CN104006560A - Tungsten oxide and zirconium oxide high-temperature solar selective absorption coating and production method thereof - Google Patents

Tungsten oxide and zirconium oxide high-temperature solar selective absorption coating and production method thereof Download PDF

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CN104006560A
CN104006560A CN201410229712.0A CN201410229712A CN104006560A CN 104006560 A CN104006560 A CN 104006560A CN 201410229712 A CN201410229712 A CN 201410229712A CN 104006560 A CN104006560 A CN 104006560A
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CN104006560B (en
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曹明刚
刘雪莲
张秀廷
席晓敏
陈步亮
邓宁
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BEIJING TRX SOLAR TECHNOLOGY Co Ltd
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BEIJING TRX SOLAR TECHNOLOGY Co Ltd
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Abstract

The invention discloses a tungsten oxide and zirconium oxide high-temperature solar selective absorption coating and a production method thereof. The tungsten oxide and zirconium oxide high-temperature solar selective absorption coating comprises three layers of films; a first layer of infrared reflective layer is a cuprum or argentum film which is located on the surface of a substrate, wherein the thickness of the cuprum or argentum film is 100 to 300 nm; a second layer of absorption layer comprises two sub-layers which are tungsten oxide and zirconium oxide films; the thickness of the first sub-layer and the thickness of the second sub-layer are both 150 to 300 nm; the volume percent of zirconium oxide in the first sub-layer is 50 to 75% and the rest is tungsten oxide; the volume percent of zirconium oxide in the second sub-layer is 30 to 50% and the rest is tungsten oxide; the first sub-layer is adjacent to the first layer of infrared reflective layer; the second sub-layer is adjacent to a third layer of antireflection layer; the third layer of antireflection layer is a zirconium oxide film, wherein the thickness of the zirconium oxide film is 120 to 200 nm. According to the tungsten oxide and zirconium oxide high-temperature solar selective absorption coating and the production method thereof, the high-temperature stability is excellent and the good thermal stability can be maintained under the 500 to 600 DEG C high-temperature vacuum conditions or under the 400 DEG C atmospheric conditions.

Description

A kind of WO x/ ZrO xhigh temperature solar energy selective absorption coating and preparation method thereof
Technical field
The invention belongs to technical field of solar utilization technique, be specifically related to a kind of WO x/ ZrO xhigh temperature solar energy selective absorption coating and preparation method thereof.
Background technology
Coating for selective absorption of sunlight spectrum has high-absorbility at Visible-to-Near InfaRed wave band, has the function of low-launch-rate at infrared band, is for solar thermal collector, improves the key of photo-thermal conversion efficiency.Along with the development of solar thermal utilization demand and technology, the range of application of solar energy heat collection pipe is from cryogenic applications (≤100 DEG C) Xiang Zhongwen application (100 DEG C-350 DEG C) and high temperature application (350 DEG C-500 DEG C) development, constantly to meet the instructions for use of high-temperature applications in desalinization, solar electrical energy generation etc.Coating for selective absorption need to possess good high high-temp stability, could meet the service condition of thermal-collecting tube in middle hot environment.
The mankind are promoting technology to the pursuit of efficiency and are constantly advancing, and in recent years, have done large quantity research and application more widely for middle high temperature solar energy selective absorption coating.Conventional material mainly contains Cr-Cr oxide, Ni-Al 2o 3, Mo-Al 2o 3, Ti/Al/Si nitride or (with) oxide etc., but these materials are only for the vacuum environment of 300 DEG C～400 DEG C, for 500 DEG C～600 DEG C vacuum of higher temperature and 450 DEG C～500 DEG C domestic reports that have no of coating that non-vacuum environment uses.
