CN111005001B - Tenebrio-bulleyana-simulated multi-stage-structure vanadium dioxide intelligent thermal control device and preparation method thereof - Google Patents

Tenebrio-bulleyana-simulated multi-stage-structure vanadium dioxide intelligent thermal control device and preparation method thereof Download PDF

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CN111005001B
CN111005001B CN201911405661.1A CN201911405661A CN111005001B CN 111005001 B CN111005001 B CN 111005001B CN 201911405661 A CN201911405661 A CN 201911405661A CN 111005001 B CN111005001 B CN 111005001B
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赵九蓬
谷金鑫
豆书亮
李垚
任飞飞
魏航
李龙
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Harbin Institute of Technology
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Abstract

A vanadium dioxide intelligent thermal control device with a skyhook-like multi-stage structure and a preparation method thereof belong to the technical field of intelligent thermal control coatings. The invention aims to solve the problem that the prior VO-based method2The emissivity change of the intelligent thermal control device is small, and the solar absorption ratio is high. The intelligent vanadium dioxide thermal control device with the imitation longicorn multi-stage structure sequentially comprises a semiconductor substrate layer, an infrared high-reflection metal layer and HfO from bottom to top2Dielectric layer and VO2A layer and a protective layer. The preparation method comprises the following steps: firstly, preparing an infrared high-reflection metal layer; secondly, preparing a dielectric film; III, VO2Preparing a film; fourthly, processing the microstructure; and fifthly, depositing a protective layer. The invention relates to a vanadium dioxide intelligent thermal control device with a skyhook-like multi-stage structure and a preparation method thereof.

Description

Tenebrio-bulleyana-simulated multi-stage-structure vanadium dioxide intelligent thermal control device and preparation method thereof
Technical Field
The invention belongs to the technical field of intelligent thermal control coatings.
Background
When the spacecraft runs in space, the spacecraft can face a complex alternating temperature field, and the energy is exchanged with the outside mainly through radiation heat exchange; the spacecraft thermal control device is used as an important part of a spacecraft surface thermal control system, and plays a key role in maintaining the stability of the internal temperature of the spacecraft and ensuring the normal work of the spacecraft. The emissivity of the traditional thermal control device is fixed and cannot be changed along with the change of the external temperature; the novel intelligent thermal control device can automatically adjust the self emissivity along with the change of the external environment temperature, and is one of hot contents of the current spacecraft thermal control technology research. The main principle is as follows: when the external environment temperature is lower than the critical temperature of the device, the self emissivity is reduced, and the energy radiated to the outside is reduced; when the external environment temperature is higher than the critical temperature, the self emissivity is improved, and the energy radiated to the outside is increased. In order to meet the requirements of low-temperature heat preservation and high-temperature heat dissipation of satellites and the like in space, the development of the intelligent thermal control coating with large emissivity change and small solar absorption ratio has important significance.
VO2The material is an important thermochromic material, but the emissivity change of the material is small when the material is applied to intelligent thermal control due to the characteristic of high temperature and high reflection of the material, and the emissivity change is generally below 0.3. VO-based reported in literature at present2The thermal control device is generally designed by adopting a multilayer film structure or utilizes the surface plasma resonance effect to perform VO2The micron-level structure is prepared on the surface, so that the high-temperature emissivity of the device is improved, and the variation range of the emissivity is enlarged. But still has the problem that the emissivity change range is large and the absorption ratio of the normal temperature sun is low, which causes the limitation of the device performance.
Disclosure of Invention
The invention aims to solve the problem that the prior VO-based method2The emissivity change of the intelligent thermal control device is small, and the solar absorption ratio is high, so that the vanadium dioxide intelligent thermal control device with the imitation longicorn multi-stage structure and the preparation method thereof are provided.
The intelligent vanadium dioxide thermal control device with the imitation longicorn multi-stage structure sequentially comprises a semiconductor substrate layer, an infrared high-reflection metal layer and HfO from bottom to top2Dielectric layer and VO2A layer and a protective layer;
said HfO2The dielectric layer is composed of multiple HfO2Micro-nano structure unit composition and HfO2The micro-nano structure unit is in the shape of a cube with a square bottom surface and a plurality of HfO2The micro-nano structure units are uniformly distributed on the upper surface of the infrared high-reflection metal layer; said HfO2The side length of a square on the bottom surface of the micro-nano structure unit is 1-10 mu m, and the height is 400-2000 nm;adjacent HfO2The distance between the micro-nano structure units is 0.5-5 mu m;
the VO2VO with layer doped with multiple W2VO formed by micro-nano structure units and doped with W2The micro-nano structure unit is conical and is provided with a plurality of W-doped VOs2Micro-nano structure units are uniformly distributed on HfO2The upper surface of the dielectric layer; the W-doped VO2The diameter of the bottom surface of the micro-nano structure unit is 20 nm-300 nm, and the height is 50 nm-500 nm; same HfO2VO (volatile organic compound) doped with adjacent W and arranged on micro-nano structure unit2The micro-nano structure units are closely arranged;
the W-doped VO2W in the micro-nano structure unit accounts for 0-2.5% of the total atomic number of W and V.
