CN114322338A - Selective absorbing coating capable of stably running in atmosphere and preparation method thereof - Google Patents
Selective absorbing coating capable of stably running in atmosphere and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a selective absorbing coating which stably operates in the atmosphere and a preparation method thereof, and the selective absorbing coating sequentially comprises the following components from inside to outside: the solar collector comprises a first diffusion-preventing barrier layer, a metal infrared reflecting layer, a second diffusion-preventing barrier layer, a high-volume metal-doped absorbing layer, a medium-volume metal-doped absorbing layer, a low-volume metal-doped absorbing layer and an antireflection layer, wherein the first diffusion-preventing barrier layer is coated on the surface of a steel pipe of the collector pipe. The solar energy absorption device can stably run in the atmosphere for a long time, is high-temperature resistant and corrosion resistant, and can selectively absorb solar energy, so that the solar energy absorption rate is improved.
Description
Technical Field
The invention relates to the technical field of photovoltaics, in particular to a selective absorption coating capable of stably running in the atmosphere and a preparation method thereof.
Background
With the progress of parabolic trough and Fresnel power station technologies, the search for efficient and low-cost heat collecting tube components becomes one of the key points of technical innovation in the photo-thermal power generation industry.
The traditional heat collecting pipe is a vacuum heat collecting pipe, namely a glass sleeve is additionally arranged outside the coated steel pipe, and the middle area between the steel pipe and the glass pipe is vacuumized to reduce the loss of heat inside the steel pipe. The selective absorption coating on the surface of the coated steel pipe can ensure the absorption rate of the steel pipe to solar energy, and simultaneously, when the steel pipe forms a high-temperature heat source, the divergence rate of infrared diffusion is reduced, and finally, high-efficiency photo-thermal conversion efficiency is realized. The absorptivity is one of the important targets of the selective absorption coating, and refers to the ratio of the solar energy absorption heat to the total solar energy radiation energy. The solar radiation energy adopts solar AM1.5 spectrum, the absorptivity of wavelength range 300-2500nm is obtained through weighted calculation, and the emissivity refers to the ratio of the total radiation energy of the black body at the temperature to the infrared ray absorbed by the selective absorption coating. The lower the emissivity is, the less the radiation heat loss is, the emissivity is the radiation spectrum under a certain temperature calculated according to the blackbody radiation law, and the emissivity of the coating is obtained by weighting calculation.
Solar selective absorbing coatings of cermet systems already in widespread use at present, such as Mo-Al2O3,W-Al2O3And the optical performance is excellent under vacuum condition. However, when the damaged coating of the heat collecting tube is exposed in the atmosphere, the degradation of the performance of the coating is accelerated due to long-term high temperature and external oxidation reaction, and certain influence is brought to the high-efficiency operation of a power station.
With the demand of reducing cost of a power station, a non-vacuum tube, namely a bare tube without an outer glass sleeve, is more and more widely applied, and a high-temperature selective absorption coating which stably runs in the atmosphere has not only good temperature resistance but also certain corrosion resistance.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of a selective absorption coating which can stably operate in the atmosphere, can stably operate in the atmosphere for a long time, is high temperature resistant and corrosion resistant, and can selectively absorb solar energy, thereby improving the absorption rate of the solar energy.
The invention mainly adopts the technical scheme that:
a selective absorption coating for stable operation in the atmosphere, comprising in order from the inside to the outside: the solar collector comprises a first diffusion-preventing barrier layer, a metal infrared reflecting layer, a second diffusion-preventing barrier layer, a high-volume metal-doped absorbing layer, a medium-volume metal-doped absorbing layer, a low-volume metal-doped absorbing layer and an antireflection layer, wherein the first diffusion-preventing barrier layer is coated on the surface of a steel pipe of the collector pipe.
Preferably, the first diffusion preventing barrier layer is Fe2O3And Cr2O3The thickness of the mixed film layer is 50nm-100 nm.
