CN119374265A - A radiation refrigeration product, a radiation refrigeration film and a preparation method thereof - Google Patents
A radiation refrigeration product, a radiation refrigeration film and a preparation method thereof Download PDFInfo
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- CN119374265A CN119374265A CN202411945481.3A CN202411945481A CN119374265A CN 119374265 A CN119374265 A CN 119374265A CN 202411945481 A CN202411945481 A CN 202411945481A CN 119374265 A CN119374265 A CN 119374265A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B23/00—Machines, plants or systems, with a single mode of operation not covered by groups F25B1/00 - F25B21/00, e.g. using selective radiation effect
- F25B23/003—Machines, plants or systems, with a single mode of operation not covered by groups F25B1/00 - F25B21/00, e.g. using selective radiation effect using selective radiation effect
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
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Abstract
The application provides a radiation refrigeration product, a radiation refrigeration film and a preparation method thereof, wherein the radiation refrigeration film comprises an emission layer and an anti-reflection layer which are sequentially laminated, and under the visible light wavelength range, the effective refractive indexes of the air, the anti-reflection layer and the emission layer are gradually increased, the emission layer and the anti-reflection layer are made of light-transmitting materials, and the anti-reflection layer is of a porous structure. The radiation refrigerating film has excellent emissivity in the middle infrared band and high transmissivity in the visible light band, and the radiation refrigerating film with high emissivity and high transmissivity in the visible light wavelength range is formed by arranging the anti-reflection layer with the porous structure on one side of the radiation refrigerating film and matching the anti-reflection layer with the porous structure with the radiation layer.
Description
Technical Field
The invention relates to the technical field of radiation refrigeration, in particular to a radiation refrigeration product, a radiation refrigeration film and a preparation method thereof.
Background
The radiation refrigeration is a green, environment-friendly and energy-saving efficient cooling technology, and on the premise of not consuming energy, the energy of objects on the earth is transmitted to the outer space in a radiation mode through an atmospheric window (8-13 mu m), so that the spontaneous cooling of the surfaces of the objects is realized. Most of radiation refrigeration materials are applied to textile and building industries at present, the transmittance of the materials in the visible light wave band is not considered, and the application of the radiation refrigeration materials to optical windows is limited.
Disclosure of Invention
The invention mainly solves the technical problems of providing a radiation refrigeration product, a radiation refrigeration film and a preparation method thereof, and solves the problem of poor transmittance in a visible light wave band when a film layer has high emissivity in the prior art.
In order to solve the technical problems, the first technical scheme adopted by the invention is to provide the radiation refrigeration film, which comprises an emission layer and an anti-reflection layer which are sequentially laminated, wherein the effective refractive indexes of air, the anti-reflection layer and the emission layer are gradually increased in the visible light wavelength range, the emission layer and the anti-reflection layer are both made of light-transmitting materials, and the anti-reflection layer is of a porous structure.
The effective refractive index of the emission layer ranges from 2.30 to 2.60, and/or the effective refractive index of the anti-reflection layer ranges from 1.18 to 1.30.
Wherein, the emitting layer and the anti-reflection layer are both inorganic materials.
The material of the emission layer is any two of silicon carbide, titanium dioxide and silicon nitride, and/or the material of the anti-reflection layer is any one of silicon dioxide and calcium fluoride.
Wherein the porosity of the anti-reflection layer is 39% -66%, and the aperture of the anti-reflection layer is 50-120 nanometers.
Wherein the thickness of the anti-reflection layer is 100-200 nm, and/or the thickness of the emission layer is 400-500 nm.
In order to solve the technical problems, the second technical scheme adopted by the invention is to provide a preparation method of a radiation refrigeration film, which comprises the following steps:
Forming an emission layer;
And forming an anti-reflection layer with a porous structure on one side of the emission layer, wherein the effective refractive indexes of the air, the anti-reflection layer and the emission layer are gradually increased in the visible light wavelength range, and the emission layer and the anti-reflection layer are made of light-transmitting materials.