A preparation method of a vanadium dioxide intelligent thermal control device with a skyhook-like multi-stage structure comprises the following steps:
firstly, preparing an infrared high-reflection metal layer:
depositing an infrared high-reflection metal layer on the semiconductor substrate layer by using a direct-current magnetron sputtering technology;
secondly, preparing a dielectric film:
preparing HfO on the infrared high-reflection metal layer by using a direct-current magnetron sputtering technology2A dielectric film;
III, VO2Preparing a film:
using high-energy pulse magnetron sputtering technique on HfO2VO preparation on dielectric film2A film;
fourthly, processing the microstructure:
firstly, adopting a plasma etching method to carry out VO2Etching the surface layer of the film in a grid structure, and then carrying out HfO2Carrying out plasma etching on the dielectric film to obtain HfO2Dielectric layer, VO after etching of grid structure2Deposition of SiO on the surface of thin film2The ball is used as a template, and then the VO with a grid structure is etched by utilizing a reactive plasma etching technology2Etching the film, and finally removing SiO2Ball to obtain VO2A layer;
said HfO2The dielectric layer is composed of multiple HfO2Micro-nano structure unit composition and HfO2The micro-nano structure unit is in a cube with a square bottom surface; said HfO2The side length of a square on the bottom surface of the micro-nano structure unit is 1-10 mu m, and the height is 400-2000 nm; adjacent HfO2The distance between the micro-nano structure units is 0.5-5 mu m;
the VO2VO with layer doped with multiple W2VO formed by micro-nano structure units and doped with W2The micro-nano structure unit is conical; the W-doped VO2The diameter of the bottom surface of the micro-nano structure unit is 20 nm-300 nm, and the height is 50 nm-500 nm; same HfO2VO (volatile organic compound) doped with adjacent W and arranged on micro-nano structure unit2The micro-nano structure units are closely arranged;
the W-doped VO2W in the micro-nano structure unit accounts for 0-2.5% of the total atomic number of W and V;
fifthly, deposition of a protective layer:
and depositing a protective layer by using high-energy pulse magnetron sputtering to obtain the intelligent vanadium dioxide thermal control device with the imitation longicorn multi-stage structure.
The invention has the beneficial effects that:
the body surface of the longicorn is covered by a blue-gray area and black spots, and the blue-gray area is of a transparent bristle structure and can form strong scattering on the visible waveband part of sunlight; the black area is formed by an umbrella-shaped-grating-herringbone three-level micro-nano structure, and can form a strong absorption effect on a visible waveband. Both regions have the characteristic of high emissivity in the infrared band. VO-based method2The special phase change characteristics of the film such as high transmission of low-temperature infrared and high reflection of high-temperature infrared are introduced, an intermediate medium film with a high reflection metal layer and excellent transmission performance from near ultraviolet to infrared bands is introduced to prepare a multilayer film structure, a multi-stage structure imitating a celesta cow is designed on the basis of the multilayer film structure, low-temperature low emission (20 ℃: 0.12-0.21) and high-temperature high emission (100 ℃: 0.44-0.81) are realized, and VO is improved2The infrared emissivity of the intelligent thermal control device ranges from 0.32 to 0.60, and the solar absorption at room temperature is reducedThe ratio is 0.35 to 0.4; furthermore, by applying to VO2The film is modified by W doping, the phase change temperature of the film is reduced, and the temperature can be reduced by 8-41 ℃, so that the film can be used at room temperature and at a temperature lower than the room temperature.
The invention relates to a vanadium dioxide intelligent thermal control device with a longicorn-like multi-stage structure and a preparation method thereof.
Drawings
FIG. 1 is a schematic structural diagram of a vanadium dioxide intelligent thermal control device with a skyhook-like multilevel structure, and 1 is VO2Layer 2 is HfO2The dielectric layer, 3, 4 and 5 are respectively an infrared high-reflection metal layer, a semiconductor substrate layer and a protective layer.
Detailed Description
The first embodiment is as follows: the present embodiment is specifically described with reference to fig. 1, and the intelligent vanadium dioxide thermal control device with a skyhook-like multilevel structure of the present embodiment sequentially comprises, from bottom to top, a semiconductor substrate layer, an infrared high-reflection metal layer, and HfO2Dielectric layer and VO2A layer and a protective layer;
said HfO2The dielectric layer is composed of multiple HfO2Micro-nano structure unit composition and HfO2The micro-nano structure unit is in the shape of a cube with a square bottom surface and a plurality of HfO2The micro-nano structure units are uniformly distributed on the upper surface of the infrared high-reflection metal layer; said HfO2The side length of a square on the bottom surface of the micro-nano structure unit is 1-10 mu m, and the height is 400-2000 nm; adjacent HfO2The distance between the micro-nano structure units is 0.5-5 mu m;
the VO2VO with layer doped with multiple W2VO formed by micro-nano structure units and doped with W2The micro-nano structure unit is conical and is provided with a plurality of W-doped VOs2Micro-nano structure units are uniformly distributed on HfO2The upper surface of the dielectric layer; the W-doped VO2The diameter of the bottom surface of the micro-nano structure unit is 20 nm-300 nm, and the height is 50 nm-500 nm; same HfO2VO (volatile organic compound) doped with adjacent W and arranged on micro-nano structure unit2The micro-nano structure units are closely arranged;
the W-doped VO2Micro-nano structure sheetIn the component, W accounts for 0 to 2.5 percent of the total atomic number of W and V.
The beneficial effects of the embodiment are as follows:
the body surface of the longicorn is covered by a blue-gray area and black spots, and the blue-gray area is of a transparent bristle structure and can form strong scattering on the visible waveband part of sunlight; the black area is formed by an umbrella-shaped-grating-herringbone three-level micro-nano structure, and can form a strong absorption effect on a visible waveband. Both regions have the characteristic of high emissivity in the infrared band. VO-based method2The special phase change characteristics of the film such as high transmission of low-temperature infrared and high reflection of high-temperature infrared are introduced, an intermediate medium film with a high reflection metal layer and excellent transmission performance from near ultraviolet to infrared bands is introduced to prepare a multilayer film structure, a multi-stage structure imitating a celesta cow is designed on the basis of the multilayer film structure, low-temperature low emission (20 ℃: 0.12-0.21) and high-temperature high emission (100 ℃: 0.44-0.81) are realized, and VO is improved2The infrared emissivity of the intelligent thermal control device is changed to 0.32-0.60, and the solar absorption ratio at room temperature is reduced to 0.35-0.4; furthermore, by applying to VO2The film is modified by W doping, the phase change temperature of the film is reduced, and the temperature can be reduced by 8-41 ℃, so that the film can be used at room temperature and at a temperature lower than the room temperature.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the semiconductor substrate layer is quartz, glass or silicon; the infrared high-reflection metal layer is Ag, Ni, Mg, Zn or Al; the protective layer is Al2O3、SiO2、TiO2Or ZrO2. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the thickness of the infrared high-reflection metal layer is 50 nm-250 nm; said HfO2The thickness of the dielectric layer is 400 nm-2000 nm; the VO2The layer thickness is 50 nm-500 nm; the thickness of the protective layer is 50 nm-100 nm. The other is the same as in one or both of the first and second embodiments.