Preferably, the metal infrared reflection layer is an Ag film layer or an Au film layer, and the thickness of the metal infrared reflection layer is 100-150 nm.
Preferably, the second anti-diffusion barrier layer is Al2O3Film layer or SiO2The thickness of the film layer is 30nm-50 nm.
Preferably, the high-volume metal-doped absorption layer, the medium-volume metal-doped absorption layer and the low-volume metal-doped absorption layer are all made of metal ceramic materials, and gradient layer deposition is realized by controlling different metal doping ratios, wherein the metal doping ratio in the high-volume metal-doped absorption layer is 50% -60%, the metal doping ratio in the medium-volume metal-doped absorption layer is 40% -48%, and the metal doping ratio in the low-volume metal-doped absorption layer is 25% -35%.
Preferably, the metal dopant in the high-volume metal-doped absorption layer, the medium-volume metal-doped absorption layer and the low-volume metal-doped absorption layer is NiCr-Al2O3、Ni-Al2O3Or Cr-Al2O3And the thicknesses of the high-volume metal-doped absorption layer, the medium-volume metal-doped absorption layer and the low-volume metal-doped absorption layer are respectively 50-100 nm.
Preferably, the antireflection layer is SiOxFilm layer, SiNyFilm layer or SiAlOXThe film layer, wherein x and y represent different doping ratios, has a thickness of 100-150 nm.
A preparation method of a selective absorbing coating which stably operates in the atmosphere comprises the following specific steps:
step 1: and mechanically polishing the surface of the steel pipe to ensure that the roughness of the steel pipe meets 0.08-0.15um, and then ultrasonically cleaning the steel pipe by adopting a cleaning agent to ensure the surface cleanliness.
Step 2: preparing a first anti-diffusion barrier layer, putting the steel pipe into an annealing furnace, carrying out oxidation treatment at 400-450 ℃, keeping the temperature for 1-1.5h, and forming uniform Fe on the surface2O3And Cr2O3A mixture of oxides, i.e. a first anti-diffusion barrier layer;
and step 3: preparing a metal infrared reflecting layer on the surface of the first diffusion barrier layer by adopting a planar metal target material with the purity of 99.95% and a direct-current magnetron sputtering method, wherein the background vacuum degree before sputtering is 5 x 10-3Pa-8*10-3Pa, introducing argon as sputtering gas, controlling the flow of argon at 600--1Pa-4*10-1Pa, starting a direct current power supply, controlling the working current to be 30-40A and the working voltage to be 500-600V;
and 4, step 4: preparing a second anti-diffusion barrier layer on the surface of the metal infrared reflecting layer by adopting a cylindrical metal target material with the purity of 99.99% and a medium-frequency reactive sputtering method, wherein the background vacuum degree before sputtering is 5 x 10-3Pa-8*10-3Pa, introducing argon as sputtering gas, controlling the flow of argon at 600-2Or N2As reaction gas, the flow rate is controlled to be 50-100sccm, the working vacuum degree is 5 x 10-1Pa～6*10-1Pa, starting the intermediate frequency power supply, controlling the working current to be 20-30A and the working voltage to be 400-600V;
step 5, preparing a high-volume metal doped absorption layer on the surface of the second diffusion barrier layer by adopting a method of co-sputtering a metal target with the purity of 99.95% and a first cylindrical target, wherein a direct-current power supply is adopted to deposit metal, and the metal target is an Ni target, a Cr target or an Ni-Cr target; sputtering an oxide by intermediate frequency reaction, the secondA cylindrical target is an Al target or a Si-Al target; background vacuum of 5 x 10 before sputtering-3Pa-8*10-3Pa, introducing argon as sputtering gas, controlling the flow rate to be 600-sccm, starting the direct current power supply and the intermediate frequency power supply, and introducing O after the two target surfaces glow stably2Or N2As reaction gas, the flow rate is 80-100sccm, and the working vacuum degree is 5 × 10-1Pa-6*10-1Pa, wherein the DC voltage of the DC power supply is 300-500V, the working current of the DC power supply is 20-30A, the intermediate frequency voltage of the intermediate frequency power supply is 400-600V, and the working current of the intermediate frequency power supply is 25-35A;
and 8: preparing an antireflection layer on the surface of the low-volume metal-doped absorption layer by adopting a second cylindrical target material with the purity of 99.95% through a medium-frequency reactive sputtering method, wherein the second cylindrical target material is a Si-Al target, a Si target or an Al target, and the background vacuum degree before sputtering is 5 x 10-3Pa-8*10-3Pa, introducing argon as a sputtering gas, controlling the flow of the argon to be 800-sccm and introducing O2Or N2As the reaction gas, the flow rate is 100--1Pa, starting the intermediate frequency power supply, wherein the working current is 30-40A, and the intermediate frequency working voltage is 500-600V.
