CN113406733A - Micro lens, micro lens array and preparation method - Google Patents

Micro lens, micro lens array and preparation method Download PDF

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Publication number
CN113406733A
CN113406733A CN202010186044.3A CN202010186044A CN113406733A CN 113406733 A CN113406733 A CN 113406733A CN 202010186044 A CN202010186044 A CN 202010186044A CN 113406733 A CN113406733 A CN 113406733A
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microlens
micro
solution
array
perovskite
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施立甫
钟海政
李建军
柏泽龙
王晶晶
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Zhijing Technology Beijing Co ltd
Beijing Institute of Technology BIT
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Zhijing Technology Beijing Co ltd
Beijing Institute of Technology BIT
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G02B3/0012—Arrays characterised by the manufacturing method
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G02B3/0012—Arrays characterised by the manufacturing method
    • G02B3/0018—Reflow, i.e. characterized by the step of melting microstructures to form curved surfaces, e.g. manufacturing of moulds and surfaces for transfer etching
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/87—Light-trapping means

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  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electromagnetism (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a micro lens, a micro lens array and a preparation method thereof. According to the invention, the perovskite nano material is doped in the micro-lens array, so that the micro-lens has multiple functions, such as the functions of filtering and condensing light, the functions of rotating light and condensing light and the like. The microlens of the invention replaces the prior microlens array and the corresponding light filtering/converting material, thereby simplifying the structure of the device, reducing the cost and generating new application scenes. The invention also provides a preparation method of the micro-lens, the method has simple process, low cost and good compatibility, and the prepared micro-lens has good application prospect in the fields of enhanced detection, multispectral imaging, liquid crystal display backlight and the like.

Description

Micro lens, micro lens array and preparation method
Technical Field
The invention belongs to the technical field of optical devices and preparation, and particularly relates to a micro lens, a micro lens array and a preparation method.
Background
The micro lens is an optical structure with wide application, can be used on an imaging detector, and is used for increasing the light acquisition and improving the detection efficiency; the method can also be used in application scenes such as three-dimensional imaging, LED enhanced light extraction, optical interconnection and the like. However, the commonly used microlenses at present are based on colorless transparent media, and cannot realize functions such as light conversion, light filtering and the like, and the functions can be realized by doping functional materials into the microlens substrate, for example, a microlens array and a light filter are generally required to be respectively integrated on a color CMOS imaging detection device, and if the light filtering material can be added into the microlenses, the cost can be saved, and the structure can be simplified; for example, the response of a CCD camera to ultraviolet light in an ultraviolet region is poor, light can be converted to a visible light region by attaching a perovskite light conversion film, and the detection efficiency is increased, and if a light conversion material is made into a microlens array, the detection efficiency can be further increased by converging light to an effective detection region.
However, at present, the related research on the incorporation of functional materials is few, and most of the research is based on dyes, and no related report is available on the perovskite. The existing microlens preparation methods are various, such as photoresist thermal reflow technology, template processing, laser direct writing, ink-jet printing and the like, the photoresist thermal reflow technology is mostly applied, the methods are also directed to transparent media, and a new method is needed for preparing the perovskite-doped microlens.
Disclosure of Invention
In order to solve the technical problems, the invention provides a micro lens, a micro lens array and a preparation method thereof, wherein the micro lens has multiple optical functions by doping perovskite nanocrystals in the micro lens.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in one aspect of the invention, a microlens is provided, wherein the microlens comprises a polymer and perovskite nanocrystals, and the perovskite nanocrystals are dispersed in the polymer.
Alternatively,the chemical formula of the perovskite nanocrystal is ABX3、A3B2X9、A2BX6At least one of (1).
The content of the perovskite nano-crystal in the micro-lens is 1 wt% -90 wt%.
Specifically, the lower limit of the content of the perovskite nanocrystal in the microlens is 1 wt%, 5 wt%, 10 wt%, 20 wt%, 30 wt%; the upper limit of the content of the perovskite nanocrystal in the microlens is 40 wt%, 50 wt%, 60 wt%, 80 wt%, 90 wt%.
