CN102689467A - A high temperature solar power selective absorption coating with a Si3N4 and AlN double ceramic structure and a preparation method thereof - Google Patents

A high temperature solar power selective absorption coating with a Si3N4 and AlN double ceramic structure and a preparation method thereof Download PDF

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CN102689467A
CN102689467A CN2012101624681A CN201210162468A CN102689467A CN 102689467 A CN102689467 A CN 102689467A CN 2012101624681 A CN2012101624681 A CN 2012101624681A CN 201210162468 A CN201210162468 A CN 201210162468A CN 102689467 A CN102689467 A CN 102689467A
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layer
sputtering
subgrade
target
aln
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张秀廷
陈步亮
范兵
刘雪莲
王静
杨兴
张晋
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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 provides a high temperature solar power selective absorption coating with a Si3N4 and AlN double ceramic structure and a preparation method thereof, belonging to a technology field of solar power utilization. An infrared emission layer, an absorbing layer, an antireflection layer are arranged in sequence from a bottom layer of the coating to a surface layer, wherein the first infrared emission layer consists of a Cu film or an Ag film, with a thickness ranging from 50 to 150 nm, the second layer absorbing layer includes a two-sublayer structure with both sublayers being an Si3N4 and AIN film, and the third antireflection layer is a SiO2 film with a thickness being 20 to 60 nm. The coating provided in the invention is characterized by a high absorption rate within a visible-infrared spectrum and a low emission rate within an infrared spectrum. The coating has favorable middle-and-high temperature heat stability by adopting an interference absorbing layer of the double ceramic structure. The coating has advantages of simply preparation technique, easy operation, easy control, and shortened production cycle.

Description

A kind of have a Si 3N 4With two ceramic structure high temperature solar energy selective absorption coatings of AlN and preparation method thereof
Technical field
The invention belongs to technical field of solar utilization technique, be specifically related to a kind of Si of having 3N 4With two ceramic structure high temperature solar energy selective absorption coatings of AlN 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 to be used for solar thermal collector, improves the key of photo-thermal conversion efficiency.Along with of the continuous development of solar thermal utilization demand with technology; The range of application of solar energy heat collection pipe is used (100 ℃-350 ℃) and high temperature application (350 ℃-500 ℃) development from cryogenic applications (≤100 ℃) Xiang Zhongwen, constantly to satisfy the instructions for use of high-temperature applications in desalinization, 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.
For films such as SS-C/SS (stainless steel) and the Al-N/Al system that solar selectively absorbing coating had been studied and had been widely used black chromium, anode oxidation coloration Ni-Al2O3 at present and had composition gradual change characteristic, be applied to temperature on 200 ℃ of thermal-collecting tubes surfaces 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 heat loss obviously to rise, the thermal efficiency significantly descends.
Heat endurance for coating for selective absorption under the high temperature service condition in improving; 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 subgrades structures that the Mo-Al2O3 absorbed layer has the composition gradual change, and the Al2O3 layer adopts RF sputtering method; The characteristics of SS-AlN/SS system are that absorbed layer has adopted the inteferometer coating structure, and heat endurance 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 serviceability temperature.But process deposits speed such as two targets or many target co-sputterings, radio-frequency sputtering are low, and the production cycle is long, complex process, and cost is high.
For the middle high temperature utilization of solar energy, need a kind of absorptivity height, low, the Heat stability is good of emissivity, and easy coating for selective absorption and the technology of preparing of technology.
Summary of the invention
To the objective of the invention is the problem that exists in the prior art in order solving, to propose a kind of Si that has 3N 4With two ceramic structure high temperature solar energy selective absorption coatings of AlN and preparation method thereof, be applicable to high temperature (300 ℃-500 ℃) operating temperature thermal-collecting tube, the coating absorptivity is high, low, the Heat stability is good of emissivity; Preparation technology is easy; Easy to operate, with short production cycle, the sputter operating mode is stable.