The fourth concrete implementation mode: the embodiment of the invention relates to a preparation method of a celestial cow multilevel structure-simulated vanadium dioxide intelligent thermal control device, which is carried out according to the following steps:
firstly, preparing an infrared high-reflection metal layer:
depositing an infrared high-reflection metal layer on the semiconductor substrate layer by using a direct-current magnetron sputtering technology;
secondly, preparing a dielectric film:
preparing HfO on the infrared high-reflection metal layer by using a direct-current magnetron sputtering technology2A dielectric film;
III, VO2Preparing a film:
using high-energy pulse magnetron sputtering technique on HfO2VO preparation on dielectric film2A film;
fourthly, processing the microstructure:
firstly, adopting a plasma etching method to carry out VO2Etching the surface layer of the film in a grid structure, and then carrying out HfO2Carrying out plasma etching on the dielectric film to obtain HfO2Dielectric layer, VO after etching of grid structure2Deposition of SiO on the surface of thin film2The ball is used as a template, and then the VO with a grid structure is etched by utilizing a reactive plasma etching technology2Etching the film, and finally removing SiO2Ball to obtain VO2A layer;
said HfO2The dielectric layer is composed of multiple HfO2Micro-nano structure unit composition and HfO2The micro-nano structure unit is in a cube with a square bottom surface; said HfO2The side length of a square on the bottom surface of the micro-nano structure unit is 1-10 mu m, and the height is 400-2000 nm; adjacent HfO2The distance between the micro-nano structure units is 0.5-5 mu m;
the VO2VO with layer doped with multiple W2VO formed by micro-nano structure units and doped with W2The micro-nano structure unit is conical; the W-doped VO2The diameter of the bottom surface of the micro-nano structure unit is 20 nm-300 nm, and the height is 50 nm-500 nm; same HfO2VO (volatile organic compound) doped with adjacent W and arranged on micro-nano structure unit2The micro-nano structure units are closely arranged;
the W-doped VO2W in the micro-nano structure unit accounts for 0-2.5% of the total atomic number of W and V;
fifthly, deposition of a protective layer:
and depositing a protective layer by using high-energy pulse magnetron sputtering to obtain the intelligent vanadium dioxide thermal control device with the imitation longicorn multi-stage structure.
The mechanism of formation of the conical structure of this embodiment: single layer SiO2The microspheres are tightly stacked, the gap part of the spheres can be etched by the reactive plasma, the influence of the monolayer spheres on the lower part is increased along with the increase of the etching depth, the etching area is reduced, and after the etching is finished, the monolayer spheres are removed to form a cone-shaped structure; by adjusting the etching process or SiO2The particle size of the microsphere can realize the regulation and control of the cone angle, the height and the diameter.
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: and the semiconductor substrate layer in the step one is obtained by cleaning the semiconductor substrate by using analytically pure absolute ethyl alcohol and ultrapure water as cleaning reagents. The rest is the same as the fourth embodiment.
The sixth specific implementation mode: the fourth or fifth embodiment is different from the fifth embodiment in that: the semiconductor substrate layer in the first step is quartz, glass or silicon; the infrared high-reflection metal layer in the first step is Ag, Ni, Mg, Zn or Al; the thickness of the infrared high-reflection metal layer in the step one is 50 nm-250 nm; HfO as described in step four2The thickness of the dielectric layer is 400 nm-2000 nm; VO described in step four2The layer thickness is 50 nm-500 nm; the protective layer in the fifth step is Al2O3、SiO2、TiO2Or ZrO2(ii) a And the thickness of the protective layer in the fifth step is 50 nm-100 nm. The other is the same as the fourth or fifth embodiment.
The seventh embodiment: this embodiment differs from one of the fourth to sixth embodiments in that: in the first step, under the condition that the temperature is between room temperature and 400 ℃, an infrared high-reflection metal layer is deposited on the semiconductor substrate layer by utilizing a direct-current magnetron sputtering technology. The others are the same as the fourth to sixth embodiments.
The specific implementation mode is eight: this embodiment is different from one of the fourth to seventh embodiments in that: in the second step, under the condition that the temperature is between room temperature and 400 ℃, the direct current magnetron sputtering technology is utilized to prepare HfO on the infrared high-reflection metal layer2A dielectric film. The rest is the same as the fourth to seventh embodiments.
The specific implementation method nine: this embodiment is different from the fourth to eighth embodiment in that: in the third step, under the condition of the temperature of 300-600 ℃, the high-energy pulse magnetron sputtering technology is adopted to perform reaction on HfO2VO preparation on dielectric film2A film. The others are the same as the fourth to eighth embodiments.
