CN105222381A - A kind of double absorption layer coating for selective absorption of sunlight spectrum and preparation method thereof - Google Patents

A kind of double absorption layer coating for selective absorption of sunlight spectrum and preparation method thereof Download PDF

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CN105222381A
CN105222381A CN201410710992.7A CN201410710992A CN105222381A CN 105222381 A CN105222381 A CN 105222381A CN 201410710992 A CN201410710992 A CN 201410710992A CN 105222381 A CN105222381 A CN 105222381A
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absorption
layer
refraction
subgrade
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CN105222381B (en
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孙志强
刘静
汪洪
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BEIJING HANGBO NEW MATERIAL TECHNOLOGY Co Ltd
China Building Materials Academy CBMA
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BEIJING HANGBO NEW MATERIAL TECHNOLOGY Co Ltd
China Building Materials Academy CBMA
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers

Abstract

The present invention relates to sunshine coating for selective absorption field, especially a kind of double absorption layer coating for selective absorption of sunlight spectrum and preparation method thereof.Described preparation method comprises the following steps: basalis cleans; Film plating process is adopted to prepare infrared reflecting layer on described basalis; Film plating process is adopted to prepare double structure absorbed layer on described infrared reflecting layer; Film plating process is adopted to prepare anti-reflection layer on described double structure absorbed layer; Described absorbed layer comprises high index of refraction absorption subgrade from bottom to top successively and low-refraction absorbs subgrade, and described high index of refraction absorption subgrade and low-refraction absorb subgrade and all adopt film plating process to prepare successively.Described absorber coatings is prepared by above-mentioned preparation method.Described coating production technique is simple, conditional request needed for filming equipment is low, is applicable to large-scale low-cost and produces.

Description

A kind of double absorption layer coating for selective absorption of sunlight spectrum and preparation method thereof
Technical field
The present invention relates to spectral selective absorbing coating field, especially a kind of double absorption layer coating for selective absorption of sunlight spectrum and preparation method thereof.
Background technology
Coating for selective absorption of sunlight spectrum is the core material realizing solar energy hot-cast socket, on the one hand, it has high absorptivity at sunshine wave band (0.3 μm-2.5 μm), absorb solar energy and be converted into heat energy, on the other hand, it has low radiance at infrared emanation wave band (2.5 μm-50 μm), effectively suppresses heat loss through radiation.Weigh the ratio that one of important indicator of coating selective absorbing performance is solar spectrum absorptivity α and infrared emittance ε (T), α/ε, the α/ε value more greatly middle high temperature of more applicable more than 200 DEG C is applied.
At present, the spectrum selective paint film structure that solar thermal collector adopts generally may be summarized to be basalis/infrared reflecting layer/solar spectrum absorbed layer/surperficial antireflection layer.Infrared reflecting layer is high conductivity metal, has very high reflectivity to infrared spectrum, is the main cause that coating obtains low radiance; Surface anti-reflection layer reduces the reflection of coating and Air Interface place sunshine, makes more solar energy enter absorbed layer, adds solar spectrum absorptivity, and then improves collecting efficiency.
In the coating for selective absorption occurred in the market, absorbed layer material mainly contains Cr 2o 3-Cr, AlN-Al (NiO x, TiN), Al (Mo, W, Ni, Co)-Al 2o 3, Al 2o 3-Mo-Al 2o 3, NiCrN xo y, TiN xo ydeng, wherein NiCrN xo y, TiN xo yuse more.Composition gradual change NiCrN is adopted in China Patent Publication No. CN1584445A xo y, solar spectrum absorptivity is up to 92%, and radiance is minimum is 10%, α/ε maximum 9.2; In China Patent Publication No. CN101240944A, CN201196495Y, by accuracy controlling nitrogen oxygen ratio, obtain absorptivity 96%, radiance 4% based on multi-gradient TiN xo ythe selective coating absorbed, α/ε (80 DEG C) maximum 24, the main cryogenic applications being applicable to less than 200 DEG C.Al (Mo, W, Ni, Co, NiO x, TiN)-Al 2o 3, Al 2o 3-Mo-Al 2o 3common feature in cermet and thin metal interference film system is coated with the absorptivity of floor height and low radiance is by strictly controlling composite material compositions, metal or metal nitride particles size, shape, or continuous or discrete island or other morphosis etc. in metallic film growth course and obtain, manufacturing process is complicated, and technology stability is larger on coating performance impact, be not easy the coating obtaining excellent performance, while causing solar spectrum absorptivity α high (generally higher than 90%), infrared emittance ε (T) is also higher (generally higher than 5%, 80 DEG C), and it is wider to absorb the transition region of infrared external reflection from sunshine, infrared emittance ε (T) rises very fast (middle high-temperature region is greater than 10%) with temperature, α/ε is generally less than 20.Therefore when coatings applications is in focusing on lower heat collector, the problem that during ubiquity operating temperature more than 200 DEG C, heat collector photo-thermal conversion efficiency is lower.
