Photosensitive resin composition as well as preparation method and application thereof

Abstract

The invention discloses a photosensitive resin composition as well as a preparation method and application thereof. The photosensitive resin composition comprises the following components in parts by weight: 0.5-2 parts of perovskite nanoparticles, 20-40 parts of photosensitive macromolecules, 1-10 parts of a photoacid compound, 0.5-1 part of a surfactant and 60-70 parts of a solvent, the photoacid compound is selected from at least one of triaryl sulfonated salt, diaryl sulfonium salt, sulfonate and sulfonate; the photosensitive polymer comprises a styrene chain segment and / or an acrylate chain segment. The photosensitive resin composition has high refractive index, high transparency and high resolution patterning and is suitable for manufacturing a micro lens array, and the refractive index of a micro lens formed by the photosensitive resin composition can be increased to 1.65-1.89 by introducing the perovskite nanoparticles.

Description

Technical Field

[0001] The invention belongs to the field of materials, and specifically relates to a photosensitive resin composition and a preparation method and application thereof. Background Art

[0002] Photosensitive resin compositions are mainly used to make microlens arrays required for many optical application components. Active optoelectronic components, such as displays and light-emitting devices (light-emitting diodes LED, laser devices), use microlens arrays to improve their light output characteristics. Passive optical components, such as typical solid-state imaging devices, include CCD (charge-coupled device) image sensors and CMOS (complementary metal oxide semiconductor) image sensors. These image sensors have a large number of microlens arrays regularly arranged on a substrate. The microlenses at the top of each element or pixel collect incident light to improve the efficiency of the photodetector array in the solid-state image sensor device, and these microlenses are required to have characteristics such as high refractive index and high transparency. At present, the method for making microlenses is to use photoresist (i.e., photosensitive resin composition) to form a microlens array. This method is generally called reflow method, which is defined as raising the temperature to above the glass softening point temperature of the photoresist layer, and by controlling the surface tension of the photoresist in the flowing state, the photoresist is finally 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 on 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 of 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 object of the present invention is to provide a method for preparing a photosensitive resin composition.

[0005] A third object of the present invention is to provide a microlens array.

[0006] A fourth object of the present invention is to provide a method for preparing a microlens array.

[0007] A fifth object of the present invention is to provide an application of a photosensitive resin composition and / or a microlens array in an optical element.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is:

[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 polymers, 1 to 10 parts of photoacid compounds, 0.5 to 1 part of surfactants, and 60 to 70 parts of solvents;

[0010] The photoacid compound is selected from at least one of triaryl sulfonate salts, diaryl sulfonium salts, sulfonates, and sulfonate esters;

[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 structural formula of the perovskite nanoparticles is ABX3, A2BX4, 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; n is an integer of 1 to 5; B is selected from Pb 2+ Sn 2+ , Cu 2+ , Mn 2+ , Fe 2+ At least one of; X is F — , Cl — Br — ,I — . .

[0014] Preferably, the photoacid compound is selected from at least one of triphenylsulfonic acid, triphenyl antimonate, triphenylsulfonyldifluoroalkylsulfonic acid, diphenyl antimonate, diphenyl antimonate, methoxydiphenyl antimonate, di-tert-butyldiphenyl antimonate, 2,6-dinitrobenzene sulfonate, pyrocatechol tri(alkyl sulfonate), N-hydroxysuccinimide trifluorate, norbornene-dicarbonimide-trifluorate, triphenyl non-fluorinated sulfonic acid sulfonate, diphenyl non-fluorinated sulfonate, methoxydiphenyl non-fluorinated sulfonate, di-butyldiphenyl non-fluorinated sulfonate, N-hydroxysuccinimide non-fluorinated sulfonate, norbornene-dicarbonyl non-fluorinated sulfonate, perfluorobutanesulfonic acid triphenylsulfonate, perfluorooctanesulfonic acid triphenylsulfonate, (triphenyl) perfluorooctanesulfonate, diphenylsulfonium, methoxydiphenylsulfonium, di-tert-butyldiphenylsulfonium trisalate, N-hydroxysuccinimide, and norbornene-dicarbonimide.

