CN104532188A - Composite film material of selective solar heat absorbing coating and preparation method of composite film material - Google Patents

Composite film material of selective solar heat absorbing coating and preparation method of composite film material Download PDF

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CN104532188A
CN104532188A CN201410785950.XA CN201410785950A CN104532188A CN 104532188 A CN104532188 A CN 104532188A CN 201410785950 A CN201410785950 A CN 201410785950A CN 104532188 A CN104532188 A CN 104532188A
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coating
magnetron
composite film
film material
selective solar
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马丁
瑞纳
眭凌杰
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Fujian Xin Yue Metal Material Science And Technology Ltd
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Fujian Xin Yue Metal Material Science And Technology Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10Glass or silica
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24Vacuum evaporation
    • C23C14/28Vacuum evaporation by wave energy or particle radiation
    • C23C14/30Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24HEATING; RANGES; VENTILATING
    • F24SSOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S70/00Details of absorbing elements
    • F24S70/10Details of absorbing elements characterised by the absorbing material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/40Solar thermal energy, e.g. solar towers

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Abstract

The invention discloses a composite film material of a selective solar heat absorbing coating. The composite film material is prepared by a method as follows: co-sputtering two different target materials in a same coating cavity, wherein the adopted target materials can be pure metals, alloys, non-metals, metallic oxides or mixtures of the metallic oxides. Furthermore, the invention further discloses a preparation method of the composite film material. The composite film material disclosed by the invention is skillful in design and strong in practicability; by virtue of the method of co-sputtering the two different target materials, the prepared selective solar heat absorbing coating is more flexible and changeable in design, and through the flexible and changeable design, the selective solar heat absorbing coating is more excellent in the aspects of performance and appearance color.

Description

Composite film material of selective solar thermal absorption coating and preparation method thereof
Technical field
The present invention relates to a kind of selective solar thermal absorption coating for flat-plate solar collector, refer in particular to composite film material of a kind of selective solar thermal absorption coating and preparation method thereof.
Background technology
For the application of flat-plate solar collector, the most common and the most general a kind of technology of preparing prepares selective solar thermal absorption coating exactly on sheet metal.For now, most selective solar thermal absorption coatings adopts the technique of vacuum plating to obtain.
Utilize the method for vacuum plating to prepare selective solar thermal absorption coating, this method includes a kind of structure of multilayer film, forms the film system of a selective solar thermal absorption coating with this.Selective solar thermal absorption coating includes one deck high reverse--bias stratum basale under normal circumstances, and this high reverse--bias stratum basale has lower infrared emittance.On infrared high reverse--bias stratum basale one or more layers intermediate sublayer stacking, the absorption layer of this intermediate sublayer Structure composing selective solar thermal absorption coating and interfere blocking layer.Top layer is that one or more layers is for reducing the rete (anti-reflection layer) of reflection.
For now, the effect of above-mentioned intermediate sublayer structure is absorptive character and the interference barrier properties of setting up solar selectively thermal absorption coating, and this intermediate sublayer is one or more layers structure of metal oxide and/or metal nitride and/or metal oxynitride under normal circumstances.Trend prepared by current selective solar thermal absorption coating is that application matrix material comprises at least two kinds of metals and their oxide M e1Me2Ox and/or nitride Me1Me2Ny and/or oxynitride Me1Me2OxNy.The general method preparing this compound coating uses reactive midfrequent AC and/or pulsed dc magnetron sputtering to carry out the preparation of coating on the alloy target material of compound or certain proportioning.The method of this compound coating of another kind of preparation is the common sputtering comprising the matrix material exceeding a kind of metal, and namely two kinds of dissimilar targets carry out sputter coating in same plated film chamber simultaneously.Adopt above two kinds of methods to prepare above-mentioned intermediate sublayer and in production and design, often not there is handiness and the performance of product and appearance color are often poor.
Summary of the invention
The invention provides composite film material of a kind of selective solar thermal absorption coating and preparation method thereof, its main purpose is to overcome existing method and prepares intermediate sublayer and producing and design is not often having handiness and the often poor defect of the performance of product and appearance color.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of composite film material of selective solar thermal absorption coating, this composite film material adopts following methods to be prepared from: in same plated film chamber, use two kinds of different target material to carry out common sputtering prepare, and the target material wherein used can be the mixture of pure metal, alloy, nonmetal, metal oxide or metal oxide.
Further, this composite film material adopts following equipment to be prepared from: two groups of AC magnetrons, these two groups of AC magnetrons are placed in same coating process chamber, and wherein one group of AC magnetron uses the first target material, and another is organized described AC magnetron and uses the second target material.