Summary of the invention
The object of the invention is, in order to address the above problem, to propose a kind of WO x/ ZrO xhigh temperature solar energy selective absorption coating and preparation method thereof, at WO x/ ZrO xafter high temperature solar energy selective absorption coating has plated, it is carried out to vacuum high-temperature annealing in process, be applicable to high temperature (300 DEG C～600 DEG C) working vacuum thermal-collecting tube and higher than 450 DEG C of antivacuum thermal-collecting tubes, coating absorptivity is high, emissivity is low, Heat stability is good.
The invention provides a kind of WO x/ ZrO xsolar selectively absorbing coating: under air quality factors A M1.5 condition, coating absorptivity is 96.2%, and normal emittance is 0.04.Carry out vacuum annealing processing, 5 × 10 -3under Pa vacuum, through 550 DEG C of vacuum annealings, after 2 hours, coating absorptivity is 97.1%, and normal emittance is 0.04,5 × 10 -3under Pa vacuum, through 600 DEG C of vacuum annealings, after 2 hours, coating absorptivity is 97.6%, and normal emittance is 0.04.Under atmospheric conditions, through 350 DEG C of insulations, after 2 hours, coating absorptivity is 97.5%, and normal emittance is 0.04; Under atmospheric conditions, through 400 DEG C of insulations, after 2 hours, coating absorptivity is 97.1%, and normal emittance is 0.05.
The present invention proposes a kind of WO x/ ZrO xhigh temperature solar energy selective absorption coating, comprises trilamellar membrane, is followed successively by infrared reflecting layer, absorbed layer and antireflection layer from bottom to surface; Ground floor infrared reflecting layer is Cu or Ag film, is positioned at matrix surface, and thickness is 100～300nm; Second layer absorbed layer comprises two sublayer structures, and two subgrades are WO x+ ZrO xfilm, the thickness of the first subgrade and the second subgrade is 150～300nm, ZrO in the first subgrade xaccounting for percent by volume is 50～75%, and all the other are WO x, the second subgrade ZrO xpercent by volume be 30～50%, all the other are WO x, wherein the first subgrade is adjacent with ground floor infrared reflecting layer, and the second subgrade is adjacent with the 3rd layer of antireflection layer; The 3rd layer of antireflection layer is ZrO xfilm, thickness is 120～200nm.
The present invention proposes a kind of WO x/ ZrO xthe preparation method of high temperature solar energy selective absorption coating, comprises following step:
Step 1: prepare ground floor infrared emission layer on matrix;
Adopt simple metal target direct current or medium frequency magnetron sputtering method, simple metal target is Cu target or Ag target (purity is 99.99%), prepares as sputter gas using Ar gas, and matrix adopting high-speed steel, is evacuated to 4.0 × 10 in advance by vacuum chamber base vacuum before sputter -3～5.0 × 10 -3pa, passes into inert gas Ar gas as sputtering atmosphere, and Ar throughput is 1000～1400sccm, and adjusting sputter distance is 130～150mm, and regulating sputtering pressure is 2 × 10 -1～4 × 10 -1pa, the sputtering target power supply of unlatching simple metal target, adjustment sputtering voltage is 380～450V, and sputtering current is 45～65A, utilizes magnetically controlled DC sputtering mode to prepare, and splash coating thickness is 100～300nm, obtains ground floor infrared emission layer;
Step 2: prepare second layer absorbed layer on ground floor infrared emission layer;
Adopt medium frequency magnetron sputtering method, taking metal W target and Zr target (purity 99.99%) as sputtering target material, first vacuum chamber is taken out to base vacuum to 4 × 10 in advance -3～5 × 10 -3pa, then passes into Ar, O 2gaseous mixture, the flow of Ar is 800～1400sccm, O 2flow be 120～150sccm, regulate sputtering pressure be 2 × 10 -1～4 × 10 -1pa, opens respectively W and Zr target power supply, and when sputter, adjusting W target sputtering voltage is 600～750V, and sputtering current is 50～60A, and Zr target sputtering voltage is 650～800V, and sputtering current is 20～30A, prepares the first subgrade WO on ground floor infrared reflecting layer x+ ZrO xfilm, thickness is 150～200nm;
Adjust sputtering pressure to 4 × 10 -1～6 × 10 -1pa, increases O 2flow be 150～190sccm, regulating W target sputtering current is 40～50A, other parameters are constant, at the first subgrade WO x+ ZrO xon film, continue sputter and obtain the second subgrade WO x+ ZrO xfilm, thickness is 150～200nm;
Step 3: prepare the 3rd layer of antireflection layer on second layer absorbed layer;
Adopt Zr target (purity 99.99%) as sputtering target material, before sputter, vacuum chamber is taken out to base vacuum to 4 × 10 in advance -3～5 × 10 -3pa, using Ar gas as sputter gas, O 2as reacting gas, O 2flow is 300～400sccm, regulates Ar and O 2flow-rate ratio is 2.5:1～4:1, and regulating sputtering pressure is 4 × 10 -1～6 × 10 -1pa, when sputter, adjustment sputtering voltage is 300～400V, sputtering current is 25～30A, utilizes medium frequency magnetron sputtering mode to obtain the ZrO that thickness is 50～150nm xfilm, i.e. the 3rd layer of antireflection layer.