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

[0016] Among them, R a Selected from H, C 1～6 The alkyl group;

[0017] R b Selected from H, C 1～6 Straight or branched alkyl, C 3～6 Cyclic alkyl, vinyloxyethyl, 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-carbonate-propylene-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 structural formula of the acrylate segment is

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

[0020] R d Selected from C 1～6Straight or branched alkyl, C 3～6 Cyclic alkyl, vinyloxyethyl, 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-carbonate-propylene-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, C 1～6 The straight-chain or branched-chain 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 a cycloalkyl group, a cyclopentyl group and a cyclohexyl group.

[0023] Preferably, the polymerizable monomer of the acrylic acid ester segment is selected from at least one of acrylic acid ester monomers, monocarboxylic acids, dicarboxylic acids, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, (meth) alkyl acrylates, (meth) hydroxyalkyl acrylates, (meth) aryl acrylates, dicarboxylic acid diesters, vinyl-containing aromatic compounds, vinyl-containing aliphatic compounds, and conjugated dienes. Among them, 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 (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and tetrahydrofuranyl (meth)acrylate.

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

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

[0027] Preferably, the alkyl (meth)acrylate is selected from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0028] Preferably, the hydroxyalkyl (meth)acrylate is selected from 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0029] Preferably, the aryl (meth)acrylate is selected from phenyl (meth)acrylate and phenyl (meth)acrylate.

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

[0031] Preferably, the vinyl aromatic compound is selected from styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, 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, and the structural formula is:

[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, and l is 1:(1-3):(1-3):(1-3).

[0038] Preferably, the surfactant is selected from at least one of a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a polysiloxane surfactant; further preferably, the surfactant is a fluorine-based surfactant. The role of the surfactant in the present invention is to improve the uniformity of the coating and to improve the wettability of the photosensitive resin composition. The fluorine content in the fluorine-based surfactant is recommended to be 7 to 25wt%. Fluorine-based surfactants with a mass percentage of fluorine within this range have better thickness uniformity and liquid-saving properties of the coating film, and also have better solubility in the composition. Examples of commercially available fluorine-based surfactants include Megaface F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 sold by DIC Corporation and 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 comprises 60 to 70 parts of a 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 isoamyl 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, ethoxyethyl propionate, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxy At least one of acetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxy-2-methylpropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxy-2-methylpropionate, acetate, and butyl acetate. The function of the solvent in the present invention is to uniformly dissolve and mix the components in the photosensitive resin composition, thereby controlling the viscosity and volatility of the composition.

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

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

[0043] The third aspect of the present invention provides a microlens array, wherein the microlens array is made of a material including the photosensitive resin composition provided by the first aspect of the present invention.

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

[0045] The fourth aspect of the present invention provides a method for preparing the microlens array provided by the third aspect of the present invention, comprising the following steps:

[0046] S1: coating a material including a photosensitive resin composition on a substrate, and then pre-baking to obtain a cured film;

[0047] S2: exposing the cured film, baking it, developing it, and then baking it again to obtain the microlens array.

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

[0049] Preferably, the optical elements include active optoelectronic elements and passive optical elements.

[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 comprises a charge coupled device image sensor or a complementary metal oxide semiconductor 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, and is suitable for making 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, and when the amount of perovskite nanoparticles added is up to 10.0% by mass of the total solid content, the transmittance still reaches 99.1%. Therefore, the photosensitive resin composition of the present invention is suitable for making microlens arrays required by many optical application components.

[0054] The microlens array in the present invention is made of the photosensitive resin composition in the present invention, and its refractive index can reach up to 1.89. The resolution of the optical device using the microlens array as an optical element is greater than 5000 PPI, and it has the characteristics of extremely high resolution and miniaturization. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0056] Figure 2 Graph showing the transmittance spectrum of the microlens array in Example 3 in the visible light band. DETAILED DESCRIPTION

[0057] The specific implementation of the present invention is further described in detail below in conjunction with the accompanying drawings and examples, but the implementation and protection of the present invention are not limited thereto. It should be noted that if there are processes that are not particularly described in detail below, they can be implemented or understood by those skilled in the art with reference to the prior art. The reagents or instruments used that do not indicate the manufacturer are all conventional products that can be purchased commercially.