Alternatively, A is selected from CH3NH3、CH(NH)NH3Cesium (Cs);
b is at least one selected from Ge, Sn, Pb, Sb, Bi, Cu, Mn, In, Ti, Ag and Al;
x is at least one selected from halogen elements.
The microlens array is a semiconductor material, and in general, when B-site atoms are lead elements, the obtained microlens is a luminous microlens and has a light down-conversion function; when the B-site atom is an element other than lead, the obtained microlens is a light filtering microlens and has a light filtering function, most of light with the wavelength lambda less than x is absorbed by the semiconductor material, most of light with the wavelength lambda more than x is transmitted, and x is an absorption edge of the semiconductor material.
When the microlens is a light emitting microlens, the role of the microlens includes convergence or divergence of light, conversion of light, encapsulation of a base material, and the like. Depending on the optical properties of the substrate and microlens selected for use.
Optionally, the polymer is selected from at least one of polyvinylidene fluoride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, polysulfone, polyamide, polyimide, polycarbonate, polystyrene, polyvinyl chloride, polyvinyl alcohol, ABS plastic, polyacrylonitrile, polyolefin elastomer, polyurethane, polyvinyl carbazole.
Wherein the ABS plastic is preferably transparent ABS plastic; the polyurethane is preferably a thermoplastic polyurethane.
Polymers have a variety of roles in microlenses: 1. the polymer is capable of forming a microlens structure and imparting a smooth surface to the microlens structure; 2. the polymer can limit the growth of the perovskite structure material, so that the perovskite structure material is kept in a nanometer size to form a semiconductor nanocrystal and protect the semiconductor nanocrystal; 3. depending on the usage scenario, the polymer may also have the function of encapsulating the material or structure on the base under the microlens.
In another aspect of the present invention, a microlens array is provided, the microlens array including a substrate and a plurality of microlenses;
the plurality of micro lenses are distributed on the surface of the substrate in an array manner;
the microlens is selected from any one of the above microlenses.
Specifically, the pitch parameter of the array is 1-500 μm, the diameter range of the micro-lens is 1-500 μm, and the array arrangement and the size and shape of the micro-lens can be regulated and controlled in the range according to different requirements.
Alternatively, the substrate is selected from any one of a semiconductor substrate, a semiconductor device, and a light emitting device.
The semiconductor substrate refers to a substrate formed as a semiconductor device, such as quartz, silicon, glass, a polymer flexible substrate, and the like.
The semiconductor device refers to a semiconductor device having a certain function, such as a detection device, a light emitting device, and other electronic devices that add a semiconductor material on a semiconductor substrate by a certain process (if the substrate is a semiconductor material, the semiconductor material is directly on the semiconductor material) and use the special electrical characteristics of the semiconductor material to complete a specific function.
Preferably, the substrate is any one of glass, quartz, silicon, an SOI (silicon on insulator) device, a CMOS (complementary metal oxide semiconductor) device, a CCD (charge coupled device) device, a detector array device, an LED, a micro LED display panel, and a MiniLED display panel.
Preferably, the lamp beads on the LED are arranged in an array.
Optionally, the substrate is any one of the microlenses described above.
When the substrate is a light emitting device or a microlens array is integrated with the light emitting device, the microlens plays a role in light dispersion or scattering, light conversion, and encapsulation.
When the micro lens is a filtering micro lens, the micro lens is integrated with a detection device to play a role in filtering and condensing light, and can be used for a spectrometer or a multispectral imaging device.
In a third aspect of the present invention, a method for manufacturing a microlens array is provided, the method at least comprising:
s001, obtaining at least one solution containing a perovskite nanocrystal precursor and a polymer source;
and S002, transferring the solution to a substrate according to the required array position, and treating the solution according to a preset mode to enable the perovskite nanocrystal precursor to generate perovskite nanocrystals in situ to form the micro-lens array.
