CN102286720B - High-temperature solar selective absorbing coating with SiO2 and Cr2O3 double-ceramic structure and preparation method thereof - Google Patents

High-temperature solar selective absorbing coating with SiO2 and Cr2O3 double-ceramic structure and preparation method thereof Download PDF

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CN102286720B
CN102286720B CN 201110243365 CN201110243365A CN102286720B CN 102286720 B CN102286720 B CN 102286720B CN 201110243365 CN201110243365 CN 201110243365 CN 201110243365 A CN201110243365 A CN 201110243365A CN 102286720 B CN102286720 B CN 102286720B
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sio
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CN102286720A (en
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刘雪莲
陈步亮
王静
施伟
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BEIJING TIANRUXING VACUUM TECHNOLOGY DEVELOPMENT Co Ltd
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BEIJING TIANRUXING VACUUM TECHNOLOGY DEVELOPMENT Co Ltd
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Abstract

The invention provides a high-temperature solar selective absorbing coating with a SiO2 and Cr2O3 double-ceramic structure and a preparation method thereof, belonging to the technical field of solar energy utilization. The coating sequentially comprises an infrared reflection layer, an absorbing layer and an anti-reflection layer from the bottom to the surface, wherein a first layer, namely the infrared reflection layer is a Cu or Ag film with the thickness of 50-250 nm; a second layer, namely the absorbing layer consists of two sub-layers, both the two sub-layers are a SiO2 and Cr2O3 film, and both the first sub-layer and the second sub-layer have the thickness of 50-100 nm; and a third layer namely the anti-reflection layer is a SiO2 film with the thickness of 40-80 nm. The coating provided by the invention has the characteristics of high absorption rate of visible-infrared spectroscopy and low emissivity of infrared spectroscopy; because of the reduction of metal atoms, the novel high-temperature selective absorbing coating with the double-ceramic structure has good thermal stability at medium and high temperature; and the preparation process of the coating is simple, is convenient to operate, is easy to control, and shortens the production cycle.

Description

A kind of have a SiO 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings and preparation method thereof
Technical field
The invention belongs to technical field of solar utilization technique, be specifically related to a kind of SiO of having 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings and preparation method thereof.
Background technology
Coating for selective absorption of sunlight spectrum has high-absorbility at the Visible-to-Near InfaRed wave band, has the function film of low-launch-rate at infrared band, is for solar energy collector, improves the key of photo-thermal conversion efficiency.Development along with solar thermal utilization demand and technology, the range of application of solar energy heat collection pipe is used (100 ℃-350 ℃) and high temperature application (350 ℃-500 ℃) development from lower temperature application (≤100 ℃) Xiang Zhongwen, constantly to satisfy the service requirements of high-temperature applications in sea water desaltination, the solar electrical energy generation etc.The coating for selective absorption that uses for thermal-collecting tube also will possess high high-temp stability, the service condition of hot environment in the adaptation.
Study at present and be widely used black chromium, anode oxidation coloration Ni-Al2O3 and had the SS-C/SS (stainless steel) of composition gradual change feature and the film system such as Al-N/Al for solar selectively absorbing coating, be applied to temperature at 200 ℃ of surfaces of collector tubes with interior plate type heat collecting device.But under middle hot conditions, obviously raise because its infrared emittance rises with temperature, cause the heat collector thermosteresis obviously to rise, thermo-efficiency significantly descends.
Thermostability for coating for selective absorption under the high-temperature service condition in improving, the material system such as Mo-Al2O3/Cu, SS-AlN/SS has obtained research and development, adopted two targets or many target metals pottery co-sputtering technology, wherein the characteristics of Mo-Al2O3/Cu system are many sublayer structures that the Mo-Al2O3 absorption layer has the composition gradual change, the Al2O3 layer adopts radio-frequency (RF) sputtering method, the characteristics of SS-AlN/SS system are that absorption layer has adopted the inteferometer coating structure, and thermostability is improved.The high-temperature heat-gathering tube-surface has obtained application in the focus type of above-mentioned coating in 350 ℃ of-500 ℃ of scopes of use temperature.But the sintering metal structure coating is because atoms metal is more, and microtexture at high temperature and physicals are all unstable.And the process deposits speed such as radio-frequency sputtering is low, and the production cycle is long, complex process, and cost is high.
For the middle high temperature utilization of sun power, need a kind of specific absorption height, low, the Heat stability is good of emittance, and the coating for selective absorption of simple process and technology of preparing.