[0058] The preparation method of the microlens array in the present invention is:

[0059] (1) Coating

[0060] The photosensitive resin composition of the present invention is suitable for a substrate (Si, SiO2, SiN, SiN, TiN, WSi, borophosphosilicate glass (BPSG), silicon-glass bonding structure (SOG), organic anti-reflective film, etc.), or a treatment layer on the substrate (Cr, CrO, CrON, MoSi, SiO2, etc.), and a coating with a film thickness of 0.1 to 10.0 μm can be obtained by using a suitable coating method, such as spin coating, roll coating, flow coating, dip coating, spray coating, and blade coating.

[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 generally pre-baked on a hot plate at 60-150°C for 10 seconds to 30 minutes, or preferably pre-baked at 80-120°C for 30 seconds to 20 minutes to remove the solvent in the photosensitive resin composition.

[0063] (3) Exposure

[0064] Use a mask with a predetermined pattern and high-energy rays, such as visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, electron beam (such as electron beam and Alpha ray), electromagnetic wave (X-ray, gamma ray and soft X-ray), excimer laser, synchrotron radiation light source, and use any of the above high-energy rays to expose to obtain the target pattern. The exposure device can use various exposure machines such as mirror projection aligner, stepper, scanner, proximity, contact, laser exposure instrument, etc. In addition, super-resolution technology can also be used for exposure, such as multiple exposures, or exposure using phase transfer shielding method, annular illumination method, etc., to form a higher precision pattern. The wavelength of the exposure light source is 190nm~450nm; the exposure amount is 1~200mJ / cm 2 , preferably 10 to 100 mJ / cm 2 ; or exposure of 0.1 to 100 μC / cm 2 , preferably 0.5 to 50 μC / cm 2 .

[0065] (4) Post-exposure baking

[0066] The pattern obtained after exposure in step (3) is baked (post-exposure baking, PEB), and PEB is performed 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 0.1-5%, preferably a developer with a mass percentage of 2-3%, can be a quaternary ammonium salt or other alkaline aqueous developer, and can be tetramethylammonium hydroxide (TMAH), choline hydroxide, tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, or can be: alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, cesium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate. The developing method can use conventional methods such as liquid filling method, immersion method, shaking immersion method and spraying method to rinse for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes, so that the exposed part of the layer is dissolved in the developing solution, the unexposed part is not dissolved, and the substrate cannot be dissolved. After the development process, for example, after washing with ultrapure water for 30 seconds or more, a desired pattern may be formed by air drying with compressed air or compressed nitrogen, for example.

[0069] (6) Heating and baking

[0070] The cured film after development is heated, and the curing reaction of the polymer can be promoted by heating the patterned film using a heating device (such as a hot plate or an oven). For example, the heating temperature is 100°C to 250°C, and the heating time depends on the type of heating device, for example, the heating plate can be set to 5 minutes to 30 minutes, and the oven can be set to 30 minutes to 90 minutes.

[0071] The microlens array prepared by using the photosensitive resin composition of the present invention has the characteristic of high resolution. For example, under the condition that the thickness of the microlens is 1.0 to 2.0 microns, its diameter (critical dimension) can be as small as 3.0 to 5.0 microns, and the minimum pitch in the microlens array can be as small as 0.2 to 0.5 microns. This lithography process capability enables the optical display device matched therewith to have a resolution greater than 5000 PPI (pixel per inch).