Optionally, in step S001, the perovskite nanocrystal precursor comprises a species a and a species b;
substance a is selected from any one of the compounds having formula i;
AX formula I
Substance b is selected from any one of compounds having formula II or III;
BX2formula II
BX3Formula III
A is selected from CH3NH3、CH(NH)NH3Any one of Cs;
b is selected from any one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, In, Ti, Ag and Al;
x is selected from any one of halogen elements.
And reacting the substance a and the substance b to generate the perovskite nanocrystal.
The mass ratio of the substances a and b is between 1:10 and 10: 1.
Alternatively, in step S001, the polymer source is selected from any one of a polymer, a monomer oligomer.
Wherein the polymer is a high molecular polymer, i.e. the polyvinylidene fluoride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, polysulfone, polyamide, polyimide, polycarbonate, polystyrene, polyvinyl chloride, polyvinyl alcohol, ABS plastic, polyacrylonitrile, polyolefin elastomer, polyurethane, polyvinyl carbazole, etc.;
the monomer refers to a monomer material forming the polymer and other acrylic monomers, methacrylic monomers and vinyl monomer materials;
specifically, the monomer may be selected from ethoxyethyl acrylate, cyclotrimethylolpropane formal acrylate, isobornyl methacrylate, isobornyl acrylate, lauryl alcohol acrylate, tetrahydrofuran acrylate, phenoxyethyl acrylate, dicyclopentadiene acrylate, 4-tert-butylcyclohexyl acrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-methyl methacrylate, 2-ethyl methacrylate, ethylene glycol acrylate, ethylene glycol dimethacrylate, beta-hydroxyethyl methacrylate, lauryl acrylate, lauryl methacrylate, ethylene glycol dimethacrylate, isobutyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, isooctyl methacrylate, decyl methacrylate, or mixtures thereof, At least one of hydroxyethyl methacrylate, methoxyethyl methacrylate, 1, 6-hexanediol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 3-butanediol dimethacrylate, propoxylated trimethylolpropane triacrylate, dimethacrylate, ethylene glycol methacrylate, ethoxylated trimethylolpropane triacrylate, tripropylene glycol diacrylate, 2-phenylthioglycol acrylate;
the monomer oligomer is an organic molecule with the molecular weight less than 10000 formed by monomer materials forming the polymer or other acrylic monomers, methacrylic monomers and vinyl monomer materials;
specifically, the monomer oligomer may be at least one of polyester acrylate and derivatives thereof, epoxy acrylate and derivatives thereof, urethane acrylate and derivatives thereof, polyethylene glycol acrylate and derivatives thereof, triethylene glycol diacrylate and derivatives thereof, triethylene glycol acrylate and derivatives thereof, diethylene glycol diacrylate and derivatives thereof, diethylene glycol acrylate and derivatives thereof, and trimethylolpropane trialkyl ester and derivatives thereof;
optionally, in step S001, the solution further comprises a solvent, wherein the solvent is at least one selected from N, N-dimethyl amide, dimethyl acetamide, dimethyl sulfoxide, ethyl acetate, N-methyl pyrrolidone, tetrahydrofuran, toluene, chloroform, and acetone;
the dosage of the solvent is 1 to 95 weight percent of the solution;
optionally, in step S001, the solution further comprises a perovskite ligand;
the perovskite ligand is at least one of acid ligand, amine ligand, quaternary ammonium salt, silane ligand, phosphine ligand and thiol ligand.
Preferably, the acid ligand is selected from at least one of oleic acid, n-dodecanoic acid, n-octanoic acid;
preferably, the amine ligand is selected from at least one of oleylamine, dodecylamine, n-octylamine and phenylenediamine;
preferably, the quaternary ammonium salt ligand is selected from at least one of didodecyl dimethyl ammonium bromide, tetraoctyl ammonium bromide and hexadecyl trimethyl ammonium bromide;
preferably, the silane ligand is selected from at least one of cage polysilsesquioxane, hexamethyldisiloxane and tetramethoxysilane;
preferably, the phosphine ligand may be selected from at least one of trioctylphosphine, trioctylphosphine;
preferably, the thiol ligand may be selected from at least one of octaalkylthiol, dodecylthiol, octadecylthiol.