Further, this composite film material adopts following equipment to be prepared from: two groups of DC magnetrons, these two groups of DC magnetrons are placed in same coating process chamber, and wherein one group of DC magnetron uses the first target material, and another is organized described DC magnetron and uses the second target material.
Further, this composite film material adopts following equipment to be prepared from: one group of DC magnetron and a kind of AC magnetron, these two groups of DC magnetrons and a kind of AC magnetron are placed in same coating process chamber, wherein one group of DC magnetron uses the first target material, and described in one group, AC magnetron uses the second target material.
A kind of preparation method of composite film material of selective solar thermal absorption coating, comprise the following steps: a, choose the first target material and the second target material after be placed in same vacuum plating chamber, b, in above-mentioned vacuum plating chamber, carry out common sputtering by the common sputtering technology of magnetic control and prepare above-mentioned composite film material.
Further, the common sputtering technology of described magnetic control adopts two groups of AC magnetrons, and these two groups of AC magnetrons are placed in same coating process chamber, and wherein one group of AC magnetron uses the first target material, and another is organized described AC magnetron and uses the second target material.
Further, the common sputtering technology of described magnetic control adopts two groups of DC magnetrons, and these two groups of DC magnetrons are placed in same coating process chamber, and wherein one group of DC magnetron uses the first target material, and another is organized described DC magnetron and uses the second target material.
Further, the common sputtering technology of described magnetic control adopts one group of DC magnetron and a kind of AC magnetron, these two groups of DC magnetrons and a kind of AC magnetron are placed in same coating process chamber, wherein one group of DC magnetron uses the first target material, and described in one group, AC magnetron uses the second target material.
A kind of selective solar thermal absorption coating, comprise the high reverse--bias stratum basale that has low infrared emissivity, one is covered in the main absorbing coating on this high reverse--bias stratum basale and is stacked in the anti-reflection layer of this main absorbing coating, described main absorbing coating is above-mentioned composite film material, described anti-reflection layer comprises one as the TCO transparent conductive oxide coating and of time anti-reflection layer as the SiO2(SiOx of main anti-reflection layer) oxide coating, described SiO2(SiOx) oxide coating is covered in described TCO transparent conductive oxide coating, this selective solar thermal absorption coating is sputtered in metallic strip substrate, described metallic strip substrate is aluminium strip, Stainless Steel Band or copper strips.
Further, described high reverse--bias stratum basale adopts Investigation of Large Area Electron Beam evaporation coating technique to be prepared from, the evaporating materials that this coating process uses is aluminium, copper or silver, the lower surface of described high reverse--bias stratum basale is coated with one for the film coating of the tack and/or erosion resistance that improve and improve selective solar thermal absorption coating, the composition of described film coating is at least one metal, at least one metal oxide, at least one metal nitride, at least one metal oxynitride or above metal, metal oxide, the arbitrary combination of metal nitride and metal oxynitride, described film coating adopts DC magnetron sputtering technique or AC magnetron sputtering technique to be sputtered at the lower surface of institute's high reverse--bias stratum basale.
Compared to the prior art, the beneficial effect that the present invention produces is:
1, the present invention designs ingenious, practical, the design of the selective solar thermal absorption coating obtained will be made more flexible and changeable and use this flexible and changeable design can be prepared in the more excellent selective solar thermal absorption coating of performance and appearance color aspect by the method using two kinds of different target material to carry out common sputtering.
2, in the present invention, by the infrared high reverse--bias stratum basale using a kind of Investigation of Large Area Electron Beam evaporation coating technique to prepare selective solar thermal absorption coating, can thicken the thickness of infrared high reverse--bias stratum basale, and these thicker coatings can make selective solar thermal absorption coating have lower infrared emission ratio easily.While having lower infrared emission ratio, selective solar thermal absorption coating is also less by the impact of base material condition.Meanwhile, when having relatively high throughput, the improvement of the infrared high reverse--bias stratum basale quality to selective solar thermal absorption coating can be realized, and then can help improve and improve the use properties of flat-plate solar collector.
3, in the present invention, the film by plating layer under the thicker high reverse--bias stratum basale that is coated with at electron beam evaporation again can improve and improve tack and/or the erosion resistance of selective solar thermal absorption coating.Being coated with this thinner method that can improve and improve the coating of film system tack and/or erosion resistance can be DC or AC magnetron sputtering technique.The composition of this film coating can be a kind of metal M e or a kind of metal oxide MeOx or a kind of metal nitride MeNy or a kind of metal oxynitride MeOxNy.Under the thicker high reverse--bias stratum basale that electron beam evaporation is coated with, plate the film that can improve and improve film system tack and/or erosion resistance of layer again, material is thus formed a kind of selective solar thermal absorption coated membrane system with infrared high reverse--bias characteristic.