The present invention provides a kind of Si of having 3N 4With the two ceramic structure high temperature solar energy selective absorption coatings of AlN, comprise trilamellar membrane, from the bottom to the surface, be followed successively by infrared emission layer, absorbed layer and antireflection layer;
Ground floor infrared emission layer is made up of Cu film or Ag film, is positioned at matrix surface, and thickness is at 50~250nm; Second layer absorbed layer comprises two subgrade structures, and two subgrades are Si 3N 4With the AlN film, the thickness of first subgrade and second subgrade is 50~100nm; Si in first subgrade 3N 4Percent by volume be 20 ~ 40%, all the other are AlN; The second subgrade Si 3N 4Percent by volume be 10 ~ 30% all the other be AlN; First subgrade is positioned on the ground floor infrared emission layer, and second subgrade is positioned on first subgrade; The 3rd layer of antireflection layer is by SiO 2Film, thickness are 20~60nm.
The present invention provides a kind of Si of having 3N 4Preparation method with the two ceramic structure high temperature solar energy selective absorption coatings of AlN comprises following step:
Step 1: preparation ground floor infrared emission layer on matrix;
Adopt simple metal target direct current or medium frequency magnetron sputtering method, the simple metal target is Cu target or Ag target, prepares as sputter gas with Ar gas, and the matrix adopting high-speed steel is taken out base vacuum to 4 * 10 with vacuum chamber before the sputter in advance -3~ 5 * 10 -3Pa feeds inert gas Ar as sputtering atmosphere, and the Ar throughput is 100 ~ 140sccm, and adjustment sputter distance is 130 ~ 150mm, and regulating sputtering pressure is 3 * 10 -1~ 4 * 10 -1Pa, the sputtering target power supply of unlatching simple metal target, the adjustment sputtering voltage is 380 ~ 450V, and sputtering current is 8 ~ 10A, and obtaining thickness is the ground floor infrared emission layer of 50~250nm;
Step 2: preparation second layer absorbed layer on ground floor infrared emission layer;
Adopt Si target and Al target medium frequency magnetron sputtering method, reacting gas is N 2, vacuum chamber is taken out base vacuum to 4 * 10 in advance -3~ 5 * 10 -3Pa feeds Ar and N then 2Gaseous mixture, the flow of Ar is 100 ~ 140sccm, N 2Flow be 5 ~ 20sccm, regulating sputtering pressure is 3 * 10 -1~ 4 * 10 -1Pa opens Si and Al target power supply respectively, and during sputter, adjustment Si target sputtering voltage is 640 ~ 750V, and sputtering current is 6 ~ 8A, and Al target sputtering voltage is 540 ~ 600V, and sputtering current is 6 ~ 8A, and preparation thickness is the first subgrade Si of 50~100nm 3N 4+ AlN film;
Reducing Si target sputtering current is 4 ~ 6A, and other each parameter constants continue the preparation second subgrade Si 3N 4+ AlN film, thickness are 50~100nm;
Step 3: the 3rd layer of antireflection layer of preparation on second layer absorbed layer;
Before adopting the sputter of Si target vacuum chamber is taken out base vacuum to 4 * 10 in advance -3~ 5 * 10 -3Pa feeds inert gas Ar as sputter gas, feeds O 2As reacting gas preparation, O 2Flow be 20 ~ 40sccm, regulate Ar and O 2Flow-rate ratio is 1.5:1 ~ 3:1, and adjustment sputter distance is 130 ~ 150mm, and regulating sputtering pressure is 3 * 10 -1~ 4 * 10 -1Pa, during sputter, the adjustment sputtering voltage is 750 ~ 800V, and sputtering current is 8 ~ 10A, and preparing thickness is the 3rd layer of antireflection layer of 20~60nm.
The invention has the advantages that:
A kind of Si that has provided by the present invention 3N 4With the two ceramic structure high temperature solar energy selective absorption coatings of AlN by infrared emission layer, Si 3N 4Interfere absorbed layer and ceramic antireflection layer to be formed with two potteries that the AlN film is formed, have visible-infrared spectrum high-absorbility, the characteristics of infrared spectrum low-launch-rate, and, have good middle high high-temp stability owing to adopt the interference absorbed layer of two ceramic structures.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 emission layer, Nb and Al 2O 3Two absorbed layers and Al of interfering of forming of mixture 2O 3Antireflection layer is compared, and the raw material SiAl that this coating is selected is a conventional material, and range of application is wider, and processability is good, can be processed into the column target, significantly improves target utilization, and price is also cheaper simultaneously, can further reduce job costs.The solar energy heat collection pipe of hot operation temperature in being applicable to.
