CN104654639A - Sub-absorbing layer with gradually-changed composite coating form and preparation method thereof - Google Patents
Sub-absorbing layer with gradually-changed composite coating form and preparation method thereof Download PDFInfo
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Abstract
The invention provides a sub-absorbing layer with a gradually-changed composite coating form. The sub-absorbing layer sequentially comprises a bottom composite coating, at least one gradually-changed composite coating and a top composite coating from bottom to top, wherein the chemical composition of the bottom composite coating is a first metal Me1; the chemical composition of the top composite coating is a second metal Me2; the chemical composition of the gradually-changed composite coating comprises the first metal Me1 and the second metal Me2. The invention further comprises a preparation method of the sub-absorbing layer. By virtue of the coating structure prepared by the preparation method, the structural design of a selective solar heat absorbing coating is relatively flexible and changeable; in addition, by virtue of the gradually-changed structure, the wavelength range of selection objects of the selective solar heat absorbing coating and the incident solar irradiance range are enlarged, and thus the performance of the selective solar heat absorbing coating is improved.
Description
Technical field
The present invention relates to a kind of selective solar heat absorption coating for flat-plate solar collector, refer in particular to a kind of sub-absorbed layer and the method for making thereof with gradually changeable composite coating form.
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 heat absorption coating exactly on sheet metal.For now, most selective solar heat absorption coatings adopts the technique of vacuum coating to obtain.
Utilize the method for vacuum coating to prepare selective solar heat absorption coating, this method includes a kind of structure of plural layers, forms the film system of a selective solar heat absorption coating with this.Selective solar heat absorption coating includes one deck high reverse--bias basalis under normal circumstances, and this high reverse--bias basalis has lower infrared emittance.On infrared high reverse--bias basalis one or more layers intermediate sublayer stacking, the absorbed layer of this intermediate sublayer Structure composing selective solar heat absorption coating and interfere barrier 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 absorbent properties and the interference barrier properties of setting up solar selectively heat 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 heat absorption coating is that application composite comprises at least two kinds of metals and their oxide M e1Me2Ox and/or nitride Me1Me2Ny and/or nitrogen oxide Me1Me2OxNy.The conventional method preparing this composite 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 composite coating of another kind of preparation is the common sputtering comprising the composite 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 the scope of above-mentioned intermediate sublayer to wave-length coverage and incident solar irradiance often narrow, be unfavorable for improving the heat absorption efficiency to solar energy.
Summary of the invention
The invention provides a kind of sub-absorbed layer and the method for making thereof with gradually changeable composite coating form, it is often narrow that its main purpose is to overcome the scope of existing intermediate sublayer to wave-length coverage and incident solar irradiance, is unfavorable for improving the defect to the heat absorption efficiency of solar energy.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of sub-absorbed layer with gradually changeable composite coating form, comprise a bottom composite coating, at least one gradual change composite coating and a top layer composite coating from lower to upper successively, the chemical composition of described bottom composite coating is the first metal M e1, the chemical composition of described top layer composite coating is the second metal M e2, and the chemical composition of described gradual change composite coating comprises the first metal M e1 and the second metal M e2.
Further, in each described gradual change composite coating, the content of the first metal M e1 reduces from lower to upper successively, and in each described gradual change composite coating, the content of the second metal M e2 increases progressively from lower to upper successively.
Further, the content stepped minimizing from lower to upper of the first metal M e1 in each described gradual change composite coating, in each described gradual change composite coating, the content of the second metal M e2 is stepped from lower to upper increases progressively.
Further, described gradual change composite coating arranges four layers altogether, be respectively the first gradual change composite coating from lower to upper, second gradual change composite coating, 3rd gradual change composite coating and the 4th gradual change composite coating, the chemical composition of described first gradual change composite coating comprises the first metal M e1 and the 20% the second metal M e2 of 80%, the chemical composition of described second gradual change composite coating comprises the first metal M e1 and the 40% the second metal M e2 of 60%, the chemical composition of described 3rd gradual change composite coating comprises the first metal M e1 and the 60% the second metal M e2 of 40%, the chemical composition of described 4th gradual change composite coating comprises the first metal M e1 and the 80% the second metal M e2 of 20%.
