CN103234292B - A kind of preparation method of film structure of solar energy optical-thermal switching film - Google Patents
A kind of preparation method of film structure of solar energy optical-thermal switching film Download PDFInfo
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- CN103234292B CN103234292B CN201310151258.7A CN201310151258A CN103234292B CN 103234292 B CN103234292 B CN 103234292B CN 201310151258 A CN201310151258 A CN 201310151258A CN 103234292 B CN103234292 B CN 103234292B
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Abstract
Provided by the present invention is a kind of preparation method of film structure of solar energy optical-thermal switching film; described film structure; it is the surface at metal film system base; Cu infrared external reflection rete, TiN thermal diffusion stop protective film from the inside to the outside successively; (Ti-Cr) NO selective absorption film of high tenor, (Ti-Cr) NO selective absorption film of low-metal content and containing a small amount of Al
2o
3siO
2antireflection film layer, has rational in infrastructure, and resistance to elevated temperatures is good; absorptivity is high; the features such as reflectivity is low, and weather resistance is good, and described preparation method is successively; the base pre-treatment of film system; be coated with Cu infrared external reflection rete, be coated with TiN thermal diffusion and stop protective film, be coated with (Ti-Cr) NO absorbing membranous layer of high tenor; be coated with (Ti-Cr) NO absorbing membranous layer of low-metal content, be coated with SiO
2-Al
2o
3antireflection film layer, have method reasonable, being coated with the features such as speed is high, coating quality is good, is a kind of preparation method being particularly suitable for industrialization continuous seepage flat-plate solar heat collector heat-collecting plate core plated film.
Description
Technical field
The present invention relates to a kind of preparation method of film structure of solar energy optical-thermal switching film, belong to Solar use equipment technology.
Background technology
In Solar use, solar energy optical-thermal conversion occupies extremely important proportion.In solar energy heat utilization, solar thermal collector is the important component of its photothermal deformation, and structure of solar selective absorbing film system and preparation method thereof, be then the core technology of solar thermal collector.
Study in the continuous practice of high-performance, high stable, long-life solar selective absorbing film system people, have employed the film structure of number of different types, such as semiconductor absorber one reflective metals tandem type film system, surface micro-not flat pattern film system and dielectric one metal composite film system etc., and its preparation method mainly contains electroplated metallization, electrochemical filming, vacuum coating and coating plated film etc.In the vacuum tube of social extensive use instantly and the film structure of flat-plate solar heat collector, its selective absorption film, adopts magnetron sputtering multilayer Al-N-Al coating mostly.This coating relies on multilayer absorbing membranous layer, improve its solar absorption ability, absorptivity is effectively promoted (reaching 92%), but be easy to the rising causing emissivity, especially, when temperature is higher, its emissivity raises with temperature and sharply raises, and the metal ingredient in rete easily spreads in high temperature, cause the aging of rete and come off, causing the loss of the heat collector thermal efficiency and the shortening in service life.
And domestic market upper flat plate heat collector development (overseas market occupation rate >=90% rapidly, domestic accounts for 10% but develops very fast), though it is fast that it has photothermal deformation, the thermal efficiency is high, the strong points such as daylighting area is large, but work because the film system layer of its heat-collecting plate core is in the condition directly contacted with natural environment for a long time, thus, require the film system layer of heat-collecting plate core, good heat resistance and weather resistance must be possessed.
Although the titanium series membranes architecture of prior art; there is the ability (such as TiNO) of higher selective absorbing solar energy; but due to titanium series membranes system; there is sedimentation rate in technique slow; the rete commercial production conditions of high-absorbility is harsh, it is expensive to produce equipment, and production efficiency and production cost are not very goodly wait deficiency, though and rete matcoveredn; but wearability is slightly poor, thus have impact on described this film and tie up to application on solar thermal collector.
Summary of the invention
The invention reside in provides a kind of and had both possessed good selective absorbing performance, possess corrosion-resistant simultaneously, wear-resistant good with weather resistance, be suitable for the preparation method of the film structure of industrialization quantity-produced titanium-chrome series row solar energy optical-thermal switching film, to overcome the deficiency of prior art.