Description of drawings
Fig. 1: the present invention proposes a kind ofly has a Si 3N 4With the two ceramic structure high temperature solar energy selective absorption coating generalized sections of AlN;
Fig. 2: the present invention proposes a kind ofly has a Si 3N 4Schematic flow sheet with the preparation method of the two ceramic structure high temperature solar energy selective absorption coatings of AlN.
The specific embodiment
To combine accompanying drawing and embodiment that the present invention is done further detailed description below.
The present invention is a kind of Si of having 3N 4With the two ceramic structure high temperature solar energy selective absorption coatings of AlN, as shown in Figure 1 in conjunction with section, coating comprises trilamellar membrane, from the bottom to the surface, is followed successively by infrared emission layer, absorbed layer and antireflection layer;
Ground floor infrared emission layer is made up of Cu film or Ag film, is positioned at matrix surface, and thickness is at 50~250nm; Second layer absorbed layer comprises two subgrade structures, and two subgrades are Si 3N 4With the AlN film, the thickness of first subgrade and second subgrade is 50~100nm, and the thickness of first subgrade and second subgrade can equate also can be unequal; Si in first subgrade 3N 4Percent by volume be 20 ~ 40%, all the other are AlN; The second subgrade Si 3N 4Percent by volume be 10 ~ 30% all the other be AlN; First subgrade is positioned on the ground floor infrared emission layer, and second subgrade is positioned on first subgrade; The 3rd layer of antireflection layer is by SiO 2Film is formed, and thickness is 20~60nm; Be positioned on second subgrade of second layer absorbed layer.
The present invention proposes a kind ofly has a Si 3N 4With the preparation method of the two ceramic structure high temperature solar energy selective absorption coatings of AlN, as shown in Figure 2, comprise following step:
Step 1: preparation ground floor infrared emission layer on matrix;
Adopt simple metal target direct current or medium frequency magnetron sputtering method, the simple metal target is Cu target or Ag target (purity 99.99%), prepares the matrix adopting high-speed 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 feeds inert gas Ar as sputtering atmosphere, and the Ar throughput is 100 ~ 140sccm, and adjustment sputter distance is 130 ~ 150mm, and regulating sputtering pressure is 3 * 10 -1~ 4 * 10 -1Pa.Open the sputtering target power supply of simple metal target, the adjustment sputtering voltage is 380 ~ 450V, and sputtering current is 8 ~ 10A; Utilize the d.c. sputtering mode to prepare, coating layer thickness obtains ground floor infrared emission layer at 50~250nm; This layer has high reflection characteristic to infrared band spectrum, and emissivity is low;
Step 2: preparation second layer absorbed layer on ground floor infrared emission layer;
Adopt Si target (purity 99.99%) and Al target (purity 99.99%) medium frequency magnetron sputtering method, reacting gas is N 2, at first, vacuum chamber is taken out base vacuum to 4 * 10 in advance -3~ 5 * 10 -3Pa feeds Ar and N simultaneously then 2Gaseous mixture, the flow of Ar is 100 ~ 140sccm, N 2Flow be 5 ~ 20sccm, regulating sputtering pressure is 3 * 10 -1~ 4 * 10 -1Pa opens Si and Al target power supply respectively, and during sputter, adjustment Si target sputtering voltage is 640 ~ 750V, and sputtering current is 6 ~ 8A, and Al target sputtering voltage is 540 ~ 600V, and sputtering current is 6 ~ 8A, and preparation thickness is 50~100nm, the first subgrade Si 3N 4With the AlN film;
Reducing Si target sputtering current is 4 ~ 6A, and other each parameter constants continue the preparation second subgrade Si 3N 4+ AlN film, thickness are 50~100nm; First subgrade and second subgrade possess the intrinsic absorption characteristic solar spectrum except that self, also form and interfere sink effect, have strengthened the optical absorption of coating;
Step 3: the 3rd layer of antireflection layer of preparation on second layer absorbed layer;
The 3rd layer of antireflection layer is by SiO 2Film constitutes; 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 feeds inert gas Ar as sputter gas, feeds O 2As reacting gas preparation, O 2Flow be 20 ~ 40sccm, regulate Ar and O 2Flow-rate ratio is 1.5:1 ~ 3:1, and adjustment sputter distance is 130 ~ 150mm, and regulating sputtering pressure is 3 * 10 -1~ 4 * 10 -1Pa.During sputter, the adjustment sputtering voltage is 750 ~ 800V, and sputtering current is 8 ~ 10A, utilizes the medium frequency magnetron sputtering mode to prepare the SiO that thickness is 20~60nm 2Film is the 3rd layer of antireflection layer.Anti-reflection, wear-resisting, oxidation resistant effect that antireflection layer has.