Wherein forming an emissive layer comprises:
The first inorganic material and the second inorganic material are different, and the first inorganic material and the second inorganic material are any two of silicon carbide, titanium dioxide and silicon nitride.
Wherein forming an emission layer with the first inorganic material and the second inorganic material as raw materials includes:
the emission layer is formed by sputtering a first inorganic material and a second inorganic material as raw materials by means of physical vapor deposition.
The preparation method comprises the following steps:
the substrate is a metal substrate, a plastic substrate, a building material substrate, a textile material substrate or a glass substrate;
forming an emissive layer comprising:
an emissive layer is formed on one side of the substrate.
Wherein an antireflection layer of a porous structure is formed on one side of the emission layer, comprising:
Forming a prefabricated layer on one side of the emission layer by using a third inorganic material and a fourth inorganic material as raw materials;
and removing the fourth inorganic material in the prefabricated layer so that the third inorganic material forms an anti-reflection layer with a porous structure.
Wherein the third inorganic material is any one of silicon dioxide and calcium fluoride, and the fourth inorganic material is magnesium oxide;
forming a prefabricated layer on one side of the emission layer with a third inorganic material and a fourth inorganic material as raw materials, comprising:
Sputtering a third inorganic material and a fourth inorganic material serving as raw materials on one side of the emission layer in a physical vapor deposition mode to form a prefabricated layer;
and/or removing the fourth inorganic material in the preformed layer to form the third inorganic material into a porous structured antireflective layer, comprising:
and removing the fourth inorganic material in the prefabricated layer by chemical etching so that the third inorganic material forms an anti-reflection layer with a porous structure.
In order to solve the technical problems, the third technical scheme adopted by the invention is to provide a radiation refrigeration product, which comprises a base material and the radiation refrigeration film, wherein the radiation refrigeration film is arranged on the base material, and an emission layer of the radiation refrigeration film is in contact with the base material.
The radiation refrigeration product, the radiation refrigeration film and the preparation method thereof have the beneficial effects that the radiation refrigeration film comprises the emission layer and the anti-reflection layer which are sequentially laminated, the effective refractive indexes of the air, the anti-reflection layer and the emission layer are gradually increased in the visible wavelength range, the emission layer and the anti-reflection layer are made of light-transmitting materials, and the anti-reflection layer is of a porous structure. The radiation refrigerating film has excellent emissivity in the middle infrared band and high transmittance in the visible light band, and the radiation refrigerating film with high transmittance in the visible light wavelength range is formed by arranging the anti-reflection layer with the porous structure on one side of the radiation refrigerating film and matching the anti-reflection layer with the porous structure with the radiation layer.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a radiation refrigeration article provided by the present invention;
FIG. 2 is a graph comparing the transparency of the original glass with the transparency of the coated glass provided by the present application;
FIG. 3 is a schematic flow chart of an embodiment of a method for preparing a radiation refrigeration film according to the present invention;
FIG. 4 is a schematic view of the structure of a substrate in a radiation refrigeration article provided by the present invention;
FIG. 5 is a schematic view of a structure of a radiation refrigeration article provided by the present invention with an emissive layer over a substrate;
FIG. 6 is a schematic flow chart of a specific embodiment of step S2 in the method for preparing a radiation refrigeration film provided in FIG. 3;
Fig. 7 is a schematic structural diagram corresponding to step S21 in the method for preparing a radiation refrigeration film provided in fig. 6.
In the figure, a radiation refrigeration product 100, a substrate 10, a radiation refrigeration film 20, an emission layer 201, an anti-reflection layer 202, a porous structure 2021 and a prefabricated layer 203 are shown.
Detailed Description
The following describes embodiments of the present application in detail with reference to the drawings.
In the following description, for purposes of explanation and not limitation, specific details are set forth such as the particular system architecture, interfaces, techniques, etc., in order to provide a thorough understanding of the present application.
The term "and/or" is merely an association relationship describing the associated object, and means that three relationships may exist, for example, a and/or B may mean that a exists alone, while a and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship. Further, "a plurality" herein means two or more than two.