Summary of the invention
For problems of the prior art, the invention provides a kind of SiO of having 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings and preparation method thereof, be applicable to high temperature (300 ℃-500 ℃) working temperature thermal-collecting tube, the coating specific absorption is high, low, the Heat stability is good of emittance, preparation technology is easy, easy to operate, with short production cycle, the sputter operating mode is stable.
A kind of SiO that has provided by the invention 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings, as shown in Figure 1, coating comprises trilamellar membrane, is followed successively by infrared reflecting layer, absorption layer and antireflection layer from the bottom to the surface;
The first layer infrared reflecting layer is Cu or Ag film, is positioned at matrix surface, and thickness is 50～250nm; Second layer absorption layer comprises two sublayer structures, and two subgrades are SiO 2+ Cr 2O 3Film, the thickness of the first subgrade and the second subgrade is 50～100nm, and the thickness of the first subgrade and the second subgrade can equate also can be unequal; SiO in the first subgrade 2Volume percent be the 50～75%, second subgrade SiO 2Volume percent be 30～50%, wherein the first subgrade is adjacent with the first layer infrared reflecting layer, the second subgrade is adjacent with the 3rd layer of antireflection layer; The 3rd layer of antireflection layer is SiO 2Film, thickness are 40～80nm.
A kind of SiO that has provided by the invention 2And Cr 2O 3The preparation method of two ceramic structure high temperature solar energy selective absorption coatings, comprise following step:
Step 1: at matrix preparation the first layer infrared emission layer;
Adopt pure metal target direct current or medium frequency magnetron sputtering method, the pure metal target is Cu target or Ag target (purity 99.99%), prepares the matrix adopting rapid steel as sputter gas with Ar gas.Before the sputter vacuum chamber is taken out base vacuum to 4 * 10 in advance -3～5 * 10 -3Pa passes into rare gas element Ar gas as sputtering atmosphere, and the Ar airshed is 100～140sccm, and adjusting the sputter distance is 130～150mm, and regulating sputtering pressure is 3 * 10 -1～4 * 10 -1Pa.Open the sputtering target power supply of pure metal target, the adjustment sputtering voltage is 380～450V, and sputtering current is 8～10A, utilize the magnetically controlled DC sputtering mode to prepare, splash coating thickness is 50～250nm, obtains the first layer infrared emission layer, this layer has high reflection characteristic to infrared band spectrum, and emittance is low;
Step 2: at the first layer infrared emission coating preparation second layer absorption layer;
Adopt Metal Cr target (purity 99.99%) and Si target (purity 99.99%) medium frequency magnetron sputtering method, at first, vacuum chamber is taken out base vacuum to 4 * 10 in advance -3～5 * 10 -3Then Pa passes into Ar, O simultaneously 2Gas mixture, the flow of Ar is 90～140sccm, O 2Flow be 20～30sccm, regulating sputtering pressure is 3 * 10 -1～5 * 10 -1Pa opens respectively Cr and Si target power supply, and during sputter, adjusting Cr target sputtering voltage is 450～530V, and sputtering current is 6～8A, and Si target sputtering voltage is 600～750V, and sputtering current is 5～7A, at the first layer infrared reflecting layer preparation the first subgrade SiO 2+ Cr 2O 3Film, thickness are 50～100nm;
Increase O 2Flow be 30～50sccm, regulating Si target sputtering voltage is 600～750V, sputtering current is 4～5A, other parameters are constant, at the first subgrade SiO 2+ Cr 2O 3Continue sputter on the film and obtain the second subgrade SiO 2+ Cr 2O 3Film, thickness are 50～100nm; The first subgrade and the second subgrade possess the inherent absorption characteristic solar spectrum except self, also form and interfere absorption effect, have strengthened the optical absorption of coating;
Step 3: at the 3rd layer of antireflection layer of second layer preparation;
Adopt Si target (purity 99.99%), before the sputter vacuum chamber is taken out base vacuum to 4 * 10 in advance -3～5 * 10 -3Pa as sputter gas, passes into O with Ar gas 2As reactant gases preparation, O 2Flow be 20～40sccm, regulate Ar and O 2Throughput ratio is 1.5: 1～2.5: 1, and adjusting the sputter distance is 130～150mm, and regulating sputtering pressure is 3 * 10 -1～5 * 10 -1Pa, during sputter, adjusting Si target sputtering voltage is 700～800V, sputtering current is 8～10A, utilizes the medium frequency magnetron sputtering mode to prepare the SiO that thickness is 40～80nm 2Film i.e. the 3rd layer of antireflection layer.The 3rd layer of antireflection layer has anti-reflection, wear-resisting, oxidation resistant effect.