The performance of solar selectively absorbing coating provided by the invention is: under air quality factors A M 1.5 conditions, the coating absorptivity is 96.0%, and normal emittance is 0.06.Carry out vacuum annealing and handle, 2 * 10 -2Under the Pa vacuum, after 1 hour, the coating absorptivity is 96.0% through 350 ℃ of vacuum annealings, and normal emittance is 0.06,2 * 10 -2Under the Pa vacuum, after 1 hour, the coating absorptivity is 95.8% through 500 ℃ of vacuum annealings, and normal emittance is 0.06.
Embodiment 1:
Present embodiment provides a kind of Si of having 3N 4With the two ceramic structure high temperature solar energy selective absorption coatings of AlN; Comprise that three coatings are ground floor infrared emission layer, second layer absorbed layer, the 3rd layer of antireflection layer, ground floor is the Cu film, and thickness is 180nm; Second layer gross thickness is 160nm; Wherein the first subgrade thickness is 100nm, and the second subgrade thickness is 60nm, Si in first subgrade 3N 4Percent by volume be 25%, all the other are AlN; The second subgrade Si 3N 4Percent by volume be 15% all the other be AlN; The 3rd layer is the AlN film, and thickness is 50nm.Preparation process is following:
Step 1: preparation ground floor infrared emission layer on matrix;
Selecting purity and purity for use is 99.99% Cu target, and base material uses high-speed steel.Before the sputter vacuum chamber is taken out base vacuum to 4.5 * 10 in advance -3Pa feeds inert gas Ar as sputtering atmosphere, and the Ar throughput is 120sccm, and adjustment sputter distance is 140mm, 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 magnetically controlled DC sputtering mode to prepare the thick Cu film of 180nm;
Step 2: preparation second layer absorbed layer on ground floor infrared emission layer;
Adopt Si target and Al target medium frequency magnetron sputtering method, vacuum chamber is taken out base vacuum to 4 * 10 in advance -3Pa feeds Ar and N simultaneously 2Gaseous mixture, the flow of Ar is 120sccm, N 2Flow be 20sccm, regulating sputtering pressure is 3.5 * 10 -1Pa opens Si and Al target power supply respectively, and adjustment Si target sputtering voltage is 700V, and sputtering current is 8A, and Al target sputtering voltage is 600V, and sputtering current is 8A, the first thick subgrade Si of preparation 100nm on the Cu film 3N 4With the AlN film;
Al target sputter sputtering current is constant, and Si target sputter sputtering current is 6A, and continuing preparation thickness is the second subgrade Si of 60nm 3N 4With the AlN film;
Step 3: the 3rd layer of antireflection layer of preparation on second layer absorbed layer;
Select the Si target of purity 99.99% for use, before the sputter vacuum chamber is taken out base vacuum to 5 * 10 in advance -3Pa feeds Ar, O simultaneously 2Gaseous mixture is regulated Ar and O 2Flow-rate ratio is 3:1, O 2Flow be 25sccm, adjustment sputter distance be 145mm, the adjusting sputtering pressure is 4 * 10 -1Pa, during sputter, the adjustment sputtering current is 8.3A, sputtering voltage is 700V, utilizes the medium frequency magnetron sputtering mode to prepare the thick SiO of 50nm 2Film.