In order to enable those skilled in the art to better understand the technical scheme of the present invention, the radiation refrigeration product, the radiation refrigeration film and the preparation method thereof provided by the present invention are described in further detail below with reference to the accompanying drawings and the specific embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing embodiments of the application only and is not intended to be limiting of the application.
Before describing embodiments of the present application in further detail, the terms and terminology involved in the embodiments of the present application will be described, and the terms and terminology involved in the embodiments of the present application will be used in the following explanation.
Physical vapor deposition (Physical Vapor Deposition, PVD), a technique that uses physical methods to gasify the surface of a material source into gaseous atoms or molecules, or to partially ionize them into ions, under vacuum conditions, and deposits a thin film with a specific function on the surface of a substrate by a low-pressure gas (or plasma) process. PVD techniques include vacuum evaporation plating, vacuum sputtering plating, arc plasma plating, ion plating, and Molecular Beam Epitaxy (MBE).
The radiation refrigeration is a passive heat dissipation mode, and heat is radiated to the outer space of a cold source in an electromagnetic wave mode through an atmospheric transparent window (8-13 mu m) to achieve the purpose of reducing temperature, and the whole process does not need any energy input, so that real zero carbon emission is achieved. The radiation refrigeration needs to have higher emissivity and low absorptivity in the 'atmospheric window' wave band. The radiation refrigeration technology can be widely applied to the fields of building cooling, radiation refrigeration clothing fabric, outdoor equipment heat dissipation, agricultural greenhouse cooling and the like, and has wide application space.
Most of radiation refrigeration materials are applied to textile and building industries at present, the transmittance of the materials in the visible light wave band is not considered, and the application of the radiation refrigeration materials to optical windows is limited.
In order to solve the problem that the radiation refrigeration material has poor transmittance in the visible light band, some researchers develop flexible transparent radiation refrigeration window materials, and the radiation refrigeration material is composed of a plurality of film layers, and the radiation refrigeration material has high transmittance and near infrared high reflection in the visible light band by adding a visible light anti-reflection layer. The radiation refrigerating material consists of a multilayer film, and sequentially comprises a middle infrared emission layer, a near infrared anti-reflection layer and a visible light anti-reflection layer, wherein polydimethylsiloxane is adopted as the middle infrared emission layer to realize middle infrared band emission, silver is adopted as the near infrared anti-reflection layer to realize reflection of solar spectrum with the wavelength of near infrared ranging from 0.8 mu m to 2.5 mu m, and polycarbonate is adopted as the visible light anti-reflection layer. By constructing a polymer-metal-polymer structure, the function of visible light transmission and near infrared high reflection is realized. However, the designed film system has the average transmittance of 0.6 in the visible light wave band of 0.4-0.8 mu m, and the transmittance is relatively low, so that the flexible transparent radiation refrigeration window material is limited in application in high-transmittance requirements such as optical glass windows, and the middle infrared emission layer and the visible light anti-reflection layer adopt organic polymers, however, the organic materials are easy to degrade, the radiation refrigeration efficiency of the film is reduced, and the application in the open air is limited.
Because the sum of the absorptivity, the transmissivity and the reflectivity of the material is 1, the anti-reflection layer is introduced to reduce the reflectivity of the radiation refrigeration material, so that the transmissivity of the radiation refrigeration material in the visible light wave band range is improved.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a radiation refrigeration product according to the present invention.
In this embodiment, a radiation refrigeration product 100 is provided, where the radiation refrigeration product 100 includes a substrate 10 and a radiation refrigeration film 20, and the radiation refrigeration film 20 is disposed on the substrate 10. Wherein the radiation refrigeration film 20 includes an emission layer 201 and an antireflection layer 202 which are sequentially stacked. The emission layer 201 is in contact with the substrate 10, and the anti-reflection layer 202 is disposed on a surface of the emission layer 201 away from the substrate 10.
In one embodiment, the substrate 10 is a metal substrate, a plastic substrate, a building material substrate, a textile material substrate, or a glass substrate. In the following examples, the substrate 10 is exemplified as a glass substrate.