The perovskite ligand accounts for 0-20 wt% of the solution.
Specifically, the lower limit of the perovskite ligand in the solution is 0, 0.4 wt%, 5 wt%, 8 wt%, 10 wt%; the perovskite ligand accounts for 12 wt%, 14 wt%, 15 wt%, 18 wt%, 20 wt% of the upper limit of the solution.
The perovskite ligand can regulate and control the crystallization and luminescence of perovskite, passivate the surface defects of perovskite nanocrystalline, limit the further growth of nanocrystalline size, and regulate and control the structure and morphology of nanocrystalline.
Optionally, in step S001, a photoinitiator or/and a thermal initiator is further included in the solution.
The photoinitiator accounts for 0-10 wt% of the solution;
the thermal initiator accounts for 0-10 wt% of the solution.
Specifically, the lower limit of the photoinitiator in the solution is 0, 0.33 wt%, 2 wt%, 3 wt%, 4 wt%; the upper limit of the amount of the photoinitiator in the solution is 5 wt%, 6 wt%, 7 wt%, 8 wt%, 10 wt%.
Specifically, the thermal initiator accounts for 0, 1 wt%, 2 wt%, 3 wt%, 4 wt% of the lower limit of the solution; the thermal initiator constitutes 5 wt%, 6 wt%, 7 wt%, 8 wt%, 10 wt% of the solution at the upper limit.
Optionally, the photoinitiator is at least one of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl methanone, 1-hydroxy-cyclohexyl-phenyl methanone, diphenyl- (4-phenylsulfide) phenylsulfonium hexafluorophosphate, 2-diethoxyacetophenone, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and α -hydroxyalkylphenone;
the thermal initiator is azobisisobutyronitrile.
The addition of the photoinitiator may initiate polymerization of the monomeric material and/or oligomer; the addition of the thermal initiator initiates and facilitates polymerization of the monomeric material and/or oligomer.
Alternatively, S002 is:
and carrying out hydrophilic treatment or hydrophobic treatment on the substrate, and transferring the solution containing the perovskite structure material to the substrate according to the required array position to form the micro lens with the micro lens array.
The appearance of the micro lens can be changed by carrying out hydrophilic treatment or hydrophobic treatment on the substrate, so that the optical property of the micro lens is changed;
the hydrophilic treatment may specifically be at least one of oxygen plasma treatment of the substrate, treatment with a wetting agent, or change in temperature of the substrate;
the hydrophobic treatment may specifically be at least one of the use of a hydrophobic coating on the substrate, or a change in the temperature of the substrate, or the preparation of hydrophobic nanostructures on the substrate, etc.
Optionally, in step S002, the preset manner includes: at least one of light irradiation, heating and microwave treatment.
Specifically, the heating and drying process can be carried out under the assistance of vacuum or nitrogen.
The pre-set pattern treatment corresponds to a curing treatment for the solution.
When the solution is a polymer solution, the curing treatment functions include promoting volatilization of the solvent, drying the solution, regulating perovskite crystallization, and the like.
When the solution is a monomer material and/or an oligomer, the curing treatment function includes controlling polymerization of the monomer, promoting volatilization of the solvent, and the like.
Optionally, the transferring method is selected from any one of inkjet printing, spraying, screen printing, air jet printing, transfer printing, roll-to-roll patterning, micro-nano imprinting, and brush coating.
Preferably, the transfer method is ink jet printing, and the printed ink droplets will form a hemisphere due to surface tension, and form a microlens after drying and/or curing.