The performance of the solar selectively absorbing coating of present embodiment preparation is following: under air quality factors A M1.5 condition, the coating absorptivity is 96.0%, and normal emittance is 0.06.Carry out vacuum annealing and handle, 2 * 10 -2Under the Pa vacuum, after 1 hour, the coating absorptivity is 96.0% through 350 ℃ of vacuum annealings, and normal emittance is 0.06,2 * 10 -2Under the Pa vacuum, after 1 hour, the coating absorptivity is 95.8% through 500 ℃ of vacuum annealings, and normal emittance is 0.06.
Embodiment 2:
Present embodiment provides a kind of Si of having 3N 4With the two ceramic structure high temperature solar energy selective absorption coatings of AlN, coating comprises trilamellar membrane, from the bottom to the surface, is followed successively by infrared emission layer, absorbed layer and antireflection layer;
Ground floor infrared emission layer is made up of the Cu film, and thickness is at 50nm; Second layer absorbed layer comprises two subgrade structures, and two subgrades are Si 3N 4With the AlN film, the thickness of first subgrade and second subgrade is 50nm, Si in first subgrade 3N 4Percent by volume be 20%, all the other are AlN; The second subgrade Si 3N 4Percent by volume be 10%, all the other are AlN; The 3rd layer of antireflection layer is by SiO 2Film, thickness are 20nm.
Present embodiment proposes a kind ofly has a Si 3N 4Preparation method with the two ceramic structure high temperature solar energy selective absorption coatings of AlN comprises following step:
Step 1: preparation ground floor infrared emission layer on matrix;
Adopt simple metal target direct current or medium frequency magnetron sputtering method, the simple metal target is Cu target (purity 99.99%), prepares the matrix adopting high-speed steel as sputter gas with Ar gas.Before the sputter vacuum chamber is taken out base vacuum to 4 * 10 in advance -3Pa feeds inert gas Ar as sputtering atmosphere, and the Ar throughput is 100sccm, and adjustment sputter distance is 130mm, and regulating sputtering pressure is 3 * 10 -1Pa.Open the sputtering target power supply of simple metal target, the adjustment sputtering voltage is 380V, and sputtering current is 8A, utilizes the d.c. sputtering mode to prepare, and coating layer thickness obtains ground floor infrared emission layer at 50nm, and this layer has high reflection characteristic to infrared band spectrum, and emissivity is low;
Step 2: preparation second layer absorbed layer on ground floor infrared emission layer;
Adopt Si target (purity 99.99%) and Al target (purity 99.99%) medium frequency magnetron sputtering method, reacting gas is N 2, at first, vacuum chamber is taken out base vacuum to 4 * 10 in advance -3Pa feeds Ar and N simultaneously then 2Gaseous mixture, the flow of Ar is 100sccm, N 2Flow be 10sccm, regulating sputtering pressure is 3 * 10 -1Pa opens Si and Al target power supply respectively, and during sputter, adjustment Si target sputtering voltage is 650V, and sputtering current is 6A, and Al target sputtering voltage is 540V, and sputtering current is 6A, and preparation thickness is the first subgrade Si of 50nm 3N 4+ AlN film;
Reducing Si target sputtering current is 4A, and other each parameter constants continue the preparation second subgrade Si 3N 4+ AlN film, thickness are 50nm; First subgrade and second subgrade possess the intrinsic absorption characteristic solar spectrum except that self, also form and interfere sink effect, have strengthened the optical absorption of coating;
Step 3: the 3rd layer of antireflection layer of preparation on second layer absorbed layer;
The 3rd layer of antireflection layer is by SiO 2Film constitutes; Adopt Si target (purity 99.99%), before the sputter vacuum chamber is taken out base vacuum to 4 * 10 in advance -3Pa feeds inert gas Ar as sputter gas, feeds O 2As reacting gas preparation, O 2Flow be 20sccm, regulate Ar and O 2Flow-rate ratio is 1.5:1, and adjustment sputter distance is 130mm, and regulating sputtering pressure is 3 * 10 -1Pa.During sputter, the adjustment sputtering voltage is 750V, and sputtering current is 8A, utilizes the medium frequency magnetron sputtering mode to prepare the SiO of thickness for 20nm 2Film is the 3rd layer of antireflection layer.Anti-reflection, wear-resisting, oxidation resistant effect that antireflection layer has.