The detailed implementation mode is ten: this embodiment is different from one of the fourth to ninth embodiments in that: step four, adopting a plasma etching method to carry out VO treatment2Etching the surface layer of the film with a latticed structure, specifically, firstly etching at VO2Coating a layer of photoresist with a grid pattern on the surface of the thin film, wherein the flow rate of Ar gas is 8 sccm-12 sccm, and CF is adopted4The VO is etched by adopting a plasma etching method under the conditions that the gas flow is 8sccm to 12sccm, the power is 90W to 120W and the gas pressure is 90mtorr to 120mtorr2Etching the surface of the film to form a grid structure, and removing the photoresist; step four to HfO2Carrying out plasma etching on the dielectric film to obtain HfO2A dielectric layer, specifically, the flow rate of Ar gas is 8 sccm-12 sccm, and CHF3For HfO, the gas flow is 8sccm to 12sccm, the power is 110W to 140W, and the gas pressure is 90mtorr to 120mtorr2Carrying out plasma etching on the dielectric film to obtain HfO2A dielectric layer; VO after grid structure etching in step four2Deposition of SiO on the surface of thin film2The ball is used as a template, and then the VO with a grid structure is etched by utilizing a reactive plasma etching technology2Etching the film, and finally removing SiO2Ball to obtain VO2Layer, in particular VO after etching of a grid-like structure2A layer of SiO with the diameter of 20 nm-300 nm is deposited on the surface of the film2A single layer ball with Ar gas flow rate of 8-12 sccm and CF4The gas flow is 8 sccm-12 sccm,VO after etching the grid structure by using the reactive plasma etching technology under the conditions that the power is 80W-100W and the air pressure is 90 mtorr-120 mtorr2Etching the film, and finally removing SiO2Ball to obtain VO2And (3) a layer. The rest is the same as the fourth to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
the intelligent vanadium dioxide thermal control device with the imitation longicorn multi-stage structure sequentially comprises a semiconductor substrate layer, an infrared high-reflection metal layer and HfO from bottom to top2Dielectric layer and VO2A layer and a protective layer;
a preparation method of a vanadium dioxide intelligent thermal control device with a skyhook-like multi-stage structure comprises the following steps:
firstly, preparing an infrared high-reflection metal layer:
depositing an infrared high-reflection metal layer on the semiconductor substrate layer by using a direct-current magnetron sputtering technology under the condition that the temperature is 200 ℃;
secondly, preparing a dielectric film:
preparing HfO on the infrared high-reflection metal layer by using a direct-current magnetron sputtering technology at the temperature of 200 DEG C2A dielectric film;
III, VO2Preparing a film:
under the condition of the temperature of 300 ℃, adopting a high-energy pulse magnetron sputtering technology to perform reaction on HfO2VO preparation on dielectric film2A film;
fourthly, processing the microstructure:
firstly, VO2Coating a layer of photoresist with a grid pattern on the surface of the film, wherein the flow rate of Ar gas is 10sccm and CF4Performing plasma etching on VO under the conditions that the gas flow is 10sccm, the power is 95W and the gas pressure is 100mtorr2Etching the surface of the thin film to form a grid structure, removing the photoresist, and then performing CHF (CHF) treatment at Ar gas flow of 10sccm3For HfO, the gas flow rate is 10sccm, the power is 110W and the gas pressure is 100mtorr2Dielectric film feedPerforming plasma etching to obtain HfO2Dielectric layer, VO after etching of grid structure2A layer of SiO with the diameter of 20nm is deposited on the surface of the film2Single layer ball with Ar gas flow rate of 10sccm and CF4VO after etching the grid structure by using the reactive plasma etching technology under the conditions that the gas flow is 10sccm, the power is 100W and the gas pressure is 100mtorr2Etching the film, and finally removing SiO2Ball to obtain VO2A layer;
said HfO2The dielectric layer is composed of multiple HfO2Micro-nano structure unit composition and HfO2The micro-nano structure unit is in a cube with a square bottom surface; said HfO2The side length of a square on the bottom surface of the micro-nano structure unit is 1 mu m, and the height of the square is 400 nm; adjacent HfO2The distance between the micro-nano structure units is 0.5 mu m;
the VO2The layer is composed of a plurality of undoped VOs2VO composed of micro-nano structure unit and not doped2The micro-nano structure unit is conical; the undoped VO2The diameter of the bottom surface of the micro-nano structure unit is 20nm, and the height of the micro-nano structure unit is 50 nm; same HfO2VO (vanadium oxide) arranged on micro-nano structure unit and not doped adjacently2The micro-nano structure units are closely arranged;
fifthly, deposition of a protective layer:
and depositing a protective layer by using high-energy pulse magnetron sputtering to obtain the intelligent vanadium dioxide thermal control device with the imitation longicorn multi-stage structure.
The semiconductor substrate layer in the first step is prepared by taking quartz glass with the size of 10mm multiplied by 1mm as a substrate, soaking the quartz glass in absolute ethyl alcohol by using analytically pure absolute ethyl alcohol and ultrapure water as cleaning reagents, ultrasonically cleaning for 30min to remove grease and dust on the surface of the quartz glass, then cleaning for multiple times by using the ultrapure water, finally cleaning for the second time by using the absolute ethyl alcohol, and sealing for later use.
The infrared high-reflection metal layer in the step one is Ag; the thickness of the infrared high-reflection metal layer in the step one is 50 nm; HfO as described in step four2The thickness of the dielectric layer is 400 nm; VO described in step four2The layer thickness is 50 nm; the protective layer in the fifth step is Al2O3(ii) a And the thickness of the protective layer in the fifth step is 50 nm.
The phase transition temperature of the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure prepared by the embodiment is 65 ℃, the low-temperature emissivity at 20 ℃ is 0.12, the high-temperature emissivity at 100 ℃ is 0.44, and the emissivity change value is 0.32 by testing the emissivity from 20 ℃ to 100 ℃.
The normal-temperature solar absorption ratio of the intelligent vanadium dioxide thermal control device with the imitation longicorn multi-stage structure prepared by the embodiment is 0.4.
Example two: the difference between the present embodiment and the first embodiment is:
depositing an infrared high-reflection metal layer on a semiconductor substrate layer by using a direct-current magnetron sputtering technology at room temperature;
in the second step, under the condition that the temperature is 100 ℃, the direct current magnetron sputtering technology is utilized to prepare HfO on the infrared high-reflection metal layer2A dielectric film;
in the third step, under the condition of 400 deg.C, adopting high-energy pulse magnetron sputtering technique and using HfO2VO preparation on dielectric film2A film;
HfO as described in step four2The side length of a square on the bottom surface of the micro-nano structure unit is 2 mu m, the height of the square is 800nm, and the adjacent HfO2The distance between the micro-nano structure units is 1 mu m;
SiO described in step four2The diameter of the monolayer ball is 150 nm; undoped VO2The diameter of the bottom surface of the micro-nano structure unit is 150nm, and the height of the micro-nano structure unit is 150 nm; same HfO2VO (vanadium oxide) arranged on micro-nano structure unit and not doped adjacently2The micro-nano structure units are closely arranged;
the infrared high-reflection metal layer in the first step is Ni; the thickness of the infrared high-reflection metal layer in the first step is 100 nm; HfO as described in step four2The thickness of the dielectric layer is 800 nm; VO described in step four2The layer thickness is 150 nm; the protective layer in the fifth step is SiO2(ii) a And the thickness of the protective layer in the fifth step is 70 nm. Others with fruitThe same applies to the first embodiment.