4, in the present invention, the anti-reflection layer in selective solar thermal absorption coating sublayer structure is used as by use transparent conductive film (TCO), in the sublayer structure of selective solar thermal absorption coating, use TCO coating anti-reflection layer can be made to have good performance as anti-reflection layer, and be also quite high for throughput prepared by big area selective solar thermal absorption coating.
Accompanying drawing explanation
Fig. 1 is the structural representation of the thermal absorption of selective solar described in the present invention coating.
Fig. 2 is the intermediate sublayer structure AZO/SiO2 anti-reflection layer of the embodiment of the present invention four and the contrast schematic diagram of individual layer SiO2 anti-reflection layer selective solar thermal absorption coated membrane system reflectance spectrum.
Fig. 3 is the intermediate sublayer structure AZO/SiO2 anti-reflection layer of the embodiment of the present invention five and the contrast schematic diagram of individual layer SiO2 anti-reflection layer selective solar thermal absorption coated membrane system reflectance spectrum.
Embodiment
The invention discloses composite film material of a kind of selective solar thermal absorption coating and preparation method thereof, those skilled in the art can use for reference present disclosure, and suitable improving technique parameter realizes.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are all deemed to be included in the present invention.Method of the present invention and application are described by preferred embodiment, related personnel obviously can not depart from content of the present invention, spirit and scope methods and applications as herein described are changed or suitably change with combination, realize and apply the technology of the present invention.
With reference to Fig. 1.A kind of selective solar thermal absorption coating, comprise the high reverse--bias stratum basale 4 that has low infrared emissivity, one is covered in the main absorbing coating 3 on this high reverse--bias stratum basale 4 and is stacked in the anti-reflection layer of this main absorbing coating 3, described main absorbing coating 3 is the sublayer structure that above-mentioned composite film material is formed, the composite film material of a kind of selective solar thermal absorption of this composite film material coating, this composite film material adopts following methods to be prepared from: the target material that use two kinds is different in same plated film chamber is carried out common sputtering and prepared, the target material wherein used can be pure metal, alloy, nonmetal, the mixture of metal oxide or metal oxide.And carrying out in the common sputter procedure of magnetic, this composite film material can adopt three kinds of equipment to obtain.
The first is: the common sputtering technology of described magnetic control adopts two groups of AC magnetrons, and these two groups of AC magnetrons are placed in same coating process chamber, and wherein one group of AC magnetron uses the first target material, and another is organized described AC magnetron and uses the second target material.
The second is: the common sputtering technology of described magnetic control adopts two groups of DC magnetrons, and these two groups of DC magnetrons are placed in same coating process chamber, and wherein one group of DC magnetron uses the first target material, and another is organized described DC magnetron and uses the second target material.
The third is: the common sputtering technology of described magnetic control adopts one group of DC magnetron and a kind of AC magnetron, these two groups of DC magnetrons and a kind of AC magnetron are placed in same coating process chamber, wherein one group of DC magnetron uses the first target material, and described in one group, AC magnetron uses the second target material.
Further, described anti-reflection layer comprises one as the TCO transparent conductive oxide coating 2 and of time anti-reflection layer as the SiO2(SiOx of main anti-reflection layer) oxide coating 1, described SiO2(SiOx) oxide coating 1 is covered in described TCO transparent conductive oxide coating 2, this selective solar thermal absorption coating is sputtered in metallic strip substrate 5, and described metallic strip substrate 5 is aluminium strip, Stainless Steel Band or copper strips.
Further, described high reverse--bias stratum basale 4 adopts Investigation of Large Area Electron Beam evaporation coating technique to be prepared from, the evaporating materials that this coating process uses is aluminium, copper or silver, the lower surface of described high reverse--bias stratum basale 4 is coated with one for the film coating of the tack and/or erosion resistance that improve and improve selective solar thermal absorption coating, the composition of described film coating is at least one metal, at least one metal oxide, at least one metal nitride, at least one metal oxynitride or above metal, metal oxide, the arbitrary combination of metal nitride and metal oxynitride, described film coating adopts DC magnetron sputtering technique or AC magnetron sputtering technique to be sputtered at the lower surface of institute's high reverse--bias stratum basale 4.
A preparation method for selective solar thermal absorption coating, comprises the following steps:
Step 1, make deposited by electron beam evaporation or AC magnetron sputtering technique, with aluminium strip, Stainless Steel Band or copper strips for metallic strip substrate 5, this metallic strip substrate 5 plates the high reverse--bias stratum basale 4 that one deck has low infrared emissivity.