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

[0073] The solvent is: propylene glycol methyl ether acetate, namely PGMEA;

[0074] The surfactant was 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 by the following preparation method: The following method was used to prepare cesium lead chloride perovskite (CsPbCl3) nanoparticle powder in air at room temperature. First, 0.9mmol of lead chloride (PbCl2, 99.999%) and 1.8mmol of methyl trioctyl ammonium chloride (MTOA, 97%) were dissolved in 9mL of anhydrous p-xylene (99%) to obtain a Pb precursor solution. Then, CsOAc solution (1mL) was quickly injected into the above Pb precursor under vigorous stirring. After about 30 seconds, 1mL 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, and the volume ratio of methyl acetate to the crude product solution was 3:1; the long-chain ligand oleylamine (OAm) can ensure the stability and dispersibility of CsPbCl3 perovskite nanocrystals. The precipitate was collected by centrifugation at 9000rpm and redispersed in 3mL of n-hexane for ligand exchange treatment. For ligand exchange treatment, EAm (50μL) was added to the above perovskite nanocrystal solution dissolved with 3mL of n-hexane. The surface of the in-situ synthesized pure perovskite nanocrystal was modified with undecene-1-amine (Eam, 95%) during the ligand exchange process, and then the perovskite nanocrystal was well dispersed in the photosensitive resin composition prepared by the present invention. After stirring for 5 minutes, MeOAc (12mL) was added to precipitate the modified perovskite nanocrystal and centrifuged at 9000rpm. The obtained perovskite nanocrystal powder was completely dried under vacuum for further use. The average size of the original perovskite nanocrystals was about 6-10 nanometers, and the size of the modified perovskite nanocrystals was almost the same. X-ray diffraction (XRD) spectra further confirmed that both the original and modified perovskite nanocrystals had a cubic perovskite structure. In addition to the organic ligand EAm used as mentioned above, it is also possible to select from primary alkylamines, secondary alkylamines, tertiary alkylamines, nitrogen-containing heterocycles, olefins, aliphatic hydrocarbons, alkyl-substituted aromatic hydrocarbons, alkyl-substituted phosphines, alkyl-substituted phosphine oxides, aromatic ethers, acids or any combination thereof. For example: hexadecylamine, trioctylamine, dioctylamine, pyridine, 1-octadecene, toluene, phenyldodecane, phenyltetradecane, phenylhexadecane, hexadecane, octadecane, squalane, trioctylphosphine, trioctylphosphine oxide, phenyl ether, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid.

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

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

[0080] The photoacid compound used in Examples 1 to 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 polymer used in Comparative Examples 2 to 4 w ) is 10000-11000 g / mol, the acid value is 90-100 mgKOH / g, and its structural formula is:

[0083] In the 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 to 3 and Comparative Examples 1 to 4 of the present invention can be prepared by free radical polymerization methods commonly used in the prior art, and the specific steps are as follows:

[0086] Under an inert gas environment, the monomer and initiator are heated in an organic solvent and copolymerized. The synthesis step adopts the drop polymerization method, and the specific steps are: under a nitrogen atmosphere, the monomer and initiator solution is dripped into the heated solvent, the organic solvent used in the polymerization is tetrahydrofuran, and the polymerization initiator is 2,2'-azobisisobutyronitrile (AIBN). The temperature is set to 60°C and the reaction time is 6 hours. After the reaction is completed, it is crystallized in methanol, further washed with hexane, separated and dried, and measured by nuclear magnetic resonance ( 1 The composition of the photosensitive polymer was determined by H-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 is further described in detail below in conjunction with 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:

[0091] The method is prepared by physically mixing the formulated amount of photosensitive polymer, photoacid compound, perovskite nanoparticles, surfactant and solvent. The order of feeding is solvent, photoacid compound, perovskite nanoparticles, photosensitive polymer (resin) and surfactant.

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

[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:

[0098] The method is prepared by physically mixing the formulated amount of photosensitive polymer, photoacid compound, perovskite nanoparticles, surfactant and solvent. The order of feeding 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:

[0102] The method is prepared by physically mixing the formulated amount of photosensitive polymer, photoacid compound, perovskite nanoparticles, surfactant and solvent. The order of feeding is solvent, photoacid compound, perovskite nanoparticles, photosensitive polymer (resin) and surfactant.