The emissive layer 201 has a high emissivity in the mid-infrared wavelength range and a high transmittance in the visible wavelength range. Wherein, the mid-infrared wavelength range is 0.8 μm to 2.5 μm, and the visible wavelength range is 0.4 μm to 0.8 μm. Emissivity is a physical quantity that characterizes an object's ability to emit infrared radiation, ranging in value from 0 to 100%, where 100% represents a complete blackbody, capable of emitting 100% of its thermal radiation. Transmittance is typically expressed in percent and ranges from 0% to 100%, where 100% indicates that all incident light is completely transmitted by the material and 0% indicates that no light is transmitted.
The anti-reflection layer 202 and the emission layer 201 are both inorganic materials. The radiation refrigeration film 20 made of inorganic materials can effectively solve the problem that the existing radiation refrigeration film 20 is easy to age and degrade, improves the binding force between the radiation refrigeration film 20 and the base material 10, is convenient for the radiation refrigeration film 20 to be suitable for outdoor scenes, and expands the application range of the radiation refrigeration film 20.
In the visible wavelength range, the effective refractive indexes of the air, the anti-reflection layer 202 and the emission layer 201 are gradually increased, the emission layer 201 and the anti-reflection layer 202 are made of light-transmitting materials, and the anti-reflection layer 202 is a porous structure 2021. The effective index of refraction represents the ratio of the reflection and refractive index of light on an object and reflects the ability of the object to absorb, penetrate, and scatter light. Wherein the effective refractive index of the glass substrate is 1.5. In this embodiment, by providing the anti-reflection layer with a porous structure, in the visible light range, incident light is easily specularly reflected on a smooth surface, and when the incident light irradiates on the porous structure, the incident light may be reflected and scattered multiple times inside the porous structure, so as to reduce the chance of direct reflection, and the porous structure may scatter the light into diffuse reflection, thereby reducing the total reflectivity and further reducing the radiation refrigeration product 100.
In the embodiment, the graded refractive index can reduce the number of scattering centers, so that scattering loss is reduced, the light transmittance of the material can be improved, and reflection loss is reduced and the transmittance can be improved because the light cannot be suddenly changed at the interface between the regions with different refractive indexes. Accordingly, the anti-reflective layer 202 and the emissive layer 201 are set to different refractive indices, and in order to ensure that the effective refractive index of the anti-reflective layer 202 is as close to 2k+1/4λ as possible in the visible wavelength range of the radiation refrigeration article 100, the effective refractive index of the anti-reflective layer 202 should be as low as possible, so that the effective refractive indices of air, the anti-reflective layer 202, and the emissive layer 201 are set to gradually increase.
The effective refractive index of the emissive layer 201 and the anti-reflective layer 202, respectively, is related to the effective refractive index of the glass substrate. The effective refractive indices of the emissive layer 201 and the anti-reflective layer 202 disposed on different substrates 10 are different.
In one embodiment, the effective refractive index of the emissive layer 201 ranges from 2.3 to 2.6. The effective refractive index of the emissive layer 201 may range from 2.35 to 2.57. Specifically, the effective refractive index of the emission layer 201 is 2.4, 2.43, 2.46, 2.50, 2.52, 2.56.
In one embodiment, the material of the emissive layer 201 is a combination of any two of silicon carbide, titanium dioxide, and silicon nitride. The effective refractive index of the emissive layer 201 is determined based on the mass ratio of the two inorganic materials in the emissive layer 201 and the refractive index of the inorganic materials. For example, when the material of the emission layer 201 includes a first inorganic material a and a second inorganic material B, the effective refractive index n Emissive layer =nA*x+nB of the emission layer 201 is (1-x), where x is the content of the first inorganic material a in the emission layer 201, n A is the refractive index of the first inorganic material a, and n B is the refractive index of the second inorganic material B. The first inorganic material a is different from the second inorganic material B, so that the phenomenon that the radiation refrigeration film 20 made of a single inorganic material is easy to be brittle broken is improved.
