A photosensitive resin composition, a method for preparing the same, and an application thereof

Abstract

This invention discloses a photosensitive resin composition, its preparation method, and its applications. The photosensitive resin composition comprises the following components in parts by weight: 0.5-2 parts perovskite nanoparticles, 20-40 parts photosensitive polymer, 1-10 parts photosensitive acid compound, 0.5-1 part surfactant, and 60-70 parts solvent. The photosensitive acid compound is selected from at least one of triaryl sulfonates, diaryl thioonium salts, sulfonates, and sulfonates. The photosensitive polymer comprises styrene segments and / or acrylate segments. The photosensitive resin composition of this invention has high refractive index, high transparency, and high-resolution patterning, making it suitable for fabricating microlens arrays. By introducing perovskite nanoparticles, the refractive index of the microlenses formed by the photosensitive resin composition can be increased to 1.65 to 1.89.

Description

Technical Field

[0001] This invention belongs to the field of materials, specifically relating to a photosensitive resin composition, its preparation method, and its application. Background Technology

[0002] Photosensitive resin compositions are primarily used to fabricate microlens arrays required for numerous optical applications. Active optoelectronic devices, such as displays and light-emitting devices (LEDs, lasers), use microlens arrays to improve their light output characteristics. Passive optical devices, such as typical solid-state imaging devices including CCD (charge-coupled device) image sensors and CMOS (complementary metal-oxide-semiconductor) image sensors, regularly arrange numerous microlens arrays on a substrate. Each element or pixel has a microlens at the top that collects incident light to improve the efficiency of the photodetector array in the solid-state image sensor. These microlenses require characteristics such as high refractive index and high transparency. Currently, microlenses are fabricated using photoresist (i.e., photosensitive resin compositions) to form microlens arrays. This method is generally called reflow, which involves raising the temperature above the glass softening point of the photoresist layer. By controlling the surface tension of the photoresist during its flow state, the photoresist is cured to form a plano-convex microlens shape of a specific size. The advantages of the reflow method are: simplicity, repeatability, and feasibility of direct integration onto the top of light-emitting or light-detecting optoelectronic devices. With the continuous development of optical application components, the transparency and refractive index of existing photosensitive resins cannot meet the requirements for high transparency and high refractive index. Summary of the Invention

[0003] In order to overcome the problems existing in the prior art, one of the objectives of the present invention is to provide a photosensitive resin composition.

[0004] A second objective of this invention is to provide a method for preparing a photosensitive resin composition.

[0005] The third objective of this invention is to provide a microlens array.

[0006] The fourth objective of this invention is to provide a method for fabricating a microlens array.

[0007] The fifth objective of this invention is to provide an application of a photosensitive resin composition and / or a microlens array in an optical element.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] The first aspect of the present invention provides a photosensitive resin composition comprising the following components in parts by weight: 0.5 to 2 parts of perovskite nanoparticles, 20 to 40 parts of photosensitive polymer, 1 to 10 parts of photoacid compound, 0.5 to 1 part of surfactant, and 60 to 70 parts of solvent.

[0010] The photoacid compound is selected from at least one of triarylsulfonates, diarylthioonates, sulfonates, and sulfonates;

[0011] The photosensitive polymer includes substituted or unsubstituted styrene segments and / or acrylate segments.

[0012] Preferably, the weight-average molecular weight of the photosensitive polymer is 1000 to 100000 g / mol.

[0013] Preferably, the perovskite nanoparticles have the structural formulas ABX3, A2BX4, and ABX4, wherein A is selected from Cs. + C n H n+ 2NH3 + C6H5C n H 2n NH3 + NH3C n H 2n NH3 + NH2CHNH3 + At least one of the following; n is an integer from 1 to 5; B is selected from Pb 2+ Sn 2+ Cu 2+ Mn 2+ Fe 2+ At least one of them; X is F — Cl — ,Br — I — ...