A kind of preparation method of above-mentioned sub-absorbed layer, comprise the following steps: a, carry out target pairing according to the quality proportioning of described first metal M e1 and the second metal M e after be placed in same vacuum coating chamber, b, in above-mentioned vacuum coating chamber, carry out successively plated film by the common sputtering technology of magnetic control, first form described bottom composite coating, this characteristic stepped is changed into again according to chemical composition proportioning, successively superposition thus complete the preparation of each gradual change composite coating, finally plates a top layer composite coating at gradual change composite coating end face.
Further, the target placed of matching in same plated film chamber is the mixture of simple metal, alloy, nonmetal, metal oxide or metal oxide.
Further, match in same plated film chamber place target be in Si or SiAl/Mo, Si or SiAl/ Al, Si or SiAl/NiCr, Sn/Ti, Sn/Al, Sn/Cr, Sn/Mo, Sn/NiCr, Ti/In, ZnO:Al2O3 (AZO)/Al or ZnO:Ga2O3 (GZO)/Al one pairing.
A kind of selective solar heat absorption coating, comprise a high reverse--bias basalis, with low infrared emissivity to be covered in the main absorbing coating on this high reverse--bias basalis and to be stacked in the anti-reflection layer of this main absorbing coating, described main absorbing coating is above-mentioned a kind of sub-absorbed layer with gradually changeable composite coating form.
Further, 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 heat absorption coating is sputtered in metallic strip substrate, and described metallic strip substrate is aluminium strip, stainless steel band or copper strips.
Further, described high reverse--bias basalis 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 basalis is coated with one for the film coating of the tack and/or corrosion resistance that improve and improve selective solar heat 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 any 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 basalis.
Compared to the prior art, the beneficial effect that the present invention produces is:
1, the present invention designs ingenious, practical, by arranging by the first metal M e1 to the second metal M e2 and percentage by weight is the gradual change composite coating of stage shape gradual change, the sub-absorbed layer that the present invention can be made to obtain has at least two kinds of metal ingredients, realizes the gradual change from the primer coating of sub-absorbed layer to top coat metal ingredient.This coating structure will allow the structural design of selective solar heat absorption coating become more flexible and changeable.In addition, this grading structure can allow the scope of the wave-length coverage of the selective object of selective solar heat absorption coating and incident solar irradiance broaden and the performance of selective solar heat absorption coating also can be improved therefrom.
2, in the present invention, by the infrared high reverse--bias basalis using a kind of Investigation of Large Area Electron Beam evaporation coating technique to prepare selective solar heat absorption coating, can thicken the thickness of infrared high reverse--bias basalis, and these thicker coatings can make selective solar heat absorption coating have lower infrared emission ratio easily.While having lower infrared emission ratio, selective solar heat absorption coating is also less by the impact of base material condition.Meanwhile, when having relatively high production capacity, the improvement of the infrared high reverse--bias basalis quality to selective solar heat absorption coating can be realized, and then can help improve and improve the serviceability of flat-plate solar collector.
3, in the present invention, the film by plating layer under the thicker high reverse--bias basalis that is coated with at electron beam evaporation again can improve and improve tack and/or the corrosion resistance of selective solar heat absorption coating.Being coated with this thinner method that can improve and improve the coating of film system tack and/or corrosion 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 basalis that electron beam evaporation is coated with, plate the film that can improve and improve film system tack and/or corrosion resistance of layer again, material is thus formed a kind of selective solar heat absorption coated film system with infrared high reverse--bias characteristic.
4, in the present invention, the anti-reflection layer in selective solar heat absorption coating sublayer structure is used as by use transparent conductive film (TCO), in the sublayer structure of selective solar heat 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 production capacity prepared by large area selective solar heat absorption coating.
Accompanying drawing explanation
Fig. 1 is the structural representation of the heat 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 heat absorption coated film 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 heat absorption coated film system reflectance spectrum.