Embodiment 3:
Present embodiment proposes a kind of Si that has 3N 4The two ceramic structure high temperature solar energy selective absorption coatings of+AlN, coating comprises trilamellar membrane, from the bottom to the surface, is followed successively by infrared emission layer, absorbed layer and antireflection layer;
Ground floor infrared emission layer is made up of the Cu film, and thickness is at 250nm; Second layer absorbed layer comprises two subgrade structures, and two subgrades are Si 3N 4+ AlN film, the thickness of first subgrade and second subgrade is 100nm, Si in first subgrade 3N 4+ percent by volume be 40%, all the other are AlN; The second subgrade Si 3N 4Percent by volume be 30%, all the other are AlN; The 3rd layer of antireflection layer is by SiO 2Film, thickness are 60nm.
Present embodiment proposes a kind ofly has a Si 3N 4The preparation method of the two ceramic structure high temperature solar energy selective absorption coatings of+AlN comprises following step:
Step 1: preparation ground floor infrared emission layer on matrix;
Adopt simple metal target direct current or medium frequency magnetron sputtering method, the simple metal target is Cu target (purity 99.99%), prepares the matrix adopting high-speed steel as sputter gas with Ar gas.Before the sputter vacuum chamber is taken out base vacuum to 5 * 10 in advance -3Pa feeds inert gas Ar as sputtering atmosphere, and the Ar throughput is 140sccm, and adjustment sputter distance is 150mm, and regulating sputtering pressure is 4 * 10 -1Pa.Open the sputtering target power supply of simple metal target, the adjustment sputtering voltage is 450V, and sputtering current is 10A, utilizes the d.c. sputtering mode to prepare, and coating layer thickness obtains ground floor infrared emission layer at 250nm, and this layer has high reflection characteristic to infrared band spectrum, and emissivity is low;
Step 2: preparation second layer absorbed layer on ground floor infrared emission layer;
Adopt Si target (purity 99.99%) and Al target (purity 99.99%) medium frequency magnetron sputtering method, reacting gas is N 2, at first, vacuum chamber is taken out base vacuum to 5 * 10 in advance -3Pa feeds Ar and N simultaneously then 2Gaseous mixture, the flow of Ar is 140sccm, N 2Flow be 15sccm, regulating sputtering pressure is 4 * 10 -1Pa opens Si and Al target power supply respectively, and during sputter, adjustment Si target sputtering voltage is 750V, and sputtering current is 8A, and Al target sputtering voltage is 540V, and sputtering current is 6A, and preparation thickness is the first subgrade Si of 100nm 3N 4+ AlN film;
Reducing Si target sputtering current is 4A, and other each parameter constants continue the preparation second subgrade Si 3N 4+ AlN film, thickness are 100nm; First subgrade and second subgrade possess the intrinsic absorption characteristic solar spectrum except that self, also form and interfere sink effect, have strengthened the optical absorption of coating;
Step 3: the 3rd layer of antireflection layer of preparation on second layer absorbed layer;
The 3rd layer of antireflection layer is by SiO 2Film constitutes; Adopt Si target (purity 99.99%), before the sputter vacuum chamber is taken out base vacuum to 5 * 10 in advance -3Pa feeds inert gas Ar as sputter gas, feeds O 2As reacting gas preparation, O 2Flow be 30sccm, regulate Ar and O 2Flow-rate ratio is 2.5:1, and adjustment sputter distance is 150mm, and regulating sputtering pressure is 4 * 10 -1Pa.During sputter, the adjustment sputtering voltage is 800V, and sputtering current is 10A, utilizes the medium frequency magnetron sputtering mode to prepare the SiO of thickness for 60nm 2Film is the 3rd layer of antireflection layer.Anti-reflection, wear-resisting, oxidation resistant effect that antireflection layer has.
Embodiment 4:
Present embodiment provides a kind of Si of having 3N 4The two ceramic structure high temperature solar energy selective absorption coatings of+AlN, coating comprises trilamellar membrane, from the bottom to the surface, is followed successively by infrared emission layer, absorbed layer and antireflection layer;
Ground floor infrared emission layer is made up of the Ag film, and thickness is at 150nm; Second layer absorbed layer comprises two subgrade structures, and two subgrades are Si 3N 4+ AlN film, the thickness of first subgrade and second subgrade is 75nm, Si in first subgrade 3N 4Percent by volume be 30%, all the other are AlN; The second subgrade Si 3N 4Percent by volume be 20%, all the other are AlN; The 3rd layer of antireflection layer is by SiO 2Film, thickness are 40nm.