Step 4: Coatings in Vacuum annealing in process
The thermal-collecting tube that is coated with coating for selective absorption is carried out to the heat treatment of vacuum after annealing, and wherein, vacuum is 3.0 × 10 -3～5 × 10 -3pa, annealing temperature is 400 DEG C～650 DEG C, annealing time is 2～5h.
The invention has the advantages that:
Coating for selective absorption provided by the present invention is by metallic red outer reflective layer, exotic material WO x/ ZrO xtwo absorbed layer and ceramic antireflection layer compositions of interfering of composition, have visible-infrared spectrum high-absorbility, the feature of infrared spectrum low-launch-rate.Due to WO x/ ZrO xthere is excellent high-temperature stability, adopt high-temperature vacuum annealing process simultaneously, make this new type high temperature coating for selective absorption under 400 DEG C of atmospheric conditions of 500 DEG C～600 DEG C high-temperature vacuum conditioned disjunctions, still to keep good heat endurance.
With employing AlN xo x, AlN xthe coating for selective absorption of material is compared, this coating is after vacuum high-temperature annealing, microstructure and physical property are at high temperature more stable, and coating hardness has high rigidity and good abrasion resistance properties, are applicable to solar vacuum heat-collecting pipe and the antivacuum thermal-collecting tube of middle hot operation.
Brief description of the drawings
Fig. 1: a kind of WO provided by the invention x/ ZrO xthe structural representation of high temperature solar energy selective absorption coating;
Fig. 2: a kind of WO provided by the invention x/ ZrO xpreparation method's flow chart of high temperature solar energy selective absorption coating.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail.
The present invention is a kind of WO x/ ZrO xhigh temperature solar energy selective absorption coating, in conjunction with section as shown in Figure 1, coating comprises trilamellar membrane, is followed successively by infrared reflecting layer, absorbed layer and antireflection layer from bottom to surface;
Ground floor infrared reflecting layer is Cu or Ag film, is positioned at matrix surface, and thickness is 100～300nm; Second layer absorbed layer comprises two sublayer structures, and two subgrades are WO x+ ZrO xfilm, the thickness of the first subgrade and the second subgrade is 150～200nm, and the thickness of the first subgrade and the second subgrade can equate also can be unequal; ZrO in the first subgrade xpercent by volume be 50～75%, all the other are WO 3, the second subgrade ZrO xpercent by volume be 30～50%, all the other are WO x; Wherein the first subgrade is adjacent with ground floor infrared reflecting layer, and the second subgrade is adjacent with the 3rd layer of antireflection layer; The 3rd layer of antireflection layer is ZrO 2film, thickness is 120～200nm.
