CN108676182B - Polymer-based functional film and preparation method thereof - Google Patents
Polymer-based functional film and preparation method thereof Download PDFInfo
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- CN108676182B CN108676182B CN201810160814.XA CN201810160814A CN108676182B CN 108676182 B CN108676182 B CN 108676182B CN 201810160814 A CN201810160814 A CN 201810160814A CN 108676182 B CN108676182 B CN 108676182B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920006254 polymer film Polymers 0.000 claims abstract description 100
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 137
- 239000010408 film Substances 0.000 claims description 130
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 111
- 239000000758 substrate Substances 0.000 claims description 46
- -1 formamidine lead bromide Chemical group 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 38
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 32
- 150000003839 salts Chemical class 0.000 claims description 32
- 238000005530 etching Methods 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 27
- 230000003287 optical effect Effects 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
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- 238000004519 manufacturing process Methods 0.000 claims description 14
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 11
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
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- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims description 6
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- YPNWGLNCDBBKNX-UHFFFAOYSA-N carbamimidoyl bromide Chemical group NC(Br)=N YPNWGLNCDBBKNX-UHFFFAOYSA-N 0.000 claims description 2
- VOWZMDUIGSNERP-UHFFFAOYSA-N carbamimidoyl iodide Chemical compound NC(I)=N VOWZMDUIGSNERP-UHFFFAOYSA-N 0.000 claims description 2
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- H—ELECTRICITY
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2383/04—Polysiloxanes
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- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a polymer-based functional film and a preparation method thereof, wherein the functional film comprises at least one layer of polymer film, and at least one layer of polymer film is a polymer film containing nano cavities. The polymer-based functional film provided by the invention can flexibly change the effective refractive index of the polymer film, realize the matching with a device and further improve the photoelectric performance of an element of an application device.
Description
Technical Field
The invention belongs to the technical field of optical films, and particularly relates to a polymer-based functional film with an adjustable refractive index and a preparation method thereof.
Background
In the development of optical technology, optical films are of great importance. Optical thin films are used in most opto-electronic devices. The optical film can change the reflection, transmission and polarization characteristics of the transmitted light, thereby realizing the improvement of the optical action interface performance of the photoelectric device element. When light enters the interface surface of two mediums with different refractive indexes, Fresnel reflection is generated due to the difference of the refractive indexes, and the reflection phenomenon reduces the performance of many photoelectric devices. For example, surface untreated single crystal silicon photovoltaic cells or silicon based photodetectors lose 30% of their energy due to reflection (300nm-400 nm); a significant portion of the light emitted by a semiconductor light emitting diode is reflected back into the semiconductor, with an energy loss of about 35%; in the biomedical field, the endoscope technology, especially the endoscope operation, is widely applied due to the characteristic of small wound, but the wet and complex working environment causes the endoscope head to be easily polluted by body fluid or atomized to increase reflection, so that the visibility of the system is reduced. The refractive index of an optical medium material is an important research parameter, and the refractive index can reflect the reflection and refraction conditions of light at two phase interfaces when the light irradiates the surface of the medium, and is an inherent physical parameter of the material. Therefore, the development of the optical film with adjustable refractive index has important significance and application value for improving the performance of the photoelectric device.
The rapid development of scientific technology meets the higher requirements of the materials on easy processability, multifunctionality, photo-thermal stability, intellectualization and the like on the premise of meeting normal use, and the single organic or inorganic material is difficult to meet the requirements of people. With the continuous progress of nanotechnology, organic-inorganic composite optical materials are gradually accepted by people and rapidly developed. The organic-inorganic composite optical material has the characteristics of good stability and controllable refractive index of inorganic materials, has the characteristics of easiness in processing, impact resistance, good transparency, wide material selection, low cost and the like of organic materials, and represents a development space with great potential among optics, electrics, biotechnology, sensing mapping, display detection and various cross subjects.
The organic-inorganic composite polymer film can reduce the reflection of light on the surface of the material and increase the transmittance of the material to the light, so the organic-inorganic composite polymer film has wide application in the field of various optical materials. Generally speaking, the refractive index of a theoretical 100% single layer antireflection film must satisfy:
wherein n is0Is the refractive index of air, nsThe refractive index of the substrate (refractive index of optical glass and optical plastic is 1.45-1.7). Therefore, it is known from theoretical calculations that reflection of light at 4-6.5% or more occurs at the interface between the glass and the optical plastic surface, and the loss of optical energy due to such reflection has an adverse effect on the performance of optical materials, such as flat panel display devices for electronic devicesIt is desirable to use an antireflection coating to eliminate the phenomenon of "ghosting" due to light reflection and the phenomenon of glare due to multiple reflections. There is technical difficulty in realizing broad spectrum antireflection by using a single-layer optical antireflection film, and in order to prepare a film having a wide wavelength antireflection characteristic that can be adapted to different photoelectric devices, people have prepared an antireflection film having a multilayer structure. Among them, a Distributed Bragg Reflector (DBR) is a typical representative, which is a periodic structure composed of two materials having different refractive indexes alternately arranged in an ABAB manner, and the optical thickness of each layer material is 1/4n of the central reflection wavelength, n being the refractive index of each layer material. Thus a quarter-wave multilayer system, corresponding to a simple set of photonic crystals. Because the electromagnetic wave with the frequency within the energy gap range can not penetrate, the reflectivity of the Bragg reflector can reach more than 99 percent, the Bragg reflector is generally used for improving the brightness of an LED, the Bragg reflector does not have the absorption problem of a metal reflector, and the position of the energy gap can be adjusted by changing the thickness or the refractive index of a material. However, in consideration of the requirement of improving the device performance by broad-spectrum antireflection, the larger the difference between the refractive indexes of the two materials constituting the DBR is, the wider the reflection spectrum bandwidth of the DBR is, and for the organic DBR, the refractive indexes of the organic polymers are relatively close to each other, which limits the wide application of the organic polymer broad-spectrum antireflection multilayer film. In addition, in the fields of photovoltaic cells and silicon-based detectors, the device material (particularly silicon-based material) is in an ultraviolet/blue light waveband (lambda)<500nm) has larger non-radiative recombination probability, reduces the response of the device to the range, and seriously hinders the practical application process of the photoelectric device. For the phenomenon, in the last 70 th century, Hovel firstly proposes to improve the short-wave response of the photovoltaic device by adopting a spectral down-conversion (LDS) technology, and the photoelectric efficiency of the photovoltaic device is improved by 0.5-2%. This requires that the spectral down-conversion material have high luminescent quantum efficiency and good monochromaticity (in the high response band range of the device), high absorption coefficient in the ultraviolet/blue band, and long-wave range (500 nm)<λ<1100nm), high transmittance, high photo-thermal stability and good matching with the refractive index of the device. But the light is limited because the refractive index mismatch of the device material and the air causes the light reflection loss of the interface to be seriousThe conversion efficiency of the photovoltaic device is improved. At the same time, this also limits the detection capability of the silicon-based detection device for the uv/blue range. In summary, in the design of optical antireflection films, people are always looking for a series of low refractive index film materials with low refractive index and adjustable in a certain range. But almost no natural product (MgF)2Is the lowest available refractive index natural material) can meet the use requirements of people for low refractive index materials. Therefore, it is considered to further obtain a material having a lower refractive index by changing the structure of the material.
Disclosure of Invention
The invention provides a polymer-based functional film and a preparation method thereof, wherein nano sacrificial templates with different geometric structures or different contents are added, and then the sacrificial templates are selectively removed, so that nano cavities with different geometric structures are formed in the polymer film, and the polymer-based functional film with adjustable refractive index is prepared. The method for preparing the polymer-based reduced-function film is simple, the whole process can be carried out at low temperature or room temperature, the range of selectable polymer materials is wide, and the polymer films with various refractive indexes can be prepared, so that the high matching between the polymer films and devices is realized, and the photoelectric performance of optical device elements is effectively improved.