[0103] Comparative Example 1

[0104] This example provides a photosensitive resin composition, and its formula is shown in Comparative Example 1 in Table 1.

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

[0106] The method is prepared by physically mixing the photosensitive polymer, photoacid compound, surfactant and solvent in the prescribed amount. The order of adding the materials is solvent, photoacid compound, photosensitive polymer (resin) and surfactant.

[0107] Comparative Example 2

[0108] This example provides a photosensitive resin composition, and its formula is shown in Comparative Example 2 in Table 1.

[0109] The method is prepared by physically mixing the formulated amount of photosensitive polymer (resin), polymerizable compound (monomer), free radical photoinitiator, surfactant and solvent. The order of adding materials 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, and its formula is shown in Comparative Example 3 in Table 1.

[0112] The method is prepared by physically mixing a formulated amount of photosensitive polymer (resin), polymerizable compound (monomer), free radical photoinitiator, perovskite nanoparticles, surfactant and solvent. The order of adding materials is: 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, and its formula is shown in Comparative Example 4 in Table 1.

[0115] The method is prepared by physically mixing a formulated amount of photosensitive polymer (resin), polymerizable compound (monomer), free radical photoinitiator, perovskite nanoparticles, surfactant and solvent. The order of adding materials is: solvent, free radical photoinitiator, perovskite nanoparticles, photosensitive polymer (resin), polymerizable compound (monomer) and surfactant.

[0116] Performance Test:

[0117] First, the photosensitive resin compositions in Examples 1 to 3 are patterned according to the following preparation method to prepare a microlens array. The specific preparation method is:

[0118] Coating: The rotary coater was set to 800 rpm and 400 rpm, and 0.3 mm thick soda glass for liquid crystal displays was selected. 3 mL of the photosensitive resin composition was taken and coated to obtain a 1.0 μm thick film.

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

[0120] Exposure: SUSS MA8 proximity exposure machine was used, i-Line filter was used to filter the light source band, and the exposure amount was 100mJ / cm 2 .

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

[0122] Development: immersion development was performed using 2.34% by mass of a developer, tetramethylammonium hydroxide (TMAH), for 1 minute, followed by air drying with compressed air to form a desired pattern.

[0123] Baking: The whole preparation process was completed by heating the patterned film after development at 150 °C in an oven for 30 minutes.

[0124] In addition, the photosensitive resin compositions in Comparative Examples 1 to 4 were also patterned according to the preparation method in Examples 1 to 3 to prepare microlens arrays of Comparative Examples 1 to 4, wherein the photosensitive resin compositions in Comparative Examples 1 to 4 differ from those in Examples 1 to 3 in that the patterning process does not include a post-exposure baking (PEB) process. Then, the performance of the photosensitive resin compositions in Examples 1 to 3 and Comparative Examples 1 to 4 was evaluated according to the following refractive index and pattern resolution test methods, and the specific test methods are:

[0125] Surface morphology test: The surface morphology of the microlens array made of the photosensitive resin composition in Example 1 was tested using a scanning electron microscope. The specific test figure is as follows: Figure 1 shown.

[0126] The refractive index test method is: using an ellipsometer VUV-VASE, manufactured by JA Volan, Japan, to measure the refractive index of the photosensitive resin compositions in Examples 1 to 3 and Comparative Examples 1 to 4 at 589 nm.

[0127] The test method of pattern resolution is as follows: after the photosensitive resin compositions in Examples 1 to 3 and Comparative Examples 1 to 4 are subjected to coating, exposure, post-exposure baking (PEB; the comparative examples do not have this step), development and baking operations, the size (critical dimension) of the smallest pattern still attached to the substrate on the silicon chip substrate is observed using an optical electron microscope. The unit is micrometer.