Detailed description of the invention
The invention discloses a kind of sub-absorbed layer and the method for making thereof with gradually changeable composite coating form, 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 heat absorption coating, comprise the high reverse--bias basalis 4 that has low infrared emissivity, one is covered in the main absorbing coating 3 on this high reverse--bias basalis 4 and is stacked in the anti-reflection layer of this main absorbing coating 3, described main absorbing coating 3 comprises a bottom composite coating 30 from lower to upper successively, at least one gradual change composite coating and a top layer composite coating 35, the chemical composition of described bottom composite coating 30 is the first metal M e1, the chemical composition of described top layer composite coating 35 is the second metal M e2, the chemical composition of described gradual change composite coating comprises the first metal M e1 and the second metal M e2.
Further, in each described gradual change composite coating, the content of the first metal M e1 reduces from lower to upper successively, and in each described gradual change composite coating, the content of the second metal M e2 increases progressively from lower to upper successively.
Further, the content stepped minimizing from lower to upper of the first metal M e1 in each described gradual change composite coating, in each described gradual change composite coating, the content of the second metal M e2 is stepped from lower to upper increases progressively.
Further, described gradual change composite coating arranges four layers altogether, be respectively the first gradual change composite coating 31 from lower to upper, second gradual change composite coating 32, 3rd gradual change composite coating 33 and the 4th gradual change composite coating 34, the chemical composition of described first gradual change composite coating 31 comprises the first metal M e1 and the 20% the second metal M e2 of 80%, the chemical composition of described second gradual change composite coating 32 comprises the first metal M e1 and the 40% the second metal M e2 of 60%, the chemical composition of described 3rd gradual change composite coating 33 comprises the first metal M e1 and the 60% the second metal M e2 of 40%, the chemical composition of described 4th gradual change composite coating 34 comprises the first metal M e1 and the 80% the second metal M e2 of 20%.
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 heat 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 basalis 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 basalis 4 is coated with one for the film coating of the tack and/or corrosion resistance that improve and improve selective solar heat 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 any 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 basalis 4.
A kind of sub-absorbed layer with gradually changeable composite coating form, comprise a bottom composite coating 30, at least one gradual change composite coating and a top layer composite coating 35 from lower to upper successively, the chemical composition of described bottom composite coating 30 is the first metal M e1, the chemical composition of described top layer composite coating 35 is the second metal M e2, and the chemical composition of described gradual change composite coating comprises the first metal M e1 and the second metal M e2.
A preparation method for above-mentioned a kind of selective solar heat 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 basalis 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 basalis 4 that step 1 obtains plates one or more coatings to set up the main absorbing coating 3 of selective solar heat absorption coated film system, be placed in same vacuum coating chamber after target pairing is carried out according to the quality proportioning of described first metal M e1 and the second metal M e in this main absorbing coating 3 one aspect, in above-mentioned vacuum coating chamber, successively plated film is carried out afterwards by the common sputtering technology of magnetic control, first form described bottom composite coating 30, this characteristic stepped is changed into again according to chemical composition proportioning, successively superposition thus complete the preparation of each gradual change composite coating, finally plate a top layer composite coating 35 at gradual change composite coating end face.In this step, the target placed of matching in same plated film chamber is the mixture of simple metal, alloy, nonmetal, metal oxide or metal oxide.Wherein being preferably paired into of above-mentioned target
si or SiAl/Mo,
si or SiAl/ Al,
si or SiAl/NiCr,
sn/Ti,
sn/Al,
sn/Cr,
sn/Mo,
sn/NiCr,
ti/In,
znO:Al2O3 (AZO)/Alor
znO:Ga2O3 (GZO)/Alin one pairing.First metal M e1 and the second metal M e2 can be
si or SiAl/Mo,
si or SiAl/ Al,
si or SiAl/NiCr,
sn/Ti,
sn/Al,
sn/Cr,
sn/Mo,
sn/NiCr,
ti/In,
znO:Al2O3 (AZO)/Alor
znO:Ga2O3 (GZO)/Alin one combination.