Step 2, make deposited by electron beam evaporation or AC magnetron sputtering technique, the high reverse--bias stratum basale 4 that step 1 obtains plates one or more coatings to set up the main absorbing coating 3 of selective solar thermal absorption coated membrane system, this main absorbing coating 3 uses two kinds of different target material to carry out common sputtering to prepare in same plated film chamber, and this target material wherein used can be the mixture of pure metal, alloy, nonmetal, metal oxide or metal oxide.The design of the selective solar thermal absorption coating obtained will be made more flexible and changeable by the method using two kinds of different target material to carry out common sputtering and use this flexible and changeable design can be prepared in the more excellent selective solar thermal absorption coating of performance and appearance color aspect.
Step 3, by using DC magnetron sputtering technique, using ZnO:Al2O3 (AZO), ZnO:Ga2O3 (GZO) or In2O3:SnO2 (ITO) as described compound TCO target, the main absorbing coating 3 that step 2 obtains plates a TCO transparent conductive oxide coating 2.
Step 4, by making deposited by electron beam evaporation or AC magnetron sputtering technique, step 3 obtain TCO transparent conductive oxide coating 2 on plate a SiO2(SiOx) oxide coating 1.
The preferred embodiment of above-mentioned anti-reflection layer in several the present invention is below provided
Embodiment one
A kind of anti-reflection layer based on TCO material, comprise one as the TCO transparent conductive oxide coating 2 and of time anti-reflection layer as the SiO2(SiOx of main anti-reflection layer) oxide coating 1, described SiO2(SiOx) oxide coating 1 is covered in described TCO transparent conductive oxide coating 2.Described TCO transparent conductive oxide coating 2 is by using the DC magnetron sputtering technique of compound TCO target to prepare.Described SiO2(SiOx) coating is prepared by making deposited by electron beam evaporation or AC magnetron sputtering technique.Described compound TCO target is the mixture of metal oxide or metal oxide.Described compound TCO target is ZnO:Al2O3 (AZO).
The present embodiment adopts the coated material of this semiconductor property of AZO to have higher specific refractory power, can substitute the secondary anti-reflection layer material in conventional selective solar heat absorber coatings film system intermediate sublayer structure.The secondary anti-reflection layer material (normally ceramic insulating material) that contrast conventional selective solar heat absorber coatings film system intermediate sublayer structure uses, generally will use MF intermediate frequency or RF radio-frequency sputtering technique to prepare these coatings.And AZO(zinc oxide aluminum) coated material of this semiconductor property can carry out the preparation of coating by DC d.c. sputtering or DC pulse direct current sputtering technology, and under DC d.c. sputtering or DC pulse direct current sputtering technology condition, prepare AZO coated semiconductor can obtain and prepare the higher deposition of ceramic insulating material than use MF intermediate frequency or RF radio-frequency sputtering technique.
The present embodiment uses the part of coated material as selective solar thermal absorption coated membrane system intermediate sublayer structure for this semiconductor property of AZO, by reducing the spectral reflectivity in some wavelength region may of selective solar thermal absorption coating prod spectrum, the spectral absorption of product spectrum on corresponding wavelength region can be improved.Use ceramic insulating material identical as the anti-reflection layer effect of intermediate sublayer structure with traditional selective solar thermal absorption coated membrane system, similar optical index parameter can be obtained.Except the advantage of use AZO semiconductor material above-mentioned, AZO target is relative to ITO target (tin indium oxide target material), and manufacturing cost and price are relatively cheap.
Embodiment two
A kind of anti-reflection layer based on TCO material, comprise one as the TCO transparent conductive oxide coating 2 and of time anti-reflection layer as the SiO2(SiOx of main anti-reflection layer) oxide coating 1, described SiO2(SiOx) oxide coating 1 is covered in described TCO transparent conductive oxide coating 2.Described TCO transparent conductive oxide coating 2 is by using the DC magnetron sputtering technique of compound TCO target to prepare.Described SiO2(SiOx) coating is prepared by making deposited by electron beam evaporation or AC magnetron sputtering technique.Described compound TCO target is the mixture of metal oxide or metal oxide.Described compound TCO target is ZnO:Ga2O3 (GZO).