Preferably, in the step 3, the planar metal target is an Ag target, a Cr target or an Al target.
Preferably, in step 4, the cylindrical metal target is a Si target or an Al target.
Has the advantages that: the invention provides a selective absorbing coating which stably operates in the atmosphere and a preparation method thereof, and the selective absorbing coating has the following advantages:
(1) based on an oxidation barrier mechanism of the stainless steel base material, a mixture of FexOy and Cr2O3 oxides is formed on the surface of the stainless steel base material, so that the diffusion of the steel pipe base material and the coating under the high-temperature condition can be effectively prevented;
(2) the high, medium and low volume metal doped absorption layers are made of metal ceramic materials which are stable in the atmosphere, and the solar radiation energy can be effectively absorbed by controlling different metal doping proportions to form gradient layer deposition;
(3) the metal infrared reflecting layer adopts noble metal film layers such as: ag and Au, which show stable reaction at higher operating temperatures to not be oxidized, and Cr and O of the first diffusion preventing barrier layer also form a passivation layer, which prevents a gradual reaction.
Drawings
FIG. 1 is a spectrophotometer spectra of the coating of example 1;
FIG. 2 is a spectrophotometer spectra of the coating of example 2;
FIG. 3 is a spectrum diagram of a spectrophotometer for a conventional heat collecting tube.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1
A solar selective absorbing coating capable of stably operating at high temperature for a long time in the atmosphere comprises the following components in sequence from inside to outside:
the first anti-diffusion barrier layer is formed on the surface of the steel pipe, the steel pipe is subjected to heat preservation for 1h at 400 ℃ in an annealing furnace, and then the steel pipe is immediately taken out and cooled, so that a golden yellow oxide layer is formed on the surface of the steel pipe, and the thickness of the golden yellow oxide layer is 100 nm;
the metal infrared reflecting layer is an Ag film layer, and the background vacuum degree before sputtering is 5 x 10-3Pa, introducing argon as sputtering gas, controlling the flow at 650sccm and the working vacuum degree at 3.5 x 10-1Pa, starting a direct-current power supply, controlling the working current to be 30A, the working voltage to be 560V and the thickness to be 150 nm;
the second diffusion barrier layer is Al2O3Background vacuum degree before sputtering is 7 x 10-3Pa, introducing argon as sputtering gas, controlling the flow at 750sccm, and introducing O2As the reaction gas, the flow rate was controlled to 50sccm, and the working vacuum degree was 5.3 × 10- 1Pa, starting an intermediate frequency power supply, controlling the working current to be 30A, the working voltage to be 450V and the thickness to be 30 nm;
the high-volume metal-doped absorption layer is NiCr-Al2O3And (3) depositing metal on the film layer by adopting a direct-current power supply, wherein the target material comprises: a Ni-Cr target; intermediate frequency reactive sputtering of oxide, target material: an Al target; background vacuum before sputtering 7 x 10-3Pa, introducing argon as sputtering gas, and controllingControlling the flow rate to be 800sccm, starting a direct current power supply and a medium-frequency power supply, and introducing O after the glow of the target surface is stable2As the reaction gas, the flow rate was 88sccm, and the working vacuum was 5.5 × 10-1Pa, direct current power supply working current 27A, intermediate frequency power supply working current 33A, NiCr volume percent of 55%, and thickness of 90 nm;
the medium-volume metal-doped absorption layer is NiCr-Al2O3And (3) depositing metal on the film layer by adopting a direct-current power supply, wherein the target material comprises: a Ni-Cr target; intermediate frequency reactive sputtering of oxide, target material: an Al target; background vacuum before sputtering 7 x 10-3Pa, introducing argon as sputtering gas, controlling the flow rate to be 800sccm, starting a direct current power supply and a medium-frequency power supply, and introducing O after the glow of the target surface is stable2As the reaction gas, the flow rate was controlled to 85sccm, and the working vacuum degree was 5.5 × 10-1Pa, working current of a direct current power supply is 17A, working current of a medium-frequency power supply is 33A, the volume percentage of NiCr is 43 percent, and the thickness is 80 nm;