In the present embodiment, the emissivity of the emission layer 201 in the mid-infrared band range can be adjusted by adjusting the ratio of the first inorganic material and the second inorganic material in the emission layer 201.
The emissive layer 201 provided in this embodiment is prepared by a physical vapor deposition process. Specifically, the emission layer 201 is prepared by a magnetron sputtering process. The emitter layer 201 manufactured by the physical vapor deposition process can improve the binding force between the emitter layer 201 and the substrate 10, and is helpful for improving the reliability of the radiation refrigeration product 100.
In one embodiment, the thickness of the emission layer 201 may be 400 nm to 500 nm. For example, the thickness of the emission layer 201 may be 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, 460 nm, 470 nm, 480 nm, 490 nm, 500 nm, etc., and may be specifically set according to practical situations. In one embodiment, the transmittance of the resulting radiant refrigerant is optimal when the thickness of the emissive layer is 450 nanometers.
In one embodiment, the effective refractive index of the anti-reflective layer 202 ranges from 1.18 to 1.30. The effective refractive index of the anti-reflection layer 202 may be 1.20 to 1.28. Specifically, the effective refractive index of the antireflection layer 202 is 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28. Specifically, the transmittance of the effective refractive index of the different emission layers corresponding to the effective refractive index of the different emission-resistant layers is shown in table 1.
TABLE 1
Since the optimum refractive index for radiant refrigerant article 100 is based on the square root of the product of the refractive index of substrate 10 and the refractive index of air should be 1.23. In order to improve the band anti-reflection range and the mid-infrared emissivity of the radiation refrigeration product 100, an emission layer 201 with a higher film thickness is introduced, the emission layer 201 has a higher effective refractive index, because the optical thickness of the radiation refrigeration product 100 is the film thickness, the effective refractive index of the anti-reflection layer is close to 2k+1/4λ in the visible light wavelength range to ensure that the radiation refrigeration product 100 is as low as possible, but the refractive index of the anti-reflection layer is low and represents the increase of the porosity, so that the light transmission effect of the radiation refrigeration product 100 is optimal when the effective refractive index of the emission layer is 2.45 and the effective refractive index of the anti-reflection layer is 1.22 after calculation and adaptation is comprehensively considered.
In one embodiment, the material of the anti-reflective layer 202 is silicon dioxide or calcium fluoride. The effective refractive index of the anti-reflection layer 202 is determined based on the refractive index of the inorganic material constituting the emission layer 201 and the material ratio. For example, the material of the anti-reflection layer 202 is a third inorganic material C, and the effective refractive index n Antireflection layer =nC*x＋n Air-conditioner of the anti-reflection layer 202 is (1-x). Where x is the content of the third inorganic material C in the anti-reflection layer 202. The third inorganic material may be the same as the first inorganic material or the second inorganic material, or may be different from the first inorganic material.
The anti-reflection layer 202 in this embodiment is prepared by a physical vapor deposition process and a chemical etching process. Wherein, the physical vapor deposition process can be a magnetron sputtering process.
By changing the effective refractive index of the emission layer 201 and the anti-reflection layer 202, the effective refractive index of the emission layer 201, the effective refractive index of the anti-reflection layer 202, and the effective refractive index of the substrate 10 satisfy the relation (n Emissive layer /n Antireflection layer ）2=n Substrate material *n Air-conditioner ), so that the transmittance of the radiant refrigeration product 100 in the visible light band is improved.
In one embodiment, the thickness of the anti-reflection layer may be 100nm to 200 nm. For example, the thickness of the emission layer 201 may be 100nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, etc., and may be specifically set according to practical situations. In one embodiment, the transmittance of the resulting radiant refrigerant is optimal when the thickness of the anti-reflective layer is 130 nanometers.
Wherein, the porosity of the anti-reflection layer is 39% -66%. For example, the porosity of the antireflection layer 202 may be 39%, 45%, 50%, 55%, 60%, 65%, or the like, and is specifically set according to the actual situation.
The aperture of the anti-reflection layer 202 is 50 nm to 120 nm. For example, the aperture of the anti-reflective layer 202 may be 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 115 nm, 120 nm.