Present embodiment proposes a kind ofly has a Si 3N 4The preparation method of the two ceramic structure high temperature solar energy selective absorption coatings of+AlN comprises following step:
Step 1: preparation ground floor infrared emission layer on matrix;
Adopt simple metal target direct current or medium frequency magnetron sputtering method, the simple metal target is Ag target (purity 99.99%), prepares the matrix adopting high-speed steel as sputter gas with Ar gas.Before the sputter vacuum chamber is taken out base vacuum to 4.5 * 10 in advance -3Pa feeds inert gas Ar as sputtering atmosphere, and the Ar throughput is 120sccm, and adjustment sputter distance is 140mm, and regulating sputtering pressure is 3.5 * 10 -1Pa.Open the sputtering target power supply of simple metal target, the adjustment sputtering voltage is 420V, and sputtering current is 9A, utilizes the d.c. sputtering mode to prepare, and coating layer thickness obtains ground floor infrared emission layer at 150nm, and this layer has high reflection characteristic to infrared band spectrum, and emissivity is low;
Step 2: preparation second layer absorbed layer on ground floor infrared emission layer;
Adopt Si target (purity 99.99%) and Al target (purity 99.99%) medium frequency magnetron sputtering method, reacting gas is N 2, at first, vacuum chamber is taken out base vacuum to 4.5 * 10 in advance -3Pa feeds Ar and N simultaneously then 2Gaseous mixture, the flow of Ar is 120sccm, N 2Flow be 12sccm, regulating sputtering pressure is 3.5 * 10 -1Pa opens Si and Al target power supply respectively, and during sputter, adjustment Si target sputtering voltage is 700V, and sputtering current is 7A, and Al target sputtering voltage is 570V, and sputtering current is 7A, and preparation thickness is the first subgrade Si of 75nm 3N 4+ AlN film;
Reducing Si target sputtering current is 4A, and other each parameter constants continue the preparation second subgrade Si 3N 4+ AlN film, thickness are 75nm; First subgrade and second subgrade possess the intrinsic absorption characteristic solar spectrum except that self, also form and interfere sink effect, have strengthened the optical absorption of coating;
Step 3: the 3rd layer of antireflection layer of preparation on second layer absorbed layer;
The 3rd layer of antireflection layer is by SiO 2Film constitutes; Adopt Si target (purity 99.99%), before the sputter vacuum chamber is taken out base vacuum to 4.5 * 10 in advance -3Pa feeds inert gas Ar as sputter gas, feeds O 2As reacting gas preparation, O 2Flow be 40sccm, regulate Ar and O 2Flow-rate ratio is 2:1, and adjustment sputter distance is 140mm, and regulating sputtering pressure is 3.5 * 10 -1Pa.During sputter, the adjustment sputtering voltage is 750V, and sputtering current is 9A, utilizes the medium frequency magnetron sputtering mode to prepare the SiO of thickness for 40nm 2Film is the 3rd layer of antireflection layer.Anti-reflection, wear-resisting, oxidation resistant effect that antireflection layer has.

Claims (6)

1. one kind has Si 3N 4With the two ceramic structure high temperature solar energy selective absorption coatings of AlN, it is characterized in that: described coating is followed successively by infrared emission layer, absorbed layer and antireflection layer from the bottom to the surface;
Ground floor infrared emission layer is made up of Cu film or Ag film, is positioned at matrix surface, and thickness is at 50~250nm; Second layer absorbed layer comprises two subgrade structures, and two subgrades are Si 3N 4With the AlN film, the thickness of first subgrade and second subgrade is 50~100nm; Si in first subgrade 3N 4Percent by volume be 20 ~ 40%, all the other are AlN; The second subgrade Si 3N 4Percent by volume be 10 ~ 30% all the other be AlN; First subgrade is positioned on the ground floor infrared emission layer, and second subgrade is positioned on first subgrade; The 3rd layer of antireflection layer is by SiO 2Film, thickness are 20~60nm.