Summary of the invention
The invention provides a kind of double absorption layer coating for selective absorption of sunlight spectrum, this coating radiance is low, and the ratio of solar spectrum absorptivity α and infrared emittance ε (T) is high, is applicable to the middle high temperature application of more than 200 DEG C.
The object of the invention to solve the technical problems realizes by the following technical solutions.
By a kind of preparation method of double absorption layer coating for selective absorption of sunlight spectrum, comprise the following steps: basalis cleans; Film plating process is adopted to prepare infrared reflecting layer on described basalis; Film plating process is adopted to prepare double structure absorbed layer on described infrared reflecting layer;
Film plating process is adopted to prepare anti-reflection layer on described double structure absorbed layer; Described absorbed layer comprises high index of refraction absorption subgrade from bottom to top successively and low-refraction absorbs subgrade, and described high index of refraction absorption subgrade and low-refraction absorb subgrade and all adopt film plating process to prepare successively.
In aforesaid double absorption layer coating for selective absorption of sunlight spectrum, the material of described basalis is glass, aluminium, copper or stainless steel;
In aforesaid double absorption layer coating for selective absorption of sunlight spectrum, basalis cleaning process comprises: first, adopts neutral detergent solution tentatively to clean described basalis; Then, bombarded by radio-frequency ion source, carrying out secondary cleaning to described substrate surface, working gas is inert gas.
In aforesaid double absorption layer coating for selective absorption of sunlight spectrum, described film plating process is magnetron sputtering method.
In aforesaid double absorption layer coating for selective absorption of sunlight spectrum, during preparation double structure absorbed layer, the target selected is chromium target.
In aforesaid double absorption layer coating for selective absorption of sunlight spectrum, when preparing infrared reflecting layer, the target selected is aluminium target, copper target, gold target, silver-colored target, nickel target or chromium target, and working gas is inert gas;
In aforesaid double absorption layer coating for selective absorption of sunlight spectrum, when preparing anti-reflection layer, the target selected is silicon target, aluminium target, thorium target, dysprosium target, europium target, gadolinium target, yttrium target, lanthanum target, magnesium target or samarium target, and working gas is inert gas and oxygen.
In aforesaid double absorption layer coating for selective absorption of sunlight spectrum, when preparation high index of refraction absorbs subgrade, pulse dc power sputtering power is 1400 ~ 1600w, operating air pressure is 2 ~ 4mTorr, working gas flow is 40 ~ 60sccm, substrate transfer speed is 0.6 ~ 1m/min, substrate back and forth movement 2 ~ 4 times under target;
In aforesaid double absorption layer coating for selective absorption of sunlight spectrum, when preparing low-refraction absorption subgrade, pulse dc power sputtering power is 1400 ~ 1600w, and operating air pressure is 2 ~ 4mTorr, and working gas inert gas flow is 40 ~ 60sccm, working gas N 2flow is 40 ~ 60sccm, working gas O 2flow is 8 ~ 12sccm, and substrate transfer speed is 0.2 ~ 0.6m/min, substrate back and forth movement 4 ~ 7 times under target.
In aforesaid double absorption layer coating for selective absorption of sunlight spectrum, when preparing infrared reflecting layer, pulse dc power sputtering power is 1180-1240w, operating air pressure is 4.8-5.2mTorr, working gas flow is 49-51sccm, substrate transfer speed is 0.2 ~ 1.6m/min, substrate back and forth movement 2-4 time under target.
In aforesaid double absorption layer coating for selective absorption of sunlight spectrum, when preparing anti-reflection layer, pulse dc power sputtering power is 1900-2050w, and operating air pressure is 4.8-5.2mTorr, and the flow of working gas inert gas is 29-31sccm, working gas O 2flow is 13-15.5sccm, and substrate transfer speed is respectively 0.8 ~ 1.2m/min, and substrate moves 8-14 time under target.
Object of the present invention can also be achieved through the following technical solutions.
By a kind of double absorption layer coating for selective absorption of sunlight spectrum, described double absorption layer coating for selective absorption of sunlight spectrum is prepared by above-mentioned preparation method, comprising: basalis; Infrared reflecting layer, double structure absorbed layer and anti-reflection layer is placed with from bottom to top successively at basalis; Described double structure absorbed layer comprises high index of refraction absorption subgrade from bottom to top successively and low-refraction absorbs subgrade; Wherein: the material of described infrared reflecting layer is conducting metal.