The technical though that the present invention realizes its object is, chromium is introduced existing solar selective absorbing film layer, and is sputtered by vacuum reaction, makes it to generate (Ti-Cr) NO selective absorption film with good absorption ability.Utilize Cr to be magnesium-yttrium-transition metal, its nitrogen oxide has good photo absorption performance, and during its vacuum magnetic-control sputtering, sedimentation rate is fast, to improve absorbent properties and the rate of film build of original TiNO photo-thermal film; Two is SiO described in outermost layer
2introduce a small amount of aluminium (8 ~ 10at%) in anti-reflection rete, by the reactive magnetron sputtering of Si target and Al target or Si-Al alloys target, generate SiO
2-Al
2o
3antireflection film layer, to strengthen hardness and the wearability on film system of the present invention surface further.Three is titanium target, chromium target, copper target and sial targets involved in coating process, all adopt hollow cylinder target, and adopt target pipe inner magnetic core magnetic field to be arranged as the orientation sputtering of unbalanced magnetic field, to realize the object of efficient, uniform sputter and maximum using, thus realize original intention of the present invention.
Based on above-described technical though, the technical scheme of film structure of the present invention is:
A kind of film structure of solar energy optical-thermal switching film; with forming metal base material for film system base; on the surface of described film system base; copper red external reflectance rete successively outside interior; titanium nitride thermal diffusion stops protective film; the titanium oxynitrides chromium selective absorption film of high tenor, the titanium oxynitrides chromium selective absorption film of low-metal content, and the silica dioxide antireflection film layer containing a small amount of alundum (Al2O3).
Can be understood by the technical scheme of above given film structure, due to selective absorption film of the present invention, be (Ti-Cr) NO, and its outermost layer is SiO
2-Al
2o
3antireflective protective film, thus achieve object of the present invention, thus, also by photothermal deformation film of the present invention, titanium-chrome series row solar energy optical-thermal switching film can be referred to as.
In technique scheme, the described film system base that the present invention advocates is stainless steel or copper or aluminium formed sheet or tubing, or glass tubing, but is not limited to this, and other has the material of good heat conductive performance, can as film system of the present invention base.
In technique scheme, the present invention also advocates, the total amount of institute's titaniferous and chromium in described high tenor titanium oxynitrides chromium selective absorption film and the titanium oxynitrides chromium selective absorption film of low-metal content, be 50 ~ 75wt% and 25 ~ 40wt% respectively and wherein the atomic percent of titanium and chromium is 3:1, wherein, the total amount ratio of described titanium and chromium, and the atomic percent of titanium and chromium, be all not limited to this.
In technique scheme, the present invention also advocates, described containing the aluminium content in the silica dioxide antireflection film layer of a small amount of alundum (Al2O3) within the scope of 8 ~ 10 at%.But be not limited to this.
In technique scheme; the present invention also advocates; the thickness of described copper red external reflectance rete is within the scope of 80 ~ 100nm; titanium oxynitrides thermal diffusion stops that the thickness of protective film is within the scope of 15 ~ 25nm; the thickness of the titanium oxynitrides chromium selective absorption film of high tenor is within the scope of 55 ~ 65nm; the thickness of the titanium oxynitrides chromium selective absorption film of low-metal content within the scope of 45 ~ 55nm, containing the thickness of the silica dioxide antireflection film layer of a small amount of alundum (Al2O3) within the scope of 80 ~ 100nm.But be not limited to this.