A kind of WO provided by the invention x/ ZrO xsolar selectively absorbing coating: under air quality factors A M1.5 condition, coating absorptivity is 96.2%, and normal emittance is 0.04.Carry out vacuum annealing processing, 5 × 10 -3under Pa vacuum, through 550 DEG C of vacuum annealings, after 2 hours, coating absorptivity is 97.1%, and normal emittance is 0.04,5 × 10 -3under Pa vacuum, through 600 DEG C of vacuum annealings, after 2 hours, coating absorptivity is 97.6%, and normal emittance is 0.04.Under atmospheric conditions, through 350 DEG C of insulations, after 2 hours, coating absorptivity is 97.5%, and normal emittance is 0.04; Under atmospheric conditions, through 400 DEG C of insulations, after 2 hours, coating absorptivity is 97.1%, and normal emittance is 0.05.
A kind of WO provided by the invention x/ ZrO xthe preparation method of high temperature solar energy selective absorption coating, as shown in Figure 2, comprises following step:
Step 1: prepare ground floor infrared emission layer on matrix;
Adopt simple metal target direct current or medium frequency magnetron sputtering method, simple metal target is Cu target or Ag target (purity is 99.99%), prepares as sputter gas using Ar gas, and matrix adopting high-speed steel, is evacuated to 4 × 10 in advance by vacuum chamber base vacuum before sputter -3～5 × 10 -3pa, passes into inert gas Ar gas as sputtering atmosphere, and Ar throughput is 1000～1400sccm, and adjusting sputter distance is 130～150mm, and regulating sputtering pressure is 2 × 10 -1～4 × 10 -1pa, open the sputtering target power supply of simple metal target, adjustment sputtering voltage is 380～450V, sputtering current is 8～10A, utilize magnetically controlled DC sputtering mode to prepare, splash coating thickness is 100～300nm, obtains ground floor infrared emission layer, this layer has high reflection characteristic to infrared band spectrum, and emissivity is low;
Step 2: prepare second layer absorbed layer on ground floor infrared emission layer;
Adopt medium frequency magnetron sputtering method, taking metal W target and target Zr (purity 99.99%) as sputtering target material, first vacuum chamber is taken out to base vacuum to 4 × 10 in advance -3～5 × 10 -3pa, then passes into Ar, O 2gaseous mixture, the flow of Ar is 800～1400sccm, O 2flow be 120～150sccm, regulate sputtering pressure be 2 × 10 -1～4 × 10 -1pa, opens respectively W and Zr target power supply, and when sputter, adjusting W target sputtering voltage is 600～750V, and sputtering current is 50～60A, and Zr target sputtering voltage is 650～800V, and sputtering current is 20～30A, prepares the first subgrade WO on ground floor infrared reflecting layer x+ ZrO xfilm, thickness is 150～200nm;
Adjust sputtering pressure to 4 × 10 -1～6 × 10 -1pa, increases O 2flow be 150～190sccm, regulating W target sputtering current is 40～50A, other parameters are constant, at the first subgrade WO x+ ZrO xon film, continue sputter and obtain the second subgrade WO x+ ZrO xfilm, thickness is 150～200nm; The first subgrade and the second subgrade, except self is to the inherent absorption characteristic of solar spectrum, also forms and interfere sink effect, have strengthened the optical absorption of coating;
Step 3: prepare the 3rd layer of antireflection layer on second layer absorbed layer;
Adopt Zr target (purity 99.99%) as sputtering target material, before sputter, vacuum chamber is taken out to base vacuum to 4 × 10 in advance -3～5 × 10 -3pa, using Ar gas as sputter gas, O 2as reacting gas, O 2flow is 300～400sccm, regulates Ar and O 2flow-rate ratio is 2.5:1～4:1, and regulating sputtering pressure is 4 × 10 -1～6 × 10 -1pa, when sputter, adjustment sputtering voltage is 300～400V, sputtering current is 25～30A, utilizes medium frequency magnetron sputtering mode to obtain the ZrO that thickness is 120～200nm xfilm, i.e. the 3rd layer of antireflection layer.The 3rd layer of antireflection layer has the transmissivity of increasing, wear-resisting, oxidation resistant effect.