The phase transition temperature of the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure prepared by the embodiment is 65 ℃, the low-temperature emissivity at 20 ℃ is 0.18, the high-temperature emissivity at 100 ℃ is 0.56, and the emissivity change value is 0.45 by testing the emissivity from 20 ℃ to 100 ℃.
The normal-temperature solar absorption ratio of the intelligent vanadium dioxide thermal control device with the imitated longicorn multistage structure prepared by the embodiment is 0.38.
Example three: the difference between the present embodiment and the first embodiment is:
in the first step, under the condition that the temperature is 300 ℃, an infrared high-reflection metal layer is deposited on a semiconductor substrate layer by utilizing a direct-current magnetron sputtering technology;
in the second step, under the condition that the temperature is 300 ℃, the direct current magnetron sputtering technology is utilized to prepare HfO on the infrared high-reflection metal layer2A dielectric film;
in the third step, under the condition of 450 deg.C, adopting high-energy pulse magnetron sputtering technique and using HfO2VO preparation on dielectric film2A film;
HfO as described in step four2The side length of a square on the bottom surface of the micro-nano structure unit is 4 mu m, the height of the square is 1.2 mu m, and the adjacent HfO2The distance between the micro-nano structure units is 2 mu m;
SiO described in step four2The diameter of the monolayer ball is 200 nm; the undoped VO2The diameter of the bottom surface of the micro-nano structure unit is 200nm, and the height of the micro-nano structure unit is 250 nm; same HfO2VO (vanadium oxide) arranged on micro-nano structure unit and not doped adjacently2The micro-nano structure units are closely arranged;
the infrared high-reflection metal layer in the step one is Mg; the thickness of the infrared high-reflection metal layer in the step one is 150 nm; HfO as described in step four2The thickness of the dielectric layer is 1.2 μm; VO described in step four2The layer thickness is 250 nm; the protective layer in the fifth step is TiO2(ii) a And the thickness of the protective layer in the fifth step is 80 nm. The rest is the same as the first embodiment.
The phase transition temperature of the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure prepared by the embodiment is 65 ℃, the low-temperature emissivity at 20 ℃ is 0.18, the high-temperature emissivity at 100 ℃ is 0.60, and the emissivity change value is 0.42 by testing the emissivity from 20 ℃ to 100 ℃.
The normal-temperature solar absorption ratio of the intelligent vanadium dioxide thermal control device with the imitated longicorn multi-stage structure prepared by the embodiment is 0.37.
Example four: the difference between the present embodiment and the first embodiment is:
in the first step, under the condition that the temperature is 200 ℃, an infrared high-reflection metal layer is deposited on a semiconductor substrate layer by utilizing a direct-current magnetron sputtering technology;
in the second step, under the condition that the temperature is 200 ℃, the direct current magnetron sputtering technology is utilized to prepare HfO on the infrared high-reflection metal layer2A dielectric film;
in the third step, under the condition of 500 ℃ temperature, the high-energy pulse magnetron sputtering technology is adopted to perform reaction on HfO2VO preparation on dielectric film2A film;
HfO as described in step four2The side length of a square on the bottom surface of the micro-nano structure unit is 6 mu m, the height of the square is 1.6 mu m, and the adjacent HfO2The distance between the micro-nano structure units is 3 mu m;
SiO described in step four2The diameter of the monolayer ball is 250 nm; the undoped VO2The diameter of the bottom surface of the micro-nano structure unit is 250nm, and the height of the micro-nano structure unit is 350 nm; same HfO2VO (vanadium oxide) arranged on micro-nano structure unit and not doped adjacently2The micro-nano structure units are closely arranged;
the infrared high-reflection metal layer in the first step is Zn; the thickness of the infrared high-reflection metal layer in the step one is 200 nm; HfO as described in step four2The thickness of the dielectric layer is 1.6 μm; VO described in step four2The layer thickness is 350 nm; the protective layer in the fifth step is ZrO2(ii) a And the thickness of the protective layer in the fifth step is 90 nm. The rest is the same as the first embodiment.
The phase transition temperature of the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure prepared by the embodiment is 65 ℃, the low-temperature emissivity at 20 ℃ is 0.21, the high-temperature emissivity at 100 ℃ is 0.73, and the emissivity change value is 0.52 by testing the emissivity from 20 ℃ to 100 ℃.
The normal-temperature solar absorption ratio of the intelligent vanadium dioxide thermal control device with the imitated longicorn multistage structure prepared by the embodiment is 0.36.
Example five: the difference between the present embodiment and the first embodiment is:
in the first step, under the condition that the temperature is 150 ℃, an infrared high-reflection metal layer is deposited on a semiconductor substrate layer by utilizing a direct-current magnetron sputtering technology;
in the second step, under the condition of room temperature, the direct current magnetron sputtering technology is utilized to prepare HfO on the infrared high-reflection metal layer2A dielectric film;
in the third step, under the condition of 600 ℃, the high-energy pulse magnetron sputtering technology is adopted to perform reaction on HfO2VO preparation on dielectric film2A film;
HfO as described in step four2The side length of a square on the bottom surface of the micro-nano structure unit is 8 mu m, the height of the square is 2 mu m, and the adjacent HfO2The distance between the micro-nano structure units is 4 mu m;
SiO described in step four2The diameter of the monolayer ball is 300 nm; the undoped VO2The diameter of the bottom surface of the micro-nano structure unit is 300nm, and the height of the micro-nano structure unit is 500 nm; same HfO2VO (vanadium oxide) arranged on micro-nano structure unit and not doped adjacently2The micro-nano structure units are closely arranged;
the infrared high-reflection metal layer in the step one is Al; the thickness of the infrared high-reflection metal layer in the step one is 250 nm; HfO as described in step four2The thickness of the dielectric layer is 2 μm; VO described in step four2The layer thickness is 500 nm; the protective layer in the fifth step is TiO2(ii) a And the thickness of the protective layer in the fifth step is 100 nm. The rest is the same as the first embodiment.
The phase transition temperature of the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure prepared by the embodiment is 65 ℃, the low-temperature emissivity at 20 ℃ is 0.21, the high-temperature emissivity at 100 ℃ is 0.81, and the emissivity change value is 0.60 by testing the emissivity from 20 ℃ to 100 ℃.