The invention has the advantages that:
Coating for selective absorption provided by the present invention is by metallic red outer reflective layer, two ceramic structure SiO 2+ Cr 2O 3Two absorption layers and ceramic antireflection layers of interfering of compositions of mixtures form, has visible-infrared spectra high-absorbility, the characteristics of infrared spectra low-launch-rate, because the minimizing of atoms metal, so that this novel pair of ceramic structure high-temperature selective absorber coatings has good middle high high-temp stability.
This preparation technology of coating is easy, easy to operate, be easy to control, shorten the production cycle, with coating for selective absorption by Nb infrared reflecting layer, Nb and Al 2O 3Two absorption layers and Al of interfering of compositions of mixtures 2O 3Antireflection layer is compared, the atoms metal content of this coating is little, microtexture at high temperature and physical property are kept stable very much, target is more common, and range of application is wider, and processability is good, can be processed into the column target, significantly improve target utilization, price is also cheaper simultaneously, can further reduce job costs.Be applicable to the solar energy heat collection pipe of middle hot operation temperature.
Description of drawings
Fig. 1: a kind of SiO that has provided by the invention 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coating diagrammatic cross-sections;
Fig. 2: a kind of SiO that has provided by the invention 2And Cr 2O 3Preparation method's schema of two ceramic structure high temperature solar energy selective absorption coatings.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
A kind of SiO that has provided by the invention 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings, as shown in Figure 1, this coating comprises trilamellar membrane, is followed successively by infrared reflecting layer, absorption layer and antireflection layer from the bottom to the surface;
The first layer infrared reflecting layer is Cu or Ag film, is positioned at matrix surface, and thickness is 50～250nm; Second layer absorption layer comprises two sublayer structures, and two subgrades are SiO 2+ Cr 2O 3Film, the thickness of the first subgrade and the second subgrade is 50～100nm, and the thickness of the first subgrade and the second subgrade can equate also can be unequal; SiO in the first subgrade 2Volume percent be the 50～75%, second subgrade SiO 2Volume percent be 30～50%, wherein the first subgrade is adjacent with the first layer infrared reflecting layer, the second subgrade is adjacent with the 3rd layer of antireflection layer; The 3rd layer of antireflection layer is SiO 2Film, thickness are 40～80nm.
A kind of SiO that has provided by the invention 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings, under air quality factors A M1.5 condition, the coating specific absorption is 96.2%, normal emittance is 0.06.Carry out vacuum annealing and process, 2 * 10 -2Under the Pa vacuum tightness, after 1 hour, the coating specific absorption is 96.2% through 350 ℃ of vacuum annealings, and normal emittance is 0.06,2 * 10 -2Under the Pa vacuum tightness, after 1 hour, the coating specific absorption is 96.0% through 500 ℃ of vacuum annealings, and normal emittance is 0.06.