According to a first aspect of the present invention, there is provided a polymer-based functional film comprising at least one layer of polymer film, at least one of the polymer films being a polymer film containing nanocavities.
When the functional film is only a layer of polymer film, the layer of polymer film is a polymer film containing nano cavities.
When the functional film comprises at least two polymer films, the nanocavities may be present in any one or more of the polymer films.
According to a preferred embodiment of the present invention, when the functional film includes at least two polymer films, refractive indices of adjacent two polymer films are different. The two polymer films having different refractive indexes are formed in any form as understood by those skilled in the art, and may be, for example, polymer films of two different polymer materials; or one layer is a polymer film containing a nano sacrificial template, and the other layer is a polymer film without the nano sacrificial template; or a polymer film with nanocavities of different geometries.
According to a preferred embodiment of the invention, the thickness of the polymer film is between 100nm and 5mm, preferably between 100nm and 1 μm.
According to a preferred embodiment of the present invention, the nanocavity-containing polymer film has a nanocavity volume percentage of 10% to 60%, for example, the nanocavity volume percentage may be 10%, 20%, 30%, 40%, 50%, 60% and any value therebetween, preferably 30% to 60%. The shape of the nanocavity includes one or more of a sphere, a polyhedron, a cylinder, a rod, a disk, and a Y shape, such as may be one or more of a sphere, a box, a tetrahedron, a cylinder, a cube, a rod, a disk, and a Y shape.
According to a preferred embodiment of the present invention, the polymer thin film further contains perovskite; preferably, the mass fraction of the perovskite is 10% -30%, preferably 15% -20%; the perovskite is formamidine lead bromide, formamidine lead iodide or has a molecular formula of R1NH3AB3Or (R)2NH3)2AB4Wherein A and B form a coordination octahedral structure, R1NH3Or R2NH3Filling the coordination octahedron gap formed by A and B, R1Is C1-C4 alkyl, preferably methyl, R2Is unsaturated olefin C2-C4, A is selected from any one of Ge, Sn, Pb, Cu, Mn, Sb and Bi, B is halogen, preferably selected from any one of Cl, Br and I.
According to another aspect of the present invention, there is provided a method for preparing the above polymer-based functional film, comprising: providing a substrate, and preparing at least one layer of polymer film on the substrate, wherein the polymer film preparation method comprises the following steps:
step I, mixing a polymer and a solvent to obtain a solution I;
step II, placing the solution I in the step I on the surface of a substrate, removing the solvent, and forming a polymer film on the surface of the substrate;
the preparation method of at least one layer of the polymer film further comprises the following steps: in step I, a nano sacrificial template is also added to the solution I, an
And III, removing the sacrificial template, and forming a nano cavity structure in the polymer film to obtain the polymer film containing the nano cavity.
According to a preferred embodiment of the present invention, when the polymer film is directly prepared on a substrate surface, the substrate surface is the substrate surface, and when the polymer film is already prepared on the substrate, the substrate surface refers to the surface of the polymer film.
According to a preferred embodiment of the present invention, when the nano sacrificial template is added to the solution I in step I, the order of adding the nano sacrificial template and the polymer to the solvent is not particularly limited, and the nano sacrificial template may be added to the solvent together with the polymer; or dissolving the nano sacrificial template and the polymer in a solvent respectively, and then mixing the two solutions; or dissolving the polymer in a solvent, and then adding the nano sacrificial template; or dissolving the nano sacrificial template in a solvent, and then adding a polymer to obtain a polymer solution containing the nano sacrificial template.
According to a preferred embodiment of the present invention, when the nano sacrificial template is added, the solvent and the polymer material are selected according to the dispersibility (i.e. oil solubility or alcohol solubility) of the nano sacrificial template, and the solvent is selected to be capable of sufficiently dispersing the nano sacrificial template, and the polymer which is also capable of being dissolved in the solvent is selected. For example, for an oil-soluble nano sacrificial template, the solvent may include any one or more of Toluene (TOL), chloroform (TCM), and Dichloromethane (DCM), and the corresponding polymer may include one or more of acrylonitrile-butadiene-styrene copolymer (ABS), ethylene-vinyl acetate copolymer (EVA), Polycarbonate (PC), Polycaprolactone (PCL), Polydimethylsiloxane (PDMS), Polymethylmethacrylate (PMMA), copolymer of ethylene and octene (POE), Polystyrene (PS), Polyurethane (PU), and polyvinyl acetate (PVAc); for alcohol-soluble nano-sacrificial templates, the solvent may comprise one or more of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and dimethylacetamide (DMAc), and the corresponding polymer may comprise one or more of Polyamide (PA), Polyacrylonitrile (PAN), Polycarbonate (PC), Polycaprolactone (PCL), Polyimide (PI), Polystyrene (PS), Polyurethane (PU), and polyvinylidene fluoride (PVDF).
According to a preferred embodiment of the invention, the substrate may be an optical crystal, glass (quartz, sapphire Al)2O3Calcium fluoride CaF2MgF, MgF2JGS1 (far ultraviolet quartz glass), JGS2 (ultraviolet quartz glass), JGS3 (infrared quartz glass), K9 (crown glass), K7 (crown glass), optical cover glass and architectural glass.
According to a preferred embodiment of the present invention, in step II, the solution I may be applied to the surface of the substrate by spin coating, doctor blading, casting, dip-coating, electrospinning, spray coating, etc., and then the solvent is removed, preferably at a low temperature, more preferably at a temperature of not higher than 100 ℃, to obtain a polymer film with a uniform surface. Among them, exemplary ways of removing the solvent at a low temperature include natural drying, vacuum drying, hot air drying, cold air drying, convection drying, microwave drying, etc., and for example, the solvent can be removed by vacuum drying at 30 to 50 ℃ for 0.01 to 0.1MPa for 0.5 to 48 hours.
According to a preferred embodiment of the present invention, in step III, the sacrificial template is removed by etching, preferably by etching with an etching solution or an etching gas. And during etching, selectively etching and removing the nano sacrificial template by using the difference of the etching rates of different materials in the same etching liquid or etching gas, releasing the structure, and forming nano cavity structures with different geometric shapes in the polymer film. The etching liquid or gas etches only the nano-sacrificial template material without damaging the polymer, substrate, and other doped materials, if present. Some nano-sacrificial templates and their corresponding optional etchings are shown belowEtching solution expressed by 'nano sacrificial template/etching solution', gold Au/potassium iodide KI, silver Ag/(ammonia NH)4OH: hydrogen peroxide H2O2: methanol CH3OH 1:1:4), aluminum Al/dilute HCl, copper Cu/(ammonia NH)3: hydrogen peroxide H2O24:1), silica SiO2BOE (hydrofluoric acid HF: 40 wt% ammonium fluoride NH)4Aqueous solution 1:5), titanium dioxide TiO2Or zinc oxide ZnO/dilute hydrochloric acid, zirconium dioxide ZrO2Hydrofluoric acid HF or dilute hydrochloric acid HCl, cadmium selenide CdSe, zinc sulfide ZnS, chromium telluride CdTe, indium phosphide InP, copper indium sulfide CuInS or copper indium selenide CuInSe/dilute hydrochloric acid HCl.
According to a preferred embodiment of the present invention, when the functional film includes at least two polymer films, a solvent used in preparing a subsequent polymer film does not dissolve a previously prepared polymer film when preparing an adjacent polymer film, and polymer materials used in preparing the adjacent two polymer films are different.