The normal-temperature solar absorption ratio of the intelligent vanadium dioxide thermal control device with the imitation longicorn multi-stage structure prepared by the embodiment is 0.35.
Example six: the difference between the present embodiment and the first embodiment is:
in the first step, under the condition that the temperature is 200 ℃, an infrared high-reflection metal layer is deposited on a semiconductor substrate layer by utilizing a direct-current magnetron sputtering technology;
in the second step, under the condition that the temperature is 100 ℃, the direct current magnetron sputtering technology is utilized to prepare HfO on the infrared high-reflection metal layer2A dielectric film;
in the third step, under the condition of 500 ℃ of temperature, the tungsten vanadium alloy target is utilized, the high-energy pulse magnetron sputtering technology is adopted, and the HfO is treated2VO preparation on dielectric film2A film;
HfO as described in step four2The side length of a square on the bottom surface of the micro-nano structure unit is 10 mu m, the height of the square is 800nm, and the adjacent HfO2The distance between the micro-nano structure units is 5 mu m;
SiO described in step four2The diameter of the monolayer ball is 150 nm; the W-doped VO2The diameter of the bottom surface of the micro-nano structure unit is 150nm, and the height of the micro-nano structure unit is 150 nm; same HfO2VO (volatile organic compound) doped with adjacent W and arranged on micro-nano structure unit2The micro-nano structure units are closely arranged;
the W-doped VO2W in the micro-nano structure unit accounts for 0.5% of the total atomic number of W and V;
the infrared high-reflection metal layer in the step one is Ag; the thickness of the infrared high-reflection metal layer in the first step is 100 nm; HfO as described in step four2The thickness of the dielectric layer is 800 nm; VO described in step four2The layer thickness is 150 nm; the protective layer in the fifth step is SiO2(ii) a And the thickness of the protective layer in the fifth step is 60 nm. The rest is the same as the first embodiment.
The phase transition temperature of the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure prepared by the embodiment is 57 ℃, compared with that of undoped vanadium dioxide, the phase transition temperature is reduced by 8 ℃, the low-temperature emissivity at 20 ℃ is 0.21, the high-temperature emissivity at 100 ℃ is 0.79, and the emissivity change value is 0.58 by testing the emissivity from 20 ℃ to 100 ℃.
The normal-temperature solar absorption ratio of the intelligent vanadium dioxide thermal control device with the imitated longicorn multistage structure prepared by the embodiment is 0.36.
Example seven: the difference between the present embodiment and the first embodiment is:
in the first step, under the condition that the temperature is 200 ℃, an infrared high-reflection metal layer is deposited on a semiconductor substrate layer by utilizing a direct-current magnetron sputtering technology;
in the second step, under the condition that the temperature is 100 ℃, the direct current magnetron sputtering technology is utilized to prepare HfO on the infrared high-reflection metal layer2A dielectric film;
in the third step, under the condition of 500 ℃ of temperature, the tungsten vanadium alloy target is utilized, the high-energy pulse magnetron sputtering technology is adopted, and the HfO is treated2VO preparation on dielectric film2A film;
HfO as described in step four2The side length of a square on the bottom surface of the micro-nano structure unit is 10 mu m, the height of the square is 800nm, and the adjacent HfO2The distance between the micro-nano structure units is 5 mu m;
SiO described in step four2The diameter of the monolayer ball is 200 nm; the W-doped VO2The diameter of the bottom surface of the micro-nano structure unit is 200nm, and the height of the micro-nano structure unit is 150 nm; same HfO2VO (volatile organic compound) doped with adjacent W and arranged on micro-nano structure unit2The micro-nano structure units are closely arranged;
the W-doped VO2W in the micro-nano structure unit accounts for 1.0% of the total atomic number of W and V;
the infrared high-reflection metal layer in the step one is Ag; the thickness of the infrared high-reflection metal layer in the first step is 100 nm; HfO as described in step four2The thickness of the dielectric layer is 800 nm; VO described in step four2The layer thickness is 150 nm; the protective layer in the fifth step is SiO2(ii) a And the thickness of the protective layer in the fifth step is 60 nm. The rest is the same as the first embodiment.
The phase transition temperature of the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure prepared by the embodiment is 47.7 ℃, the emissivity is reduced by 17.3 ℃ compared with that of undoped vanadium dioxide, the low-temperature emissivity at 20 ℃ is 0.16, the emissivity at high temperature at 100 ℃ is 0.67, and the emissivity change value is 0.51 by testing the emissivity from 20 ℃ to 100 ℃.
The solar absorption ratio of the intelligent vanadium dioxide thermal control device with the imitated longicorn multistage structure prepared by the embodiment is 0.36.
Example eight: the difference between the present embodiment and the first embodiment is:
in the first step, under the condition that the temperature is 200 ℃, an infrared high-reflection metal layer is deposited on a semiconductor substrate layer by utilizing a direct-current magnetron sputtering technology;
in the second step, under the condition that the temperature is 100 ℃, the direct current magnetron sputtering technology is utilized to prepare HfO on the infrared high-reflection metal layer2A dielectric film;
in the third step, under the condition of 500 ℃ of temperature, the tungsten vanadium alloy target is utilized, the high-energy pulse magnetron sputtering technology is adopted, and the HfO is treated2VO preparation on dielectric film2A film;
HfO as described in step four2The side length of a square on the bottom surface of the micro-nano structure unit is 10 mu m, the height of the square is 800nm, and the adjacent HfO2The distance between the micro-nano structure units is 5 mu m;
SiO described in step four2The diameter of the monolayer ball is 250 nm; the W-doped VO2The diameter of the bottom surface of the micro-nano structure unit is 250nm, and the height of the micro-nano structure unit is 150 nm; same HfO2VO (volatile organic compound) doped with adjacent W and arranged on micro-nano structure unit2The micro-nano structure units are closely arranged;
the W-doped VO2W in the micro-nano structure unit accounts for 1.5% of the total atomic number of W and V;
the infrared high-reflection metal layer in the step one is Ag; the thickness of the infrared high-reflection metal layer in the first step is 100 nm; HfO as described in step four2The thickness of the dielectric layer is 800 nm; VO described in step four2The layer thickness is 150 nm; the protective layer in the fifth step is SiO2(ii) a And the thickness of the protective layer in the fifth step is 60 nm. The rest is the same as the first embodiment.