A kind of SiO that has provided by the invention 2And Cr 2O 3The preparation method of two ceramic structure high temperature solar energy selective absorption coatings, as shown in Figure 2, comprise following step:
Step 1: at matrix preparation the first layer infrared emission layer;
Adopt pure metal target direct current or medium frequency magnetron sputtering method, the pure metal target is Cu target or Ag target (purity 99.99%), prepares the matrix adopting rapid steel as sputter gas with Ar gas.Before the sputter vacuum chamber is taken out base vacuum to 4 * 10 in advance -3～5 * 10 -3Pa passes into rare gas element Ar gas as sputtering atmosphere, and the Ar airshed is 100～140sccm, and adjusting the sputter distance is 130～150mm, and regulating sputtering pressure is 3 * 10 -1～4 * 10 -1Pa.Open the sputtering target power supply of pure metal target, the adjustment sputtering voltage is 380～450V, and sputtering current is 8～10A, utilize the magnetically controlled DC sputtering mode to prepare, splash coating thickness is 50～250nm, obtains the first layer infrared emission layer, this layer has high reflection characteristic to infrared band spectrum, and emittance is low;
Step 2: at the first layer infrared emission coating preparation second layer absorption layer;
Adopt Metal Cr target (purity 99.99%) and Si target (purity 99.99%) medium frequency magnetron sputtering method, at first, vacuum chamber is taken out base vacuum to 4 * 10 in advance -3～5 * 10 -3Then Pa passes into Ar, O simultaneously 2Gas mixture, the flow of Ar is 90～140sccm, O 2Flow be 20～30sccm, regulating sputtering pressure is 3 * 10 -1～5 * 10 -1Pa opens respectively Cr and Si target power supply, and during sputter, adjusting Cr target sputtering voltage is 450～530V, and sputtering current is 6～8A, and Si target sputtering voltage is 600～750V, and sputtering current is 5～7A, at the first layer infrared reflecting layer preparation the first subgrade SiO 2+ Cr 2O 3Film, thickness are 50～100nm;
Increase O 2Flow be 30～50sccm, regulating Si target sputtering voltage is 600～750V, sputtering current is 4～5A, other parameters are constant, at the first subgrade SiO 2+ Cr 2O 3Continue sputter on the film and obtain the second subgrade SiO 2+ Cr 2O 3Film, thickness are 50～100nm; The first subgrade and the second subgrade possess the inherent absorption characteristic solar spectrum except self, also form and interfere absorption effect, have strengthened the optical absorption of coating;
Step 3: at the 3rd layer of antireflection layer of second layer preparation;
Adopt Si target (purity 99.99%), before the sputter vacuum chamber is taken out base vacuum to 4 * 10 in advance -3～5 * 10 -3Pa as sputter gas, passes into O with Ar gas 2As reactant gases preparation, O 2Flow be 20～40sccm, regulate Ar and O 2Throughput ratio is 1.5: 1～2.5: 1, and adjusting the sputter distance is 130～150mm, and regulating sputtering pressure is 3 * 10 -1～5 * 10 -1Pa, during sputter, adjusting Si target sputtering voltage is 700～800V, sputtering current is 8～10A, utilizes the medium frequency magnetron sputtering mode to prepare the SiO that thickness is 40～80nm 2Film i.e. the 3rd layer of antireflection layer.The 3rd layer of antireflection layer has anti-reflection, wear-resisting, oxidation resistant effect.
Embodiment 1:
Present embodiment provides a kind of solar selectively absorbing coating, comprise that three coatings are the first layer infrared reflecting layer, second layer absorption layer, the 3rd layer of antireflection layer, the first layer thickness is 200nm, second layer total thickness is 150nm, wherein the first subgrade thickness is 90nm, the second subgrade thickness is 60nm, SiO in the first subgrade 2Volume percent be 60%, the second subgrade SiO 2Volume percent be that 40%, the threeply degree is 60nm.Preparation process is as follows:
Step 1: at matrix preparation the first layer infrared emission layer;
Select the Cu target of purity 99.99%, base material uses rapid steel.Before the sputter vacuum chamber is taken out base vacuum to 4.5 * 10 in advance -3Pa passes into rare gas element Ar as sputtering atmosphere, and the Ar airshed is 120sccm, and adjusting the sputter distance is 145mm, and regulating sputtering pressure is 4 * 10 -1Pa.Open the Cu target, the adjustment sputtering voltage is 400V, and sputtering current is 8A, utilizes the d.c. sputtering mode to prepare the thick Cu film of 200nm;
Step 2: at the first layer coating preparation second layer absorption layer;
Adopt metal Si target and Cr target medium frequency magnetron sputtering method, vacuum chamber is taken out base vacuum to 4 * 10 in advance -3Pa passes into Ar, O simultaneously 2Gas mixture, the flow of Ar is 120sccm, O 2Flow be 20sccm, regulating sputtering pressure is 3 * 10 -1Pa opens respectively Cr and Si target power supply, and adjusting Cr target sputtering voltage is 480V, and sputtering current is 8A, and Si target sputtering voltage is 670V, and sputtering current is 6.3A, at the first thick subgrade SiO of Cu film preparation 90nm 2+ Cr 2O 3Film;
Regulate O 2Flow be 30sccm, regulating Si target sputtering voltage is 622V, sputtering current is 4.3A, other parameters are constant, continuing preparation thickness is the second subgrade SiO of 60nm 2+ Cr 2O 3Film;
Step 3: at the 3rd layer of antireflection layer of second layer preparation;
Select the Si target of purity 99.99%, before the sputter vacuum chamber is taken out base vacuum to 4.8 * 10 in advance -3Pa passes into Ar, O simultaneously 2Gas mixture is regulated Ar and O 2Throughput ratio is 2: 1, O 2Flow be 20sccm, adjusting the sputter distance be 145mm, the adjusting sputtering pressure is 3 * 10 -1Pa, during sputter, the adjustment sputtering current is 8.3A, sputtering voltage is 750V, utilizes the medium frequency magnetron sputtering mode to prepare the thick SiO of 60nm 2Film.