In above-mentioned double absorption layer coating for selective absorption of sunlight spectrum, the material of described basalis is glass, aluminium, copper or stainless steel; The material of described infrared reflecting layer is aluminium, copper, gold, silver, nickel or chromium; The material that described high index of refraction absorbs subgrade is CrN x; The material that described low-refraction absorbs subgrade is CrN xo y; The material of described anti-reflection layer is SiO 2, Al 2o 3, ThO 2, Dy 2o 3, Eu 2o 3, Gd 2o 3, Y 2o 3, La 2o 3, MgO or Sm 2o 3;
In above-mentioned double absorption layer coating for selective absorption of sunlight spectrum, the thickness of described basalis is 0.2 ~ 10mm; The thickness of described infrared reflecting layer is 50 ~ 200nm; The gross thickness of double structure absorbed layer is 45nm ~ 125nm, and wherein: the thickness that described high index of refraction absorbs subgrade is 25nm ~ 55nm, the thickness that low-refraction absorbs subgrade is 20nm ~ 70nm; The thickness of described anti-reflection layer is 50 ~ 150nm.
Object of the present invention can also be achieved through the following technical solutions.
By a kind of heat collector, comprise housing, on the housing cover plate, be provided with heat-sink shell and heat-insulation layer below described cover plate, described heat-sink shell is above-mentioned double absorption layer coating for selective absorption of sunlight spectrum.
By technique scheme, a kind of double absorption layer coating for selective absorption of sunlight spectrum that the present invention proposes and preparation method thereof at least has following advantages:
1) double absorption layer coating for selective absorption of sunlight spectrum disclosed by the invention has excellent spectral selection.Absorption-reflection transition district is precipitous, middle high temperature (200 DEG C-400 DEG C) the radiance ε of coating for selective absorption is lower than 3%, absorptivity α higher (about 90%), α/ε, higher than existing commercial product, are applicable to the middle high-temp solar heat collector of low zoom and focus.
2) absorbed layer is that internal layer high index of refraction absorbs subgrade and outer low-refraction and absorbs the double structure absorbed layer that subgrade forms, and material good thermal stability.Due to CrN xwith CrN xo yhave the advantages that middle high high-temp stability is good, so the coating for selective absorption of sunlight spectrum in the present invention has good middle high high-temp stability.
3) needed for simple, the filming equipment of preparation technology of coating, conditional request is low, is applicable to large-scale low-cost and produces.
4) when the Material selec-tion of infrared metallic reflector is aluminium, at whole light-wave band (sunshine wave band and heat radiation infrared band) compared to the metal such as gold, silver, copper with close infrared radiation property, there is high index of refraction and extinction coefficient, realize coating for selective absorption while there is low-infrared radiation rate, participate in by aluminium the solar spectrum absorptivity that the spectral absorption of sunshine wave band further increases coating.
5) when wavelength is greater than 2000nm, CrN x, CrN xo ythe extinction coefficient (being greater than 21) of extinction coefficient ratio infrared reflecting layer Al is much little, so very little on the impact of Al Infrared Reflective Spectra, therefore the radiance of coating is low.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technological means of the present invention, and can be implemented according to the content of description, coordinates accompanying drawing to be described in detail as follows below with preferred embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is the structural representation of the coating for selective absorption of sunlight spectrum that the present invention proposes;
Fig. 2 is embodiment of the present invention ultraviolet-infrared waveband absorbing spectrogram.
Detailed description of the invention
For further setting forth the present invention for the technological means reaching predetermined goal of the invention and take and effect, below in conjunction with accompanying drawing and preferred embodiment, to a kind of double absorption layer coating for selective absorption of sunlight spectrum proposed according to the present invention, be described in detail as follows.
A preparation method for double absorption layer coating for selective absorption of sunlight spectrum, comprises the following steps: basalis cleans; Film plating process is adopted to prepare infrared reflecting layer on described basalis; Film plating process is adopted to prepare double structure absorbed layer on described infrared reflecting layer; Film plating process is adopted to prepare anti-reflection layer on described double structure absorbed layer; Described absorbed layer comprises high index of refraction absorption subgrade from bottom to top successively and low-refraction absorbs subgrade, and described high index of refraction absorption subgrade and low-refraction absorb subgrade and all adopt film plating process to prepare successively.
Another embodiment of the present invention proposes a kind of double absorption layer coating for selective absorption of sunlight spectrum, and compared with above-described embodiment, the material of described basalis is glass, aluminium, copper or stainless steel; Basalis cleaning process comprises: first, adopts neutral detergent solution tentatively to clean described basalis; Then, bombarded by radio-frequency ion source, carrying out secondary cleaning to described substrate surface, working gas is inert gas.
During concrete enforcement, described basalis can adopt thickness range to be the glass plate of 0.5-10mm; Also thickness range can be adopted to be the metal material of 0.2-2mm, such as copper, aluminium or stainless steel.For increasing the surface-active of basalis, need to carry out radio frequency-ion cleaning after mechanical cleaning, thus remove pollution layer and the oxide layer of substrate surface.