Step 4: Coatings in Vacuum annealing in process
The thermal-collecting tube that is coated with coating for selective absorption is carried out to the heat treatment of vacuum after annealing, and wherein, vacuum is 3.0 × 10 -3～5 × 10 -3pa, annealing temperature is 400 DEG C～650 DEG C, annealing time is 2～5h.
embodiment 1:
The present embodiment provides a kind of WO x/ ZrO xsolar selectively absorbing coating, this coating comprises three coatings, is divided into ground floor infrared reflecting layer, second layer absorbed layer, the 3rd layer of antireflection layer, and ground floor Cu film thickness is 170nm, and second layer gross thickness is 360nm, wherein the first subgrade WO x+ ZrO xfilm thickness is 200nm, the second subgrade WO x+ ZrO xfilm thickness is 160nm, ZrO in the first subgrade xpercent by volume be 60%, all the other are WO x; The second subgrade ZrO xpercent by volume be 40%, all the other are WO x; The 3rd layer of Zr O xfilm thickness is 120nm.Prepare above-mentioned WO x/ ZrO xthe method of solar selectively absorbing coating, comprises following step:
Step 1: prepare ground floor infrared emission layer on matrix;
Select the Cu target of purity 99.99%, base material uses high-speed steel.Before sputter, vacuum chamber is taken out to base vacuum to 4.5 × 10 in advance -3, passing into inert gas Ar as sputtering atmosphere, Ar throughput is 1300sccm, and adjusting sputter distance is 140mm, and regulating sputtering pressure is 2.0 × 10 -1pa.Open Cu target, adjustment sputtering voltage is 440V, and sputtering current is 10A, utilizes d.c. sputtering mode to prepare the Cu film that 150nm is thick;
Step 2: prepare second layer absorbed layer on ground floor infrared emission layer;
Adopt metal W target and Zr target medium frequency magnetron sputtering method, vacuum chamber is taken out to base vacuum to 4.5 × 10 in advance -3pa passes into Ar, O simultaneously 2gaseous mixture, the flow of Ar is 1300sccm, O 2flow be 125sccm, regulate sputtering pressure be 2.0 × 10 -1pa, opens respectively W and Zr target power supply, and adjusting W target sputtering current is 60A, and voltage is 735V, and Zr target sputtering current is 28A, and voltage is 800V, prepares the first subgrade WO that 150nm is thick on Cu film x+ ZrO xfilm;
Adjust O 2flow be 160sccm, regulating W target sputtering current is 40A, continues to prepare the second subgrade WO that thickness is 60nm x+ ZrO xfilm;
Step 3: prepare the 3rd layer of antireflection layer on the second layer;
Select the Zr target of purity 99.99%, before sputter, vacuum chamber is taken out to base vacuum to 4.5 × 10 in advance -3pa passes into Ar, O simultaneously 2gaseous mixture, regulates Ar and O 2flow-rate ratio is 2:1, and adjusting sputter distance is 140mm, and regulating sputtering pressure is 6.0 × 10 -1pa, when sputter, adjustment sputtering current is 30A, sputtering voltage is 750V, utilizes medium frequency magnetron sputtering mode to prepare the thick Zr O of 120nm xfilm.
Step 4: Coatings in Vacuum annealing in process
The thermal-collecting tube that is coated with coating for selective absorption is carried out to the heat treatment of vacuum after annealing, and wherein, vacuum is 4 × 10 -3pa, annealing temperature is 600 DEG C, annealing time is 5h.