[0014] Preferably, the photoacid compound is selected from at least one of triphenylsulfonic acid, triphenylantimonate, triphenylsulfonyl difluoroalkylsulfonic acid, diphenylantimonate, diphenylantimonate, methoxydiphenylantimonate, di-tert-butyldiphenylantimonate, 2,6-dinitrobenzenesulfonate, pyrogallol tris(alkylsulfonate), N-hydroxysuccinimide trifluoroate, norbornene-dicarbonimide-trifluoroate, triphenylnonfluorosulfonic acid sulfonate, diphenylnonfluorosulfonate, methoxydiphenylnonfluorosulfonate, di-butyldiphenylnonfluorosulfonate, N-hydroxysuccinimide nonfluorosulfonate, norbornene-dicarbonimide nonfluorosulfonate, perfluorobutyric acid triphenylsulfonate, perfluorooctylsulfonic acid triphenylsulfonate, (triphenyl)perfluorooctylsulfonate, diphenylthionium, methoxydiphenylthionium, di-tert-butyldiphenylthionium triacid, N-hydroxysuccinimide, and norbornene-dicarbonimide.

[0015] Preferably, the structural formula of the styrene segment is:

[0016] Among them, R a Selected from H, C 1～6 Alkyl groups;

[0017] R b Selected from H, C 1～6 Straight-chain or branched alkyl groups, C 3～6 Cycloalkyl, ethyleneoxyethyl, tetrahydropyranyl, tetraalkylsilyl, isononyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 3-tetrahydrofuranyl, 3-oxocyclohexyl, γ-butyrolactone-3-yl, cyanolactone, γ-butyrolactone-2-yl, 3-methyl-γ-butyrolactone-3-yl, 2-tetrahydrofuranyl, 2-tetrahydrofuranyl, 2,3-propenyl carbonate-1-yl, 1-methoxyethyl, 1-(2-methoxyethyl)ethyl 1-(2-methoxyethyl)ethyl, 1-(2-ethoxyethyl)ethyl, t-butoxycarbonylmethyl, methoxymethyl, ethoxymethyl, trimethoxysilyl, triethoxysilyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxyethyl, cyclohexyloxy, methoxypropyl, ethoxypropyl, 1-methoxy-1-methylethyl, 1-ethoxy-1-methylethyl, tert-butoxycarbonyl, tert-butoxycarbonyl.

[0018] Preferably, the acrylate segment has the following structural formula:

[0019] Among them, R c Selected from H, F, C1-6 straight-chain or branched alkyl groups, and C1-6 straight-chain or branched fluoroalkyl groups;

[0020] R d Selected from C 1～6Straight-chain or branched alkyl groups, C 3～6 Cycloalkyl groups, ethyleneoxyethyl, tetrahydropyranyl, tetraalkylsilyl, isononyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 3-tetrahydrofuranyl, 3-oxocyclohexyl, γ-butyrolactone-3-yl, cyanolactone, γ-butyrolactone-2-yl, 3-methyl-γ-butyrolactone-3-yl, 2-tetrahydrofuranyl, 2-tetrahydrofuranyl, 2,3-propenyl carbonate-1-yl, 1-methoxyethyl, 1-(2-methoxyethyl)ethyl, 1-(2-methoxyethyl)ethyl, 1-(2-ethoxyethyl)ethyl, t-butoxycarbonylmethyl, methoxymethyl, ethoxymethyl, trimethoxysilyl, triethoxysilyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxyethyl, cyclohexyloxy, methoxypropyl, ethoxypropyl, 1-methoxy-1-methylethyl, 1-ethoxy-1-methylethyl, tert-butoxycarbonyl, tert-butoxycarbonylmethyl.

[0021] Preferably, the R b and R d In the middle, C 1～6 The straight-chain or branched alkyl group is selected from at least one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl.

[0022] Preferably, the R b and R d In, the C 3～6 The cyclic alkyl group is selected from at least one of cycloalkyl, cyclopentyl, and cyclohexyl.