In order to realize foregoing invention object, the present invention also adopts following technical scheme, carries out the preparation of described double absorption layer coating for selective absorption of sunlight spectrum.Above basalis, infrared reflecting layer, double structure absorbed layer and anti-reflection layer are prepared into plated film successively by being coated with, the described method be coated with is the film plating process that can form above material, as magnetron sputtering method, electron beam or thermal evaporation, ion plating method, chemical vapour deposition technique and spraying process etc.
Have at the bottom of cost by spraying process, the simple advantage of technique, but ubiquity coating adhesion is poor, easily peel off, the shortcomings such as emissivity is high, and equally with electrochemical process there is pollution problem, magnetron sputtering method is adopted to prepare spectral selection absorbing membrane, then can overcome these shortcomings, improve photo-thermal conversion efficiency and coating service life, simultaneously to have film deposition rate fast for magnetron sputtering technique method, even film layer is fine and close, be convenient to the feature such as large area film forming and technique environmental protection, when preparing plate type solar energy heat collector plate core coating, be conducive to building extensive horizontal continuous and automatic production line, enhance productivity, reduce costs further.
During concrete enforcement, described film plating process is magnetron sputtering method, and during preparation double structure absorbed layer, the target selected is chromium target.When preparing infrared reflecting layer, the target selected is aluminium target, copper target, gold target, silver-colored target, nickel target or chromium target, and working gas is inert gas; When preparing anti-reflection layer, the target selected is silicon target, aluminium target, thorium target, dysprosium target, europium target, gadolinium target, yttrium target, lanthanum target, magnesium target or samarium target, and working gas is inert gas and oxygen.
When preparing infrared reflecting layer, double structure absorbed layer and anti-reflection layer on the base layer successively by magnetron sputtering method, design parameter scope is as follows:
When preparing infrared reflecting layer, pulse dc power sputtering power is 1180-1240w, and operating air pressure is 4.8-5.2mTorr, and working gas flow is 49-51sccm, and substrate transfer speed is 0.2 ~ 1.6m/min, substrate back and forth movement 2-4 time under target.
When preparation high index of refraction absorbs subgrade, pulse dc power sputtering power is 1400 ~ 1600w, and operating air pressure is 2 ~ 4mTorr, and working gas flow is 40 ~ 60sccm, and substrate transfer speed is 0.6 ~ 1m/min, substrate back and forth movement 2 ~ 4 times under target.
When preparing low-refraction absorption subgrade, pulse dc power sputtering power is 1400 ~ 1600w, and operating air pressure is 2 ~ 4mTorr, and working gas inert gas flow is 40 ~ 60sccm, working gas N 2flow is 40 ~ 60sccm, working gas O 2flow is 8 ~ 12sccm, and substrate transfer speed is 0.2 ~ 0.6m/min, substrate back and forth movement 4 ~ 7 times under target.
When preparing anti-reflection layer, pulse dc power sputtering power is 1900-2050w, and operating air pressure is 4.8-5.2mTorr, and the flow of working gas inert gas is 29-31sccm, working gas O 2flow is 13-15.5sccm, and substrate transfer speed is respectively 0.8 ~ 1.2m/min, and substrate moves 8-14 time under target.
The double absorption layer coating for selective absorption of sunlight spectrum prepared by above-mentioned parameter, as shown in Figure 1, described double absorption layer coating for selective absorption of sunlight spectrum comprises concrete structure: basalis; Infrared reflecting layer 2, double structure absorbed layer 3 and anti-reflection layer 4 is placed with from bottom to top successively at basalis; Described double structure absorbed layer 3 comprises high index of refraction absorption subgrade 31 from bottom to top successively and absorbs subgrade 32 with low-refraction; Wherein: the material of described infrared reflecting layer 2 is conducting metal.
By the acting in conjunction of infrared reflecting layer 2, double structure absorbed layer 3 and anti-reflection layer 4, sunshine is made to realize multiple reflections and absorption between double structure absorbed layer 3 and infrared reflecting layer 2, and infrared reflecting layer 2 also participates in part solar spectrum to be absorbed, thus described double absorption layer coating for selective absorption of sunlight spectrum is made to have excellent spectral selection.Absorption-reflection transition the district of described double absorption layer coating for selective absorption of sunlight spectrum is precipitous, at solar energy spectral limit (0.3-2.5 micron), there is higher absorptivity α, at heat radiation region of ultra-red (2-50 micron), there is extremely low radiance ε, in described double absorption layer coating for selective absorption of sunlight spectrum, high temperature (200 DEG C-400 DEG C) radiance ε is lower than 3%, absorptivity α higher (about 90%), α/ε, higher than existing commercial product, is suitable for the middle high-temp solar heat collector of low zoom and focus; And preparation technology is simple, filming equipment requires low, is applicable to large-scale low-cost and produces.