[0128] The transmittance spectrum of the microlens array of Example 3 in the visible light band was tested 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 light 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 to 3 and Comparative Examples 1 to 4

[0130]

[0131] The calculation method of the ratio (%) of the perovskite nanoparticles to the total solid content of the photosensitive resin composition in Table 2 is: [(weight percentage of the perovskite nanoparticle dispersion / total weight percentage of the photosensitive resin composition*100%)*perovskite nanoparticle solid content mass percentage] / total solid content of the photosensitive resin composition, and the perovskite nanoparticle solid content mass percentage is the mass percentage of the perovskite nanoparticles in the perovskite nanoparticle dispersion. It can be seen from Table 2 that the microlens array made of the photosensitive resin composition in Examples 1 to 3 of the present invention has both a high refractive index and a high pattern resolution; if the pattern resolution in Table 2 is less than or equal to 5 microns, it may be applied to display screen products with a resolution greater than or equal to 5000ppi.

[0132] The above is a detailed description of the embodiments of the present invention, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in the relevant technical field without departing from the purpose of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

Claims

1. A photosensitive resin composition, characterized in that: The invention comprises the following components in parts by weight: 0.5 to 2 parts of perovskite nanoparticles, 20-40 parts of photosensitive polymer, 1-10 parts of photoacid compound, 0.5-1 parts of surfactant, 60-70 parts of solvent; The photoacid compound is selected from at least one of triaryl sulfonate salts, diaryl sulfonium salts, sulfonates, and sulfonate esters; The photosensitive polymer includes styrene segments and / or acrylate segments.

2. The photosensitive resin composition according to claim 1, characterized in that: The structural formula of the perovskite nanoparticles is ABX3, A2BX4, ABX4, wherein A is selected from Cs + , C n H n+2 NH3 + 、C6H5C n H 2n NH3 + NH3C n H 2n NH3 + 、NH2CHNH3 + At least one of; n is an integer of 1 to 5; B is selected from Pb 2+ Sn 2+ , Cu 2+ , Mn 2+ , Fe 2+ At least one of; X is F — , Cl — Br — ,I — .

3. The photosensitive resin composition according to claim 1, characterized in that: The structural formula of the styrene chain segment is: Among them, R a Selected from H, C 1～6 The alkyl group; R b Selected from H, C 1～6 Straight or branched alkyl, C 3～6 Cyclic alkyl, vinyloxyethyl, 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-carbonate-propylene-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.

4. The photosensitive resin composition according to claim 1, characterized in that: The structural formula of the acrylate segment is Among them, R c Selected from H, F, C1-6 straight chain or branched alkyl, C1-6 straight chain or branched fluoroalkyl; R d Selected from C 1～6 Straight or branched alkyl, C 3～6 Cyclic alkyl, vinyloxyethyl, 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-carbonate-propylene-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; and / or, The polymerizable monomer of the acrylic ester segment is selected from at least one of acrylic ester monomers, monocarboxylic acids, dicarboxylic acids, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, (meth) alkyl acrylates, (meth) hydroxyalkyl acrylates, (meth) aryl acrylates, dicarboxylic acid diesters, vinyl-containing aromatic compounds, vinyl-containing aliphatic compounds, and conjugated dienes.

5. The photosensitive resin composition according to claim 1, characterized in that: The surfactant is selected from at least one of a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a polysiloxane surfactant.

6. The photosensitive resin composition according to claim 1, characterized in that: The structural formula of the photosensitive polymer is: In the structural formula of the photosensitive polymer, the molar ratio of i, j, k, and l is 1:(1-3):(1-3):(1-3); And / or, the photoacid compound is 2-(2-(((propylsulfonyl)oxy)imino)thiophene-3(2H)-ylidene)-2-(o-tolyl)acetonitrile.

7. The method for preparing the photosensitive resin composition according to any one of claims 1 to 6, characterized in that: The following steps are involved: The photosensitive resin composition is prepared by mixing the raw materials.

8. 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 6.

9. The method for preparing a microlens array according to claim 8, characterized in that: The following steps are involved: S1: coating a material including a photosensitive resin composition on a substrate, and then pre-baking to obtain a cured film; S2: exposing the cured film, baking it, developing it, and then baking it again to obtain the microlens array.

10. Use of the photosensitive resin composition according to any one of claims 1 to 6 and / or the microlens array according to claim 8 in an optical element.

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