The present embodiment preparation has SiO 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings, under air quality factors A M1.5 condition, the coating specific absorption is 95.9%, normal emittance is 0.06.Carry out vacuum annealing and process, 2 * 10 -2Under the Pa vacuum tightness, after 1 hour, the coating specific absorption is 95.9% through 350 ℃ of vacuum annealings, and normal emittance is 0.06,2 * 10 -2Under the Pa vacuum tightness, after 1 hour, the coating specific absorption is 95.7% through 500 ℃ of vacuum annealings, and normal emittance is 0.06.
Embodiment 2:
A kind of SiO of having that present embodiment provides 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings, this coating comprises trilamellar membrane, is followed successively by infrared reflecting layer, absorption layer and antireflection layer from the bottom to the surface;
The first layer infrared reflecting layer is Cu or Ag film, is positioned at matrix surface, and thickness is 50nm; Second layer absorption layer comprises two sublayer structures, and two subgrades are SiO 2+ Cr 2O 3Film, the thickness of the first subgrade and the second subgrade is 50nm, SiO in the first subgrade 2Volume percent be 50%, the second subgrade SiO 2Volume percent be 30%, wherein the first subgrade is adjacent with the first layer infrared reflecting layer, the second subgrade is adjacent with the 3rd layer of antireflection layer; The 3rd layer of antireflection layer is SiO 2Film, thickness are 40nm.
A kind of SiO of having that present embodiment provides 2And Cr 2O 3The preparation method of two ceramic structure high temperature solar energy selective absorption coatings, comprise following step:
Step 1: at matrix preparation the first layer infrared emission layer;
Adopt pure metal target direct current or medium frequency magnetron sputtering method, the pure metal target is Cu target (purity 99.99%), prepares the matrix adopting rapid steel as sputter gas with Ar gas.Before the sputter vacuum chamber is taken out base vacuum to 4 * 10 in advance -3Pa passes into rare gas element Ar gas as sputtering atmosphere, and the Ar airshed is 100sccm, and adjusting the sputter distance is 130mm, and regulating sputtering pressure is 3 * 10 -1Pa.Open the sputtering target power supply of pure metal target, the adjustment sputtering voltage is 380V, and sputtering current is 8～10A, utilize the magnetically controlled DC sputtering mode to prepare, splash coating thickness is 50nm, obtains the first layer infrared emission layer, this layer has high reflection characteristic to infrared band spectrum, and emittance is low;
Step 2: at the first layer infrared emission coating preparation second layer absorption layer;
Adopt Metal Cr target (purity 99.99%) and Si target (purity 99.99%) medium frequency magnetron sputtering method, at first, vacuum chamber is taken out base vacuum to 4 * 10 in advance -3Then Pa passes into Ar, O simultaneously 2Gas mixture, the flow of Ar is 90sccm, O 2Flow be 20sccm, regulating sputtering pressure is 3 * 10 -1Pa opens respectively Cr and Si target power supply, and during sputter, adjusting Cr target sputtering voltage is 450V, and sputtering current is 6A, and Si target sputtering voltage is 600V, and sputtering current is 5A, at the first layer infrared reflecting layer preparation the first subgrade SiO 2+ Cr 2O 3Film, thickness are 50nm;
Increase O 2Flow be 30sccm, regulating Si target sputtering voltage is 600V, sputtering current is 4A, other parameters are constant, at the first subgrade SiO 2+ Cr 2O 3Continue sputter on the film and obtain the second subgrade SiO 2+ Cr 2O 3Film, thickness are 50nm; The first subgrade and the second subgrade possess the inherent absorption characteristic solar spectrum except self, also form and interfere absorption effect, have strengthened the optical absorption of coating;
Step 3: at the 3rd layer of antireflection layer of second layer preparation;
Adopt Si target (purity 99.99%), before the sputter vacuum chamber is taken out base vacuum to 4 * 10 in advance -3Pa as sputter gas, passes into O with Ar gas 2As reactant gases preparation, O 2Flow be that 25sccm regulates Ar and O 2Throughput ratio is 1.5: 1, and adjusting the sputter distance is 130mm, and regulating sputtering pressure is 3 * 10 -1Pa, during sputter, adjusting Si target sputtering voltage is 700V, sputtering current is 8A, utilizes the medium frequency magnetron sputtering mode to prepare thickness and is the SiO of 40nm 2Film i.e. the 3rd layer of antireflection layer.The 3rd layer of antireflection layer has anti-reflection, wear-resisting, oxidation resistant effect.