the low-volume metal-doped absorption layer is NiCr-Al2O3And (3) depositing metal on the film layer by adopting a direct-current power supply, wherein the target material comprises: a Ni-Cr target; intermediate frequency reactive sputtering of oxide, target material: an Al target; background vacuum before sputtering 7 x 10-3Pa, introducing argon as sputtering gas with the flow of 800sccm, starting a direct current power supply and a medium-frequency power supply, and introducing O after the glow of the target surface is stable2As the reaction gas, the flow rate was 80sccm, and the working vacuum degree was 5.5 × 10-1Pa, working current of a direct current power supply is 13A, working current of a medium-frequency power supply is 33A, the volume percentage of NiCr is 28%, and the thickness is 65 nm;
the antireflection layer is SiAlOxFilm layer with background vacuum degree of 5 x 10 before sputtering-3Pa, introducing argon as sputtering gas with the flow of 1000sccm and introducing O2The flow rate of the reaction gas is 150sccm, the working vacuum is 9 x 10 < -1 > Pa, the intermediate frequency power supply is started, the working current is 35A, the working voltage is 580V, and the thickness is 130 nm.
Example 2
A solar selective absorbing coating capable of stably operating at high temperature for a long time in the atmosphere comprises the following components in sequence from inside to outside:
the first anti-diffusion barrier layer is formed on the surface of the steel pipe, the steel pipe is placed in an annealing furnace at the temperature of 400 ℃ and is kept warm for 1h20min, and then the steel pipe is immediately taken out and cooled, so that a golden yellow oxide layer is formed on the surface of the steel pipe, and the thickness of the golden yellow oxide layer is 120 nm;
the metal infrared reflecting layer is an Ag film layer, and the background vacuum degree before sputtering is 5 x 10-3Pa, introducing argon as sputtering gas, controlling the flow at 650sccm and the working vacuum degree at 3.5 x 10-1Pa, starting a direct-current power supply, controlling the working current to be 30A, the working voltage to be 560V and the thickness to be 150 nm;
the second diffusion barrier layer is Al2O3Background vacuum degree before sputtering is 7 x 10-3Pa, introducing argon as sputtering gas, controlling the flow at 750sccm, and introducing O2As the reaction gas, the flow rate was controlled to 50sccm, and the working vacuum degree was 5.3 × 10- 1Pa, starting an intermediate frequency power supply, controlling the working current to be 30A, the working voltage to be 450V and the thickness to be 30 nm;
the high-volume metal-doped absorption layer is NiCr-Al2O3And (3) depositing metal on the film layer by adopting a direct-current power supply, wherein the target material comprises: a Ni-Cr target; intermediate frequency reactive sputtering of oxide, target material: an Al target; background vacuum before sputtering 7 x 10-3Pa, introducing argon as sputtering gas, controlling the flow at 800sccm, starting a direct current power supply and a medium-frequency power supply, and introducing O after the glow of the target surface is stable2As the reaction gas, the flow rate was 89sccm, the working vacuum degree was 5.6 x 10-1Pa, the working current of a direct current power supply is 29A, the working current of a medium-frequency power supply is 33A, the volume percentage of NiCr is 60 percent, and the thickness is 97 nm;