Another embodiment of the present invention proposes a kind of double absorption layer coating for selective absorption of sunlight spectrum, and compared with above-described embodiment, the material that described high index of refraction absorbs subgrade 31 is CrN x, described CrN xin the wave-length coverage of 350nm ~ 2500nm, refractive index is 2.4 ~ 4.4, and in the wave-length coverage of 350 ~ 1250nm, extinction coefficient is 1.76 ~ 1.24, and the extinction coefficient being greater than the wavelength of 2000nm is less than 0.9.The good thermal stability of CrNx.
Another embodiment of the present invention proposes a kind of double absorption layer coating for selective absorption of sunlight spectrum, and compared with above-described embodiment, the material that described low-refraction absorbs subgrade 32 is CrN xo y, described CrN xo yin the wave-length coverage of 350nm-2500nm, refractive index is 2.2 ~ 2.4, and in the wave-length coverage of 350 ~ 1250nm, extinction coefficient is 0.52 ~ 0.11, and the extinction coefficient being greater than the wavelength of 2000nm is less than 0.07.CrN xo ygood thermal stability.
Described absorbed layer is arranged on infrared reflecting layer 2, and structure is that internal layer high index of refraction absorbs subgrade 31 and outer low-refraction and absorbs the double structure absorbed layer 3 that subgrade 32 forms, and thickness is preferably 75nm-115nm.This layer of major optical is characterized as CrN in the 350-1250nm wave-length coverage accounting for solar spectrum energy distribution more than 80% xextinction coefficient is 1.76-1.24; CrN xo yextinction coefficient 0.52-0.11; And all near the 480nm that solar spectrum energy distribution is the highest, extinction coefficient reaches peak value.After 2000nm, CrN xextinction coefficient is less than 0.9, CrN xo yextinction coefficient is less than 0.07.
Described coating for selective absorption of sunlight spectrum choose account for solar spectrum energy distribution more than 80% 350-1250nm within the scope of extinction coefficient reach peak value, and refractive index CrN from high to low xwith CrN xo yform double structure absorbed layer, formed and reduce from the refractive index of absorbed layer 3, anti-reflection layer 4, air successively gradient, effectively reduce sunshine at the higher CrN of refractive index xthe reflection on surface, defines the successively absorption to sunshine, achieves the effective absorption to 350-1250nm wave-length coverage solar spectrum, absorptivity more than 90%.
When wave-length coverage is greater than 2000nm, CrN x, CrN xo ythe extinction coefficient (being greater than 21) of extinction coefficient ratio infrared reflecting layer 2 is much little, so very little on the impact of Infrared Reflective Spectra, therefore the radiance of coating is low.Further, due to CrN xwith CrN xo yhave the advantages that middle high high-temp stability is good, so the coating for selective absorption of sunlight spectrum in the present invention has good middle high high-temp stability.
Another embodiment of the present invention proposes a kind of double absorption layer coating for selective absorption of sunlight spectrum, compared with above-described embodiment, the gross thickness of described double structure absorbed layer 3 is 45nm ~ 125nm, wherein: the thickness that described high index of refraction absorbs subgrade 31 is 25nm ~ 55nm, the thickness that low-refraction absorbs subgrade 32 is 20nm ~ 70nm.
Another embodiment of the present invention proposes a kind of double absorption layer coating for selective absorption of sunlight spectrum, and compared with above-described embodiment, the thickness of described infrared reflecting layer 2 is 50 ~ 200nm.
Another embodiment of the present invention proposes a kind of double absorption layer coating for selective absorption of sunlight spectrum, and compared with above-described embodiment, the material of described infrared reflecting layer 2 is aluminium, copper, gold, silver, nickel or chromium.Infrared metallic reflector, preferred Al at whole light-wave band (sunshine wave band and heat radiation infrared band) compared to the metal such as gold, silver, copper with close infrared radiation property, there is high index of refraction and extinction coefficient, realize coating for selective absorption while there is low-infrared radiation rate, participate in by Al the solar spectrum absorptivity that the spectral absorption of sunshine wave band further increases coating.
Described infrared reflecting layer 2 is arranged on basalis 1, and the effect of this infrared reflecting layer 2 is that the spectrum of the whole wave band to incidence reflects, and particularly to infrared spectrum, especially the infrared light of wavelength more than 2.5 microns reflects.The material of this infrared reflecting layer 2 is aluminium, the preferred 50nm-130nm of thickness.
Another embodiment of the present invention proposes a kind of double absorption layer coating for selective absorption of sunlight spectrum, and compared with above-described embodiment, the thickness of described anti-reflection layer 4 is 50 ~ 150nm.Described anti-reflection layer 4 is the SiO of desirable chemical proportioning 2dielectric layer, within the scope of wavelength 350nm-2500nm, refractive index is between 1.47-1.43, and extinction coefficient is less than 0.03; Thickness is preferably 80nm-120nm.