The technical scheme that the present invention realizes its object is:
A kind of technical scheme preparing the method for the film structure of described solar energy optical-thermal switching film is:
A preparation method for solar energy optical-thermal switching film film structure, adopts intermediate frequency vacuum magnetron sputtering film plating machine to be process equipment, with film system base for processing issuance of materials, the step of the method successively:
(1), the pre-treatment of film system base; Described pre-treatment is film system base film system base being obtained clean surface by alkali, acid treatment and water flushing, and then implements to dry degasification;
(2), being coated with of rete, first the film system base through pre-treatment is placed in the vacuum chamber of described coating machine, by the heater in vacuum chamber, makes the heating temperatures of vacuum chamber to 140 ~ 160 DEG C, and continue insulation at such a temperature; Then:
(a), be coated with copper red external reflectance rete;
Adopt DC cathode copper target sputtering mode, in film system, primary surface is coated with copper red outer reflective layer;
Its coating process parameter is: background vacuum is at 6.0E
-3below, the argon flow amount of vacuum film coating chamber is passed within the scope of 145 ~ 155sccm, process pressure 2.5E
-1~ 2.7E
-1; The sputtering voltage of dc source is within the scope of 450 ~ 470V, and electric current, within the scope of 38 ~ 40A, implements sputter coating, until described rete reaches required design thickness;
B () is coated with titanium nitride thermal diffusion and stops protective film;
Adopt twin titanium target medium frequency reactive sputtering mode;
Its coating process parameter is: pass into the argon flow amount of vacuum film coating chamber within the scope of 155 ~ 165sccm, and the flow of reacting gas nitrogen is within the scope of 55 ~ 65sccm, and its process pressure is>=3.0E
-1; The sputtering voltage of intermediate frequency power supply is within the scope of 580 ~ 585V, and electric current, within the scope of 55 ~ 60A, implements reactive sputtering plated film, until described rete reaches required design thickness;
(c), be coated with the selective absorption film of high tenor; Its plated film mode has 2 kinds:
Its first plated film mode is, adopts twin titanium target and twin chromium target to carry out reactive sputtering plated film simultaneously;
Its coating process parameter is: pass into the argon flow amount of vacuum film coating chamber within the scope of 175 ~ 185sccm, and nitrogen flow is within the scope of 50 ~ 60sccm, and oxygen flow within the scope of 10 ~ 15sccm, and keeps nitrogen/oxygen flow than being 4.6:1; Technique vacuum is at 3.4 ~ 3.5E
-1in scope, 2 groups of intermediate frequency power supplies are adopted individually to power to twin titanium target and twin chromium target to 2 respectively, frequency is within the scope of 50 ~ 55KHZ, wherein titanium target voltage is within the scope of 640 ~ 660V, electric current is within the scope of 36 ~ 40A, and chromium target voltage is within the scope of 530 ~ 545V, and electric current is within the scope of 36 ~ 40A, implement reactive sputtering plated film, until described rete reaches required design thickness;
Its second plated film mode is, adopts a pair titanium chromium atom percentage to be the twin titanium chrome alloy target of 3:1, carries out reactive sputtering plated film,
Its coating process parameter is: pass into the argon flow amount of vacuum film coating chamber within the scope of 175 ~ 185sccm, nitrogen flow is within the scope of 50 ~ 60sccm, oxygen flow is within the scope of 10 ~ 15sccm, frequency is that intermediate frequency power supply sputtering voltage within the scope of 50 ~ 55KHZ is within the scope of 600 ~ 620V, electric current is within the scope of 48 ~ 52A, implement reactive sputtering plated film, until described rete) reach required design thickness;
D () is coated with the selective absorption film of low-metal content, its plated film mode has 2 kinds;
Its first plated film mode is, adopts twin titanium target and twin chromium target to carry out reactive sputtering plated film simultaneously;
Its coating process parameter is: pass into the argon flow amount of vacuum film coating chamber within the scope of 195 ~ 205sccm, and nitrogen flow is within the scope of 75 ~ 85sccm, and oxygen flow is within the scope of 15 ~ 20sccm, and technique vacuum is at 4.1 ~ 4.3E
-1in scope, 2 class frequencys are adopted to be that the intermediate frequency power supply of 50 ~ 55KHZ is powered separately to twin titanium target and chromium target respectively, frequency is within the scope of 50 ~ 55KHZ, wherein within the scope of titanium target voltage 590 ~ 610V, electric current is within the scope of 52 ~ 55A, and chromium target voltage is within the scope of 530 ~ 540V, and electric current is within the scope of 37 ~ 39A, implement reactive sputtering plated film, until described rete reaches required design thickness;
Its second plated film mode is: employing titanium chromium atom percentage is the twin titanium chrome alloy target of 3:1, carries out reactive sputtering plated film;
Its coating process parameter is: technique vacuum with pass into the argon gas of vacuum film coating chamber, nitrogen, oxygen flow all identical with its first plated film mode, single frequency is adopted to be the intermediate frequency power supply of 50 ~ 55KHZ, power to twin titanium chrome alloy target, voltage is within the scope of 575 ~ 585V, electric current is within the scope of 46 ~ 49A, implement reactive sputtering plated film, until described rete reaches required design thickness;
(e), be coated with silica dioxide antireflection film layer containing a small amount of alundum (Al2O3)
Employing aluminium atomic percentage is the silico-aluminum target mid frequency sputtering plated film mode of 8 ~ 10%;
Its coating process parameter is: pass into the argon flow amount of vacuum film coating chamber within the scope of 155 ~ 165sccm, and oxygen flow is within the scope of 20 ~ 25sccm, and technique vacuum is 2.6E
-1, implement reactive sputtering plated film, until described rete reaches required design thickness;
Then, described film ties up in vacuum chamber and namely obtains described film structure after cooling.