the medium-volume metal-doped absorption layer is NiCr-Al2O3And (3) depositing metal on the film layer by adopting a direct-current power supply, wherein the target material comprises: a Ni-Cr target; intermediate frequency reactive sputtering of oxide, target material: an Al target; background vacuum before sputtering 7 x 10-3Pa, introducing argon as sputtering gas, controlling the flow rate to be 800sccm, starting a direct current power supply and a medium-frequency power supply, and introducing O after the glow of the target surface is stable2As the reaction gas, the flow rate was controlled to 86sccm, and the working vacuum degree was 5.5 × 10-1Pa, the working current of a direct-current power supply is 19A, the working current of a medium-frequency power supply is 33A, the volume percentage of NiCr is 48%, and the thickness is 87 nm;
low volume goldThe metal-doped absorption layer is NiCr-Al2O3And (3) depositing metal on the film layer by adopting a direct-current power supply, wherein the target material comprises: a Ni-Cr target; intermediate frequency reactive sputtering of oxide, target material: an Al target; background vacuum before sputtering 7 x 10-3Pa, introducing argon as sputtering gas with the flow of 800sccm, starting a direct current power supply and a medium-frequency power supply, and introducing O after the glow of the target surface is stable2As the reaction gas, the flow rate was 80sccm, and the working vacuum degree was 5.5 × 10-1Pa, working current of a direct-current power supply is 15A, working current of an intermediate-frequency power supply is 33A, the volume percentage of NiCr is 32%, and the thickness is 68 nm;
the antireflection layer is SiAlOxFilm layer with background vacuum degree of 5 x 10 before sputtering-3Pa, introducing argon as sputtering gas with the flow of 1000sccm and introducing O2As the reaction gas, the flow rate was 150sccm, and the working vacuum was 9. about.10-1Pa, starting the intermediate frequency power supply, wherein the working current is 35A, the working voltage is 580V, and the thickness is 130 nm.
(1) High temperature accelerated aging test
The heat collecting pipe short tubes prepared in the examples 1 and 2 can be subjected to high-temperature accelerated aging tests by using a high-temperature vacuum annealing furnace. The specific method comprises the following steps:
and placing the short tube of the heat collecting tube in a vacuum annealing furnace, and then vacuumizing. According to the set time (1000h) and the heating temperature (480 ℃), the sample is heated at high temperature, and the high-temperature accelerated aging performance of the sample is evaluated by heating for a long time and measuring the performance change of the sample before and after annealing for multiple times. Tests prove that the coating absorptivity of the short heat collecting pipe pipes prepared in the embodiment 1 and the embodiment 2 is less than or equal to 2% after 1000 hours.
(2) Spectral absorptance contrast test
The heat collecting tube coatings of the heat collecting tubes of the embodiment 1 and the embodiment 2 and the existing heat collecting tube (UVAC-2010 heat collecting tube, Siemens) are detected by a spectrophotometer. As shown in fig. 1, which is a spectrophotometer detection spectrum of the heat collecting tube coating of example 1, the selective absorption coating prepared in example 1 has an absorptivity of 96.5% and an emissivity of 9.5%, which are calculated according to ASTM G173-03 standard. As shown in fig. 2, which is a spectrophotometer-measured spectrum of the coating of example 2, the selective absorption coating prepared in example 2 has an absorption rate of 96.7% and an emissivity of 9.8%, which are calculated according to ASTM G173-03. As shown in fig. 3, a spectrophotometer detection spectrogram of the coating of the conventional heat collecting tube is calculated according to ASTM G173-03 standard, and the absorptivity of the conventional heat collecting tube is 95.4%, and the emissivity is 8.4%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A selective absorbing coating for stable operation in the atmosphere, comprising, in order from the inside to the outside: the solar collector comprises a first diffusion-preventing barrier layer, a metal infrared reflecting layer, a second diffusion-preventing barrier layer, a high-volume metal-doped absorbing layer, a medium-volume metal-doped absorbing layer, a low-volume metal-doped absorbing layer and an antireflection layer, wherein the first diffusion-preventing barrier layer is coated on the surface of a steel pipe of the collector pipe.