For example, when preparing the n-th polymer film, a polymer corresponding to the oil-soluble nano sacrificial template and a solvent are used, i.e., the polymer is one or more of acrylonitrile-butadiene-styrene copolymer (ABS), ethylene-vinyl acetate copolymer (EVA), Polycarbonate (PC), Polycaprolactone (PCL), Polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA), a high polymer of ethylene and octene (POE), Polystyrene (PS), Polyurethane (PU) and polyvinyl acetate (PVAc), and the solvent is one or more of Toluene (TOL), chloroform (TCM) and Dichloromethane (DCM); then, in the preparation of the n +1 th polymer film, a solvent is used which does not dissolve the n-th polymer film, and the polymer which can be used is, for example, polyvinylpyrrolidone (PVP), and the solvent can be selected from water (H)2O), Ethanol (ET), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and dimethylacetamide (DMAc). For another example, when the n-th polymer film is prepared, the polymer corresponding to the alcohol-soluble nano sacrificial template and the solvent are used, that is, the polymer is Polyamide (PA), Polyacrylonitrile (PAN), Polycarbonate (PC), Polycaprolactone (PCL), Polyimide (PI), Polystyrene (PS), or polyurethane (pu)One or more of ester (PU) and polyvinylidene fluoride (PVDF) and solvent is one or more of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and dimethylacetamide (DMAc), then, in the preparation of the N +1 th layer of the polymer film, one or more of parylene (PPX-N), poly (p-xylylene chloride) (PPX-C) and poly (p-xylylene dichloride) (PPX-D) may be used as the polymer, and one or more of Toluene (TOL), chloroform (TCM) and dichloromethane may be used as the solvent. Wherein n is an integer of 1 or more.
According to a preferred embodiment of the present invention, the nano sacrificial template is selected from one or more of nano metal particles, nano non-metal particles and semiconductor quantum dots, preferably, the nano metal particles comprise one or more of Au, Ag, Al and Cu; and/or, the nanoscale non-metallic particles comprise SiO2、TiO2ZnO and ZrO2One or more of; and/or the semiconductor quantum dots comprise one or more of cadmium selenide CdSe, zinc sulfide ZnS, chromium telluride CdTe, indium phosphide InP, copper indium sulfide CuInS and copper indium selenide CuInSe. The shape of the nano sacrificial template comprises one or more of a sphere, a polyhedron, a column, a rod, a disc and a Y shape, and can be one or more of a sphere, a box, a tetrahedron, a cylinder, a cube, a rod, a disc and a Y shape.
According to a preferred embodiment of the invention, the solution I further contains a precursor of perovskite; the precursor of the perovskite is a mixture of inorganic halide salt and organic ammonium halide salt, wherein the molar ratio of the inorganic halide salt to the organic ammonium halide salt is 1: (0.1 to 3). When the solution I contains a precursor of a perovskite, the order of addition of the precursor of a perovskite, the polymer and, if present, the nano sacrificial template is not particularly limited.
According to a preferred embodiment of the present invention, a precursor solution of perovskite is prepared first, and then the precursor solution of perovskite is mixed with the polymer and the nano sacrificial template (if present), and when mixing, the order of addition of the precursor solution of perovskite to the polymer and the nano sacrificial template is not particularly limited. The preparation method of the precursor solution of the perovskite comprises the following steps: mixing inorganic halide salt and organic ammonium halide salt, then adding an organic solvent, uniformly mixing, filtering, and filtering to obtain a filtrate, namely the precursor solution of the perovskite. The precursor solution of the perovskite prepared by the method can avoid introducing impurities into the perovskite, and further can improve the quality of the prepared polymer film. Preferably, the mass ratio of the organic solvent to the inorganic halide salt is 1: (0.01-0.1). Wherein the mixing can be accelerated by auxiliary mixing commonly used in the art, for example, ultrasonic treatment can be performed after mixing, such as ultrasonic treatment for 10-30min, and in a preferred embodiment of the present invention, the ultrasonic treatment time is 15 min.
In a preferred embodiment of the present invention, when preparing the solution I, the polymer solution, the solution containing the nano sacrificial template, and the precursor solution of the perovskite may be prepared separately, and then the three solutions may be mixed in a desired ratio to obtain the solution I.
The polymer solution may be formulated as: dissolving a polymer in an organic solvent, wherein the mass percent is controlled as follows: polymer (b): organic solvent ═ 1: (1-50), and after the polymer is completely dissolved, obtaining a uniform, transparent and different-viscosity polymer solution.
The precursor solution of perovskite may be prepared by: mixing inorganic halide salt and organic ammonium halide salt powder, and controlling the molar ratio as follows: inorganic halide salt: organic ammonium halide salts ═ 1: (0.1-3), adding an organic solvent, and controlling the mass percentage concentration as follows: organic solvent: inorganic halide salt ═ 1: (0.01-0.1), uniformly mixing to obtain a transparent mixed solution, filtering the transparent mixed solution subjected to ultrasonic treatment, and taking the filtrate obtained by filtering to obtain a precursor solution of the perovskite; the inorganic halide salt is any one of halide salts of Ge, Sn, Pb, Sb, Bi, Cu and Mn; the inorganic halide salt is any one of halide salts of Ge, Sn, Pb, Sb, Bi, Cu and Mn; the organic amine halide salt is selected from bromoformamidine and iodoformamidine and has a general formula CmH2m+1NH3A saturated alkylamine halide salt of B or a compound of formula CnH2n-1NH3Unsaturated alkylamine halide or arylate of BOne or more of vanillyl amine halide salts, wherein m is more than or equal to 1, n is more than or equal to 2, preferably m is more than or equal to 1 and less than or equal to 4, n is more than or equal to 2 and less than or equal to 4, and B is halogen, preferably any one of Cl, Br and I. Wherein the organic solvent is any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and dimethylacetamide (DMAc).
The preparation of the nano sacrificial template solution can be as follows: dispersing the sacrificial template in an organic solvent, and controlling the mass concentration as follows: sacrifice of the template: organic solvent ═ 1: (1-50), and uniformly dispersing to obtain a solution containing the nano sacrificial template.
When the polymer film contains the nano sacrificial template and the perovskite, the polymer solution is prepared, and the same organic solvent is preferably used for the precursor solution of the perovskite and the solution containing the nano sacrificial template.
According to a preferred embodiment of the invention, in the solution I, the mass fraction of polymer is between 1% and 20%, preferably between 10% and 15%; the mass fraction of the nano sacrificial template is 0.02-5%, preferably 0.1-3%; if a precursor of the perovskite is present, the mass fraction thereof is between 10% and 30%, preferably between 15% and 20%.
According to a preferred embodiment of the present invention, the method for preparing a polymer-based functional film comprising a polymer film comprises:
a, dissolving a polymer and a nano sacrificial template in a solvent to obtain a solution A; optionally, the solution a contains a precursor of the perovskite;
b, placing the solution A in the step I on the surface of a substrate, and then removing the solvent to form a polymer film on the surface of the substrate;
and step C, removing the sacrificial template, and forming a nano cavity structure in the polymer film to obtain the polymer-based functional film containing the nano cavity structure.
According to a preferred embodiment of the present invention, the method for preparing a polymer-based functional film comprising at least two polymer films comprises: providing a substrate, and sequentially preparing polymer films on the substrate, wherein the preparation method of the polymer films comprises the following steps:
step N-i, dispersing the Nth polymer in an Nth solvent to obtain an Nth solution, and optionally, the Nth solution also contains a precursor of perovskite;
step N-ii, placing the Nth solution in the step N-i on the surface of a substrate, removing the Nth solvent, and forming a polymer film on the surface of the substrate;
wherein the method of making at least one layer of the polymer film further comprises: in step N-i, a nano sacrificial template is further added to the Nth solution, an
And N-iii, removing the nano sacrificial template, and forming a nano cavity in the polymer film to obtain the polymer film containing the nano cavity.