The performance of solar selectively absorbing coating prepared by the present embodiment is as follows: under air quality factors A M1.5 condition, coating absorptivity is 96.3%, and normal emittance is 0.04.Carry out vacuum annealing processing, 5 × 10 -3under Pa vacuum, through 550 DEG C of vacuum annealings, after 2 hours, coating absorptivity is 97.2%, and normal emittance is 0.05,5 × 10 -3under Pa vacuum, through 600 DEG C of vacuum annealings, after 2 hours, coating absorptivity is 97.7%, and normal emittance is 0.04.Under atmospheric conditions, through 350 DEG C of insulations, after 2 hours, coating absorptivity is 97.5%, and normal emittance is 0.04; Under atmospheric conditions, through 400 DEG C of insulations, after 2 hours, coating absorptivity is 97.0%, and normal emittance is 0.05.
embodiment 2:
The present embodiment provides a kind of WO x/ ZrO xsolar selectively absorbing coating, this coating comprises three coatings, is divided into ground floor infrared reflecting layer, second layer absorbed layer, the 3rd layer of antireflection layer, and ground floor Cu film thickness is 140nm, and second layer gross thickness is 300nm, wherein the first subgrade WO x+ ZrO xfilm thickness is 150nm, the second subgrade WO x+ ZrO xfilm thickness is 150nm, ZrO in the first subgrade xpercent by volume be 55%, all the other are WO x; The second subgrade ZrO 2percent by volume be 35%, all the other are WO x; The 3rd layer of Zr O 2film thickness is 150nm.Prepare above-mentioned WO x/ ZrO xthe method of solar selectively absorbing coating, comprises following step:
Step 1: prepare ground floor infrared emission layer on matrix;
Select the Cu target of purity 99.99%, base material uses high-speed steel.Before sputter, vacuum chamber is taken out to base vacuum to 4.5 × 10 in advance -3, passing into inert gas Ar as sputtering atmosphere, Ar throughput is 1400sccm, and adjusting sputter distance is 130mm, and regulating sputtering pressure is 3.0 × 10 -1pa.Open Cu target, adjustment sputtering voltage is 400V, and sputtering current is 10A, utilizes d.c. sputtering mode to prepare the Cu film that 140nm is thick;
Step 2: prepare second layer absorbed layer on ground floor infrared emission layer;
Adopt metal W target and Zr target medium frequency magnetron sputtering method, vacuum chamber is taken out to base vacuum to 4.0 × 10 in advance -3pa passes into Ar, O simultaneously 2gaseous mixture, the flow of Ar is 1300sccm, O 2flow be 120sccm, regulate sputtering pressure be 2.0 × 10 -1pa, opens respectively W and Zr target power supply, and adjusting W target sputtering current is 65A, and voltage is 750V, and Zr target sputtering current is 25A, and voltage is 770V, prepares the first subgrade WO that 150nm is thick on Cu film x+ ZrO xfilm;
Adjust O 2flow be 140sccm, regulating W target sputtering current is 45A, continues to prepare the second subgrade WO that thickness is 100nm x+ ZrO xfilm;
Step 3: prepare the 3rd layer of antireflection layer on the second layer;
Select the Zr target of purity 99.99%, before sputter, vacuum chamber is taken out to base vacuum to 4.0 × 10 in advance -3pa passes into Ar, O simultaneously 2gaseous mixture, regulates Ar and O 2flow-rate ratio is 2:1, and adjusting sputter distance is 130mm, and regulating sputtering pressure is 6.0 × 10 -1pa, when sputter, adjustment sputtering current is 30A, sputtering voltage is 720V, utilizes medium frequency magnetron sputtering mode to prepare the thick Zr O of 150nm 2film.
