein, The structure of the N-heterocyclic-containing enamine is shown as formula (i): In formula (i), R1 and R2 are methyl or hydrogen atom; Z is one of N-containing aromatic heterocycle or N-containing aliphatic heterocycle; and / or, the structure of the film-forming resin is represented by formula (1): In formula (1), n = 60-180; R1, R2 and R4 are methyl or hydrogen atom; R3 is H or C2-C20 alkyl; Y is unsaturated aromatic hydrocarbon group or cyclic hydrocarbon structure; Z is one of N-containing aromatic heterocycle or N-containing aliphatic heterocycle; and / or, the structure of the side chain containing an alkenyl chain of aromatic rings is as shown in formula (ii): In formula (ii), R4 is methyl or hydrogen atom; R3 is H or C2-C20 alkyl; Y is unsaturated aromatic hydrocarbon group or cyclic hydrocarbon structure.

3. The transparent photoresist composition of claim 2, wherein, The groups for Z include one of the following groups: And / or, the group of Y includes one of phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, isopropylphenyl, butylphenyl, hydroxyphenyl, methoxyphenyl, acetyloxyphenyl, butoxyphenyl, chlorophenyl, bromophenyl, dichlorophenyl, chloromethylphenyl.

4. The transparent photoresist composition according to any one of claims 1 to 3, wherein The preparation material of the transparent photoresist composition includes, by weight fraction: Acrylic resin 5-40 parts; Photoinitiator 0.5-10 parts; Photocuring monomer 5-50 parts; Film forming resin 5-50 parts; Auxiliary agent 0.2-5 parts; Solvent 10-200 parts.

5. The transparent photoresist composition of claim 4, wherein, The acrylic resin includes one or more of methyl methacrylic acid and methyl methacrylate copolymer, methyl methacrylic acid and methyl methacrylate cyclohexyl ester copolymer, methyl methacrylic acid and methyl methacrylate glycidyl ester copolymer, methyl methacrylic acid and methyl methacrylate-2-hydroxyethyl ester copolymer, methyl methacrylic acid and methyl methacrylate cyclohexyl ester and styrene and methyl methacrylate-2-hydroxyethyl ester copolymer; And / or, the photoinitiator includes oxime ester type initiator and imidazole type initiator; And / or, the photocuring monomer includes oligomer crosslinking agent containing olefin double bond; And / or, the auxiliary agent includes one or more of coupling agent, leveling agent, defoaming agent, ultraviolet absorber, stabilizer; And / or, the solvent includes one or more of N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethyl urea, 1,3-dimethyl-2-imidazoline, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethyl phosphoramide, pyridine, γ-butyrolactone, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether.

6. The transparent photoresist composition of claim 5, wherein, The average acid value of the acrylic resin is 75-140 mgKOH / g; and / or, The amount ratio of the oxime ester type initiator and the imidazole type initiator is 1:1-1:3; and / or, The amount ratio of the photoinitiator and the photocuring monomer is 1:6-1:100; The photocuring monomer includes one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, 3-hydroxymethyl pentaerythritol triacrylate, 3-hydroxyethyl pentaerythritol triacrylate, bis-pentaerythritol pentaacrylate, bis-pentaerythritol hexaacrylate.

7. A method for producing a transparent photoresist composition according to any one of claims 1 to 6, wherein The preparation method of the transparent photoresist composition includes an N-heterocyclic intermediate as claimed in claim 3, and the N-heterocyclic enamine is prepared by Stork synthesis reaction.

8. The method for preparing a transparent photoresist composition according to claim 7, wherein The film-forming resin is prepared by copolymerization of (i) a radical solution with an enamine group of N-heterocycle and (ii) a radical solution with an enchain of aromatic ring in side chain.

9. A pixel device, wherein, The pixel device includes a substrate and a dry film layer provided on the substrate, and the dry film layer is cured by the transparent photoresist composition as claimed in any one of claims 1 to 6. The substrate is a glass substrate, a Si substrate, a PET substrate, a CPI substrate, a COP substrate or a PEN substrate. The transparent photoresist composition is cured into the dry film layer by a spin coating (Spin), pre-baking, exposure, middle baking, development, post-UV and post-baking process.

10. A semiconductor device, wherein, The semiconductor device includes a Micro-LED display and / or a carrier board pixel device of a radio frequency chip, and the carrier board pixel device includes the pixel device as claimed in claim 9, and the pixel device includes a Micro-LED display with an upper layer, a lower layer or a double-layer structure containing the dry film layer, and the dry film layer is prepared by a black photoresist composition. The black photoresist composition includes, in parts by weight, 2 to 20 parts of a bisphenol fluorene acrylic resin, 1 to 10 parts of a tertiary amine resin containing β-H atoms, 0.1 to 2 parts of a perfluorosubstituted ethylene monomer aid A, 0.2 to 5 parts of an aromatic peroxide aid B, 0.5 to 2 parts of a photoinitiator, 5 to 10 parts of a photocuring resin monomer, 10 to 50 parts of a black colorant and 50 to 500 parts of a polar organic solvent.

11. A modular device, wherein, The module device includes a vehicle-mounted display screen, a wearable device display screen or a chip packaging device, and the vehicle-mounted display screen, the wearable device display screen or the chip packaging device includes the semiconductor device as claimed in claim 10. The module device includes a vehicle-mounted display screen, a wearable device display screen or a chip packaging device, and the vehicle-mounted display screen, the wearable device display screen or the chip packaging device includes the semiconductor device as claimed in claim 10.

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