Embodiment 3:
A kind of SiO of having that present embodiment provides 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings, coating comprises trilamellar membrane, is followed successively by infrared reflecting layer, absorption layer and antireflection layer from the bottom to the surface;
The first layer infrared reflecting layer is Cu or Ag film, is positioned at matrix surface, and thickness is 250nm; Second layer absorption layer comprises two sublayer structures, and two subgrades are SiO 2+ Cr 2O 3Film, the thickness of the first subgrade and the second subgrade is 100nm, SiO in the first subgrade 2Volume percent be 75%, the second subgrade SiO 2Volume percent be 50%, wherein the first subgrade is adjacent with the first layer infrared reflecting layer, the second subgrade is adjacent with the 3rd layer of antireflection layer; The 3rd layer of antireflection layer is SiO 2Film, thickness are 80nm.
A kind of SiO of having that present embodiment provides 2And Cr 2O 3The preparation method of two ceramic structure high temperature solar energy selective absorption coatings, comprise following step:
Step 1: at matrix preparation the first layer infrared emission layer;
Adopt pure metal target direct current or medium frequency magnetron sputtering method, the pure metal target is Ag target (purity 99.99%), prepares the matrix adopting rapid steel as sputter gas with Ar gas.Before the sputter vacuum chamber is taken out base vacuum to 5 * 10 in advance -3Pa passes into rare gas element Ar gas as sputtering atmosphere, and the Ar airshed is 140sccm, and adjusting the sputter distance is 150mm, and regulating sputtering pressure is 4 * 10 -1Pa.Open the sputtering target power supply of pure metal target, the adjustment sputtering voltage is 450V, and sputtering current is 10A, utilize the magnetically controlled DC sputtering mode to prepare, splash coating thickness is 250nm, obtains the first layer infrared emission layer, this layer has high reflection characteristic to infrared band spectrum, and emittance is low;
Step 2: at the first layer infrared emission coating preparation second layer absorption layer;
Adopt Metal Cr target (purity 99.99%) and Si target (purity 99.99%) medium frequency magnetron sputtering method, at first, vacuum chamber is taken out base vacuum to 5 * 10 in advance -3Then Pa passes into Ar, O simultaneously 2Gas mixture, the flow of Ar is 140sccm, O 2Flow be 30sccm, regulating sputtering pressure is 5 * 10 -1Pa opens respectively Cr and Si target power supply, and during sputter, adjusting Cr target sputtering voltage is 530V, and sputtering current is 8A, and Si target sputtering voltage is 750V, and sputtering current is 5～7A, at the first layer infrared reflecting layer preparation the first subgrade SiO 2+ Cr 2O 3Film, thickness are 100nm;
Increase O 2Flow be 50sccm, regulating Si target sputtering voltage is 750V, sputtering current is 5A, other parameters are constant, at the first subgrade SiO 2+ Cr 2O 3Continue sputter on the film and obtain the second subgrade SiO 2+ Cr 2O 3Film, thickness are 50～100nm; The first subgrade and the second subgrade possess the inherent absorption characteristic solar spectrum except self, also form and interfere absorption effect, have strengthened the optical absorption of coating;
Step 3: at the 3rd layer of antireflection layer of second layer preparation;
Adopt Si target (purity 99.99%), before the sputter vacuum chamber is taken out base vacuum to 5 * 10 in advance -3Pa as sputter gas, passes into O with Ar gas 2As reactant gases preparation, O 2Flow be 30sccm, regulate Ar and O 2Throughput ratio is 2.5: 1, and adjusting the sputter distance is 150mm, and regulating sputtering pressure is 5 * 10 -1Pa, during sputter, adjusting Si target sputtering voltage is 800V, sputtering current is 10A, utilizes the medium frequency magnetron sputtering mode to prepare thickness and is the SiO of 80nm 2Film i.e. the 3rd layer of antireflection layer.The 3rd layer of antireflection layer has anti-reflection, wear-resisting, oxidation resistant effect.