Step 4: Coatings in Vacuum annealing in process
The thermal-collecting tube that is coated with coating for selective absorption is carried out to the heat treatment of vacuum after annealing, and wherein, vacuum is 3.0 × 10 -3, annealing temperature is 650 DEG C, annealing time is 3h.
embodiment 3:
The present embodiment provides a kind of WO x/ ZrO xsolar selectively absorbing coating, this coating comprises three coatings, is divided into ground floor infrared reflecting layer, second layer absorbed layer, the 3rd layer of antireflection layer, and ground floor Cu film thickness is 240nm, and second layer gross thickness is 600nm, wherein the first subgrade WO x+ ZrO xfilm thickness is 300nm, the second subgrade WO x+ ZrO xfilm thickness is 300nm, ZrO in the first subgrade 2percent by volume be 70%, all the other are WO x; The second subgrade ZrO xpercent by volume be 50%, all the other are WO x; The 3rd layer of Zr O xfilm thickness is 200nm.Prepare above-mentioned WO x/ ZrO xthe method of solar selectively absorbing coating, comprises following step:
Step 1: prepare ground floor infrared emission layer on matrix;
Select the Cu target of purity 99.99%, base material uses high-speed steel.Before sputter, vacuum chamber is taken out to base vacuum to 4.0 × 10 in advance -3, passing into inert gas Ar as sputtering atmosphere, Ar throughput is 1300sccm, and adjusting sputter distance is 130mm, and regulating sputtering pressure is 3.0 × 10 -1pa.Open Cu target, adjustment sputtering voltage is 400V, and sputtering current is 10A, utilizes d.c. sputtering mode to prepare the Cu film that 140nm is thick;
Step 2: prepare second layer absorbed layer on ground floor infrared emission layer;
Adopt metal W target and Zr target medium frequency magnetron sputtering method, vacuum chamber is taken out to base vacuum to 4.0 × 10 in advance -3pa passes into Ar, O simultaneously 2gaseous mixture, the flow of Ar is 1300sccm, O 2flow be 135sccm, regulate sputtering pressure be 2.0 × 10 -1pa, opens respectively W and Zr target power supply, and adjusting W target sputtering current is 65A, and voltage is 750V, and Zr target sputtering current is 24A, and voltage is 760V, prepares the first subgrade WO that 150nm is thick on Cu film x+ ZrO xfilm;
Adjust O 2flow be 190sccm, regulating W target sputtering current is 45A, continues to prepare the second subgrade WO that thickness is 100nm x+ ZrO xfilm;
Step 3: prepare the 3rd layer of antireflection layer on the second layer;
Select the Zr target of purity 99.99%, before sputter, vacuum chamber is taken out to base vacuum to 4.0 × 10 in advance -3pa passes into Ar, O simultaneously 2gaseous mixture, regulates Ar and O 2flow-rate ratio is 2:1, and adjusting sputter distance is 130mm, and regulating sputtering pressure is 6.0 × 10 -1pa, when sputter, adjustment sputtering current is 30A, sputtering voltage is 720V, utilizes medium frequency magnetron sputtering mode to prepare the thick Zr O of 200nm xfilm.
Step 4: Coatings in Vacuum annealing in process
The thermal-collecting tube that is coated with coating for selective absorption is carried out to the heat treatment of vacuum after annealing, and wherein, vacuum is 3.0 × 10 -3, annealing temperature is 650 DEG C, annealing time is 3h.
The performance of solar selectively absorbing coating prepared by the present embodiment is as follows: under air quality factors A M1.5 condition, coating absorptivity is 96.5%, and normal emittance is 0.03.Carry out vacuum annealing processing, 5 × 10 -3under Pa vacuum, through 550 DEG C of vacuum annealings, after 2 hours, coating absorptivity is 97.1%, and normal emittance is 0.04,5 × 10 -3under Pa vacuum, through 600 DEG C of vacuum annealings, after 2 hours, coating absorptivity is 97.9%, and normal emittance is 0.04.