2. a kind of Si that has according to claim 1 3N 4With the two ceramic structure high temperature solar energy selective absorption coatings of AlN, it is characterized in that: described coating is under air quality factors A M1.5 condition, and its absorptivity is 96.0%, and normal emittance is 0.06.
3. a kind of Si that has according to claim 1 3N 4With the two ceramic structure high temperature solar energy selective absorption coatings of AlN, it is characterized in that: described coating is 2 * 10 -2Under the Pa vacuum, after 1 hour, its absorptivity is 96.0% through 350 ℃ of vacuum annealings, and normal emittance is 0.06.
4. a kind of Si that has according to claim 1 3N 4With the two ceramic structure high temperature solar energy selective absorption coatings of AlN, it is characterized in that: described coating is 2 * 10 -2Under the Pa vacuum, after 1 hour, its absorptivity is 95.8% through 500 ℃ of vacuum annealings, and normal emittance is 0.06.
5. a kind of Si that has according to claim 1 3N 4With the two ceramic structure high temperature solar energy selective absorption coatings of AlN, it is characterized in that: the thickness of described first subgrade and second subgrade is for equating perhaps unequal.
6. one kind is applied to the described a kind of Si of having of claim 1 3N 4Preparation method with the two ceramic structure high temperature solar energy selective absorption coatings of AlN is characterized in that: comprise following step:
Step 1: preparation ground floor infrared emission layer on matrix;
Adopt simple metal target direct current or medium frequency magnetron sputtering method, the simple metal target is Cu target or Ag target, prepares as sputter gas with Ar gas, and the matrix adopting high-speed steel is taken out base vacuum to 4 * 10 with vacuum chamber before the sputter in advance -3~ 5 * 10 -3Pa feeds inert gas Ar as sputtering atmosphere, and the Ar throughput is 100 ~ 140sccm, and adjustment sputter distance is 130 ~ 150mm, and regulating sputtering pressure is 3 * 10 -1~ 4 * 10 -1Pa, the sputtering target power supply of unlatching simple metal target, the adjustment sputtering voltage is 380 ~ 450V, and sputtering current is 8 ~ 10A, and obtaining thickness is the ground floor infrared emission layer of 50~250nm;
Step 2: preparation second layer absorbed layer on ground floor infrared emission layer;
Adopt Si target and Al target medium frequency magnetron sputtering method, reacting gas is N 2, vacuum chamber is taken out base vacuum to 4 * 10 in advance -3~ 5 * 10 -3Pa feeds Ar and N then 2Gaseous mixture, the flow of Ar is 100 ~ 140sccm, N 2Flow be 5 ~ 20sccm, regulating sputtering pressure is 3 * 10 -1~ 4 * 10 -1Pa opens Si and Al target power supply respectively, and during sputter, adjustment Si target sputtering voltage is 640 ~ 750V, and sputtering current is 6 ~ 8A, and Al target sputtering voltage is 540 ~ 600V, and sputtering current is 6 ~ 8A, and preparation thickness is the first subgrade Si of 50~100nm 3N 4+ AlN film;
Reducing Si target sputtering current is 4 ~ 6A, and other each parameter constants continue the preparation second subgrade Si 3N 4+ AlN film, thickness are 50~100nm;
Step 3: the 3rd layer of antireflection layer of preparation on second layer absorbed layer;
Before adopting the sputter of Si target vacuum chamber is taken out base vacuum to 4 * 10 in advance -3~ 5 * 10 -3Pa feeds inert gas Ar as sputter gas, feeds O 2As reacting gas preparation, O 2Flow be 20 ~ 40sccm, regulate Ar and O 2Flow-rate ratio is 1.5:1 ~ 3:1, and adjustment sputter distance is 130 ~ 150mm, and regulating sputtering pressure is 3 * 10 -1~ 4 * 10 -1Pa, during sputter, the adjustment sputtering voltage is 750 ~ 800V, and sputtering current is 8 ~ 10A, and preparing thickness is the 3rd layer of antireflection layer of 20~60nm.
CN2012101624681A 2012-05-23 2012-05-23 A high temperature solar power selective absorption coating with a Si3N4 and AlN double ceramic structure and a preparation method thereof Pending CN102689467A (en)

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Application publication date: 20120926