Embodiment 4:
A kind of SiO of having that present embodiment provides 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings, this coating comprises trilamellar membrane, is followed successively by infrared reflecting layer, absorption layer and antireflection layer from the bottom to the surface;
The first layer infrared reflecting layer is Cu or Ag film, is positioned at matrix surface, and thickness is 150nm; Second layer absorption layer comprises two sublayer structures, and two subgrades are SiO 2+ Cr 2O 3Film, the thickness of the first subgrade and the second subgrade is 75nm, SiO in the first subgrade 2Volume percent be 60%, the second subgrade SiO 2Volume percent be 40%, wherein the first subgrade is adjacent with the first layer infrared reflecting layer, the second subgrade is adjacent with the 3rd layer of antireflection layer; The 3rd layer of antireflection layer is SiO 2Film, thickness are 60nm.
A kind of SiO of having that present embodiment provides 2And Cr 2O 3The preparation method of two ceramic structure high temperature solar energy selective absorption coatings, comprise following step:
Step 1: at matrix preparation the first layer infrared emission layer;
Adopt pure metal target direct current or medium frequency magnetron sputtering method, the pure metal target is Ag target (purity 99.99%), prepares the matrix adopting rapid steel as sputter gas with Ar gas.Before the sputter vacuum chamber is taken out base vacuum to 4.5 * 10 in advance -3Pa passes into rare gas element Ar gas as sputtering atmosphere, and the Ar airshed is 120sccm, and adjusting the sputter distance is 140mm, and regulating sputtering pressure is 3.5 * 10 -1Pa.Open the sputtering target power supply of pure metal target, the adjustment sputtering voltage is 410V, and sputtering current is 9A, utilize the magnetically controlled DC sputtering mode to prepare, splash coating thickness is 150nm, obtains the first layer infrared emission layer, this layer has high reflection characteristic to infrared band spectrum, and emittance is low;
Step 2: at the first layer infrared emission coating preparation second layer absorption layer;
Adopt Metal Cr target (purity 99.99%) and Si target (purity 99.99%) medium frequency magnetron sputtering method, at first, vacuum chamber is taken out base vacuum to 4.5 * 10 in advance -3Then Pa passes into Ar, O simultaneously 2Gas mixture, the flow of Ar is 120sccm, O 2Flow be 25sccm, regulating sputtering pressure is 4 * 10 -1Pa opens respectively Cr and Si target power supply, and during sputter, adjusting Cr target sputtering voltage is 490V, and sputtering current is 7A, and Si target sputtering voltage is 680V, and sputtering current is 6A, at the first layer infrared reflecting layer preparation the first subgrade SiO 2+ Cr 2O 3Film, thickness are 75nm;
Increase O 2Flow be 40sccm, regulating Si target sputtering voltage is 700V, sputtering current is 4～5A, other parameters are constant, at the first subgrade SiO 2+ Cr 2O 3Continue sputter on the film and obtain the second subgrade SiO 2+ Cr 2O 3Film, thickness are 75nm; The first subgrade and the second subgrade possess the inherent absorption characteristic solar spectrum except self, also form and interfere absorption effect, have strengthened the optical absorption of coating;
Step 3: at the 3rd layer of antireflection layer of second layer preparation;
Adopt Si target (purity 99.99%), before the sputter vacuum chamber is taken out base vacuum to 4.5 * 10 in advance -3Pa as sputter gas, passes into O with Ar gas 2As reactant gases preparation, O 2Flow be 40sccm, regulate Ar and O 2Throughput ratio is 2: 1, and adjusting the sputter distance is 140mm, and regulating sputtering pressure is 4 * 10 -1Pa, during sputter, adjusting Si target sputtering voltage is 750V, sputtering current is 9A, utilizes the medium frequency magnetron sputtering mode to prepare thickness and is the SiO of 60nm 2Film i.e. the 3rd layer of antireflection layer.The 3rd layer of antireflection layer has anti-reflection, wear-resisting, oxidation resistant effect.