In technique scheme, the present invention also advocates, described copper target, titanium target, chromium target, titanium chrome alloy target and silico-aluminum target are hollow cylinder target, and target inner magnetic core magnetic field is arranged as the orientation sputtering of unbalanced magnetic field; And target center is fixed, target body rotates; Magnetic direction is in the face of film system base; Distance between 5 kinds of described targets and film system base remains within the scope of 8 ~ 10cm.The object of this technical scheme, is obviously to avoid target to ftracture, and realizes efficient, uniform sputter and the maximum using of target, to enhance productivity and materials saving.
After technique scheme is implemented in full, main feature of the present invention has:
1, the excellent combination property of film system.While the hot property that maintenance is high, its weather resistance is splendid.Sample routine test result shows: its absorptivity reaches 94 ~ 95%, emissivity < 6%; Its SiO
2-Al
2o
3antireflection film layer, while possessing anti-reflective effect, rete is anti-corrosion, anti-wear performance is able to further lifting, and in atmospheric environment, weather resistance is excellent, and performance and the outward appearance of rete are unchanged.
2, during film forming, speed is fast, and target is simple and easy to get, and utilization rate is high, is particularly suitable for factorial praluction.When plating selective absorption film, Ti target can generate the TiNO of high durable, high-absorbility, and Cr target has high sputter rate.Adopt Ti-Cr binary target system, its absorptivity, rate of film build and weather resistance obtain desirable coupling.Especially SiO is coated with
2antireflection film layer, adopts hollow cylinder target (Si-Al alloys target), effectively avoids cracking, target utilization > 75%, and owing to generating a small amount of Al
2o
3, its surface hardness and anti-wear performance are further enhanced.
Accompanying drawing explanation
Fig. 1 is the structural representation of film system of the present invention.
Detailed description of the invention
Embodiment 1
A film structure for typical solar energy optical-thermal switching film, as shown in Figure 1.It with forming metal base material for film system base 1; on the surface of described film system base 1; copper red external reflectance rete 2 successively outside interior; titanium nitride thermal diffusion stops protective film 3; the titanium oxynitrides chromium selective absorption film 4 of high tenor; the titanium oxynitrides chromium selective absorption film 5 of low-metal content, and the silica dioxide antireflection film layer 6 containing a small amount of alundum (Al2O3).
Described film system base 1 is stainless steel or copper or aluminium formed sheet or tubing, or glass tubing.
In described high tenor titanium oxynitrides chromium selective absorption film 4 and the titanium oxynitrides chromium selective absorption film 5 of low-metal content, the total amount of institute's titaniferous and chromium, be 50 ~ 75wt% and 25 ~ 40wt% respectively, and wherein the atomic percent of titanium and chromium is 3:1.
Described containing the aluminium content in the silica dioxide antireflection film layer 6 of a small amount of alundum (Al2O3) within the scope of 8 ~ 10 at%.
The thickness of described copper red external reflectance rete 2 is within the scope of 80 ~ 100nm; titanium oxynitrides thermal diffusion stops that the thickness of protective film 3 is within the scope of 15 ~ 25nm; the thickness of the titanium oxynitrides chromium selective absorption film 4 of high tenor is within the scope of 55 ~ 65nm; the thickness of the titanium oxynitrides chromium selective absorption film 5 of low-metal content within the scope of 45 ~ 55nm, containing the thickness of the silica dioxide antireflection film layer 6 of a small amount of alundum (Al2O3) within the scope of 80 ~ 100nm.