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 coating material of this semiconductor property of AZO to have higher refractive index, 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) coating 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 coating material as selective solar heat absorption coated film system intermediate sublayer structure for this semiconductor property of AZO, by reducing the spectral reflectivity in some wavelength region of selective solar heat absorption coating product 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 heat absorption coated film system, similar optical index parameter can be obtained.Except the advantage of use AZO semi-conducting 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 coating material of this semiconductor property of GZO to have higher refractive index, 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) coating 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 coating material as selective solar heat absorption coated film system intermediate sublayer structure for this semiconductor property of GZO, by reducing the spectral reflectivity in some wavelength region of selective solar heat absorption coating product 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 heat absorption coated film 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 coating material of this semiconductor property of ITO to have higher refractive index, 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) coating 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 coating material, this coated semiconductor of ITO material topmostly a kind ofly prepares the material that selective solar heat 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 heat absorption coated film system reflectance spectrum.
Can clearly see in the diagram, the reflectivity of reflectance spectrum in some wavelength region with the selective solar heat absorption coated film system of AZO/SiO2 intermediate sublayer structure anti-reflection layer is lower.By this phenomenon, the overall thermal absorptivity of selective solar heat absorption product on visible ray and near-infrared wavelength region can be made to become higher.This visible ray and the overall thermal absorptivity 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 absorptivity of heat absorption product as the anti-reflection layer of selective solar heat absorption coated film 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 heat absorption coated film 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 heat absorption product are brought qualitative leap by this!
The preferred embodiment of above-mentioned high reverse--bias basalis 4 in several the present invention is below provided
Embodiment six
A kind of high reverse--bias basalis 4, this high reverse--bias basalis 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 basalis 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 evaporation rate as evaporating materials.With aluminium as infrared high reverse--bias basalis 4, the selective solar heat absorption coating product prepared by other coating structures is coordinated to have certain production capacity.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 basalis 4, this high reverse--bias basalis 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 basalis 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 evaporation rate.With silver as infrared high reverse--bias basalis 4, the selective solar heat absorption coating product prepared by other coating structures is coordinated to have certain production capacity.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 basalis 4, this high reverse--bias basalis 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 basalis 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 weatherability and the corrosion 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 evaporation rate, this just means also can obtain certain thickness copper coating with the band speed of service faster to a certain extent, further increases the production capacity of selective solar heat absorption coating product.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 basalis 4 being used as selective solar heat 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.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 sizes 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 heat absorption coating.And if the quantity needing greatly to increase magnetron sputtering apparatus owing to using magnetron sputtering technique to prepare infrared high reverse--bias basalis 4 thicker in selective solar heat 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 basalis 4 and obtain the quality of selective solar heat absorption film system to used metallic strip substrate 5 material have higher requirement.Because thinner infrared high reverse--bias basalis 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 heat absorption coated film system.Such as: if the surface roughness 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 coating layer 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 heat absorption coating surface occur some similar surfaces relaxation, surface reconstruction, crystal structure, then cause being occurred pin-hole phenomena by plating coating.And thinner infrared high reverse--bias basalis 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 basalis 4.Along with the reduction of infrared high reverse--bias basalis 4 reflectivity, will produce the overall emission ratio of selective solar heat absorption coated film system and have a strong impact on.Can address these problems to a certain extent by the infrared high reverse--bias basalis 4 in selective solar heat absorption coated film system is coated with thicker way.
In large 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 basalis 4.And thicker infrared high reverse--bias basalis 4 is for selective solar heat absorption coated film system, under the prerequisite ensureing film system absorptance, the transmitting ratio of selective solar heat absorption film system entirety can be reduced further, thus improve the photo-thermal conversion efficiency of selective solar heat absorption product.So, the most important thing is here, from the angle of optical index " transmitting ratio " to improve the quality of selective solar heat absorption product, also can reduce metallic strip substrate 5 quality of materials to the impact of selective solar heat 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 heat absorption product at large area PVD plated film, can successfully utilize one group of high power electronic rifle to prepare the thicker infrared high reverse--bias basalis 4 of one deck.This thicker infrared high reverse--bias basalis 4 can be applied to reduce the transmitting ratio parameter of film system entirety in selective solar heat absorption coated film system, improves the quality of selective solar heat absorption product further.And the thicker infrared high reverse--bias basalis 4 simultaneously prepared by this coating process method also can reduce selective solar heat absorption product to a certain extent to the dependence of metallic strip substrate 5 quality of materials.