Alternatively, when the solution containing the perovskite structure material is a polymer solution, the printing device used is a Sonoplot high precision micro-nano material deposition inkjet printing system, which can be used for printing of high viscosity solutions.
Preferably, ink droplets may be printed on the microlenses formed by the above method to form microlenses having a shell structure.
Optionally, in step S001, a plurality of different solutions containing perovskite nanocrystal precursors and polymer sources are obtained, the plurality of solutions differing from each other in the perovskite nanocrystal precursors and/or polymer sources contained therein.
Optionally, the method further comprises S003:
the microlens array is integrated with an optical device or/and an electrical device.
A combination of corresponding functions can be achieved by integrating the microlens array with other optical devices.
Optionally, the obtained microlens may be further processed, such as by illumination, heating, and the like, so as to further adjust and control the morphology and optical properties of the microlens.
The invention has the beneficial effects that:
1. according to the invention, the perovskite structure material is doped in the micro-lens array, so that the micro-lens has multiple functions, such as the functions of filtering and condensing light, the functions of rotating light and condensing light and the like, and the functions of the micro-lens are expanded.
2. The microlens of the invention replaces the prior microlens array and the corresponding light filtering/converting material, thereby simplifying the structure of the device, reducing the cost and generating new application scenes.
3. The invention also provides a preparation method of the micro-lens, the method has simple process, low cost and good compatibility, and the prepared micro-lens has good application prospect in the fields of enhanced detection, multispectral imaging, liquid crystal display backlight and the like.
Drawings
FIG. 1 is a schematic view of a microlens based on a CMOS probe device fabricated in example 1;
FIG. 2 is a photograph of a transmission electron microscope of a microlens prepared in example 1;
FIG. 3 is a schematic view of a microlens based on an LED backplane made in example 3;
FIG. 4 is a schematic view of a MiniLED backplane-based microlens fabricated in example 4;
FIG. 5 is a schematic view of a microlens based on a CMOS probe device manufactured in example 5.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the method of carrying out the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; materials and the like used in the following examples are commercially available unless otherwise specified; the equipment used in the following examples, unless otherwise specified, was subject to the manufacturer's recommended use parameters.
The characterization instrument for the materials used in the following examples was: a transmission electron microscope (model HT7700, Hitachi, manufactured by Kabushiki Kaisha), an absorption spectrometer (model UV-6100, Shanghai Mei spectral instruments Co., Ltd.), a fluorescence spectrometer (model F-380, Tianjin Hongkong science and technology Co., Ltd.), and the like.
Example 1
1. Preparing a semiconductor precursor solution S1: 1mmol of PbBr23mmol of MABr and 1g of PAN in 10ml of DMF.
2. Printing the solution as ink on a CMOS imaging detector by adopting a Sonoplot high-precision micro-nano material deposition ink-jet printing system, so that each ink drop hits on a single pixel of a CMOS device, then heating the printed CMOS device at 45 ℃ to dry the ink drop, and separating out MAPbBr3Perovskite nanocrystals, forming a photoconversion microlens array, as sample # 1.
Example 2
1. Preparing a perovskite precursor solution S1:
0.04mmol of PbBr20.04mmol CsBr, dissolved in 1g DMF and added with 50mg oleylamine and 75mg oleic acid as ligands; 50mg of the above solution was added to a mixed monomer solution of 1.5g of Methyl Methacrylate (MMA) and 28mg of ethylene glycol dimethacrylate (EDMA), and 5.19mg of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) as a photoinitiator was further added and stirred until all was dissolved.
2. Printing the solution as ink on a CCD device by using a printing electronic ink-jet printer to make each ink drop aim at and fall on a pixel of the CCD, and then curing the printed CMOS device under ultraviolet light to make monomer materials polymerized into high molecular polymers to obtain the CsPbBr-embedded material3Solid microlenses of perovskite nanocrystals, noted sample # 2.