In this embodiment, the radiation refrigeration film 20 including the anti-reflection layer 202 and the emission layer 201 is prepared by a physical vapor deposition process and a chemical etching process, and the radiation refrigeration film 20 has simple composition components and simple preparation process, and is easy for mass production and application.
The effective refractive index of the anti-reflection layer 202 can be adjusted by adjusting the material ratio of the two inorganic materials forming the emission layer 201 to adjust the effective refractive index of the emission layer 201, thereby improving the emissivity of the radiant refrigerant film 20 in the mid-infrared wavelength range, and by adjusting the porosity of the porous structure 2021 in the anti-reflection layer 202. By adjusting the relation between the effective refractive index of the anti-reflection layer 202 and the effective refractive index of the emission layer 201, the transmittance of the radiation refrigeration film 20 in the visible light wave band range is improved, the anti-reflection effect of the radiation refrigeration film 20 is realized, and the application range of the radiation refrigeration film 20 is further improved.
Referring to fig. 2, fig. 2 is a graph comparing the transparency of the original glass with the transparency of the coated glass provided by the present application.
In one embodiment, as shown in fig. 2, the original glass is formed by coating the radiation refrigerating material on the glass in the current market, and the coated glass is formed by coating the radiation refrigerating film 20 provided by the embodiment on the glass. When the visible light wavelength range is 450-600 nm, the transparency of the original glass is about 92%, the transparency of the coated glass is improved to about 95%, and compared with the original glass, the transparency of the coated glass is improved by 3%, so that the application range of the radiation refrigeration film 20 is further improved.
In the radiation refrigeration product 100 provided in this embodiment, the radiation refrigeration film 20 includes an emission layer 201 and an anti-reflection layer 202 which are sequentially stacked, and under the visible light wavelength range, the effective refractive indexes of air, the anti-reflection layer 202 and the emission layer 201 are gradually increased, the emission layer 201 and the anti-reflection layer 202 are both made of light-transmitting materials, and the anti-reflection layer 202 is a porous structure 2021. The application forms the radiation refrigeration film 20 with high transmittance in the visible wavelength range by arranging the anti-reflection layer 202 with the porous structure 2021 on one side of the emission layer 201 and matching the anti-reflection layer 202 with the emission layer 201 through the porous structure 2021.
Referring to fig. 3, fig. 3 is a schematic flow chart of an embodiment of a method for preparing a radiation refrigeration film according to the present invention.
In this embodiment, a method for preparing a radiation refrigeration film 20 is provided, and the method for preparing the radiation refrigeration film 20 includes the following steps.
S1, forming an emitting layer.
S2, forming an anti-reflection layer with a porous structure on one side of the emission layer, wherein the effective refractive indexes of the air, the anti-reflection layer and the emission layer are gradually increased in the visible light wavelength range, and the emission layer and the anti-reflection layer are made of light-transmitting materials.
Referring to fig. 4, fig. 4 is a schematic structural diagram of a substrate in a radiation refrigeration product according to the present invention.
In one embodiment, the method of preparing the radiant refrigerant film 20 further comprises obtaining the substrate 10. The substrate 10 is a metal substrate, a plastic substrate, a building material substrate, a textile material substrate or a glass substrate. An emission layer 201 is formed on one side of the substrate 10. In the following examples, the substrate 10 is exemplified as a glass substrate.
Specifically, the embodiment of forming the emission layer 201 in step S1 is as follows.
In an embodiment, the emission layer 201 is formed using a first inorganic material and a second inorganic material as raw materials, the first inorganic material and the second inorganic material being different, and the first inorganic material and the second inorganic material being any two of silicon carbide, titanium dioxide, and silicon nitride.
Referring to fig. 5, fig. 5 is a schematic structural diagram of a substrate covered with an emission layer in a radiation refrigeration product according to the present invention.
In a specific embodiment, the emission layer 201 is formed by sputtering with a first inorganic material and a second inorganic material as raw materials by means of physical vapor deposition.