Embodiment 2,
Accompanying drawings 1, a kind of preparation method of film structure of solar energy optical-thermal switching film, adopts intermediate frequency vacuum magnetron sputtering film plating machine to be process equipment, with film system base 1 for processing issuance of materials, the step of the method successively:
(1), the pre-treatment of film system base 1; Described pre-treatment is film system base film system base 1 being obtained clean surface by alkali cleaning, sour neutralisation treatment and water flushing, and then implements to dry degasification;
(2), being coated with of rete;
First the film system base 1 through pre-treatment is placed in the vacuum chamber of described coating machine, by the heater in vacuum chamber, makes the heating temperatures of vacuum chamber to 140 ~ 160 DEG C, and continue insulation at such a temperature; Then:
(a), be coated with copper red external reflectance rete 2;
Adopt DC cathode copper target sputtering mode, be coated with copper red outer reflective layer 2 on film system base 1 surface;
Its coating process parameter is: background vacuum is at 6.0E
-3below, pass into the argon flow amount of vacuum film coating chamber within the scope of 145 ~ 155sccm, process pressure is at 2.5E
-1left and right; The sputtering voltage of dc source is within the scope of 450 ~ 470V, and electric current, within the scope of 38 ~ 40A, implements sputter coating, until described rete 2 reaches required design thickness;
B () is coated with titanium nitride thermal diffusion and stops protective film 3;
Adopt twin target medium frequency reactive sputtering mode, be coated with titanium nitride thermal diffusion on copper red outer reflective layer 2 surface and stop protective film 3;
Its coating process parameter is: pass into the argon flow amount of vacuum film coating chamber within the scope of 155 ~ 165sccm, and the flow of reacting gas nitrogen is within the scope of 55 ~ 65sccm, and its process pressure is>=3.0E
-1; The sputtering voltage of intermediate frequency dc source is within the scope of 580 ~ 585V, and electric current, within the scope of 55 ~ 60A, implements reactive sputtering plated film, until described rete (3) reaches required design thickness;
(c), be coated with the selective absorption film 4 of high tenor; Its plated film mode has 2 kinds:
Simultaneously its first plated film mode adopts twin titanium target and twin chromium target to carry out reactive sputtering plated film;
Its coating process parameter is: pass into the argon flow amount of vacuum film coating chamber within the scope of 175 ~ 185sccm, and nitrogen flow is within the scope of 50 ~ 60sccm, and oxygen flow within the scope of 10 ~ 15sccm, and keeps nitrogen/oxygen flow than being 4.6:1; Technique vacuum is at 3.4 ~ 3.5E
-1in scope, 2 groups of intermediate frequency power supplies are adopted to power separately to twin titanium target and twin chromium target to 2 respectively, frequency is within the scope of 50 ~ 55KHZ, wherein, titanium target voltage is within the scope of 640 ~ 660V, and electric current is within the scope of 36 ~ 40A, chromium target voltage is within the scope of 530 ~ 545V, electric current, within the scope of 36 ~ 40A, implements reactive sputtering plated film, until described rete 4 reaches required design thickness;
Its second plated film mode is, adopts a pair titanium chromium atom percentage to be the twin titanium chrome alloy target of 3:1, carries out reactive sputtering plated film,
Its coating process parameter is, pass into the argon flow amount of vacuum film coating chamber within the scope of 175 ~ 185sccm, nitrogen flow is within the scope of 50 ~ 60sccm, oxygen flow is within the scope of 10 ~ 15sccm, frequency is that intermediate frequency power supply sputtering voltage within the scope of 50 ~ 55KHZ is within the scope of 600 ~ 620V, electric current, within the scope of 48 ~ 52A, implements reactive sputtering plated film, until described rete 4 reaches required design thickness;
D () is coated with the selective absorption film 5 of low-metal content, its plated film mode has 2 kinds;
Its first plated film mode is, adopts twin titanium target and twin chromium target to carry out reactive sputtering plated film simultaneously;