Example 3
1. Preparing precursor solutions S1 and S2 of the semiconductor material:
1mmol of PbBr23mmol CsBr and 1g PVDC were dissolved in 10ml DMSO to prepare a solution S1.
1mmol of PbBr23mmol of CsI and 1g of PVDF were dissolved in 10ml of DMSO to prepare a solution S2.
2. The solution is used as ink, a Sonoplot high-precision micro-nano material deposition ink-jet printing system is adopted, the solution S1 and the solution S2 are respectively printed in a light emitting area of the same blue light LED backboard, the two solutions are printed at intervals, then the printed blue light LED backboard is heated at 90 ℃, ink drops are dried, green light perovskite nanocrystals and red light perovskite nanocrystals are respectively separated out, microlenses with a green fluorescence light conversion microlens array and a red fluorescence light conversion microlens array are obtained, partial blue light can be respectively converted into green light and red light, the three-color light is mixed into white light, the white light is used as a white light backlight module of liquid crystal, and the sample is marked as # 3.
Example 4
1. Preparing precursor solutions of the semiconductor material S1, S2 and S3:
1mmol of PbBr23mmol of MABr and 1g of PAN were dissolved in 10ml of DMF to prepare a solution S1.
1mmol of PbBr23mmol of MAI and 1g of PMMA were dissolved in 10ml of DMSO to prepare a solution S2.
A solution S3 was prepared by dissolving 1g of PMMA in 10ml of DMSO.
2. The solution is used as ink, a Sonoplot high-precision micro-nano material deposition ink-jet printing system is adopted, the solution S1, the solution S2 and the solution S3 are respectively printed on different LED lamp beads of the same blue-light MiniLED backboard, the micro LED lamp beads are covered by the micro lens, the three solutions are sequentially printed at intervals, then the printed blue-light MiniLED backboard is heated at 90 ℃, ink drops are dried, the ink drops printed by the solution S1 and the solution S2 are respectively separated out green-light perovskite nano crystals and red-light perovskite nano crystals, the micro lens with the green fluorescence light conversion micro lens array and the red fluorescence light conversion micro lens array is obtained, and the micro lens is marked as a sample No. 4.
Example 5
1. Preparing precursor solutions of the semiconductor material S1, S2, S3 and S4:
1mmol of BiBr34mmol of MABr and 1g of PAN were dissolved in 10ml of DMF to prepare a solution S1.
1mmol of BiBr32mmol of MABr, 2mmol of MAI and 1g of PAN were dissolved in 10ml of DMF to prepare a solution S2.
1mmol of BiBr34mmol of MAI and 1g of PAN were dissolved in 10ml of DMF to prepare a solution S3.
1mmol of PbI23mmol of MAI and 1g of PAN were dissolved in 10ml of DMF to prepare a solution S4.
2. The solution is used as ink, a Sonoplott high-precision micro-nano material deposition ink-jet printing system is adopted, the solution S1, the solution S2, the solution S3 and the solution S4 are respectively printed on different pixels of the same CMOS detection device, the four solutions are sequentially printed at intervals, then the printed CMOS detection device is heated at 90 ℃, ink drops are dried, and microlenses of microlens arrays T1, T2, T3 and T4 are formed and recorded as sample No. 5.
Example 6 samples 1# to 5# were tested
The structure of sample 1# is shown in fig. 1, the array structure is a matrix array, the array pitch is 10 micrometers, the diameter of the micro lens is 5 micrometers, and the formed micro lens array can converge light in a non-detection region of a CMOS pixel to a detection region, and can convert light in an ultraviolet region with less absorption into green light, so that the quantum efficiency of a CMOS detection device is increased. The microlens in sample No. 1 was ultrathin sectioned and observed by transmission electron microscopy, and the photograph of the observation is shown in FIG. 2, in which the dark color point is MAPbBr3Perovskite nanocrystalline, the rest is polymer PAN.