The present embodiment uses the coated material of this semiconductor property of GZO to have higher specific refractory power, can substitute the secondary anti-reflection layer material in conventional selective solar heat absorber coatings film system intermediate sublayer structure.The secondary anti-reflection layer material (normally ceramic insulating material) that contrast conventional selective solar heat absorber coatings film system intermediate sublayer structure uses, generally will use MF intermediate frequency or RF radio-frequency sputtering technique to prepare these coatings.And GZO(zinc-gallium oxide) coated material of this semiconductor property can carry out the preparation of coating by DC d.c. sputtering or DC pulse direct current sputtering technology, and under DC d.c. sputtering or DC pulse direct current sputtering technology condition, prepare GZO coated semiconductor can obtain and prepare the higher deposition of ceramic insulating material than use MF intermediate frequency or RF radio-frequency sputtering technique.GZO coated semiconductor material, relative to AZO coated semiconductor material, has higher chemical stability.
The present embodiment uses the part of coated material as selective solar thermal absorption coated membrane system intermediate sublayer structure for this semiconductor property of GZO, by reducing the spectral reflectivity in some wavelength region may of selective solar thermal absorption coating prod spectrum, the spectral absorption of product spectrum on corresponding wavelength region can be improved.Use ceramic insulating material identical as the anti-reflection layer effect of intermediate sublayer structure with traditional selective solar thermal absorption coated membrane system, similar optical index parameter can be obtained.
Embodiment three
A kind of anti-reflection layer based on TCO material, comprise one as the TCO transparent conductive oxide coating 2 and of time anti-reflection layer as the SiO2(SiOx of main anti-reflection layer) oxide coating 1, described SiO2(SiOx) oxide coating 1 is covered in described TCO transparent conductive oxide coating 2.Described TCO transparent conductive oxide coating 2 is by using the DC magnetron sputtering technique of compound TCO target to prepare.Described SiO2(SiOx) coating is prepared by making deposited by electron beam evaporation or AC magnetron sputtering technique.Described compound TCO target is the mixture of metal oxide or metal oxide.Described compound TCO target is In2O3:SnO2 (ITO).
The present embodiment uses the coated material of this semiconductor property of ITO to have higher specific refractory power, can substitute the secondary anti-reflection layer material in conventional selective solar heat absorber coatings film system intermediate sublayer structure.The secondary anti-reflection layer material (normally ceramic insulating material) that contrast conventional selective solar heat absorber coatings film system intermediate sublayer structure uses, generally will use MF intermediate frequency or RF radio-frequency sputtering technique to prepare these coatings.And ITO(tin indium oxide) coated material of this semiconductor property can carry out the preparation of coating by DC d.c. sputtering or DC pulse direct current sputtering technology, and under DC d.c. sputtering or DC pulse direct current sputtering technology condition, prepare ITO coated semiconductor can obtain and prepare the higher deposition of ceramic insulating material than use MF intermediate frequency or RF radio-frequency sputtering technique.TCO(transparent conductive oxide all) among coated material, this coated semiconductor of ITO material topmostly a kind ofly prepares the material that selective solar thermal absorption is coated with level anti-reflection layer, because it has relatively high optics (and electricity) performance.
Embodiment four: the relevant experimental data of the embodiment of the present invention one and chart
Fig. 2 is the contrast schematic diagram of intermediate sublayer structure AZO/SiO2 anti-reflection layer and individual layer SiO2 anti-reflection layer selective solar thermal absorption coated membrane system reflectance spectrum.Can clearly see in the diagram, the reflectivity of reflectance spectrum in some wavelength region may with the selective solar thermal absorption coated membrane system of AZO/SiO2 intermediate sublayer structure anti-reflection layer is lower.By this phenomenon, the overall thermal specific absorption of selective solar thermal absorption product on visible ray and near-infrared wavelength region can be made to become higher.This visible ray and the overall thermal specific absorption on near-infrared wavelength region carry out calculating according to relevant ISO 9050 international standard obtaining.In curve of spectrum contrast in the diagram, main difference is: the relative thermal absorptivity of individual layer SiO2 anti-reflection layer is 94.32%, and the relative thermal absorptivity of intermediate sublayer structure AZO/SiO2 anti-reflection layer is up to 95.5%.This just means that use intermediate sublayer structure AZO/SiO2 can bring the index more than 1% to promote for the overall thermal specific absorption of thermal absorption product as the anti-reflection layer of selective solar thermal absorption coated membrane system.
The relevant experimental data of embodiment five embodiment of the present invention one and chart
Fig. 3 (the details display of spectral curve on visible ray and near-infrared wavelength region): the contrast schematic diagram of intermediate sublayer structure AZO/SiO2 anti-reflection layer and individual layer SiO2 anti-reflection layer selective solar thermal absorption coated membrane system reflectance spectrum.