Its coating process parameter is: pass into the argon flow amount of vacuum film coating chamber within the scope of 195 ~ 205sccm, and nitrogen flow is within the scope of 75 ~ 85sccm, and oxygen flow is within the scope of 15 ~ 20sccm, and technique vacuum is at 4.1 ~ 4.3E
-1in scope, 2 class frequencys are adopted to be that the intermediate frequency power supply of 50 ~ 55KHZ is powered separately to twin titanium target and chromium target respectively, frequency is within the scope of 50 ~ 55KHZ, wherein within the scope of titanium target voltage 590 ~ 610V, electric current is within the scope of 52 ~ 55A, and chromium target voltage is within the scope of 530 ~ 540V, and electric current is within the scope of 37 ~ 39A, implement reactive sputtering plated film, until described rete 5 reaches required design thickness;
Its second plated film mode is: employing titanium chromium atom percentage is the twin titanium chrome alloy target of 3:1, carries out reactive sputtering plated film;
Its coating process parameter is, technique vacuum with pass into the argon gas of vacuum film coating chamber, nitrogen, oxygen flow all identical with its first plated film mode, single frequency is adopted to be the intermediate frequency power supply of 50 ~ 55KHZ, power to twin titanium chrome alloy target, voltage is within the scope of 575 ~ 585V, electric current, within the scope of 46 ~ 49A, implements reactive sputtering plated film, until described rete 5 reaches required design thickness;
(e), be coated with silica dioxide antireflection film layer 6 containing a small amount of alundum (Al2O3)
Employing aluminium atomic percentage is the silico-aluminum target mid frequency sputtering plated film of 8 ~ 10%;
Its coating process parameter is: pass into argon flow amount within the scope of 155 ~ 165sccm, and oxygen flow is within the scope of 20 ~ 25sccm, and technique vacuum is 2.6E
-1, implement reactive sputtering plated film, until described rete 6 reaches required design thickness;
Then, after described photothermal deformation film cools in vacuum chamber, i.e. obtained solar energy optical-thermal switching film.Complete described preparation method.
Described 5 kinds of targets are hollow cylinder target above, and its external diameter is within the scope of 65 ~ 75mm, and internal diameter is within the scope of 50 ~ 60mm; Target pipe inner magnetic core magnetic field is arranged as the orientation sputtering of unbalanced magnetic field; And target center is fixed, and hollow cylinder target pipe rotates; Magnetic direction is in the face of film system base 1; Distance between 5 kinds of described targets and film system base 1 remains within the scope of 8 ~ 10cm.
The performance test results of sample of the present invention is
Under the baking oven of 210 DEG C, carry out insulation 30 days, to simulate the air drying test of rete in flat plate collector, except absorbent properties decline except a point (93%) at first day, the remaining absorptivity of 29 days remains on 93% and does not decline, and transmitting ratio remains on 5% and do not rise.The air drying temperature of actual plate heat collector is generally below 160 DEG C.This rete possesses the thermal ageing resistant performance under good atmospheric environment.
Carry out 72 hours salt mist experiments (neutral salt spray test case), PE Lamada950 spectrophotometric measurement absorptivity, Optosolk3v4 absorbs emissivity instrument and surveys emissivity.Experimental result is in table 1 and table 2.
Table 1 launches the relation curve table with wavelength, wave band for the light of the present invention that the salt fog time tests
Table 2 simulates the statistical form of absorptivity measured by salt spray test and transmitting ratio for the present invention
Table 1
table 2
| Measure numbering | Time | Absorptivity | Transmitting ratio (70 DEG C) |
| 1 | 0h | 95.1% | 4.3% |
| 2 | 8h | 94.6% | 5.9% |
| 3 | 12h | 94.3 | 5.7 |
| 4 | 24h | 94.6% | 5.4% |
| 5 | 36h | 94.4% | 5.6% |
| 6 | 48h | 94.2% | 5.4% |
| 7 | 72h | 94.0% | 5.9% |
72 hours xenon lamp aging experiment tests, absorption of sample rate is 94.8%, and reflectivity is 4.5%, almost remains unchanged.
Experiment shows the flat plate collector of the photothermal deformation film with this film structure, possesses good heat aging performance and weather resistance in atmospheric conditions.