Another embodiment of the present invention proposes a kind of double absorption layer coating for selective absorption of sunlight spectrum, and compared with above-described embodiment, the material of described anti-reflection layer 4 is SiO 2, Al 2o 3, ThO 2, Dy 2o 3, Eu 2o 3, Gd 2o 3, Y 2o 3, La 2o 3, MgO or Sm 2o 3.
Lower mask body, for magnetron sputtering coating method, is further described.Depositing Al, CrN successively on the basalises 1 such as glass, aluminium, copper, stainless steel x, CrN xo yand SiO 2film.
The preparation of basalis 1, selects metallic plate or the glass plate of polishing, carries out the cleaning of radio frequency argon ion and removes surface contamination layer and oxide layer, promote basalis 1 surface-active after mechanical cleaning.
The preparation of infrared reflecting layer 2, prepares layer of metal infrared reflecting layer 2 by (pulse) direct current magnetron sputtering process at above-mentioned substrate surface, and selected target can be metallic aluminium (purity more than 99.7%).
The preparation of absorbed layer 3, prepares absorbed layer 3 by (pulse) direct current magnetron sputtering process on above-mentioned infrared reflecting layer 2, and selected target is Metal Cr (purity more than 99.7%).
The preparation of anti-reflection layer 4, prepares anti-reflection layer 4 by (pulse) DC reactive magnetron sputtering technique on above-mentioned absorbed layer, and selected target is sial target (aluminium content 30%wt, purity more than 99.7%).
Be further described with the thickness example of concrete infrared reflecting layer 2, double structure absorbed layer 3 and anti-reflection layer 4 below:
Table 1 prepares the technology controlling and process thickness of each monofilm in a kind of embodiment of double absorption layer spectral selective absorbing coating for magnetron sputtering method.
The technology controlling and process thickness of each monofilm in table 1 embodiment
Sample Al layer/nm CrN xLayer/nm CrN xO yLayer/nm SiO 2/nm
Example 120 45 50 110
Carry out the preparation of embodiment according to above-mentioned preparation method, concrete operation step is as follows:
1) cleaning of glass substrate: first adopt neutral detergent solution tentatively to clean glass substrate; Then enter sheet room at filming equipment and carry out secondary cleaning by radio-frequency ion source bombardment glass substrate surface, its technological parameter arranges as follows: radio-frequency power supply sputtering power is 200w, working gas Ar (purity 99.99%) flow is 45sccm, and operating air pressure is 9.8 × 10 -2mTorr, sputtering time is 360s.
2) glass substrate is entered the transmission of sheet room via filming equipment and enter sputtering chamber, wherein the base vacuum of sputtering chamber is better than 6 × 10 -6torr.
3) infrared reflecting layer Al is prepared on a glass substrate: adopt pulse dc power magnetron sputtering method by bombardment metallic aluminium target (purity 99.7%) plated metal Al film on a glass substrate.Its technological parameter arranges as follows: pulse dc power sputtering power is 1200w, operating air pressure is 5mTorr, working gas Ar (purity 99.99%) flow is 50sccm, substrate transfer speed is 0.4m/min, glass substrate is at the below back and forth movement 3 times of metallic aluminium target, and substrate temperature is room temperature.
4) on (Al/ glass), absorbed layer CrN is prepared x: adopt pulse dc power magnetron sputtering method on (Al/ glass), to deposit CrN by bombardment Cr target (purity 99.7%) xfilm.Its technological parameter arranges as follows: pulse dc power sputtering power is 1500w, operating air pressure is 3mTorr, working gas Ar (purity 99.99%) flow is 50sccm, N2 (purity 99.99%) flow is 50sccm, substrate is with transmission speed 0.8m/min back and forth movement 2 times under Metal Cr target, move 1 time under Metal Cr target with 1m/min transmission speed, substrate temperature is room temperature.
5) at (CrN x/ Al/ glass) upper preparation absorption subgrade CrN xo y: adopt pulse dc power oxidation reaction magnetron sputtering C r target (purity 99.7%) method at (CrN x/ Al/ glass) on deposit CrN xo yfilm.Its technological parameter arranges as follows: pulse dc power sputtering power is 1500w, and operating air pressure is 3mTorr, and working gas Ar (purity 99.99%) flow is 50sccm, N 2(purity 99.99%) flow is 50sccm, O 2(purity 99.99%) flow is 10sccm, and substrate transfer speed is 0.4m/min, and basalis 1 glass back and forth movement 5 times below Cr target, substrate temperature is room temperature.
6) at (CrN xo y/ CrN x/ Al/ glass) on prepare anti-reflection layer SiO 2: adopt pulse dc power oxidation reaction magnetron sputtering sial target (aluminium content 30%wt, purity 99.7%) method at (CrN xo y/ CrN x/ Al/ glass) on deposit SiO 2film.Its coating process optimum configurations is as follows: pulse dc power sputtering power is 2000w, and operating air pressure is 5mTorr, and working gas Ar (purity 99.99%) flow is 30sccm, O 2(purity 99.99%) flow is 14sccm, and substrate transfer speed is 1m/min, and basalis 1 glass back and forth movement 11 times below sial target, substrate temperature is room temperature.