Can demonstrate in further detail in the figure and use intermediate sublayer structure AZO/SiO2 anti-reflection layer contrast individual layer SiO2 anti-reflection layer, the lifting of thermal absorptivity optical parametric index on solar spectrum visible ray and near-infrared wavelength region.The optical index and performance of giving selective solar thermal absorption product are brought qualitative leap by this!
The preferred embodiment of above-mentioned high reverse--bias stratum basale 4 in several the present invention is below provided
Embodiment six
A kind of high reverse--bias stratum basale 4, this high reverse--bias stratum basale 4 adopts Investigation of Large Area Electron Beam evaporation coating technique to be prepared from, and the evaporating materials that this coating process uses is aluminium.The thickness of described high reverse--bias stratum basale 4 is more than or equal to 50nm and is less than or equal to 1000nm.
The present embodiment adopts aluminium as the advantage of evaporating materials to be: aluminium is comparatively light and have good conduction and heat conductivility, can obtain higher rate of evaporation as evaporating materials.With aluminium as infrared high reverse--bias stratum basale 4, the selective solar thermal absorption coating prod prepared by other coating structures is coordinated to have certain throughput.Higher reflectivity can be provided as infrared reflecting layer in IR regions, to obtain lower solar heat absorber coatings transmitting ratio, improve the photo-thermal conversion efficiency of solar heat absorber coatings further.Aluminum ratio is comparatively cheap, and for the infrared reflecting layer of the excellent low transmitting ratio solar heat absorber coatings of processability, cost is lower.
Embodiment seven
A kind of high reverse--bias stratum basale 4, this high reverse--bias stratum basale 4 adopts Investigation of Large Area Electron Beam evaporation coating technique to be prepared from, and the evaporating materials that this coating process uses is silver.The thickness of described high reverse--bias stratum basale 4 is more than or equal to 50nm and is less than or equal to 1000nm.
The present embodiment employing silver as the advantage of evaporating materials is: silver, as evaporating materials, has the highest conduction and thermal conductivity in all metals.Compare aluminum evaporation material, under identical hydatogenesis condition, there is higher rate of evaporation.With silver as infrared high reverse--bias stratum basale 4, the selective solar thermal absorption coating prod prepared by other coating structures is coordinated to have certain throughput.The reflectivity higher than aluminium can be provided as infrared reflecting layer in IR regions, to obtain lower solar heat absorber coatings transmitting ratio, improve the photo-thermal conversion efficiency of solar heat absorber coatings further.
Embodiment eight
A kind of high reverse--bias stratum basale 4, this high reverse--bias stratum basale 4 adopts Investigation of Large Area Electron Beam evaporation coating technique to be prepared from, and the evaporating materials that this coating process uses is copper.The thickness of described high reverse--bias stratum basale 4 is more than or equal to 50nm and is less than or equal to 1000nm.
The present embodiment employing copper as the advantage of evaporating materials is: copper is not too active heavy metal, does not close at normal temperatures with the oxidation in dry air, improves weathering resistance and the erosion resistance of solar heat absorber coatings.Copper contrast aluminium, as evaporating materials, has better conduction and thermal conductivity.Copper is in these three kinds of evaporating materials, under identical hydatogenesis condition, there is the highest rate of evaporation, this just means also can obtain certain thickness copper coating with band travelling speed faster to a certain extent, further increases the throughput of selective solar thermal absorption coating prod.Higher reflectivity can be provided as infrared reflecting layer in IR regions, to obtain lower solar heat absorber coatings transmitting ratio, improve the photo-thermal conversion efficiency of solar heat absorber coatings further.
In sum, these three kinds of evaporating materials of aluminium, silver and copper are all highly suitable in the present invention the evaporating materials of the infrared high reverse--bias stratum basale 4 being used as selective solar thermal absorption coating.
In addition, in the present invention, electron beam evaporation is the same with magnetron sputtering is all physical vapor deposition technology and they can be used in various different Application Areas.Magnetron sputtering is used to carry out the vacuum coating technology that large-area coating film is a kind of extensive distribution and use.The distribution of Investigation of Large Area Electron Beam evaporation coating techniques and use have certain scope restriction, because the patent right problem of fairly large electron beam evaporation system brings certain technical difficulty to other domestic producer.Current of home make electron beam evaporation system is apply in some scientific research institutions and laboratory in colleges and universities mostly, and the scale of these electron beam evaporation system is less, the electron beam evaporation deposition technique performing some small areas can only be used to, such as: the plated film of semiconductor wafers.So, if other domestic producer wants applying electronic beam evaporation technique to carry out large-area coating film must overcome following technology barriers:
1, the extensive electron beam evaporation system high demand that there is higher system complexity and electron beam is controlled;
2, need larger vacuum cavity and have higher requirement to configured vacuum-pumping system.