2. The atmospheric-stable selective absorption coating of claim 1 wherein the first diffusion barrier layer is Fe2O3And Cr2O3The thickness of the mixed film layer is 50nm-100 nm.
3. The selective absorbing coating layer operating stably in the atmosphere as claimed in claim 1, wherein the metal infrared reflecting layer is an Ag film layer or an Au film layer with a thickness of 100-150 nm.
4. The atmospheric-stable selective absorption coating of claim 1 wherein the second anti-diffusion barrier layer is Al2O3Film layer or SiO2The thickness of the film layer is 30nm-50 nm.
5. The atmospheric-stable selective absorber coating according to claim 1, wherein the high-volume metal-doped absorber layer, the medium-volume metal-doped absorber layer and the low-volume metal-doped absorber layer are all made of cermet materials, and gradient layer deposition is performed by controlling different metal doping ratios, wherein the metal doping ratio in the high-volume metal-doped absorber layer is 50-60%, the metal doping ratio in the medium-volume metal-doped absorber layer is 40-48%, and the metal doping ratio in the low-volume metal-doped absorber layer is 25-35%.
6. The atmospheric-stable selective absorption coating of claim 5 wherein the metal dopant in the high-, medium-, and low-volume metal-doped absorption layers is NiCr-Al2O3、Ni-Al2O3Or Cr-Al2O3And the thicknesses of the high-volume metal-doped absorption layer, the medium-volume metal-doped absorption layer and the low-volume metal-doped absorption layer are respectively 50-100 nm.
7. The atmospheric-stable selective absorption coating of claim 1 wherein the anti-reflective layer is SiOxFilm layer, SiNyFilm or SiAlOXThe film layer, wherein x and y represent different doping ratios, has a thickness of 100-150 nm.
8. The method for preparing a selective absorbing coating layer which stably operates in the atmosphere according to claims 1 to 7, characterized by comprising the following steps:
step 1: and mechanically polishing the surface of the steel pipe to ensure that the roughness of the steel pipe meets 0.08-0.15um, and then ultrasonically cleaning the steel pipe by adopting a cleaning agent to ensure the surface cleanliness.
Step 2: preparing a first anti-diffusion barrier layer, putting the steel pipe into an annealing furnace, carrying out oxidation treatment at 400-450 ℃, keeping the temperature for 1-1.5h, and forming uniform Fe on the surface2O3And Cr2O3Of oxidesThe mixture, i.e., the first anti-diffusion barrier layer;
and step 3: preparing a metal infrared reflecting layer on the surface of the first diffusion barrier layer by adopting a planar metal target material with the purity of 99.95% and a direct-current magnetron sputtering method, wherein the background vacuum degree before sputtering is 5 x 10-3Pa-8*10-3Pa, introducing argon as sputtering gas, controlling the flow of argon at 600--1Pa-4*10-1Pa, starting a direct current power supply, controlling the working current to be 30-40A and the working voltage to be 500-600V;
and 4, step 4: preparing a second anti-diffusion barrier layer on the surface of the metal infrared reflecting layer by adopting a cylindrical metal target material with the purity of 99.99% and a medium-frequency reactive sputtering method, wherein the background vacuum degree before sputtering is 5 x 10-3Pa-8*10-3Pa, introducing argon as sputtering gas, controlling the flow of argon at 600-2Or N2As reaction gas, the flow rate is controlled to be 50-100sccm, the working vacuum degree is 5 x 10-1Pa～6*10-1Pa, starting the intermediate frequency power supply, controlling the working current to be 20-30A and the working voltage to be 400-600V;