This coating process method makes thicker infrared high reverse--bias basalis 4 to be applied to large area PVD plated film and prepares selective solar heat 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 basalis 4 using electron beam evaporation deposition technique to prepare selective solar heat absorption coated film 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. one kind has the sub-absorbed layer of gradually changeable composite coating form, it is characterized in that: comprise a bottom composite coating, at least one gradual change composite coating and a top layer composite coating from lower to upper successively, the chemical composition of described bottom composite coating is the first metal M e1, the chemical composition of described top layer composite coating is the second metal M e2, and the chemical composition of described gradual change composite coating comprises the first metal M e1 and the second metal M e2.
2. a kind of sub-absorbed layer with gradually changeable composite coating form as claimed in claim 1, it is characterized in that: in each described gradual change composite coating, the content of the first metal M e1 reduces from lower to upper successively, in each described gradual change composite coating, the content of the second metal M e2 increases progressively from lower to upper successively.
3. a kind of sub-absorbed layer with gradually changeable composite coating form as claimed in claim 2, it is characterized in that: the content stepped minimizing from lower to upper of the first metal M e1 in each described gradual change composite coating, in each described gradual change composite coating, the content of the second metal M e2 is stepped from lower to upper increases progressively.
4. a kind of sub-absorbed layer with gradually changeable composite coating form as claimed in claim 3, it is characterized in that: described gradual change composite coating arranges four layers altogether, be respectively the first gradual change composite coating from lower to upper, second gradual change composite coating, 3rd gradual change composite coating and the 4th gradual change composite coating, the chemical composition of described first gradual change composite coating comprises the first metal M e1 and the 20% the second metal M e2 of 80%, the chemical composition of described second gradual change composite coating comprises the first metal M e1 and the 40% the second metal M e2 of 60%, the chemical composition of described 3rd gradual change composite coating comprises the first metal M e1 and the 60% the second metal M e2 of 40%, the chemical composition of described 4th gradual change composite coating comprises the first metal M e1 and the 80% the second metal M e2 of 20%.
5. the preparation method as the sub-absorbed layer as described in arbitrary in claim 1-4, it is characterized in that, comprise the following steps: a, be placed on after carrying out target pairing according to the quality proportioning of described first metal M e1 and the second metal M e in same vacuum coating chamber, b, in above-mentioned vacuum coating chamber, successively plated film is carried out by the common sputtering technology of magnetic control, first form described bottom composite coating, this characteristic stepped is changed into again according to chemical composition proportioning, successively superposition thus complete the preparation of each gradual change composite coating, finally plate a top layer composite coating at gradual change composite coating end face.
6. the preparation method of sub-absorbed layer as claimed in claim 5, is characterized in that: the target placed of matching in same plated film chamber is the mixture of simple metal, alloy, nonmetal, metal oxide or metal oxide.
7. the preparation method of sub-absorbed layer as claimed in claim 5, is characterized in that: match in same plated film chamber place target be in Si or SiAl/Mo, Si or SiAl/ Al, Si or SiAl/NiCr, Sn/Ti, Sn/Al, Sn/Cr, Sn/Mo, Sn/NiCr, Ti/In, ZnO:Al2O3 (AZO)/Al or ZnO:Ga2O3 (GZO)/Al one pairing.
8. a selective solar heat absorption coating, it is characterized in that: comprise a high reverse--bias basalis, with low infrared emissivity and be covered in the main absorbing coating on this high reverse--bias basalis and be stacked in the anti-reflection layer of this main absorbing coating, described main absorbing coating is as a kind of sub-absorbed layer with gradually changeable composite coating form as described in arbitrary in claim 1-4.
9. a kind of selective solar heat absorption coating as claimed in claim 9, it is characterized in that: 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 heat absorption coating is sputtered in metallic strip substrate, and described metallic strip substrate is aluminium strip, stainless steel band or copper strips.
10. a kind of selective solar heat absorption coating as claimed in claim 9, it is characterized in that: described high reverse--bias basalis 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 basalis is coated with one for the film coating of the tack and/or corrosion resistance that improve and improve selective solar heat 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 any 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 basalis.
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