The array structure of sample 2# is the same as that of sample 1#, and the formed microlens array can converge light at the non-detection region of the CCD pixel to the detection region, and can convert light in the ultraviolet region with less absorption into green light, thereby increasing the quantum efficiency of the CCD device.
The structure of sample 3# is shown in fig. 3, the array structure is a matrix arrangement, the center-to-center distance between adjacent microlenses is 20 micrometers, the diameter of the microlenses is 20 micrometers, and a green-fluorescence light conversion microlens array and a red-fluorescence light conversion microlens array are formed on the blue LED backplane. The detection of a fluorescence spectrometer proves that partial blue light from the bottom blue light LED backboard is converted into green light and red light through the green fluorescence and red fluorescence micro-lenses respectively, the micro-lenses play a role in light scattering and dispersion, so that three kinds of colored light can be mixed into uniform white light, a prepared sample can be used as a white light backboard of liquid crystal or a white light LED, and the micro-lens structure can improve the light emitting efficiency of the LED under the light scattering and scattering effects except the light conversion effect.
The structure of sample 4# is shown in fig. 4, the array structure is a matrix array, the center-to-center distance of the microlenses is 300 micrometers, the diameter of the microlenses is 200 micrometers, and a green-fluorescence light conversion microlens array and a red-fluorescence light conversion microlens array are formed on the blue MiniLED backplane. The fluorescence spectrometer is adopted for detection and verification, all or part of blue light from the bottom blue light LED lamp beads is converted into red light and green light through the green fluorescence and red fluorescence micro lenses respectively, the ink drops of S3 form colorless transparent micro lenses, the micro lenses play a role in light scattering and divergence, each lamp bead can emit light controllably, and the monochromatic blue light display panel can realize color display. Besides the function of realizing light conversion, the micro-lens structure can improve the light emitting efficiency of the LED by the light scattering and scattering effect, and plays a role in packaging the LED at the bottom.
In sample No. 5, the array structure is a matrix array, and the material of the microlens T1 is PAN and MA2Bi3Br9The composite material and the micro-lens T2 are made of PAN and MA2Bi3Br6I3The composite material and the micro-lens T3 are made of PAN and MA2Bi3Br3I6The composite material and the micro-lens T4 are made of PAN and MA2Bi3I9The composite material is formed. Detecting the transmission wavelength of each microlens by using an absorption spectrometer, wherein the transmission wavelength of each microlens T1, T2, T3 and T4 is divided intoIs other than λ1＞450nm、λ2＞510nm、λ3＞550nm、λ4> 610 nm. The micro-lens array can converge light at a non-detection region of a CMOS pixel to a detection region on one hand, and micro-lenses made of different materials can filter light with different wavelengths on the other hand, so that the CMOS pixel which does not have the spectrum resolution function originally has the spectrum resolution function, as shown in FIG. 5, a pixel under the micro-lens T1 can only detect light with the wavelength being more than 450nm, a pixel under the micro-lens T2 can only detect light with the wavelength being more than 510nm, a pixel under the micro-lens T3 can only detect light with the wavelength being more than 550nm, and a pixel under the micro-lens T4 can only detect light with the wavelength being more than 610 nm. And the spectrometer device or the multispectral imaging device can be manufactured through subsequent integration and processing.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A microlens comprising a polymer and a perovskite nanocrystal dispersed in the polymer.
2. The microlens of claim 1 wherein the perovskite nanocrystal is of the formula ABX3、A3B2X9、A2BX6At least one of;
preferably, the content of the perovskite nanocrystal in the microlens is 1 wt% to 90 wt%;
preferably, said A is selected from CH3NH3、CH(NH)NH3At least one of Cs;
preferably, the B is selected from at least one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, In, Ti, Ag and Al;
preferably, the X is selected from at least one of the halogen elements.
3. The microlens of claim 1 wherein the polymer is selected from at least one of polyvinylidene fluoride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, polysulfone, polyamide, polyimide, polycarbonate, polystyrene, polyvinyl chloride, polyvinyl alcohol, ABS plastic, polyacrylonitrile, polyolefin elastomer, polyurethane, polyvinyl carbazole.