Be more than why for most domestic manufacturer, their first-selection uses magnetron sputtering technique to prepare relevant selective solar thermal absorption coating.And if the quantity needing greatly to increase magnetron sputtering equipment owing to using magnetron sputtering technique to prepare infrared high reverse--bias stratum basale 4 thicker in selective solar thermal absorption coating, could by corresponding coating stack to certain thickness.Will indirectly improve equipment and production cost like this, simultaneously apply magnetron sputtering technique preparation thinner infrared high reverse--bias stratum basale 4 and obtain the quality of selective solar thermal absorption film system to used metallic strip substrate 5 material have higher requirement.Because thinner infrared high reverse--bias stratum basale 4 cannot make up the impact that metallic strip substrate 5 material (such as: the purity of base surface roughness and substrate surface) brings to selective solar thermal absorption coated membrane system.Such as: if the surfaceness of metallic strip substrate 5 is undesirable, the coating sometimes on metallic strip substrate 5 plated surface means and there is certain projection, pit and the uneven phenomenon of surface height on substrate surface, so cannot cover these positions that is protruding or pit.Or say from strict meaning, even if the coat-thickness of preparation is enough to cover these defects, but this can cause the fault, dislocation and the stepped interface problem that the interface of selective solar thermal absorption coatingsurface occur some similar surfaces relaxation, surface reconstruction, crystalline structure, then cause being occurred pin-hole phenomena by plating coating.And thinner infrared high reverse--bias stratum basale 4 is through coating process and after contacting atmospheric environment, some activity gases (such as: N2, O2 or CO2 etc.) more easily and in atmospheric environment produce chemical reaction and form corresponding metal oxide or metal nitride, and then reduce the reflectivity of infrared high reverse--bias stratum basale 4.Along with the reduction of infrared high reverse--bias stratum basale 4 reflectivity, will produce the overall emission ratio of selective solar thermal absorption coated membrane system and have a strong impact on.Can address these problems to a certain extent by the infrared high reverse--bias stratum basale 4 in selective solar thermal absorption coated membrane system is coated with thicker way.
In big area PVD plated film is produced, use electron beam evaporation process to have certain advantage, applying electronic beam evaporation technique can be reduced equipment and production cost to a certain extent and be utilized this technique more easily can prepare thicker infrared high reverse--bias stratum basale 4.And thicker infrared high reverse--bias stratum basale 4 is for selective solar thermal absorption coated membrane system, under the prerequisite ensureing film system specific absorption, the transmitting ratio of selective solar thermal absorption film system entirety can be reduced further, thus improve the photo-thermal conversion efficiency of selective solar thermal absorption product.So, the most important thing is here, from the angle of optical index " transmitting ratio " to improve the quality of selective solar thermal absorption product, also can reduce metallic strip substrate 5 quality of materials to the impact of selective solar thermal absorption product simultaneously.The applicant states that the coating process method related in this patent has following characteristics: prepare in the application of selective solar thermal absorption product at big area PVD plated film, can successfully utilize one group of high power electronic rifle to prepare the thicker infrared high reverse--bias stratum basale 4 of one deck.This thicker infrared high reverse--bias stratum basale 4 can be applied to reduce the transmitting ratio parameter of film system entirety in selective solar thermal absorption coated membrane system, improves the quality of selective solar thermal absorption product further.And the thicker infrared high reverse--bias stratum basale 4 simultaneously prepared by this coating process method also can reduce selective solar thermal absorption product to a certain extent to the dependency of metallic strip substrate 5 quality of materials.
This coating process method makes thicker infrared high reverse--bias stratum basale 4 to be applied to big area PVD plated film and prepares selective solar thermal absorption product and become a kind of feasible means of production.Meanwhile, consider the factor of saving equipment and production cost, the infrared high reverse--bias stratum basale 4 using electron beam evaporation deposition technique to prepare selective solar thermal absorption coated membrane system is a kind of effective methods.
Above are only the specific embodiment of the present invention, but design concept of the present invention is not limited thereto, all changes utilizing this design the present invention to be carried out to unsubstantiality, all should belong to the behavior of invading scope.

Claims (10)

1. the composite film material of a selective solar thermal absorption coating, it is characterized in that, this composite film material adopts following methods to be prepared from: in same plated film chamber, use two kinds of different target material to carry out common sputtering prepare, and the target material wherein used can be the mixture of pure metal, alloy, nonmetal, metal oxide or metal oxide.