7), after above preparation process to be done, make sample cool 20min, slice, shut down.
Fig. 2 shows the embodiment of the present invention and conventional Ti N xo ycoating for selective absorption material is in the abosrption spectrogram of 0.3-48 mu m waveband and solar spectrum energy distribution and 100 DEG C, 200 DEG C, 300 DEG C, 400 DEG C black body radiation Energy distribution.Wherein 0.3-2.5 mu m waveband absorption spectrum is tested by Hitachi U-4100 spectrophotometer and is obtained, and 2.5-48 mu m waveband absorption spectrum is tested by the Tensor27 Fourier infrared spectrograph of Bruker and obtained.
Table 2 gives the embodiment of the present invention and conventional Ti N xo ythe absorptivity α of coating for selective absorption material, radiance ε (T) at different temperatures, and α/ε (T).
The radiance of embodiment different temperatures (100 DEG C, 200 DEG C, 300 DEG C, 400 DEG C) obtains according to following formulae discovery.
ϵ = ∫ 2 um 48 um E T ( λ ) [ 1 - R ( λ ) ] dλ / ∫ 2 um 48 um E T ( λ ) dλ
Wherein E t(λ) for black body radiation time work temperature (100 DEG C, 200 DEG C, 300 DEG C, 400 DEG C) is with Wavelength distribution (2 μm-48 μm)
Wherein solar spectrum absorptivity calculates as follows:
α = ∫ 300 um 2500 um A ( λ ) [ 1 - R ( λ ) ] dλ / ∫ 300 um 2500 um A ( λ ) dλ
Wherein A (λ) is solar radiation spectral irradiance (W/m2 μm) during air quality AM=1.5, and R (λ) is that the coating for selective absorption of sunlight spectrum reflectance spectrum (300-2500nm) obtained tested by spectrophotometer.
The embodiment of the present invention and conventional Ti N in comparison diagram 2, table 2 xo ycoating performance is known: the embodiment of the present invention compared to conventional selective absorber coatings absorption-reflection transition district closer to solar spectrum region, and near the 480nm that solar spectrum energy distribution is the highest, absorptivity is comparatively large, and in infrared waveband absorbing rate (i.e. radiance), comparatively conventional selective absorber coatings material is lower.Embodiment has higher absorptivity α at solar energy spectral limit (0.3-2.5 micron), and have low radiance ε at heat radiation region of ultra-red (2-50 micron), α/ε is higher than traditional TiN xo ydeng coating product, be suitable for the middle high temperature application of more than 100 DEG C of low zoom and focus.
The test result of absorption of sample rate, radiance and Evaluation of Thermal Stability value PC (performancecriterion, PC=△ α-0.5 △ ε) before and after the annealing in process that table 3 carries out more than 120 hours for embodiment coating sample under 400 DEG C of vacuum conditions, 250 DEG C of atmospheric conditions.Before and after the sample heat treatment can finding out the embodiment of the present invention, the change of PC value is less than 1.5%, under the middle temperature atmospheric environment that coating has had is described and vacuum environment stability inferior.
TiN in table 2. embodiment and prior art xo ycoating solar spectrum absorptivity and infrared emittance
Table 3. embodiment different condition annealing after absorptivity and radiance
Unannealed 400 DEG C of vacuum 250 DEG C of air
α 90.9 89.1 89.5
ε(250℃) 3.2 2.5
ε(400℃) 4.1 3.2
△α-0.5△ε 1.35 1.05
Concentrator embodiments
A kind of heat collector, comprise housing, on the housing cover plate, be provided with heat-sink shell and heat-insulation layer below described cover plate, described heat-sink shell is the continuously adjustable coating for selective absorption of sunlight spectrum of ABSORPTION EDGE in above-described embodiment.
By selecting the different continuously adjustable coating for selective absorption of sunlight spectrum of described ABSORPTION EDGE, low-temperature heat collection device, medium-temperature collectors and high temperature heat collector can be prepared.
The above, it is only preferred embodiment of the present invention, not do any pro forma restriction to the present invention, any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.

Claims (10)

1. a preparation method for double absorption layer coating for selective absorption of sunlight spectrum, is characterized in that, comprises the following steps:
Basalis cleans;
Film plating process is adopted to prepare infrared reflecting layer on described basalis;
Film plating process is adopted to prepare double structure absorbed layer on described infrared reflecting layer;
Film plating process is adopted to prepare anti-reflection layer on described double structure absorbed layer;
Described absorbed layer comprises high index of refraction absorption subgrade from bottom to top successively and low-refraction absorbs subgrade, and described high index of refraction absorption subgrade and low-refraction absorb subgrade and all adopt film plating process to prepare successively.