[0023] Preferably, the monomer for the polymerization of the acrylate segment is selected from at least one of acrylate monomers, monocarboxylic acids, dicarboxylic acids, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, aryl (meth)acrylates, dicarboxylic acid diesters, vinyl-containing aromatic compounds, vinyl-containing aliphatic compounds, and conjugated dienes. Among these, 2-methacryloyloxyethyl hexahydrophthalic acid is a methacrylic acid derivative having a carboxyl group and an ester bond.

[0024] Preferably, the acrylate monomer is selected from 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, acrylate, ethanol-based (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, and tetrahydrofuranyl (meth)acrylate.

[0025] Preferably, the monocarboxylic acid is selected from acrylic acid, methacrylic acid, and crotonic acid.

[0026] Preferably, the dicarboxylic acid is selected from maleic acid, fumaric acid, and itaconic acid.

[0027] Preferably, the alkyl methacrylate is selected from methacrylate, ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate.

[0028] Preferably, the hydroxyalkyl methacrylate is selected from 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0029] Preferably, the aryl methacrylate is selected from phenyl methacrylate or phenyl methacrylate.

[0030] Preferably, the dicarboxylic acid diester is selected from diethyl maleate and dibutyl fumarate.

[0031] Preferably, the vinyl-containing aromatic compound is selected from styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene.

[0032] Preferably, the vinyl-containing aliphatic compound is vinyl acetate.

[0033] Preferably, the conjugated diene is selected from butadiene and isoprene.

[0034] Preferably, the photoacid compound is 2-(2-(((propylsulfonyl)oxy)imino)thiophene-3(2H)-ylidene)-2-(o-tolyl)acetonitrile, with the following structural formula:

[0035] Preferably, the structural formula of the photosensitive polymer is:

[0036]

[0037] In the structural formula of the photosensitive polymer, the molar ratio of i, j, k, l is 1:(1~3):(1~3):(1~3).

[0038] Preferably, the surfactant is selected from at least one of fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and polysiloxane surfactants; more preferably, the surfactant is a fluorinated surfactant. The surfactant in this invention functions to improve the uniformity of the coating and enhance the wettability of the photosensitive resin composition. The fluorine content in the fluorinated surfactant is recommended to be 7–25 wt%. Fluorinated surfactants with a fluorine mass percentage within this range exhibit better coating thickness uniformity and liquid-saving properties, and also better solubility in the composition. Examples of commercially available fluorinated surfactants include Megaface F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 sold by DIC; Fluorad FC430, FC431, FC171 manufactured by Sumitomo 3M Limited; Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 manufactured by Asahi Glass; and PF636, PF656, PF6320, PF6520, PF7002 manufactured by OMNOVA Solutions Inc. PolyFox.

[0039] Preferably, the photosensitive resin composition further includes 60 to 70 parts of solvent.

[0040] Preferably, the solvent is selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol methyl ethyl ether propylene glycol, propylene glycol monoacetate, propylene glycol methyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isopentyl ketone, cyclohexanone, dioxane, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, ethoxyethylpropionate, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxy The solvent comprises at least one of the following: acetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxy-2-methylpropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxy-2-methylpropionate, acetate, and butyl acetate. The solvent in this invention serves to uniformly dissolve and mix the components in the photosensitive resin composition, thereby controlling the viscosity and volatility of the composition.

[0041] A second aspect of the present invention provides a method for preparing the photosensitive resin composition provided in the first aspect of the present invention, comprising the following steps:

[0042] The photosensitive resin composition is prepared by mixing the raw materials.

[0043] A third aspect of the present invention provides a microlens array made of a material comprising the photosensitive resin composition provided in the first aspect of the present invention.

[0044] Preferably, the refractive index of the microlens array is 1.58 to 1.89.

[0045] A fourth aspect of the present invention provides a method for fabricating the microlens array provided in the third aspect of the present invention, comprising the following steps:

[0046] S1: Coat a material including a photosensitive resin composition onto a substrate, and then pre-bake to obtain a cured film;

[0047] S2: After the cured film is exposed to light, it is baked, developed, and then baked again to obtain the microlens array.