Specifically, the glass substrate is pretreated. For example, the glass substrate is placed in an ethanol solution for ultrasonic treatment for 15-30 minutes, then the glass substrate is taken out, and the surface of the glass substrate is dried by blowing nitrogen gas, so that the surface of the glass substrate is cleaned.
And placing the pretreated glass substrate in magnetic control equipment, and setting parameters of the magnetic control equipment. For example, the magnetron equipment can be pumped to the vacuum degree range of 3X 10 -4Pa~5×10-4 Pa, the argon flow range can be set to 15mL/min-30mL/min, the working air pressure range can be set to 0.6 Pa-1.2 Pa, the sputtering power range can be set to 80W-120W, the temperature range of the sample stage can be set to 200 ℃ to 400 ℃, and the sputtering time range can be set to 3 h-30 h. The emission layer 201 is formed in a magnetron apparatus by co-sputtering an a target and a B target. Wherein, the target A and the target B respectively adopt any two of silicon carbide, titanium dioxide and silicon nitride. After the sputtering time is reached, the targets A and B stop working.
The emission layer 201 formed of the first inorganic material and the second inorganic material may be formed on the glass substrate through the above steps.
In one embodiment, the glass substrate is placed in an ethanol solution for 20 minutes, and then the glass substrate is removed and the surface of the glass substrate is dried with nitrogen to clean the surface of the glass substrate. The pretreated glass substrate is placed in a magnetic control device, the magnetic control device is pumped until the vacuum degree reaches 4.5 multiplied by 10 -4 Pa, the argon flow is set to be 30mL/min, the working air pressure is set to be 1.0Pa, the sputtering power is set to be 120W, the temperature of a sample stage is set to be 200 ℃, and an emission layer 201 is formed by co-sputtering an A target and a B target in the magnetic control device. Wherein, the A target is sputtered with silicon carbide and the B target is sputtered with titanium dioxide.
In one embodiment, when the A target is silicon carbide, the power of the radio frequency power supply is 120W, the working air pressure is 1.0Pa, the sputtering time is 18 hours, the temperature of the sample stage is 200 ℃, and when the B target is titanium dioxide, the radio frequency power supply is 120W, the working air pressure is 1.0Pa, and the sputtering time is 15 hours. The sample stage temperature was 200 ℃. The emission layer 201 is formed in a magnetron apparatus by co-sputtering an a target and a B target.
In one embodiment, when the A target is silicon carbide, the power of the radio frequency power supply is 120W, the working air pressure is 1.0Pa, the sputtering time is 17h, the temperature of the sample stage is 200 ℃, and when the B target is silicon nitride, the radio frequency power supply is 120W, the working air pressure is 1.0Pa, the sputtering time is 23h, and the temperature of the sample stage is 200 ℃. The emission layer 201 is formed in a magnetron apparatus by co-sputtering an a target and a B target.
In one embodiment, when the A target is titanium dioxide, the power of the radio frequency power supply is 120W, the working air pressure is 1.0Pa, the sputtering time is 15 hours, the temperature of the sample stage is 200 ℃, and when the B target is silicon nitride, the radio frequency power supply is 120W, the working air pressure is 1.0Pa, the sputtering time is 20 hours, and the temperature of the sample stage is 200 ℃. The emission layer 201 is formed in a magnetron apparatus by co-sputtering an a target and a B target.
Specifically, the embodiment of forming the antireflection layer 202 of the porous structure 2021 on one side of the emission layer 201 in step S2 is as follows.
Referring to fig. 6, fig. 6 is a schematic flow chart of a specific embodiment of step S2 in the method for preparing a radiation refrigeration film provided in fig. 3.
And S21, forming a prefabricated layer on one side of the emission layer by taking a third inorganic material and a fourth inorganic material as raw materials, wherein the third inorganic material and the fourth inorganic material are different.
Specifically, the third inorganic material is silicon dioxide, and the fourth inorganic material is magnesium oxide.
Referring to fig. 7, fig. 7 is a schematic structural diagram corresponding to step S21 in the method for preparing a radiation refrigeration film provided in fig. 6.