4. A microlens array, comprising a substrate and a plurality of microlenses;
the plurality of micro lenses are distributed on the surface of the substrate in an array manner;
the microlens is selected from any one of the microlenses of any one of claims 1-3.
5. The microlens array as claimed in claim 4, wherein the substrate is selected from any one of a semiconductor substrate, a semiconductor device, and a light emitting device;
preferably, the substrate is any one of glass, quartz, silicon, an SOI device, a complementary metal oxide semiconductor device, a charge coupled device, a detector array device, an LED, a micro LED display panel, and a MiniLED display panel.
6. The microlens array according to claim 4, wherein the substrate is any one of the microlenses according to any one of claims 1 to 3.
7. A method for manufacturing a microlens array as claimed in any one of claims 4 to 6, the method comprising at least:
s001, obtaining at least one solution containing a perovskite nanocrystal precursor and a polymer source;
and S002, transferring the solution to a substrate according to the required array position, and treating the solution according to a preset mode to enable the perovskite nanocrystal precursor to generate perovskite nanocrystals in situ to form the micro-lens array.
8. The method for producing a microlens array as claimed in claim 7, wherein in step S001, the perovskite nanocrystal precursor contains a substance a and a substance b;
the substance a is selected from any one of compounds having formula I;
AX formula I
The substance b is selected from any one of compounds with a formula II or a formula III;
BX2formula II
BX3Formula III
A is selected from CH3NH3、CH(NH)NH3Any one of Cs;
b is selected from any one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, In, Ti, Ag and Al;
the X is selected from any one of halogen elements.
9. The method for manufacturing a microlens array as claimed in claim 7, wherein in step S001, the polymer source is selected from any one of a polymer, a monomer, an oligomer;
preferably, in step S001, the solution further comprises a solvent selected from at least one of N, N-dimethyl amide, dimethyl acetamide, dimethyl sulfoxide, ethyl acetate, N-methyl pyrrolidone, tetrahydrofuran, toluene, chloroform, and acetone;
preferably, in step S001, the solution further comprises a perovskite ligand;
the perovskite ligand is at least one of acid ligand, amine ligand, quaternary ammonium salt, silane ligand, phosphine ligand and thiol ligand;
the perovskite ligand accounts for 0-20 wt% of the solution;
preferably, in step S001, a photoinitiator or/and a thermal initiator is/are further included in the solution;
the photoinitiator accounts for 0-10 wt% of the solution;
the thermal initiator accounts for 0-10 wt% of the solution;
further preferably, the photoinitiator is at least one of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl methanone, 1-hydroxy-cyclohexyl-phenyl methanone, diphenyl- (4-phenylsulfide) phenylsulfonium hexafluorophosphate, 2-diethoxyacetophenone, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and α -hydroxyalkylphenone;
the thermal initiator is azobisisobutyronitrile;
preferably, S002 is:
carrying out hydrophilic treatment or hydrophobic treatment on a substrate, and transferring the solution containing the perovskite nanocrystal precursor and the polymer source to the substrate according to the required array position to form a micro lens with a micro lens array;
preferably, in step S002, the preset manner includes: at least one of light irradiation, heating and microwave treatment;
preferably, the transferring method is any one selected from ink-jet printing, spraying, screen printing, air-jet printing, transfer printing, roll-to-roll patterning, micro-nano imprinting and brush painting;
preferably, in step S001, a plurality of different solutions containing perovskite nanocrystal precursors and polymer sources are obtained, the plurality of solutions differing from each other in the perovskite nanocrystal precursors and/or polymer sources contained therein.
10. The method of manufacturing a microlens array according to claim 7, further comprising S003:
integrating the microlens array with an optical device or/and an electrical device.
CN202010186044.3A 2020-03-17 2020-03-17 Micro lens, micro lens array and preparation method Pending CN113406733A (en)

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