The phase transition temperature of the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure prepared by the embodiment is 34.2 ℃, the emissivity at the low temperature of 20 ℃ is 0.17, the emissivity at the high temperature of 100 ℃ is 0.66, and the emissivity change value is 0.49 when the emissivity is tested from 20 ℃ to 100 ℃ compared with that of undoped vanadium dioxide.
The normal-temperature solar absorption ratio of the intelligent vanadium dioxide thermal control device with the imitated longicorn multi-stage structure prepared by the embodiment is 0.37.
Example nine: the difference between the present embodiment and the first embodiment is:
in the first step, under the condition that the temperature is 200 ℃, an infrared high-reflection metal layer is deposited on a semiconductor substrate layer by utilizing a direct-current magnetron sputtering technology;
in the second step, under the condition that the temperature is 100 ℃, the direct current magnetron sputtering technology is utilized to prepare HfO on the infrared high-reflection metal layer2A dielectric film;
in the third step, under the condition of 500 ℃ of temperature, the tungsten vanadium alloy target is utilized, the high-energy pulse magnetron sputtering technology is adopted, and the HfO is treated2VO preparation on dielectric film2A film;
HfO as described in step four2The side length of a square on the bottom surface of the micro-nano structure unit is 10 mu m, the height of the square is 800nm, and the adjacent HfO2The distance between the micro-nano structure units is 5 mu m;
SiO described in step four2The diameter of the monolayer ball is 300 nm; the W-doped VO2The diameter of the bottom surface of the micro-nano structure unit is 300nm, and the height of the micro-nano structure unit is 150 nm; same HfO2VO (volatile organic compound) doped with adjacent W and arranged on micro-nano structure unit2Micro-nano close arrangement;
the W-doped VO2W in the micro-nano structure unit accounts for 2.0% of the total atomic number of W and V;
the infrared high-reflection metal layer in the step one is Ag; the thickness of the infrared high-reflection metal layer in the first step is 100 nm; HfO as described in step four2The thickness of the dielectric layer is 800 nm; VO described in step four2The layer thickness is 150 nm; the protective layer in the fifth step is SiO2(ii) a And the thickness of the protective layer in the fifth step is 60 nm. The rest is the same as the first embodiment.
The phase transition temperature of the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure prepared by the embodiment is 29.8 ℃, the emissivity at the low temperature of 20 ℃ is 0.18, the emissivity at the high temperature of 100 ℃ is 0.63, and the emissivity change value is 0.45 when the emissivity is tested from 20 ℃ to 100 ℃ compared with that of undoped vanadium dioxide.
The normal-temperature solar absorption ratio of the intelligent vanadium dioxide thermal control device with the imitated longicorn multi-stage structure prepared by the embodiment is 0.37.
Example ten: the difference between the present embodiment and the first embodiment is:
in the first step, under the condition that the temperature is 200 ℃, an infrared high-reflection metal layer is deposited on a semiconductor substrate layer by utilizing a direct-current magnetron sputtering technology;
in the second step, under the condition that the temperature is 100 ℃, the direct current magnetron sputtering technology is utilized to prepare HfO on the infrared high-reflection metal layer2A dielectric film;
in the third step, under the condition of 500 ℃ of temperature, the tungsten vanadium alloy target is utilized, the high-energy pulse magnetron sputtering technology is adopted, and the HfO is treated2VO preparation on dielectric film2A film;
HfO as described in step four2The side length of a square on the bottom surface of the micro-nano structure unit is 10 mu m, the height of the square is 800nm, and the adjacent HfO2The distance between the micro-nano structure units is 5 mu m;
SiO described in step four2The diameter of the monolayer ball is 300 nm; the W-doped VO2The diameter of the bottom surface of the micro-nano structure unit is 300nm, and the height of the micro-nano structure unit is 150 nm; same HfO2VO (volatile organic compound) doped with adjacent W and arranged on micro-nano structure unit2The micro-nano structure units are closely arranged;
the W-doped VO2The doping content of W in the micro-nano structure unit is 2.5%;
the infrared high-reflection metal layer in the step one is Ag; the thickness of the infrared high-reflection metal layer in the first step is 100 nm; HfO as described in step four2The thickness of the dielectric layer is 800 nm; VO described in step four2The layer thickness is 150 nm; the protective layer in the fifth step is SiO2(ii) a Step five isThe thickness of the protective layer is 60 nm. The rest is the same as the first embodiment.
The variable temperature of the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure prepared by the embodiment is 24 ℃, compared with that of undoped vanadium dioxide, the variable temperature is reduced by 41 ℃, the low-temperature emissivity at 20 ℃ is 0.19, the high-temperature emissivity at 100 ℃ is 0.60, and the emissivity change value of the intelligent vanadium dioxide thermal control device is obtained by testing the emissivity from 20 ℃ to 100 ℃.
The solar absorption ratio of the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure prepared by the embodiment is 0.35.

Claims (10)

1. An intelligent vanadium dioxide thermal control device with a skyhook-like multi-stage structure is characterized in that the intelligent vanadium dioxide thermal control device with the skyhook-like multi-stage structure sequentially comprises a semiconductor substrate layer, an infrared high-reflection metal layer, and HfO (hafnium oxide)2Dielectric layer and VO2A layer and a protective layer;
said HfO2The dielectric layer is composed of multiple HfO2Micro-nano structure unit composition and HfO2The micro-nano structure unit is in the shape of a cube with a square bottom surface and a plurality of HfO2The micro-nano structure units are uniformly distributed on the upper surface of the infrared high-reflection metal layer; said HfO2The side length of a square on the bottom surface of the micro-nano structure unit is 1-10 mu m, and the height is 400-2000 nm; adjacent HfO2The distance between the micro-nano structure units is 0.5-5 mu m;
the VO2VO with layer doped with multiple W2VO formed by micro-nano structure units and doped with W2The micro-nano structure unit is conical and is provided with a plurality of W-doped VOs2Micro-nano structure units are uniformly distributed on HfO2The upper surface of the dielectric layer; the W-doped VO2The diameter of the bottom surface of the micro-nano structure unit is 20 nm-300 nm, and the height is 50 nm-500 nm; same HfO2VO (volatile organic compound) doped with adjacent W and arranged on micro-nano structure unit2The micro-nano structure units are closely arranged;
the W-doped VO2W in the micro-nano structure unit accounts for 0-2.5% of the total atomic number of W and V.