Claims (2)

1. a WO x/ ZrO xhigh temperature solar energy selective absorption coating, comprises trilamellar membrane, is followed successively by infrared reflecting layer, absorbed layer and antireflection layer from bottom to surface; Ground floor infrared reflecting layer is Cu or Ag film, is positioned at matrix surface, and thickness is 100～300nm; Second layer absorbed layer comprises two sublayer structures, and two subgrades are WO x+ ZrO xfilm, the thickness of the first subgrade and the second subgrade is 150～300nm, ZrO in the first subgrade xaccounting for percent by volume is 50～75%, and all the other are WO x, the second subgrade ZrO xpercent by volume be 30～50%, all the other are WO x, wherein the first subgrade is adjacent with ground floor infrared reflecting layer, and the second subgrade is adjacent with the 3rd layer of antireflection layer; The 3rd layer of antireflection layer is ZrO xfilm, thickness is 120～200nm.
2. a WO x/ ZrO xthe preparation method of high temperature solar energy selective absorption coating, comprises following step:
Step 1: prepare ground floor infrared emission layer on matrix;
Adopt simple metal target direct current or medium frequency magnetron sputtering method, simple metal target is Cu target or Ag target, prepares as sputter gas using Ar gas, and matrix adopting high-speed steel, is evacuated to 4.0 × 10 in advance by vacuum chamber base vacuum before sputter -3～5.0 × 10 -3pa, passes into inert gas Ar gas as sputtering atmosphere, and Ar throughput is 1000～1400sccm, and adjusting sputter distance is 130～150mm, and regulating sputtering pressure is 2 × 10 -1～4 × 10 -1pa, the sputtering target power supply of unlatching simple metal target, adjustment sputtering voltage is 380～450V, and sputtering current is 45～65A, utilizes magnetically controlled DC sputtering mode to prepare, and splash coating thickness is 100～300nm, obtains ground floor infrared emission layer;
Step 2: prepare second layer absorbed layer on ground floor infrared emission layer;
Adopt medium frequency magnetron sputtering method, taking metal W target and Zr target as sputtering target material, first vacuum chamber is taken out to base vacuum to 4 × 10 in advance -3～5 × 10 -3pa, then passes into Ar, O 2gaseous mixture, the flow of Ar is 800～1400sccm, O 2flow be 120～150sccm, regulate sputtering pressure be 2 × 10 -1～4 × 10 -1pa, opens respectively W and Zr target power supply, and when sputter, adjusting W target sputtering voltage is 600～750V, and sputtering current is 50～60A, and Zr target sputtering voltage is 650～800V, and sputtering current is 20～30A, prepares the first subgrade WO on ground floor infrared reflecting layer x+ ZrO xfilm, thickness is 150～200nm;
Adjust sputtering pressure to 4 × 10 -1～6 × 10 -1pa, increases O 2flow be 150～190sccm, regulating W target sputtering current is 40～50A, other parameters are constant, at the first subgrade WO x+ ZrO xon film, continue sputter and obtain the second subgrade WO x+ ZrO xfilm, thickness is 150～200nm;
Step 3: prepare the 3rd layer of antireflection layer on second layer absorbed layer;
Adopt Zr target as sputtering target material, before sputter, vacuum chamber is taken out to base vacuum to 4 × 10 in advance -3～5 × 10 -3pa, using Ar gas as sputter gas, O 2as reacting gas, O 2flow is 300～400sccm, regulates Ar and O 2flow-rate ratio is 2.5:1～4:1, and regulating sputtering pressure is 4 × 10 -1～6 × 10 -1pa, when sputter, adjustment sputtering voltage is 300～400V, sputtering current is 25～30A, utilizes medium frequency magnetron sputtering mode to obtain the ZrO that thickness is 50～150nm xfilm, i.e. the 3rd layer of antireflection layer;
Step 4: Coatings in Vacuum annealing in process
The thermal-collecting tube that is coated with coating for selective absorption is carried out to the heat treatment of vacuum after annealing, and wherein, vacuum is 3.0 × 10 -3～5 × 10 -3pa, annealing temperature is 400 DEG C～650 DEG C, annealing time is 2～5h.
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CN107270564A (en) * 2016-04-07 2017-10-20 北京有色金属研究总院 A kind of sunlight heat absorber coatings
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