[0048] The fifth aspect of the present invention provides the application of the photosensitive resin composition provided in the first aspect of the present invention and / or the microlens array provided in the third aspect of the present invention in optical elements.

[0049] Preferably, the optical element includes an active optoelectronic element and a passive optical element.

[0050] Preferably, the active optoelectronic element includes a display and a light-emitting device.

[0051] Preferably, the light-emitting device includes a light-emitting diode (LED) or a laser device.

[0052] Preferably, the passive optical element includes a charge-coupled device (CCD) image sensor and a complementary metal-oxide-semiconductor (CMOS) image sensor.

[0053] The beneficial effects of the present invention are as follows: The photosensitive resin composition of the present invention has high refractive index, high transparency, and high resolution patterning, making it suitable for fabricating microlens arrays. By introducing perovskite nanoparticles, the refractive index of the microlens formed by the photosensitive resin composition can be increased to 1.80 to 1.89. Moreover, when the amount of perovskite nanoparticles added is up to 10.0% of the total solids by mass, the transmittance still reaches 99.1%. Therefore, the photosensitive resin composition of the present invention is suitable for fabricating microlens arrays required for many optical applications.

[0054] The microlens array in this invention is made using the photosensitive resin composition of this invention, and its refractive index can reach up to 1.89. Furthermore, the optical device using this microlens array as an optical element has a resolution greater than 5000 PPI, exhibiting extremely high resolution and miniaturization characteristics. Attached Figure Description

[0055] Figure 1 This is a scanning electron microscope image of the microlens array in Example 1.

[0056] Figure 2 The transmittance spectrum of the microlens array in Example 3 in the visible light band is shown. Detailed Implementation

[0057] The specific implementation of the present invention will be further described in detail below with reference to the accompanying drawings and examples, but the implementation and protection of the present invention are not limited thereto. It should be noted that any processes not specifically described in detail below are those that can be implemented or understood by those skilled in the art by referring to the prior art. Reagents or instruments used without specified manufacturers are all conventional products that can be purchased commercially.

[0058] The method for fabricating the microlens array in this invention is as follows:

[0059] (1) Coating

[0060] The photosensitive resin composition of this invention is suitable for substrates (Si, SiO2, SiN, TiN, WSi, borosilicate glass (BPSG), silicon-glass bonded structure (SOG), organic antireflective film, etc.) or treatment layers on substrates (Cr, CrO, CrON, MoSi, SiO2, etc.). Using appropriate coating methods, such as spin coating, roller coating, flow coating, dip coating, spray coating, and doctor blade coating, a coating with a film thickness of 0.1 to 10.0 μm can be obtained.

[0061] (2) Pre-baking

[0062] The coating obtained in step (1) is pre-baked. The pre-baking conditions depend on the type and mixing ratio of each component in the photosensitive resin composition, but are usually pre-baked on a hot plate at 60-150°C for 10 seconds to 30 minutes, or preferably at 80-120°C for 30 seconds to 20 minutes to remove the solvent in the photosensitive resin composition.

[0063] (3) Exposure

[0064] Exposure is performed using a photomask with a predetermined pattern and high-energy rays, such as visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, electron beams (e.g., electron beams and alpha rays), electromagnetic waves (X-rays, gamma rays, and soft X-rays), excimer lasers, and synchrotron radiation sources. The target pattern is obtained by exposure using any of these high-energy light sources. Various exposure devices can be used, including mirror projection aligners, stepper aligners, scanners, proximity aligners, contact aligners, and laser occultators. Alternatively, super-resolution techniques can be used, such as multiple exposures, phase-transfer shielding, or ring illumination, to create even finer patterns. The wavelength of the exposure light source is 190 nm to 450 nm; the exposure dose is 1 to 200 mJ / cm². 2 Preferably, it is 10–100 mJ / cm 2 Or an exposure of 0.1–100 μC / cm. 2 Preferably, it is 0.5–50 μC / cm 2 .