2. the preparation method of double absorption layer coating for selective absorption of sunlight spectrum according to claim 1, is characterized in that,
The material of described basalis is glass, aluminium, copper or stainless steel;
Basalis cleaning process comprises: first, adopts neutral detergent solution tentatively to clean described basalis; Then, bombarded by radio-frequency ion source, carrying out secondary cleaning to described substrate surface, working gas is inert gas.
3. the preparation method of double absorption layer coating for selective absorption of sunlight spectrum according to claim 1, is characterized in that,
Described film plating process is magnetron sputtering method.
4. the preparation method of double absorption layer coating for selective absorption of sunlight spectrum according to claim 3, is characterized in that,
During preparation double structure absorbed layer, the target selected is chromium target.
5. the preparation method of double absorption layer coating for selective absorption of sunlight spectrum according to claim 3, is characterized in that,
When preparing infrared reflecting layer, the target selected is aluminium target, copper target, gold target, silver-colored target, nickel target or chromium target, and working gas is inert gas;
When preparing anti-reflection layer, the target selected is silicon target, aluminium target, thorium target, dysprosium target, europium target, gadolinium target, yttrium target, lanthanum target, magnesium target or samarium target, and working gas is inert gas and oxygen.
6. the preparation method of double absorption layer coating for selective absorption of sunlight spectrum according to claim 3, is characterized in that,
When preparation high index of refraction absorbs subgrade, pulse dc power sputtering power is 1400 ~ 1600w, and operating air pressure is 2 ~ 4mTorr, and working gas flow is 40 ~ 60sccm, and substrate transfer speed is 0.6 ~ 1m/min, substrate back and forth movement 2 ~ 4 times under target;
When preparing low-refraction absorption subgrade, pulse dc power sputtering power is 1400 ~ 1600w, and operating air pressure is 2 ~ 4mTorr, and working gas inert gas flow is 40 ~ 60sccm, working gas N 2flow is 40 ~ 60sccm, working gas O 2flow is 8 ~ 12sccm, and substrate transfer speed is 0.2 ~ 0.6m/min, substrate back and forth movement 4 ~ 7 times under target.
7. the preparation method of double absorption layer coating for selective absorption of sunlight spectrum according to claim 3, is characterized in that,
When preparing infrared reflecting layer, pulse dc power sputtering power is 1180-1240w, and operating air pressure is 4.8-5.2mTorr, and working gas flow is 49-51sccm, and substrate transfer speed is 0.2 ~ 1.6m/min, substrate back and forth movement 2-4 time under target.
When preparing anti-reflection layer, pulse dc power sputtering power is 1900-2050w, and operating air pressure is 4.8-5.2mTorr, and the flow of working gas inert gas is 29-31sccm, working gas O 2flow is 13-15.5sccm, and substrate transfer speed is 0.8 ~ 1.2m/min, and substrate moves 8-14 time under target.
8. a double absorption layer coating for selective absorption of sunlight spectrum, is characterized in that, described double absorption layer coating for selective absorption of sunlight spectrum is prepared by the preparation method according to any one of claim 1 to 7, comprising:
Basalis; Infrared reflecting layer, double structure absorbed layer and anti-reflection layer is placed with from bottom to top successively at basalis; Described double structure absorbed layer comprises high index of refraction absorption subgrade from bottom to top successively and low-refraction absorbs subgrade; Wherein: the material of described infrared reflecting layer is conducting metal.
9. double absorption layer coating for selective absorption of sunlight spectrum according to claim 8, is characterized in that,
The material of described basalis is glass, aluminium, copper or stainless steel; The material of described infrared reflecting layer is aluminium, copper, gold, silver, nickel or chromium; The material that described high index of refraction absorbs subgrade is CrN x; The material that described low-refraction absorbs subgrade is CrN xo y; The material of described anti-reflection layer is SiO 2, Al 2o 3, ThO 2, Dy 2o 3, Eu 2o 3, Gd 2o 3, Y 2o 3, La 2o 3, MgO or Sm 2o 3;
The thickness of described basalis is 0.2 ~ 10mm; The thickness of described infrared reflecting layer is 50 ~ 200nm; The gross thickness of double structure absorbed layer is 45nm ~ 125nm, and wherein: the thickness that described high index of refraction absorbs subgrade is 25nm ~ 55nm, the thickness that low-refraction absorbs subgrade is 20nm ~ 70nm; The thickness of described anti-reflection layer is 50 ~ 150nm.
10. a heat collector, comprises housing, on the housing cover plate, is provided with heat-sink shell and heat-insulation layer below described cover plate, the double absorption layer coating for selective absorption of sunlight spectrum of described heat-sink shell according to any one of claim 8 to 10.
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