Wherein N is an integer greater than or equal to 1. Wherein, the refractive index of the (N + 1) th polymer is different from that of the N-th polymer, and the (N + 1) th solvent can not dissolve the N-th polymer. When preparing the (N + 1) th polymer film, the substrate surface refers to the surface of the Nth polymer film. According to the present invention, when the functional film includes at least 3 polymer films, the N +2 th polymer film may be the same as or different from the nth polymer film, and the N +2 th polymer film may use the same polymer, solvent and nano sacrificial template as the nth polymer film. When the N +2 th polymer film is identical to the N-th polymer film and the N +2 th solution is preferably identical to the nth solution, the desired solution may be prepared at one time when the nth solution is prepared, and the solution preparation process may be omitted during the preparation of the N +2 th polymer film. In addition, in the process of preparing the film containing a plurality of layers of polymers, the above steps are not strictly limited, and for example, the solutions required for the respective layers of polymer films may be prepared first, and then the polymer films may be prepared.
In a preferred embodiment of the present invention, in the functional film comprising at least two polymer films, all the polymer films of the odd-numbered layers are the same and all the polymer films of the even-numbered layers are the same.
In the present invention, "optionally" is contained or not contained, or added or not, i.e., one skilled in the art can select presence or absence according to need.
According to another aspect of the invention, the application of the functional film in an optical device is also provided, such as the functional film is used as a spectrum down-conversion collector of a photovoltaic cell, and the utilization efficiency of the photovoltaic cell on ultraviolet light is improved; the spectrum response range of the silicon-based detector is expanded to realize the backlight material in the fields of wide spectrum detection and display.
The invention has the beneficial effects that:
(1) the polymer-based functional film provided by the invention is formed into a nano cavity structure in the polymer film by doping the nano sacrificial template in the polymer solution and then selectively removing the nano sacrificial template, and the method adopting the nano sacrificial template doping does not need to introduce a chemical reaction process, thereby eliminating the process uncertainty and improving the yield. In addition, in the method for preparing the functional film, the processes of dissolving the polymer and the nano sacrificial template, removing the solvent and etching the nano sacrificial template can be carried out at low temperature even at room temperature, the processing technology is simple, the condition is mild, and the working efficiency is improved. The polymer-based functional thin film with adjustable refractive index can be provided by doping nano sacrificial templates with different proportions or doping nano sacrificial templates with different geometric shapes.
(2) The method for removing the nano sacrificial template adopts a wet etching process without a high-temperature process, so that the range of selectable polymer materials for preparing the functional film is increased, more functional films with different refractive indexes can be prepared, the matching degree of the film and a photoelectric functional device is improved, and the application of the polymer-based functional film with more excellent performance is promoted.
(3) The nano sacrificial template has highly uniform geometric morphology characteristics and excellent monodispersity, so that the nano sacrificial template can be uniformly dispersed in a polymer film, and nano geometric cavities left after the nano sacrificial template is etched and removed also have uniform dispersion degree and the same geometric size.
(4) The geometric shape of the nano sacrificial template has various selectivities (sphere, box, tetrahedron, column, cube, disc, Y-shaped and the like), so that the preparation of polymer-based films with different cavity structures is possible, and the optical regulation performance (polarization) of the optical functional film is widened.
(5) The solvent removal and the nano sacrificial template etching process are carried out at low temperature, so that the film shrinkage caused by solvent volatilization in the film forming process is inhibited, the compatibility of the polymer functional film and devices is improved, and the requirements of large-area industrial production can be met.
Drawings
Fig. 1 is a transmission spectrum of a nano-cavity-containing PDMS film prepared in example 1 and a PDMS film prepared in comparative example 1.
FIG. 2 is a photograph of a film Q (before etching) and a film H (after etching) on a quartz substrate of example 2 under 365nm ultraviolet light excitation and sunlight.
FIG. 3 shows a silicon-based photovoltaic cell and compatible MAPbBr in example 33Current density voltage curve (A), external quantum efficiency (B) and reflectivity (B), MAPbBr, of silicon-based photovoltaic cell of PAN composite film3Luminescence spectrum (C), transmission spectrum (C) and luminescence physical photograph (D) of the PAN composite film;
wherein 1 is the external quantum efficiency of the silicon-based photovoltaic cell;
2 is the reflectivity of the silicon-based photovoltaic cell;
3 for compatibility with MAPbBr3External quantum efficiency of silicon-based photovoltaic cells of PAN composite films;
4 is compatible with MAPbBr3Reflectivity of silicon-based photovoltaic cells of PAN composite films.
FIG. 4 shows a CdTe photovoltaic cell and compatible MAPbBr in embodiment 4 of the invention3Current density voltage curve (A) and external quantum efficiency (B) of CdTe photovoltaic cell of PAN and PPX-N multilayer spectrum down-conversion composite film, compatibility with MAPbBr3A schematic structural diagram (C) and a physical photograph (D) of a CdTe photovoltaic cell of a multi-layer spectral down-conversion composite film of PAN and PPX-N;
FIG. 5 is a schematic view of a photodiode compatible with a single-layer PDMS polarization detection film in example 5;
FIG. 6 shows MAPbBr compatibility in example 63A silicon-based ultraviolet EMCCD schematic diagram of a down-conversion polarization film in a PAN spectrum.
FIG. 7 shows a compatible FAPBR prepared in example 7 and containing a nanocavity3Current density voltage curves (A) of silicon-based photovoltaic cells of PAN composite films and silicon-based photovoltaic cells of undoped sacrificial template light conversion films prepared in comparative example 2, FAPBR containing nano-cavities prepared in example 73Reflection spectrum (B) of undoped sacrificial template light conversion film prepared by PAN composite film and comparative example 2, FAPBR containing nano-cavity3Luminescence spectrum (C) and transmission spectrum (C) of the/PAN composite film.
Fig. 8 is a transmission spectrum of the nano-cavity containing PDMS film prepared in example 8 of the present invention and the PDMS film prepared in comparative example 1.
Fig. 9 is a transmission spectrum of the nano-cavity containing PDMS film prepared in example 9 of the present invention and the PDMS film prepared in comparative example 1.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Example 1
(1) Dissolving a polymer in toluene, wherein the mass ratio of the polymer to the toluene is 1: and 7, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, and ultrasonically treating for 1h to obtain a uniform and transparent toluene solution of the polymer after the polymer is completely dissolved. Dispersing the nano sacrificial template in toluene, wherein the mass ratio of the nano sacrificial template to the toluene is 1: and (5) performing ultrasonic treatment for 2 hours to obtain a uniformly mixed toluene solution containing the nano sacrificial template. And then mixing the toluene solution of the polymer and the toluene solution containing the nano sacrificial template in an amount of 0.5 wt% of the mass ratio of the nano sacrificial template in the finally formed solution to obtain a composite colloidal solution (wherein the mass fraction of the polymer is 15%), wherein the nano sacrificial template is oily monodisperse cadmium selenide (CdSe) quantum dots (3-5nm), and the polymer is Polydimethylsiloxane (PDMS).
(2) The composite colloidal solution obtained in the above (1) was deposited on the surface of a quartz substrate (3 cm. times.3 cm) by a spin coating method (500rpm/10sec., 5000rpm/30sec.), so that the composite colloidal solution was uniformly dispersed on the surface of the substrate, and then the quartz substrate coated with the composite colloidal solution was placed in a vacuum drying oven and dried at 45 ℃ under 0.01MPa for 2 hours to remove the organic solvent, to obtain a composite film having a uniform surface, with the film thickness being controlled to 1 μm.