[0065] (4) Baking after exposure

[0066] The pattern obtained after exposure in step (3) is post-exposure baked (PEB) at a temperature of 80 to 120°C for 30 seconds to 20 minutes.

[0067] (5) Development

[0068] A developer with a mass percentage of 0.1% to 5%, preferably 2% to 3%, is used. The developer can be a quaternary ammonium salt or other alkaline aqueous solution developer. The developer can be tetramethylammonium hydroxide (TMAH), choline hydroxide, tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, or alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; or alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate. The development method can use conventional methods such as liquid filling, immersion, shaking immersion, and spraying, rinsing for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes, to dissolve the exposed layer in the developing solution while leaving the unexposed areas undissolved, and without dissolving the substrate. After the development process, for example, after washing with ultrapure water for more than 30 seconds, the desired pattern can be formed by air drying, for example, using compressed air or compressed nitrogen.

[0069] (6) Heating and baking

[0070] After heat development, the cured film can be further cured by heating the patterned film using a heating device (such as a hot plate or oven). For example, the heating temperature can be 100°C to 250°C, and the heating time depends on the type of heating equipment. For example, a hot plate can be set to 5 to 30 minutes, while an oven can be set to 30 to 90 minutes.

[0071] The microlens array prepared using the photosensitive resin composition of the present invention has high resolution characteristics. For example, with a thickness of 1.0 to 2.0 micrometers, the critical dimension of the microlens can be as small as 3.0 to 5.0 micrometers, and the spacing in the microlens array can be as small as 0.2 to 0.5 micrometers. This photolithography capability enables the optical display device to have a resolution of more than 5000 PPI (pixels per inch).

[0072] The raw material information used in Examples 1-3 and Comparative Examples 1-4 of this invention is as follows:

[0073] The solvent is propylene glycol methyl ether acetate, i.e., PGMEA;

[0074] The surfactant is DIC / F554, purchased from DIC Corporation;

[0075] The free radical photoinitiator was BASF IRGACURE 907 photoinitiator, purchased from BASF;

[0076] The polymerizable compound is 9,10-diphenylanthracene, DPHA;

[0077] Perovskite nanoparticles were prepared using the following method: Cesium lead chloride perovskite (CsPbCl3) nanoparticle powder was prepared from air at room temperature using the method described below. First, 0.9 mmol of lead chloride (PbCl2, 99.999%) and 1.8 mmol of methyltrioctylammonium chloride (MTOA, 97%) were dissolved in 9 mL of anhydrous p-xylene (99%) to obtain a Pb precursor solution. Then, a CsOAc solution (1 mL) was rapidly injected into the above Pb precursor solution under vigorous stirring. After approximately 30 seconds, 1 mL of oleylamine (OAm, 90%) was added and stirred for 2 minutes to obtain a crude product solution. Subsequently, methyl acetate (MeOAc, 99%, purchased from Acros Organics) was added to the crude product solution at a volume ratio of methyl acetate to crude product solution of 3:1; the long-chain ligand oleylamine (OAm) ensured the stability and dispersibility of the CsPbCl3 perovskite nanocrystals. The precipitate was collected by centrifugation at 9000 rpm and redispersed in 3 mL of n-hexane for ligand exchange treatment. For ligand exchange treatment, EAm (50 μL) was added to the perovskite nanocrystal solution containing 3 mL of n-hexane. The surface of the in-situ synthesized pure perovskite nanocrystals was modified with undecene-1-amine (Eam, 95%) during the ligand exchange process, after which the perovskite nanocrystals were well dispersed in the photosensitive resin composition prepared in this invention. After stirring for 5 minutes, MeOAc (12 mL) was added to precipitate the modified perovskite nanocrystals, and the mixture was centrifuged at 9000 rpm. The resulting perovskite nanocrystal powder was completely dried under vacuum for further use. The average size of the original perovskite nanocrystals was approximately 6-10 nm, and the modified perovskite nanocrystals were almost identical in size. X-ray diffraction (XRD) patterns further confirmed that both the original and modified perovskite nanocrystals possessed a cubic perovskite structure. In addition to the organic ligand EAm mentioned above, it can also be selected from primary alkylamines, secondary alkylamines, tertiary alkylamines, nitrogen-containing heterocycles, alkenes, aliphatic hydrocarbons, alkyl-substituted aromatic hydrocarbons, alkyl-substituted phosphines, alkyl-substituted phosphine oxides, aromatic ethers, acids, or any combination thereof. Examples include: hexadecylamine, trioctylamine, dioctylamine, pyridine, 1-octadecene, toluene, phenyldodecane, phenyltetradecane, phenylhexadecane, hexadecane, octadecane, squalane, trioctylphosphine, trioctylphosphine oxide, phenyl ethers, myristic acid, palmitic acid, stearic acid, arachidic acid, and oleic acid.