2. the composite film material of a kind of selective solar thermal absorption coating as claimed in claim 1, it is characterized in that, this composite film material adopts following equipment to be prepared from: two groups of AC magnetrons, these two groups of AC magnetrons are placed in same coating process chamber, wherein one group of AC magnetron uses the first target material, and another is organized described AC magnetron and uses the second target material.
3. the composite film material of a kind of selective solar thermal absorption coating as claimed in claim 1, it is characterized in that, this composite film material adopts following equipment to be prepared from: two groups of DC magnetrons, these two groups of DC magnetrons are placed in same coating process chamber, wherein one group of DC magnetron uses the first target material, and another is organized described DC magnetron and uses the second target material.
4. the composite film material of a kind of selective solar thermal absorption coating as claimed in claim 1, it is characterized in that, this composite film material adopts following equipment to be prepared from: one group of DC magnetron and a kind of AC magnetron, these two groups of DC magnetrons and a kind of AC magnetron are placed in same coating process chamber, wherein one group of DC magnetron uses the first target material, and described in one group, AC magnetron uses the second target material.
5. the preparation method of the composite film material of a selective solar thermal absorption coating, it is characterized in that, comprise the following steps: a, choose the first target material and the second target material after be placed in same vacuum plating chamber, b, in above-mentioned vacuum plating chamber, carry out common sputtering by the common sputtering technology of magnetic control and prepare above-mentioned composite film material.
6. the preparation method of composite film material as claimed in claim 5, it is characterized in that: the common sputtering technology of described magnetic control adopts two groups of AC magnetrons, these two groups of AC magnetrons are placed in same coating process chamber, wherein one group of AC magnetron uses the first target material, and another is organized described AC magnetron and uses the second target material.
7. the preparation method of composite film material as claimed in claim 5, it is characterized in that: the common sputtering technology of described magnetic control adopts two groups of DC magnetrons, these two groups of DC magnetrons are placed in same coating process chamber, wherein one group of DC magnetron uses the first target material, and another is organized described DC magnetron and uses the second target material.
8. the preparation method of composite film material as claimed in claim 5, it is characterized in that: the common sputtering technology of described magnetic control adopts one group of DC magnetron and a kind of AC magnetron, these two groups of DC magnetrons and a kind of AC magnetron are placed in same coating process chamber, wherein one group of DC magnetron uses the first target material, and described in one group, AC magnetron uses the second target material.
9. a selective solar thermal absorption coating, it is characterized in that: comprise the high reverse--bias stratum basale that has low infrared emissivity, one is covered in the main absorbing coating on this high reverse--bias stratum basale and is stacked in the anti-reflection layer of this main absorbing coating, described main absorbing coating is as composite film material as described in arbitrary in claim 1-4, described anti-reflection layer comprises one as the TCO transparent conductive oxide coating and of time anti-reflection layer as the SiO2(SiOx of main anti-reflection layer) oxide coating, described SiO2(SiOx) oxide coating is covered in described TCO transparent conductive oxide coating, this selective solar thermal absorption coating is sputtered in metallic strip substrate, described metallic strip substrate is aluminium strip, Stainless Steel Band or copper strips.
10. a kind of selective solar thermal absorption coating as claimed in claim 9, it is characterized in that: described high reverse--bias stratum basale adopts Investigation of Large Area Electron Beam evaporation coating technique to be prepared from, the evaporating materials that this coating process uses is aluminium, copper or silver, the lower surface of described high reverse--bias stratum basale is coated with one for the film coating of the tack and/or erosion resistance that improve and improve selective solar thermal absorption coating, the composition of described film coating is at least one metal, at least one metal oxide, at least one metal nitride, at least one metal oxynitride or above metal, metal oxide, the arbitrary combination of metal nitride and metal oxynitride, described film coating adopts DC magnetron sputtering technique or AC magnetron sputtering technique to be sputtered at the lower surface of institute's high reverse--bias stratum basale.
CN201410785950.XA 2014-12-18 2014-12-18 Composite film material of selective solar heat absorbing coating and preparation method of composite film material Pending CN104532188A (en)

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CN105698416A (en) * 2016-03-01 2016-06-22 江苏贝德莱特太阳能科技有限公司 Selective solar absorbing coating for flat-plate solar collector
CN106048535A (en) * 2016-06-06 2016-10-26 南宁可煜能源科技有限公司 High-temperature-resistant and corrosion-resistant solar selective absorption coating
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CN106091442A (en) * 2016-06-06 2016-11-09 南宁可煜能源科技有限公司 A kind of slective solar energy absorbing coating with double ceramic structure
CN114457312A (en) * 2022-01-13 2022-05-10 厦门建霖健康家居股份有限公司 Radio frequency and direct current co-sputtering gray decorative film layer and method and application thereof

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