step 5, preparing a high-volume metal doped absorption layer on the surface of the second diffusion barrier layer by adopting a method of co-sputtering a metal target with the purity of 99.95% and a first cylindrical target, wherein a direct-current power supply is adopted to deposit metal, and the metal target is an Ni target, a Cr target or an Ni-Cr target; sputtering an oxide by adopting intermediate-frequency reaction, wherein the first cylindrical target is an Al target or a Si-Al target; background vacuum of 5 x 10 before sputtering-3Pa-8*10-3Pa, introducing argon as sputtering gas, controlling the flow rate to be 600-sccm, starting the direct current power supply and the intermediate frequency power supply, and introducing O after the two target surfaces glow stably2Or N2As reaction gas, the flow rate is 80-100sccm, and the working vacuum degree is 5 × 10-1Pa-6*10-1Pa, wherein the DC voltage of the DC power supply is 300-500V, the working current of the DC power supply is 20-30A, the intermediate frequency voltage of the intermediate frequency power supply is 400-600V, and the working current of the intermediate frequency power supply is 25-35A;
step 6, adopting a method of co-sputtering a metal target with the purity of 99.95 percent and a first cylindrical target to mix metal in high volumePreparing a medium-volume metal-doped absorption layer on the surface of the hybrid absorption layer, wherein metal is deposited by adopting a direct-current power supply, and the metal target material is a Ni target, a Cr target or a Ni-Cr target; sputtering an oxide by adopting intermediate-frequency reaction, wherein the first cylindrical target is an Al target or a Si-Al target; background vacuum of 5 x 10 before sputtering-3Pa-8*10-3Pa, introducing argon as sputtering gas, controlling the flow of argon to be 600-flow and 800sccm, starting the direct current power supply and the medium frequency power supply, and introducing O after the two target surfaces glow stably2Or N2As the reaction gas, the flow rate of the reaction gas is controlled to be 80-100sccm, and the working vacuum degree is controlled to be 5 x 10-1Pa-6*10-1Pa, the DC voltage of the DC power supply is 300-500V, the DC working current is 10-20A, the intermediate frequency voltage of the intermediate frequency power supply is 400-600V, and the working current of the intermediate frequency power supply is 30-40A;
step 7, preparing a low-volume metal-doped absorption layer on the surface of the medium-volume metal-doped absorption layer by adopting a method of co-sputtering a metal target with the purity of 99.95% and a first cylindrical target, wherein metal is deposited by adopting a direct-current power supply, and the metal target is an Ni target, a Cr target or an Ni-Cr target; sputtering an oxide by adopting intermediate-frequency reaction, wherein the first cylindrical target is an Al target or a Si-Al target; background vacuum of 5 x 10 before sputtering-3Pa～8*10-3Pa, introducing argon as sputtering gas, controlling the flow of argon to be 600-flow and 800sccm, starting the direct current power supply and the medium frequency power supply, and introducing O after the glow of the target surface is stable2Or N2As the reaction gas, the flow rate is 80sccm-100sccm, the working vacuum degree is 5 x 10-1Pa-6*10-1Pa, the DC voltage of the DC power supply is 300-500V, the DC working current is 10A-15A, the intermediate frequency voltage of the intermediate frequency power supply is 400-600V, and the intermediate frequency working current is 30-40A; and 8: preparing an antireflection layer on the surface of the low-volume metal-doped absorption layer by adopting a second cylindrical target material with the purity of 99.95% through a medium-frequency reactive sputtering method, wherein the second cylindrical target material is a Si-Al target, a Si target or an Al target, and the background vacuum degree before sputtering is 5 x 10-3Pa-8*10-3Pa, introducing argon as a sputtering gas, controlling the flow of the argon to be 800-sccm and introducing O2Or N2As the reaction gas, the flow rate is 100--1Pa, turn on the medium frequency powerThe source has an operating current of 30A-40A and an intermediate frequency operating voltage of 500-600V.
9. The method according to claim 8, wherein in the step 3, the planar metal target is an Ag target, a Cr target or an Al target.
10. The method according to claim 8, wherein in the step 4, the cylindrical metal target is a Si target or an Al target.
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