[0078] The molecular weight (M) of the photosensitive polymers used in Examples 1-3 and Comparative Example 1 w Its concentration is 10000–11000 g / mol, its acid value is 90–100 mg KOH / g, and its structural formula is:

[0079] In this photosensitive polymer, The molar ratio of the four segments is 1:2:1:2;

[0080] The photoacid compound used in Examples 1-3 and Comparative Example 1 (trade name: 2-(2-(((propylsulfonyl)oxy)imino)thiophene-3(2H)-ylidene)-2-(o-tolyl)acetonitrile, purchased from BASF, model PAG 103, CAS No. 852246-55-0) is:

[0081]

[0082] The molecular weight (M) of the photosensitive polymers used in Comparative Examples 2-4 w Its concentration is 10000–11000 g / mol, its acid value is 90–100 mg KOH / g, and its structural formula is:

[0083] In this photosensitive polymer,

[0084] The molar ratio of the five segments is 1:2:2:2:1.

[0085] The photosensitive polymers (resins) used in Examples 1-3 and Comparative Examples 1-4 of this invention can all be prepared using free radical polymerization methods commonly used in the prior art. The specific steps are as follows:

[0086] In an inert gas environment, monomers and initiators were heated and copolymerized in an organic solvent. The synthesis employed a dropwise polymerization method, specifically: under a nitrogen atmosphere, a solution of monomers and initiator was added dropwise to a heated solvent. The organic solvent used for polymerization was tetrahydrofuran, and the polymerization initiator was 2,2'-azobisisobutyronitrile (AIBN). The temperature was set at 60°C, and the reaction time was 6 hours. After the reaction was complete, crystallization was performed in methanol, followed by washing with hexane, separation, and drying. The crystals were then analyzed using nuclear magnetic resonance (NMR). 1 The composition of the photosensitive polymer was determined by 1H-NMR, and the molecular weight (Mw) and dispersity (Mw / Mn) were determined by gel permeation chromatography (GPC) (solvent: tetrahydrofuran, standard: polystyrene).

[0087] The specific implementation of the present invention will be further described in detail below with reference to specific embodiments.

[0088] Example 1

[0089] This example provides a photosensitive resin composition, the formulation of which is shown in Example 1 in Table 1.

[0090] The preparation method of the photosensitive resin composition in this example is as follows:

[0091] The product is prepared by physically mixing the prescribed amounts of photosensitive polymer, photoacid compound, perovskite nanoparticles, surfactant, and solvent. The order of addition is: solvent, photoacid compound, perovskite nanoparticles, photosensitive polymer (resin), and surfactant.

[0092] Table 1. Formulations (parts by weight) of the photosensitive resin compositions in Examples 1-3 and Comparative Examples 1-4.

[0093]

[0094]

[0095] Example 2

[0096] This example provides a photosensitive resin composition, the formulation of which is shown in Example 2 in Table 1.

[0097] The preparation method of the photosensitive resin composition in this example is as follows:

[0098] The product is prepared by physically mixing the prescribed amounts of photosensitive polymer, photoacid compound, perovskite nanoparticles, surfactant, and solvent. The order of addition is: solvent, photoacid compound, perovskite nanoparticles, photosensitive polymer (resin), and surfactant.