The prefabricated layer 203 is formed by sputtering a third inorganic material and a fourth inorganic material as raw materials on one side of the emission layer 201 by means of physical vapor deposition.
In an embodiment, the emission layer 201 is further placed in a magnetic control device, and parameters of the magnetic control device forming the pre-fabricated layer 203 are parameters of the emission layer 201.
The prefabricated layer 203 is formed by co-sputtering a C target and a D target in a magnetron device. And sputtering a third inorganic material in the C target, wherein the third inorganic material is silicon dioxide. And sputtering a fourth inorganic material in the D target, wherein the fourth inorganic material is magnesium oxide. After the sputtering time is reached, the C target and the D target stop working.
A preformed layer 203 of a third inorganic material and a fourth inorganic material may be formed on the anti-reflective layer 202 by the above steps.
In one embodiment, the sputtering power of the magnetron device is set to 100W, and the parameters of the other magnetron devices are consistent with the parameters of forming the emission layer 201. And closing the target A and the target B of the magnetron equipment, opening the target C and the target D, and forming a prefabricated layer 203 on the side of the emission layer 201, which is far from the glass substrate, after sputtering is finished. Wherein, the C target is used for sputtering silicon dioxide, and the D target is used for sputtering magnesium oxide.
In one embodiment, when the C target is silicon dioxide, the power of the radio frequency power supply is 100W, the working air pressure is 1.0Pa, the sputtering time is 3 hours, the temperature of the sample stage is 200 ℃, and when the D target is magnesium oxide, the radio frequency power supply is 100W, the working air pressure is 1.0Pa, and the sputtering time is 3 hours. And closing the target A and the target B of the magnetron equipment, opening the target C and the target D, and forming a prefabricated layer 203 on the side of the emission layer 201, which is far from the glass substrate, after sputtering is finished.
In one embodiment, when the C target is calcium fluoride, the power of the radio frequency power supply is 100W, the working air pressure is 1.0Pa, the sputtering time is 3h, the temperature of the sample stage is 200 ℃, the D target is magnesium oxide, the radio frequency power supply is 100W, the working air pressure is 1.0Pa, and the sputtering time is 3 hours. And closing the target A and the target B of the magnetron equipment, opening the target C and the target D, and forming a prefabricated layer 203 on the side of the emission layer 201, which is far from the glass substrate, after sputtering is finished.
And S22, removing the fourth inorganic material in the prefabricated layer so that the third inorganic material forms an anti-reflection layer with a porous structure.
In one embodiment, as shown in fig. 1, the fourth inorganic material in the pre-formed layer 203 is removed by chemical etching, such that the third inorganic material forms the anti-reflective layer 202 of the porous structure 2021.
In one embodiment, the magnesium oxide in the pre-formed layer 203 is chemically etched with hydrochloric acid to remove the magnesium oxide in the pre-formed layer 203. The porous structure 2021 is formed in the preformed layer 203 from which magnesium oxide is removed, so that the preformed layer 203 forms the antireflection layer 202 of the porous structure 2021.
By the above steps, the radiation refrigeration product 100 in which the glass substrate, the emission layer 201, and the antireflection layer 202 are laminated in this order can be obtained.
In the method for preparing the radiation refrigeration film 20 provided in this embodiment, the emission layer 201 disposed in the radiation refrigeration film 20 makes the radiation refrigeration film 20 have excellent emissivity in the mid-infrared band and high transmittance in the visible light band, and the radiation refrigeration film 20 having high emissivity in the mid-infrared wavelength range and high transmittance in the visible light wavelength range is formed by disposing the anti-reflection layer 202 having the porous structure 2021 on one side of the emission layer 201 and by combining the anti-reflection layer 202 having the porous structure 2021 with the emission layer 201.
The foregoing is only the embodiments of the present invention, and therefore, the patent protection scope of the present invention is not limited thereto, and all equivalent structures or equivalent flow changes made by the content of the present specification and the accompanying drawings, or direct or indirect application in other related technical fields, are included in the patent protection scope of the present invention.
Claims (13)
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