Claims (2)
1. the preparation method of the film structure of a solar energy optical-thermal switching film, described film structure with forming metal base material for film system base (1), it is characterized in that: on the surface of described film system base (1), copper red external reflectance rete (2) from the inside to the outside successively, titanium nitride thermal diffusion stops protective film (3), the titanium oxynitrides chromium selective absorption film (4) of high tenor, the titanium oxynitrides chromium selective absorption film (5) of low-metal content, and the silica dioxide antireflection film layer (6) containing a small amount of alundum (Al2O3), and the total amount of the middle institute's titaniferous of the titanium oxynitrides chromium selective absorption film (5) of described high tenor titanium oxynitrides chromium selective absorption film (4) and low-metal content and chromium, be 50 ~ 75wt% and 25 ~ 40wt% respectively, and wherein the atomic percent of titanium and chromium is 3:1, and described containing the aluminium content in the silica dioxide antireflection film layer (6) of a small amount of alundum (Al2O3) within the scope of 8 ~ 10at%, and the thickness of described copper red external reflectance rete (2) is within the scope of 80 ~ 100nm, titanium nitride thermal diffusion stops that the thickness of protective film (3) is within the scope of 15 ~ 25nm, the thickness of the titanium oxynitrides chromium selective absorption film (4) of high tenor is within the scope of 55 ~ 65nm, the thickness of the titanium oxynitrides chromium selective absorption film (5) of low-metal content is within the scope of 45 ~ 55nm, containing the thickness of the silica dioxide antireflection film layer (6) of a small amount of alundum (Al2O3) within the scope of 80 ~ 100nm, and described preparation method is, intermediate frequency vacuum magnetron sputtering film plating machine is adopted to be process equipment, with film system base (1) for processing issuance of materials, it is characterized in that: the step of the method successively:
(1), the pre-treatment of film system base (1);
Described pre-treatment is film system base film system base (1) being obtained clean surface by alkali, acid treatment and deionized water rinsing, and then implements to dry degasification;
(2), being coated with of rete;
First by film system base (1) through pre-treatment, be placed in the vacuum chamber of described coating machine, by the heater in vacuum chamber, make the heating temperatures of vacuum chamber to 140 ~ 160 DEG C, and continue insulation at such a temperature; Then:
(a), be coated with copper red external reflectance rete (2);
Adopt DC cathode copper target sputtering mode, be coated with copper red external reflectance rete (2) on film system base (1) surface;
Its coating process parameter is: background vacuum is at 6.0E
-3below, the argon flow amount of vacuum film coating chamber is passed within the scope of 145 ~ 155sccm, process pressure 2.5E
-1~ 2.7E
-1; The sputtering voltage of dc source is within the scope of 450 ~ 470V, and electric current, within the scope of 38 ~ 40A, implements sputter coating, until described rete (2) reaches required design thickness;
B () is coated with titanium nitride thermal diffusion and stops protective film (3);
Adopt twin titanium target medium frequency reactive sputtering mode;
Its coating process parameter is: pass into the argon flow amount of vacuum film coating chamber within the scope of 155 ~ 165sccm, and the flow of reacting gas nitrogen is within the scope of 55 ~ 65sccm, and its process pressure is 3.0E
-1~ 3.2E
-1; Intermediate frequency power supply sputtering voltage is within the scope of 580 ~ 585V, and electric current, within the scope of 55 ~ 60A, implements reactive sputtering plated film, until described rete (3) reaches required design thickness;
(c), be coated with the selective absorption film (4) of high tenor; Its plated film mode has 2 kinds:
Its first plated film mode is, adopts twin titanium target and twin chromium target to carry out reactive sputtering plated film simultaneously;
The technological parameter of its plated film is: pass into the argon flow amount of vacuum film coating chamber within the scope of 175 ~ 185sccm, and nitrogen flow is within the scope of 50 ~ 60sccm, and oxygen flow within the scope of 10 ~ 15sccm, and keeps nitrogen/oxygen flow than being 4.6:1; Technique vacuum is at 3.4 ~ 3.6E