[0099] Example 3

[0100] This example provides a photosensitive resin composition, the formulation of which is shown in Example 3 in Table 1.

[0101] The preparation method of the photosensitive resin composition in this example is as follows:

[0102] The product is prepared by physically mixing the prescribed amounts of photosensitive polymer, photoacid compound, perovskite nanoparticles, surfactant, and solvent. The order of addition is: solvent, photoacid compound, perovskite nanoparticles, photosensitive polymer (resin), and surfactant.

[0103] Comparative Example 1

[0104] This example provides a photosensitive resin composition, the formulation of which is shown in Comparative Example 1 in Table 1.

[0105] The preparation method of the photosensitive resin composition in this example is as follows:

[0106] The product is prepared by physically mixing the prescribed amounts of photosensitive polymer, photoacid compound, surfactant, and solvent. The order of addition is: solvent, photoacid compound, photosensitive polymer (resin), and surfactant.

[0107] Comparative Example 2

[0108] This example provides a photosensitive resin composition, the formulation of which is shown in Comparative Example 2 in Table 1.

[0109] The product is prepared by physically mixing the prescribed amounts of photosensitive polymer (resin), polymerizable compound (monomer), free radical photoinitiator, surfactant, and solvent. The order of addition is: solvent, free radical photoinitiator, photosensitive polymer (resin), polymerizable compound (monomer), and surfactant.

[0110] Comparative Example 3

[0111] This example provides a photosensitive resin composition, the formulation of which is shown in Comparative Example 3 in Table 1.

[0112] The product is prepared by physically mixing the prescribed amounts of photosensitive polymer (resin), polymerizable compound (monomer), free radical photoinitiator, perovskite nanoparticles, surfactant, and solvent. The order of addition is as follows: solvent, free radical photoinitiator, perovskite nanoparticles, photosensitive polymer (resin), polymerizable compound (monomer), and surfactant.

[0113] Comparative Example 4

[0114] This example provides a photosensitive resin composition, the formulation of which is shown in Comparative Example 4 in Table 1.

[0115] The product is prepared by physically mixing the prescribed amounts of photosensitive polymer (resin), polymerizable compound (monomer), free radical photoinitiator, perovskite nanoparticles, surfactant, and solvent. The order of addition is as follows: solvent, free radical photoinitiator, perovskite nanoparticles, photosensitive polymer (resin), polymerizable compound (monomer), and surfactant.

[0116] Performance testing:

[0117] First, the photosensitive resin compositions from Examples 1-3 were patterned according to the following preparation method to form a microlens array. The specific preparation method is as follows:

[0118] Coating: Using a rotary coater, set the rotation speed to 800 rpm and the acceleration to 400 rpm, and select 0.3 mm thick sodium glass for liquid crystal displays. Take 3 mL of photosensitive resin composition and coat to obtain a 1.0 μm thick film.

[0119] Pre-baking: Place the glass on the heating plate device, set it to 90°C, and bake for 150 seconds.

[0120] Exposure: A SUSS MA8 proximity exposure unit was used, with an i-Line filter to filter the light source wavelength. The exposure dose was 100 mJ / cm². 2 .

[0121] Post-exposure baking: After exposure, the glass is baked at 90°C for 10 minutes.

[0122] Development: Immersion development for 1 minute using 2.34% (w / w) tetramethylammonium hydroxide (TMAH) developer, followed by air drying with compressed air to form the desired pattern.

[0123] Baking: The entire preparation process is completed by heating the developed and patterned film in an oven at 150°C for 30 minutes.