Claims (5)

1. one kind has SiO 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings, it is characterized in that: described coating is followed successively by infrared reflecting layer, absorption layer and antireflection layer from the bottom to the surface;
The first layer infrared reflecting layer is Cu or Ag film, is positioned at matrix surface, and thickness is 50～250nm; Second layer absorption layer comprises two sublayer structures, and two subgrades are SiO 2+ Cr 2O 3Film, the thickness of the first subgrade and the second subgrade is 50～100nm, and the thickness of the first subgrade and the second subgrade can equate or is unequal; SiO in the first subgrade 2Volume percent be the 50 ~ 75%, second subgrade SiO 2Volume percent be 30 ~ 50%, wherein the first subgrade is adjacent with the first layer infrared reflecting layer, the second subgrade is adjacent with the 3rd layer of antireflection layer; The 3rd layer of antireflection layer is SiO 2Film, thickness are 40～80nm.
2. a kind of SiO that has according to claim 1 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings, it is characterized in that: described coating is under air quality factors A M1.5 condition, and its specific absorption is 96.2%, and normal emittance is 0.06.
3. a kind of SiO that has according to claim 1 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings, it is characterized in that: described coating is 2 * 10 -2Under the Pa vacuum tightness, after 1 hour, its specific absorption is 96.2% through 350 ℃ of vacuum annealings, and normal emittance is 0.06.
4. a kind of SiO that has according to claim 1 2And Cr 2O 3Two ceramic structure high temperature solar energy selective absorption coatings, it is characterized in that: described coating is 2 * 10 -2Under the Pa vacuum tightness, after 1 hour, its specific absorption is 96.0% through 500 ℃ of vacuum annealings, and normal emittance is 0.06.
5. one kind according to claim 1ly has a SiO 2And Cr 2O 3The preparation method of two ceramic structure high temperature solar energy selective absorption coatings, it is characterized in that: comprise following step:
Step 1: at matrix preparation the first layer infrared emission layer;
Adopt pure metal target direct current or medium frequency magnetron sputtering method, the pure metal target is Cu target or Ag target, prepares as sputter gas with Ar gas, and the matrix adopting rapid steel is taken out base vacuum to 4 * 10 in advance with vacuum chamber before the sputter -3~ 5 * 10 -3Pa passes into rare gas element Ar gas as sputtering atmosphere, and the Ar airshed is 100 ~ 140sccm, and adjusting the sputter distance is 130 ~ 150mm, and regulating sputtering pressure is 3 * 10 -1~ 4 * 10 -1Pa, the sputtering target power supply of unlatching pure metal target, the adjustment sputtering voltage is 380 ~ 450V, and sputtering current is 8 ~ 10A, and splash coating thickness is 50～250nm, obtains the first layer infrared emission layer;
Step 2: at the first layer infrared emission coating preparation second layer absorption layer;
Adopt Metal Cr target and Si target medium frequency magnetron sputtering method, vacuum chamber is taken out base vacuum to 4 * 10 in advance -3~ 5 * 10 -3Then Pa passes into Ar, O 2Gas mixture, the flow of Ar is 90 ~ 140sccm, O 2Flow be 20 ~ 30sccm, regulating sputtering pressure is 3 * 10 -1~ 5 * 10 -1Pa opens respectively Cr and Si target power supply, and adjusting Cr target sputtering voltage is 450 ~ 530V, and sputtering current is 6 ~ 8A, and Si target sputtering voltage is 600 ~ 750V, and sputtering current is 5 ~ 7A, at the first layer infrared reflecting layer preparation the first subgrade SiO 2+ Cr 2O 3Film, thickness are 50～100nm;
Increase O 2Flow be 30 ~ 50sccm, regulating Si target sputtering voltage is 600 ~ 750V, sputtering current is 4 ~ 5A, other parameters are constant, at the first subgrade SiO 2+ Cr 2O 3Continue sputter on the film and obtain the second subgrade SiO 2+ Cr 2O 3Film, thickness are 50～100nm;
Step 3: at the 3rd layer of antireflection layer of second layer absorption layer preparation;
Adopt the Si target, before the sputter vacuum chamber is taken out base vacuum to 4 * 10 in advance -3~ 5 * 10 -3Pa as sputter gas, passes into O with Ar gas 2As reactant gases preparation, O 2Flow be 20 ~ 40sccm, regulate Ar and O 2Throughput ratio is 1.5:1～2.5:1, and adjusting the sputter distance is 130 ~ 150mm, and regulating sputtering pressure is 3 * 10 -1~ 5 * 10 -1Pa, during sputter, adjusting Si target sputtering voltage is 700 ~ 800V, sputtering current is 8 ~ 10A, prepares the SiO that thickness is 40～80nm 2The 3rd layer of antireflection layer that film consists of.
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