(3) And (3) soaking the composite film material prepared in the step (2) in dilute hydrochloric acid, selectively removing cadmium selenide quantum dots by utilizing the difference of etching rates to realize the release of the structure, and finally forming a spherical cavity structure in the polymer main body material to obtain a single-layer PDMS film containing a nano cavity, wherein the volume percentage of the nano cavity is 50%, and the film realizes the anti-reflection in the spectral range of 400nm-1100 nm.
Example 2
(1) Dissolving a polymer in an organic solvent toluene, wherein the mass ratio of the polymer to the toluene is 1: 7, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, ultrasonically treating for 1h, and obtaining a uniform and transparent toluene solution of the polymer after the polymer is completely dissolved; dissolving a nano sacrificial template in toluene, wherein the mass ratio of the nano sacrificial template to the toluene is 1: and (3) performing ultrasonic treatment for 2h to obtain a uniformly mixed toluene solution containing the nano sacrificial template, and then mixing the toluene solution of the polymer and the toluene solution containing the nano sacrificial template in an amount of 1 wt% of the mass ratio of the nano sacrificial template in the finally formed solution to obtain a composite colloidal solution (wherein the mass fraction of the polymer is 10%) as a first solution. The nano sacrificial template is oil-soluble monodisperse cadmium selenide (CdSe) quantum dots (3-5nm), and the polymer is polymethyl methacrylate (PMMA).
(2) And (2) depositing the composite colloidal solution in the step (1) on the surface of the quartz substrate by a spin coating method to uniformly disperse the composite colloidal solution on the surface of the quartz substrate, then placing the quartz substrate coated with the composite colloidal solution in a vacuum drying oven, and drying for 0.5h at 100 ℃ and 0.01MPa to remove the organic solvent to obtain a composite thin film material with a uniform surface, wherein the thickness of the thin film is controlled to be 1 mu m, and the thin film is marked as a thin film Q.
(3) Soaking the film material with the composite structure in the step (2) in dilute hydrochloric acid, selectively removing the nano sacrificial template by utilizing the difference of etching rates to realize the release of the structure, forming a spherical cavity structure in the polymer main body material, and obtaining a single-layer polymer film containing a nano cavity, which is marked as a film A, wherein the volume percentage of the nano cavity is 50%.
(4) Selecting a polymer having a refractive index different from that of the polymer in (1) as a second polymer, and a solvent incapable of dissolving the polymer in (1) as a second organic solvent; dissolving a second polymer in a second organic solvent, wherein the mass ratio of the second polymer to the second solvent is 1: 10, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, ultrasonically treating for 1h, and after the second polymer is completely dissolved, obtaining a uniform and transparent second polymer solution which is marked as a second solution; the second polymer is polyvinylpyrrolidone (PVP); the second organic solvent is N, N-Dimethylformamide (DMF).
(5) And (3) depositing the second solution obtained in the step (4) on the film A by a spin coating method to uniformly disperse the second solution on the film A, then placing the quartz substrate coated with the second solution in a vacuum drying oven, and drying for 0.5h under the conditions of 100 ℃ and 0.01MPa to remove the organic solvent, wherein the thickness of the film is controlled to be 1 mu m, so as to obtain a polymer film material with a uniform surface as a film B.
(6) The above-mentioned five cycles (2), (3) and (5) are repeated in this order to obtain a polymer-based antireflection film including 12 polymer films having a periodic structure of "film a film B", and such a polymer-based antireflection film including 12 polymer films is referred to as film H.
FIG. 2 shows the photographs of a film Q (before etching) and a film H (after etching) on a quartz substrate in 365nm ultraviolet light excitation and sunlight.
Example 3
(1) Dissolving a polymer in an organic solvent N, N-Dimethylformamide (DMF), wherein the mass ratio of the polymer to the organic solvent is 1: 8, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, ultrasonically treating for 1h, and after the polymer is completely dissolved, obtaining a uniform and transparent polymer solution as a first solution; the polymer is Polyacrylonitrile (PAN).
(2) Mixing an inorganic halide salt with an organic ammonium halide salt powder, wherein,inorganic halide salt: the molar ratio of the organic ammonium halide salt is 1: 1.5, then adding N, N-Dimethylformamide (DMF), wherein the mass ratio of the N, N-Dimethylformamide (DMF) to the inorganic halide salt is 1: 0.09, carrying out ultrasonic treatment after mixing, obtaining transparent mixed liquor after the ultrasonic treatment is carried out for 15 minutes, filtering the transparent mixed liquor after the ultrasonic treatment, and taking filtrate obtained by filtering as second solution; the inorganic halide salt in the step is lead bromide (PbBr)2) (ii) a The organic amine halide salt is methylamine bromide (MABr).
(3) Dispersing the nano sacrificial template in N, N-Dimethylformamide (DMF), wherein the mass ratio of the nano sacrificial template to the N, N-Dimethylformamide (DMF) is 1: 20, ultrasonically mixing for 2 hours to obtain a uniformly mixed N, N-Dimethylformamide (DMF) solution containing the nano sacrificial template as a third solution; the nano sacrificial template is alcohol-soluble cadmium selenide (CdSe) quantum dots.
(4) Mixing the first solution in (1), the second solution in (2) and the third solution in (3), wherein the first solution: a second solution: third solution ═ 1:1: 0.1 (volume ratio), and performing ultrasonic treatment for 2 hours to obtain a uniformly mixed solution 3, wherein the polymer content is 15 wt%, the nano sacrificial template content is 3 wt%, and the precursor content of the perovskite is 15 wt%.
(5) And (3) coating the solution 3 in the step (4) on the surface of the silicon-based photovoltaic cell by a spin coating method to uniformly disperse the solution 3 on the surface of the silicon-based photovoltaic cell, then placing the silicon-based photovoltaic cell coated with the solution 3 in a vacuum drying oven, and drying for 1h at 50 ℃ and 0.01MPa to remove the organic solvent to obtain a composite thin film material with a uniform surface, wherein the thickness of the thin film is controlled to be 3 microns.
(6) Immersing the film material with the composite structure in the step (5) in dilute hydrochloric acid, selectively removing the nano sacrificial template by utilizing the difference of etching rates to realize the release of the structure, forming a spherical cavity structure in the polymer main body material to obtain a single-layer polymer-based perovskite luminescence down-conversion film containing a nano cavity, and marking the film as MAPBBr3The PAN composite film comprises 55% of nanocavities by volume.
FIG. 3 is a drawing showingCompatible MAPBR in example 33Silicon-based photovoltaic cell of PAN composite film and IV (A) and external quantum efficiency (B), MAPbBr of silicon-based photovoltaic cell3Luminescence spectrum (C), transmission spectrum (C) and luminescence physical photograph (D) of the/PAN composite film.
Example 4
(1) Dissolving a polymer in an organic solvent N, N-Dimethylformamide (DMF), and controlling the mass percent: polymer (b): organic solvent ═ 1: 10, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, ultrasonically treating for 1h, and after the polymer is completely dissolved, obtaining a uniform and transparent polymer solution as a first solution; the polymer is Polyacrylonitrile (PAN).
(2) Mixing inorganic halide salt and organic ammonium halide salt powder, and controlling the molar ratio as follows: inorganic halide salt: organic ammonium halide salts ═ 1: and 2, adding an organic solvent N, N-Dimethylformamide (DMF), and controlling the mass percentage concentration as follows: organic solvent: inorganic halide salt ═ 1: 0.1, carrying out ultrasonic treatment after mixing, obtaining transparent mixed liquor after the ultrasonic treatment is carried out for 15 minutes, filtering the transparent mixed liquor after the ultrasonic treatment, and taking filtrate obtained by filtering as second solution; the inorganic halide salt in the step is lead bromide (PbBr)2) (ii) a The organic amine halide salt is methylamine bromide (MABr).