-1in scope, adopt 2 groups of intermediate frequency power supplies to power separately to twin titanium target and twin chromium target to 2 respectively, frequency is within the scope of 50 ~ 55KHZ, and wherein titanium target voltage is within the scope of 640 ~ 660V, and electric current is within the scope of 50 ~ 55A; Chromium target voltage is within the scope of 530 ~ 545V, and electric current, within the scope of 36 ~ 40A, implements reactive sputtering plated film, until described rete (4) reaches required design thickness;
Its second plated film mode is, adopts a pair titanium chromium atom percentage to be the twin titanium chrome alloy target of 3:1, carries out reactive sputtering plated film,
Its coating process parameter is: pass into the argon flow amount of vacuum film coating chamber within the scope of 175 ~ 185sccm, nitrogen flow is within the scope of 50 ~ 60sccm, oxygen flow is within the scope of 10 ~ 15sccm, the intermediate frequency power supply sputtering voltage of frequency within the scope of 50 ~ 55KHZ is within the scope of 600 ~ 620V, electric current is within the scope of 48 ~ 52A, implement reactive sputtering plated film, until described rete (4) reaches required design thickness;
D () is coated with the selective absorption film (5) of low-metal content, its plated film mode has 2 kinds;
Its first plated film mode is, adopts twin titanium target and twin chromium target to carry out reactive sputtering plated film simultaneously;
Its coating process parameter is: pass into the argon flow amount of vacuum film coating chamber within the scope of 195 ~ 205sccm, and nitrogen flow is within the scope of 75 ~ 85sccm, and oxygen flow is within the scope of 15 ~ 20sccm, and technique vacuum is at 4.1 ~ 4.3E
-1in scope, adopt 2 groups of intermediate frequency power supplies, power separately to respectively twin titanium target and twin chromium target, frequency is within the scope of 50 ~ 55KHZ, and wherein within the scope of titanium target voltage 590 ~ 610V, electric current is within the scope of 52 ~ 55A, chromium target voltage is within the scope of 530 ~ 540V, electric current, within the scope of 37 ~ 39A, implements reactive sputtering plated film, until described rete (5) reaches required design thickness;
Its second plated film mode is: employing titanium chromium atom percentage is the twin titanium chrome alloy target of 3:1, carries out reactive sputtering plated film;
Its coating process parameter is: technique vacuum with pass into the argon gas of vacuum film coating chamber, nitrogen, oxygen flow all identical with its first plated film mode, single frequency is adopted to be the intermediate frequency power supply of 50 ~ 55KHZ, power to twin titanium chrome alloy target, voltage is within the scope of 575 ~ 585V, electric current is within the scope of 46 ~ 49A, implement reactive sputtering plated film, until described rete (5) reaches required design thickness;
(e), be coated with silica dioxide antireflection film layer (6) containing a small amount of alundum (Al2O3)
Employing aluminium atomic percentage is the silico-aluminum target mid frequency sputtering plated film mode of 8 ~ 10%;
Its coating process parameter is: pass into the argon flow amount of vacuum film coating chamber within the scope of 155 ~ 165sccm, and oxygen flow is within the scope of 20 ~ 25sccm, and technique vacuum is 2.6E
-1, implement reactive sputtering plated film, until described rete (6) reaches required design thickness;
Then, described film ties up in vacuum chamber after cooling, i.e. the obtained photothermal deformation film with described film structure.
2. preparation method according to claim 1, is characterized in that, described copper target, titanium target, chromium target, titanium chrome alloy target and silico-aluminum target are hollow cylinder target, and target inner magnetic core magnetic field is arranged as the orientation sputtering of unbalanced magnetic field; And target center is fixed, target body rotates, and magnetic direction is in the face of film system base (1); Distance between 5 kinds of described targets and film system base (1) remains within the scope of 8 ~ 10cm.
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| CN101886848A (en) * | 2009-05-11 | 2010-11-17 | 范天方 | Solar spectrum selective absorbing film and preparation method thereof |
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| CN102620456A (en) * | 2012-04-06 | 2012-08-01 | 中国科学院宁波材料技术与工程研究所 | Medium-and-low-temperature solar selective absorption thin film and preparation method thereof |
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Address after: 213000 no.6-5, hengluo Road, Henglin Town, Wujin District, Changzhou City, Jiangsu Province Patentee after: Jiangsu Xia PhD environment Polytron Technologies Inc Address before: 213101 Jiangsu city of Changzhou Province Wang Zhen Wujin District No. 2 loglo cross Patentee before: Jiangsu Doctorxia Solar Energy Inc. |