2. The intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure according to claim 1, wherein the semiconductor substrate layer is quartz, glass or silicon; the infrared high-reflection metal layer is Ag, Ni, Mg, Zn or Al; the protective layer is Al2O3、SiO2、TiO2Or ZrO2。
3. The intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure according to claim 1, wherein the thickness of the infrared high-reflection metal layer is 50nm to 250 nm; said HfO2The thickness of the dielectric layer is 400 nm-2000 nm; the VO2The layer thickness is 50 nm-500 nm; the thickness of the protective layer is 50 nm-100 nm.
4. The preparation method of the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure as claimed in claim 1, characterized by comprising the following steps:
firstly, preparing an infrared high-reflection metal layer:
depositing an infrared high-reflection metal layer on the semiconductor substrate layer by using a direct-current magnetron sputtering technology;
secondly, preparing a dielectric film:
preparing HfO on the infrared high-reflection metal layer by using a direct-current magnetron sputtering technology2A dielectric film;
III, VO2Preparing a film:
using high-energy pulse magnetron sputtering technique on HfO2VO preparation on dielectric film2A film;
fourthly, processing the microstructure:
firstly, adopting a plasma etching method to carry out VO2Etching the surface layer of the film in a grid structure, and then carrying out HfO2Carrying out plasma etching on the dielectric film to obtain HfO2Dielectric layer, VO after etching of grid structure2Deposition of SiO on the surface of thin film2The ball is used as a template, and then the VO with a grid structure is etched by utilizing a reactive plasma etching technology2Etching the film, and finally removing SiO2Ball to obtain VO2A layer;
fifthly, deposition of a protective layer:
and depositing a protective layer by using high-energy pulse magnetron sputtering to obtain the intelligent vanadium dioxide thermal control device with the imitation longicorn multi-stage structure.
5. The method for preparing a celestial cow multilevel structure-imitated vanadium dioxide intelligent thermal control device as claimed in claim 4, wherein the semiconductor substrate layer in the step one is obtained by cleaning a semiconductor substrate with analytically pure absolute ethanol and ultrapure water as cleaning reagents.
6. The method for preparing a celestial cow multilevel structure-imitated vanadium dioxide intelligent thermal control device according to claim 4, wherein the semiconductor substrate layer in the first step is quartz, glass or silicon; the infrared high-reflection metal layer in the first step is Ag, Ni, Mg, Zn or Al; the thickness of the infrared high-reflection metal layer in the step one is 50 nm-250 nm; HfO as described in step four2The thickness of the dielectric layer is 400 nm-2000 nm; VO described in step four2The layer thickness is 50 nm-500 nm; the protective layer in the fifth step is Al2O3、SiO2、TiO2Or ZrO2(ii) a And the thickness of the protective layer in the fifth step is 50 nm-100 nm.
7. The method for preparing a celestial cow multilevel structure-imitated vanadium dioxide intelligent thermal control device as claimed in claim 4, wherein in the step one, an infrared high-reflection metal layer is deposited on the semiconductor substrate layer by using a direct current magnetron sputtering technology at a temperature of between room temperature and 400 ℃.
8. The method for preparing a celestial cow multilevel structure-imitated vanadium dioxide intelligent thermal control device according to claim 4, wherein in the second step, HfO is prepared on the infrared high-reflection metal layer by using a direct-current magnetron sputtering technology at a temperature of between room temperature and 400 DEG C2A dielectric film.
9. The method for preparing a celestial cow multilevel structure-imitated vanadium dioxide intelligent thermal control device according to claim 4, characterized in that in the third step, a high-energy pulse magnetron sputtering technology is adopted at a temperature of 300 ℃ -600 ℃, and a HfO (high-frequency oxide) is adopted2VO preparation on dielectric film2A film.
10. The method for preparing the intelligent vanadium dioxide thermal control device with the imitation longicorn multistage structure according to claim 4, wherein the VO is etched by plasma in the fourth step2Etching the surface layer of the film with a latticed structure, specifically, firstly etching at VO2Coating a layer of photoresist with a grid pattern on the surface of the thin film, wherein the flow rate of Ar gas is 8 sccm-12 sccm, and CF is adopted4The VO is etched by adopting a plasma etching method under the conditions that the gas flow is 8sccm to 12sccm, the power is 90W to 120W and the gas pressure is 90mtorr to 120mtorr2Etching the surface of the film to form a grid structure, and removing the photoresist; step four to HfO2Carrying out plasma etching on the dielectric film to obtain HfO2A dielectric layer, specifically, the flow rate of Ar gas is 8 sccm-12 sccm, and CHF3For HfO, the gas flow is 8sccm to 12sccm, the power is 110W to 140W, and the gas pressure is 90mtorr to 120mtorr2Carrying out plasma etching on the dielectric film to obtain HfO2A dielectric layer; VO after grid structure etching in step four2Deposition of SiO on the surface of thin film2The ball is used as a template, and then the VO with a grid structure is etched by utilizing a reactive plasma etching technology2Etching the film, and finally removing SiO2Ball to obtain VO2Layer, in particular VO after etching of a grid-like structure2A layer of SiO with the diameter of 20 nm-300 nm is deposited on the surface of the film2A single layer ball with Ar gas flow rate of 8-12 sccm and CF4VO after etching the grid structure by using the reactive plasma etching technology under the conditions that the gas flow is 8 sccm-12 sccm, the power is 80W-100W and the gas pressure is 90 mtorr-120 mtorr2Etching the film and removingSiO2Ball to obtain VO2And (3) a layer.
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