(3) Dissolving the nano sacrificial template in N, N-Dimethylformamide (DMF), and controlling the mass concentration as follows: nano sacrificial template: n, N-Dimethylformamide (DMF) ═ 1: 20, ultrasonically mixing for 2 hours to obtain evenly mixed N, N-Dimethylformamide (DMF) containing the nano sacrificial template, and marking as a third solution; the nano sacrificial template is alcohol-soluble cadmium selenide (CdSe) quantum dots.
(4) Dissolving a second polymer in a second organic solvent, wherein the mass percentage is controlled as follows: a second polymer: second organic solvent ═ 1: 10, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, ultrasonically treating for 1h, and after the second polymer is completely dissolved, obtaining a uniform and transparent polymer solution as a fourth solution; the second polymer is parylene (PPX-N); the second organic solvent is chloroform (TCM).
(5) Mixing the first solution in the above (1), the second solution in the above (2) and the third solution in the above (3) at a volume ratio of: a first solution: a second solution: third solution ═ 1:1: and (3) carrying out ultrasonic treatment for 2h at 0.1 to obtain a uniformly mixed solution 4, wherein the polymer content is 10 wt%, the nano sacrificial template content is 1 wt%, and the precursor content of the perovskite is 20 wt%.
(6) Taking the solution 4 in the step (5) and carrying out blade coating on the surface (15cm multiplied by 15cm) of a chromium telluride (CdTe) photovoltaic cell by a blade coating method, so that the solution 4 is uniformly distributed on the surface of the photovoltaic cell, then placing the photovoltaic cell coated with the solution 4 in a vacuum drying oven, drying for 1h at 70 ℃ under the air pressure of 0.01MPa in the vacuum drying oven, and removing the organic solvent to obtain a composite film material with a uniform surface, wherein the thickness of the film is controlled to be 1 mu m.
(7) And (3) soaking the composite film material in the step (6) in dilute hydrochloric acid, selectively removing the nano sacrificial template by utilizing the difference of etching rates to realize the release of the structure, forming a spherical cavity structure in the polymer main body material, and obtaining a single-layer polymer film, which is marked as a film A, wherein the volume percentage of the nano cavity is 50%.
(8) Depositing the fourth solution in the above (4) on the film A by a blade coating method to uniformly distribute the fourth solution on the film A, then placing the photovoltaic cell coated with the fourth solution in a vacuum drying oven, wherein the air pressure in the vacuum drying oven is 0.01MPa, the temperature is 70 ℃, drying is carried out for 1h, removing the organic solvent, and the thickness of the film is controlled to be 1 μm, thus obtaining a film material with a uniform surface as a film B.
(9) Repeating the steps (6), (7) and (8) for five periods in sequence to obtain a polymer-based perovskite luminescence down-conversion film which has a periodic structure of a film A and a film B and comprises 12 polymer films and is marked as MAPbBr3A/PAN and PPX-N multilayer spectral down-conversion composite film.
FIG. 4 shows CdTe photovoltaic cell and compatible MAPbBr3IV and external quantum efficiency of CdTe photovoltaic cell of composite film converted under PAN and PPX-N multilayer spectrum, compatibility with MAPbBr3Schematic structural diagram and practical structure of CdTe photovoltaic cell of/PAN and PPX-N multilayer spectral down-conversion composite filmAnd (4) photo of the object.
Example 5
(1) Dissolving a polymer in an organic solvent Toluene (TOL), and controlling the mass percent: polymer (b): organic solvent ═ 1:5, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, and ultrasonically treating for 1h to obtain a uniform and transparent polymer solution after the polymer is completely dissolved; dissolving the nano sacrificial template in the same toluene, and controlling the mass concentration as follows: nano sacrificial template: organic solvent ═ 1: 10, ultrasonically mixing for 2 hours to obtain a uniformly mixed toluene solution containing the nano sacrificial template; then mixing the polymer solution with a toluene solution containing a nano sacrificial template to obtain a composite colloidal solution, wherein the mass ratio of the nano sacrificial template is 1 wt%, the mass fraction of the polymer is 15%, and the nano sacrificial template is an oily monodisperse cadmium selenide (CdSe) nanorod; the polymer is Polydimethylsiloxane (PDMS).
(2) And (2) periodically arranging and depositing CdSe nanorods on the surface of a silicon-based photodiode packaging quartz cover plate by using the composite colloidal solution in the step (1) through an electrostatic spinning method to realize uniform and regular arrangement, then placing the quartz substrate coated with the composite colloidal solution in a vacuum drying oven, wherein the air pressure in the vacuum drying oven is 0.01MPa, the temperature is 50 ℃, drying is carried out for 2 hours, and organic solvent is removed to obtain a composite thin film material with a uniform surface, wherein the thickness of the thin film is controlled to be 3 mu m.
(3) And (3) soaking the composite film material in the step (2) in dilute hydrochloric acid, selectively removing the cadmium selenide nanorods by using the difference of etching rates, realizing the release of the structure, and finally forming a periodically arranged rod-shaped cavity structure in the polymer main body material to obtain the single-layer PDMS polarized light detection film with the adjustable refractive index, wherein the volume percentage of the nanometer cavity is 60%.
FIG. 5 is a schematic diagram of a photodiode compatible with a single-layer PDMS polarization detection film.
Example 6
(1) Dissolving a polymer in an organic solvent N, N-Dimethylformamide (DMF), and controlling the mass percent: polymer (b): organic solvent ═ 1:5, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, ultrasonically treating for 1h, and after the polymer is completely dissolved, obtaining a uniform and transparent polymer solution as a first solution; the polymer is Polyacrylonitrile (PAN).
(2) Mixing inorganic halide salt and organic ammonium halide salt powder, and controlling the molar ratio as follows: inorganic halide salt: organic ammonium halide salts ═ 1: 1.5, adding an organic solvent N, N-Dimethylformamide (DMF), and controlling the mass percentage concentration as follows: organic solvent: inorganic halide salt ═ 1: 0.1, carrying out ultrasonic treatment after mixing, obtaining transparent mixed liquor after the ultrasonic treatment is carried out for 15 minutes, filtering the transparent mixed liquor after the ultrasonic treatment, and taking filtrate obtained by filtering as second solution; the inorganic halide salt in the step is lead bromide (PbBr)2) (ii) a The organic amine halide salt is methylamine bromide (MABr).
(3) Dissolving the nano sacrificial template in N, N-Dimethylformamide (DMF), and controlling the mass concentration as follows: nano sacrificial template: organic solvent ═ 1: 20, ultrasonically mixing for 2 hours to obtain a uniformly mixed composite colloidal solution as a third solution; the nano sacrificial template is a cadmium selenide (CdSe) nanorod.
(4) Mixing the first solution in the step (1), the second solution in the step (2) and the third solution in the step (3), and controlling the volume ratio to be: a first solution: a second solution: third solution ═ 1:1: and (3) carrying out ultrasonic treatment for 2h at 0.1 to obtain a uniformly mixed solution 6, wherein the polymer content is 15 wt%, the nano sacrificial template content is 1 wt%, and the precursor content of the perovskite is 20 wt%.
(5) And (3) coating the solution 6 in the step (4) on the surface of a silicon-based EMCCD packaging cover plate by an electrostatic spinning method to uniformly disperse the solution 6, then placing a substrate coated with the solution 6 in a vacuum drying box, drying for 1h at the pressure of 0.01MPa and the temperature of 50 ℃ in the vacuum drying box, and removing an organic solvent to obtain a composite film material with a uniform surface, wherein the thickness of the film is controlled to be 3 microns.