[0124] In addition, the photosensitive resin compositions of Comparative Examples 1-4 were also patterned using the preparation methods described in Examples 1-3 to form microlens arrays of Comparative Examples 1-4. The difference between the patterning process of the photosensitive resin compositions of Comparative Examples 1-4 and Examples 1-3 and Examples 1-4 was that the post-exposure baking (PEB) process was omitted. Then, the performance of the photosensitive resin compositions of Examples 1-3 and Comparative Examples 1-4 was evaluated according to the following test methods for refractive index and pattern resolution. The specific test methods are as follows:

[0125] Surface morphology testing: The surface morphology of the microlens array made from the photosensitive resin composition in Example 1 was tested using scanning electron microscopy. Specific test images are shown below. Figure 1 As shown.

[0126] The refractive index was tested using an ellipsometry VUV-VASE (manufactured by JA Woran, Japan) to measure the refractive index of the photosensitive resin compositions in Examples 1-3 and Comparative Examples 1-4 at 589 nm.

[0127] The method for testing pattern resolution is as follows: After the photosensitive resin compositions in Examples 1-3 and Comparative Examples 1-4 are coated, exposed, baked after exposure (PEB; this step is not performed in the comparative examples), developed, and baked, the size of the smallest critical dimension of the pattern still attached to the silicon chip substrate is observed using an optical electron microscope. The unit is micrometer.

[0128] The transmittance spectrum of the microlens array in Example 3 in the visible light band was measured using a visible light absorption spectrometer. The specific test results are as follows: Figure 2 As shown, by Figure 2 It can be seen that the transmittance of the microlens array in Example 3 reaches 99.1%.

[0129] Table 2. Performance test results of the photosensitive resin compositions in Examples 1-3 and Comparative Examples 1-4

[0130]

[0131] The percentage of perovskite nanoparticles in the total solids of the photosensitive resin composition in Table 2 is calculated as follows: [(weight parts of perovskite nanoparticle dispersion / total weight parts of photosensitive resin composition * 100%) * mass percentage of solids in perovskite nanoparticles] / total solids of the photosensitive resin composition. The mass percentage of solids in perovskite nanoparticles is the mass percentage of perovskite nanoparticles in the perovskite nanoparticle dispersion. As shown in Table 2, the microlens arrays made from the photosensitive resin compositions in Examples 1-3 of this invention simultaneously possess high refractive index and high pattern resolution. If the pattern resolution in Table 2 is less than or equal to 5 micrometers, it can potentially be applied to display screen products with a resolution greater than or equal to 5000 ppi.

[0132] The embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features thereof can be combined with each other unless otherwise specified.

Claims

1. A photosensitive resin composition, characterized in that: The composition includes the following components in parts by weight: 0.5 to 2 parts perovskite nanoparticles. 20-40 parts of photosensitive polymer, 1-10 parts of photoacid compound, 0.5-1 part of surfactant, and 60-70 parts of solvent; The photoacid compound is 2-(2-(((propylsulfonyl)oxy)imino)thiophene-3(2H)-ylidene)-2-(o-tolyl)acetonitrile; The structural formula of the photosensitive polymer is: In the structural formula of the photosensitive polymer, the molar ratio of i, j, k, l is 1:(1~3):(1~3):(1~3); The weight-average molecular weight of the photosensitive polymer is 1000–100000 g / mol; The perovskite nanoparticles are ABX3, where A is selected from Cs. + B is selected from Pb 2+ X is F — Cl — ,Br — or I — .

2. The photosensitive resin composition according to claim 1, characterized in that: The surfactant is selected from at least one of fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and polysiloxane surfactants.

3. The method for preparing the photosensitive resin composition according to any one of claims 1 to 2, characterized in that: Includes the following steps: The photosensitive resin composition is prepared by mixing the raw materials.

4. A microlens array, characterized in that: The microlens array is made of a material comprising the photosensitive resin composition according to any one of claims 1 to 2.

5. The method for fabricating the microlens array according to claim 4, characterized in that: Includes the following steps: S1: Coat a material including a photosensitive resin composition onto a substrate, and then pre-bake to obtain a cured film; S2: After the cured film is exposed to light, it is baked, developed, and then baked again to obtain the microlens array.

6. The use of the photosensitive resin composition according to any one of claims 1 to 2 or the microlens array according to claim 4 in an optical element.

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