(6) Soaking the composite film material in the step (5) in dilute hydrochloric acid, selectively removing the nano sacrificial template by utilizing the difference of etching rates to realize the release of the structure, forming a rod-shaped cavity structure in the polymer main body material and obtaining the single-layer polymer-based perovskite with the adjustable refractive indexLuminescence down-conversion polarization detection film, marked as MAPbBr3a/PAN spectral down-conversion polarizing film, wherein the nanocavity is 60% by volume. FIG. 6 is a compatible MAPbBr3A silicon-based ultraviolet detection EMCCD schematic diagram of a down-conversion polarization film in a PAN spectrum.
Example 7
(1) Dissolving a polymer in an organic solvent N, N-Dimethylformamide (DMF), wherein the mass ratio of the polymer to the organic solvent is 1: 7, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, ultrasonically treating for 1h, and after the polymer is completely dissolved, obtaining a uniform and transparent polymer solution as a first solution; the polymer is Polyacrylonitrile (PAN).
(2) Mixing an inorganic halide salt with an organic ammonium halide salt powder, wherein the ratio of inorganic halide salt: the molar ratio of the organic ammonium halide salt is 1: 1.5, then adding N, N-Dimethylformamide (DMF), wherein the mass ratio of the N, N-Dimethylformamide (DMF) to the inorganic halide salt is 1: 0.09, carrying out ultrasonic treatment after mixing, obtaining transparent mixed liquor after the ultrasonic treatment is carried out for 15 minutes, filtering the transparent mixed liquor after the ultrasonic treatment, and taking filtrate obtained by filtering as second solution; the inorganic halide salt in the step is lead bromide (PbBr)2) (ii) a The organic amine halide salt is formamidine bromide (FABr).
(3) Dispersing the nano sacrificial template in N, N-Dimethylformamide (DMF), wherein the mass ratio of the nano sacrificial template to the N, N-Dimethylformamide (DMF) is 1: 20, ultrasonically mixing for 2 hours to obtain a uniformly mixed N, N-Dimethylformamide (DMF) solution containing the nano sacrificial template as a third solution; the nano sacrificial template is alcohol-soluble cadmium selenide (CdSe) quantum dots.
(4) Mixing the first solution in (1), the second solution in (2) and the third solution in (3), wherein the first solution: a second solution: third solution ═ 1:1: 0.1 (volume ratio), and performing ultrasonic treatment for 2 hours to obtain a uniformly mixed solution 7, wherein the polymer content is 15 wt%, the nano sacrificial template content is 3 wt%, and the precursor content of the perovskite is 15 wt%.
(5) And (3) coating the solution 7 in the step (4) on the surface of a quartz substrate by a spin coating method to uniformly disperse the solution 7 on the surface of the silicon-based photovoltaic cell, then placing the silicon-based photovoltaic cell coated with the solution 7 in a vacuum drying oven, and drying for 1h at 50 ℃ and 0.01MPa to remove an organic solvent to obtain a composite thin film material with a uniform surface, wherein the thickness of the thin film is controlled to be 3 micrometers.
(6) Immersing the film material with the composite structure in the step (5) in dilute hydrochloric acid, selectively removing the nano sacrificial template by utilizing the difference of etching rates to realize the release of the structure, forming a spherical cavity structure in the polymer main body material to obtain a single-layer polymer-based perovskite luminescence down-conversion film containing the nano cavity, and recording the film as FAPBBr containing the nano cavity3The PAN composite film comprises 55% of nanocavities by volume.
FAPBR compatible with nano-cavity prepared by the embodiment3IV (A) of silicon-based photovoltaic cell of PAN composite film, FAPBR containing nano-cavity3The reflection spectrum (B), luminescence spectrum (C) and transmission spectrum of the/PAN composite film are shown in FIG. 7.
Example 8
(1) Dissolving a polymer in toluene, wherein the mass ratio of the polymer to the toluene is 1: and 7, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, and ultrasonically treating for 1h to obtain a uniform and transparent toluene solution of the polymer after the polymer is completely dissolved. Dispersing the nano sacrificial template in toluene, wherein the mass ratio of the nano sacrificial template to the toluene is 1: and (5) performing ultrasonic treatment for 2 hours to obtain a uniformly mixed toluene solution containing the nano sacrificial template. And then mixing the toluene solution of the polymer and the toluene solution containing the nano sacrificial template in an amount of 0.08 wt% of the mass ratio of the nano sacrificial template in the finally formed solution to obtain a composite colloidal solution (wherein the mass fraction of the polymer is 15%), wherein the nano sacrificial template is oily monodisperse cadmium selenide (CdSe) quantum dots (3-5nm), and the polymer is Polydimethylsiloxane (PDMS).
(2) The composite colloidal solution obtained in the above (1) was deposited on the surface of a quartz substrate (3 cm. times.3 cm) by a spin coating method (500rpm/10sec., 5000rpm/30sec.), so that the composite colloidal solution was uniformly dispersed on the surface of the substrate, and then the quartz substrate coated with the composite colloidal solution was placed in a vacuum drying oven and dried at 45 ℃ under 0.01MPa for 2 hours to remove the organic solvent, to obtain a composite film having a uniform surface, with the film thickness being controlled to 1 μm.
(3) Immersing the composite film material prepared in the step (2) in dilute hydrochloric acid, selectively removing cadmium selenide quantum dots by utilizing the difference of etching rates to realize the release of the structure, and finally forming a spherical cavity structure in the polymer main body material to obtain a single-layer PDMS film containing a nano cavity, wherein the volume percentage of the nano cavity is 10%, and the anti-reflection of the film in the spectral range of 600nm-1100nm is realized as shown in figure 8.
Example 9
(1) Dissolving a polymer in toluene, wherein the mass ratio of the polymer to the toluene is 1: and 7, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, and ultrasonically treating for 1h to obtain a uniform and transparent toluene solution of the polymer after the polymer is completely dissolved. Dispersing the nano sacrificial template in toluene, wherein the mass ratio of the nano sacrificial template to the toluene is 1: and (5) performing ultrasonic treatment for 2 hours to obtain a uniformly mixed toluene solution containing the nano sacrificial template. And then mixing the toluene solution of the polymer and the toluene solution containing the nano sacrificial template in an amount of 0.3% by mass of the nano sacrificial template in the finally formed solution to obtain a composite colloidal solution (wherein the mass fraction of the polymer is 15%), wherein the nano sacrificial template is oily monodisperse cadmium selenide (CdSe) quantum dots (3-5nm), and the polymer is Polydimethylsiloxane (PDMS).
(2) The composite colloidal solution obtained in the above (1) was deposited on the surface of a quartz substrate (3 cm. times.3 cm) by a spin coating method (500rpm/10sec., 5000rpm/30sec.), so that the composite colloidal solution was uniformly dispersed on the surface of the substrate, and then the quartz substrate coated with the composite colloidal solution was placed in a vacuum drying oven and dried at 45 ℃ under 0.01MPa for 2 hours to remove the organic solvent, to obtain a composite film having a uniform surface, with the film thickness being controlled to 1 μm.
(3) Immersing the composite film material prepared in the step (2) in dilute hydrochloric acid, selectively removing cadmium selenide quantum dots by utilizing the difference of etching rates to realize the release of the structure, and finally forming a spherical cavity structure in the polymer main body material to obtain a single-layer PDMS film containing a nano cavity, wherein the volume percentage of the nano cavity is 33%, and the anti-reflection of the film is realized in the spectral range of 450nm-1100nm as shown in figure 9.
Comparative example 1
(1) Dissolving a polymer in an organic solvent, wherein the mass ratio of the polymer to the organic solvent is 1: 7, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, and ultrasonically treating for 1h to obtain a uniform and transparent polymer solution after the polymer is completely dissolved; the polymer is Polydimethylsiloxane (PDMS), and the organic solvent is Toluene (TOL).
(2) The polymer solution obtained in the above (1) was deposited on the surface of a quartz substrate by a spin coating method (500rpm/10sec., 5000rpm/30sec.) to uniformly disperse the polymer solution on the surface of the substrate, and then the quartz substrate coated with the polymer solution was placed in a vacuum drying oven and dried at 45 ℃ under 0.01MPa for 2 hours to remove the organic solvent, to obtain a PDMS film with a uniform surface, and the film thickness was controlled to be 1 μm.
Comparative example 2
(1) Dissolving a polymer in an organic solvent N, N-Dimethylformamide (DMF), wherein the mass ratio of the polymer to the organic solvent is 1: 7, magnetically stirring for 1h, stirring at a high speed of 5000rpm/min for 10min, ultrasonically treating for 1h, and after the polymer is completely dissolved, obtaining a uniform and transparent polymer solution as a first solution; the polymer is Polyacrylonitrile (PAN).
(2) Mixing an inorganic halide salt with an organic ammonium halide salt powder, wherein the ratio of inorganic halide salt: the molar ratio of the organic ammonium halide salt is 1: 1.5, then adding N, N-Dimethylformamide (DMF), wherein the mass ratio of the N, N-Dimethylformamide (DMF) to the inorganic halide salt is 1: 0.09, carrying out ultrasonic treatment after mixing, obtaining transparent mixed liquor after the ultrasonic treatment is carried out for 15 minutes, filtering the transparent mixed liquor after the ultrasonic treatment, and taking filtrate obtained by filtering as second solution; the inorganic halide salt in the step is lead bromide (PbBr)2) (ii) a The organic amine halide salt is formamidine bromide (FABr).
(3) Mixing the first solution in (1) and the second solution in (2), wherein the first solution: a second solution: third solution ═ 1:1 (volume ratio), and performing ultrasonic treatment for 2h to obtain a uniformly mixed solution 8, wherein the polymer content is 15 wt%, and the precursor content of the perovskite is 15 wt%.
(4) And (3) coating the solution 8 on the surface of the quartz substrate by a spin coating method to uniformly disperse the solution 8 on the surface of the silicon-based photovoltaic cell, then placing the silicon-based photovoltaic cell coated with the solution 8 in a vacuum drying oven, and drying for 1h at 50 ℃ and 0.01MPa to remove the organic solvent to obtain a single-layer polymer-based perovskite luminescence down-conversion film with a uniform surface, wherein the thickness of the film is controlled to be 3 microns.
The reflection spectrum (B) of a silicon-based photovoltaic cell compatible with the single-layer polymer-based perovskite luminescence down-conversion thin film prepared in this example is shown in fig. 7.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (21)
1. A method of making a polymer-based functional film, comprising: providing a substrate, and preparing at least one layer of polymer film on the substrate, wherein the preparation method of the polymer film comprises the following steps:
step I, dissolving a polymer in a solvent to obtain a solution I;
step II, placing the solution I on the surface of a substrate, and then removing the solvent to form a polymer film on the surface of the substrate;
wherein, the preparation method of at least one layer in the polymer film further comprises the following steps: in the step I, a nano sacrificial template is also added into the solution I; and
III, removing the nano sacrificial template, forming a nano cavity in the polymer film to obtain the polymer film containing the nano cavity,
wherein, the functional film comprises at least one layer of polymer film, and at least one layer of the polymer film is a polymer film containing nano cavities.
2. The method according to claim 1, wherein the nanocavity-containing polymer film has a nanocavity volume percentage of 30% to 60%, and the shape of the nanocavity includes one or more of a sphere, a polyhedron, a cylinder, a disk and a Y-shape.
3. The production method according to claim 1, wherein when the functional film comprises at least two polymer films, refractive indices of adjacent two polymer films are different; the thickness of the polymer film is 100nm-5 mm.
4. The method according to claim 3, wherein the polymer thin film has a thickness of 100nm to 1 μm.
5. The production method according to claim 1, wherein the polymer thin film further contains perovskite; the mass fraction of the perovskite is 10-30%; the perovskite is formamidine lead bromide, formamidine lead iodide or has a molecular formula of R1NH3AB3Or (R)2NH3)2AB4Wherein A and B form a coordination octahedral structure, R1NH3Or R2NH3Filling the coordination octahedron gap formed by A and B, R1Is C1-C4 alkyl, R2Is C2-C4 unsaturated alkyl, A is selected from any one of Ge, Sn, Pb, Cu, Mn, Sb and Bi, and B is halogen.
6. The production method according to claim 5, wherein the mass fraction of perovskite in the polymer thin film is 15% to 20%.
7. The method according to claim 5, wherein B is selected from any one of Cl, Br and I.
8. The method of claim 1, wherein the nano sacrificial template is selected from one or more of nano metal particles, nano nonmetal particles and semiconductor quantum dots, and the solvent comprises one or more of toluene, chloroform and dichloromethane, N-dimethylformamide, dimethyl sulfoxide and dimethylacetamide.
9. The method of claim 1, wherein the solvent is removed at a temperature of not higher than 100 ℃ in step II, and the sacrificial template is removed by etching in step III.
10. The method of claim 9, wherein the sacrificial template is removed by etching with an etching liquid or an etching gas.
11. The production method according to claim 1, wherein the nanoscale metal particles comprise one or more of Au, Ag, Al, and Cu;
the nanoscale non-metallic particles comprise SiO2、TiO2ZnO and ZrO2One or more of;
the semiconductor quantum dots comprise one or more of cadmium selenide CdSe, zinc sulfide ZnS, chromium telluride CdTe, indium phosphide InP, copper indium sulfide CuInS and copper indium selenide CuInSe.
12. The manufacturing method according to claim 1, wherein when the functional film includes at least two polymer films, a solvent used in manufacturing a subsequent polymer film does not dissolve a previously manufactured polymer film in manufacturing adjacent two polymer films, and polymer materials used in manufacturing adjacent two polymer films are different.
13. The production method according to claim 1, wherein the solution I further contains a precursor of perovskite; the precursor of the perovskite is a mixture of inorganic halide salt and organic ammonium halide salt.
14. The method of claim 13, wherein the molar ratio of the inorganic halide salt to the organic ammonium halide salt is 1: (0.1 to 3).
15. The production method according to claim 13, wherein the inorganic halide salt is any one of halide salts of metals Ge, Sn, Pb, Sb, Bi, Cu, and Mn;
the organic amine halide salt is selected from bromoformamidine and iodoformamidine and has a general formula CmH2m+1NH3A saturated alkylamine halide salt of B or a compound of formula CnH2n-1NH3One or more of unsaturated alkylamine halide salt or aromatic amine halide salt of B, wherein m is more than or equal to 1 and less than or equal to 4, n is more than or equal to 2 and less than or equal to 4, and B is halogen.
16. The method according to claim 15, wherein B is any one of Cl, Br and I.
17. The preparation method according to claim 1, wherein in the solution I, the mass fraction of the polymer is 1% to 20%; the mass fraction of the nano sacrificial template is 0.02-5%; if the precursor of the perovskite is present, the mass fraction of the precursor is 10-30%.
18. The method according to claim 17, wherein the mass fraction of the polymer in the solution I is 10% to 15%.
19. The preparation method according to claim 17, wherein in the solution I, the mass fraction of the nano sacrificial template is 0.1 to 3%.
20. The production method according to claim 17, wherein the mass fraction of the perovskite precursor, if present, in the solution I is 15% to 20%.
21. Use of the functional film produced by the production method according to any one of claims 1 to 20 in an optical device.
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| CN104952698A (en) * | 2013-12-27 | 2015-09-30 | 伊利诺斯州立大学托管会 | Method and device for transferring lamination of nanostructured material |
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| CN104952698A (en) * | 2013-12-27 | 2015-09-30 | 伊利诺斯州立大学托管会 | Method and device for transferring lamination of nanostructured material |
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