WO2020125440A1 - 一种两步法制备柔性氧化钒薄膜的方法 - Google Patents

一种两步法制备柔性氧化钒薄膜的方法 Download PDF

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WO2020125440A1
WO2020125440A1 PCT/CN2019/123451 CN2019123451W WO2020125440A1 WO 2020125440 A1 WO2020125440 A1 WO 2020125440A1 CN 2019123451 W CN2019123451 W CN 2019123451W WO 2020125440 A1 WO2020125440 A1 WO 2020125440A1
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vanadium oxide
film
substrate
temperature
thin film
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French (fr)
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鲁远甫
李锐
刘文权
李光元
刘波
焦国华
吕建成
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深圳先进技术研究院
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment

Definitions

  • the invention relates to a method for preparing a thin film of microelectronic semiconductor technology, in particular to a method for preparing a thermosensitive thin film material of a flexible vanadium oxide terahertz detector by a two-step method.
  • the application its unique properties such as transient, low energy, coherence, penetration and characteristic absorption of the spectrum have been generally recognized.
  • terahertz technology we not only need a good solution to reliable and stable terahertz sources, high-sensitivity and high signal-to-noise ratio terahertz detectors, but also need to provide good terahertz waveguides and filters , Modulation, switching, beam splitting, polarization and other new functional devices.
  • terahertz waveguides and filters Modulation, switching, beam splitting, polarization and other new functional devices.
  • natural materials lack effective response to terahertz waves, and existing electronic devices and optical devices cannot achieve terahertz transmission and control.
  • the lack of terahertz materials and devices severely restricts the development of terahertz technology to practicality, and has become one of the key issues in the terahertz field that needs to be solved urgently.
  • the related terahertz detectors reported so far are prepared directly on the silicon substrate, and the device processing is more difficult: according to the " ⁇ /4 principle" of the infrared microbolometer microbridge, it is applied to the terahertz detection, if the wavelength needs to be detected For 100 ⁇ m (3THz), the height of the micro-bridge resonant cavity needs to reach 25 ⁇ m (Note: the infrared detector is only 1 ⁇ 2 ⁇ m), and the manufacturing accuracy of the microbridge is 0.1 ⁇ 1 ⁇ m.
  • Current device materials and processing technology (MEMS) are difficult to meet the relevant requirements.
  • a VO x terahertz detector based on a flexible substrate can avoid the use of complex CMOS processes on a silicon substrate, reduce the difficulty of the preparation process, and reduce the cost of manufacturing the detector.
  • flexible terahertz detectors mainly because the preparation of good quality VO x thermosensitive films on flexible substrates requires growth at high temperatures (>400°C), and most flexible materials Does not have high temperature resistance.
  • VO x thin film based on flexible materials 1. Higher temperature coefficient of resistance; 2. Dense and uniform surface; 3. Good film formation quality and good interface bonding with the substrate.
  • the VO x film formed by the chemical gel sol method is difficult to meet the above requirements, and the magnetron sputtering deposition method is selected to prepare the VO x film formed under the appropriate process conditions, which can meet the above Conditional requirements.
  • the patent application with the application number CN201310272361.7 discloses a preparation method of a THz modulator film material based on a flexible substrate, and specifically discloses a VO x film based on a flexible substrate polyimide.
  • a metal V thin film is prepared by magnetron sputtering at a low temperature, and then the V thin film is heat-treated for 30 to 180 s in an oxygen atmosphere within a temperature range of 250 to 300° C. to obtain a VO x thin film.
  • the above method belongs to the thin film oxidation method.
  • the thin film is grown at a low temperature and the heat treatment temperature is low. It is difficult to control the process under the preparation of an oxygen atmosphere. It is difficult to grow a thin film of good quality VO x and is not suitable for use in flexible terahertz detectors.
  • the invention proposes a two-step method for preparing a flexible VO x composite film.
  • the first step is to prepare the vanadium oxide precursor at a low temperature by using magnetron sputtering with a high temperature resistant polyimide PI (thermal decomposition temperature of 494°C) as the substrate; the second step is heat treatment at high temperature that is in situ annealing.
  • the composite flexible film obtained by the method of the present invention has a uniform surface, dense structure, good film formation quality, and good crystallization, and VO x is tightly combined with polyimide and is not easy to fall off.
  • the present invention prepares a vanadium oxide precursor at a low temperature by using magnetron sputtering, and then heat-treats the precursor to form a uniform surface, dense structure, good film formation quality, and good crystallization ⁇ Vanadium oxide composite flexible film which is tightly combined with polyimide and not easy to fall off.
  • the invention relates to a method for preparing a vanadium oxide composite film, which includes: step one, forming a high temperature resistant flexible material film on a substrate to form a substrate; step two, forming oxidation on the flexible material on the substrate Vanadium precursor film; step three, the substrate formed with the vanadium oxide precursor film is annealed at high temperature to form a composite film with a vanadium oxide film.
  • a substrate preparation step is further included; wherein, the substrate is a silicon substrate.
  • the substrate preparation step further includes forming a silicon nitride layer on the silicon substrate to form a silicon substrate having a silicon nitride layer; in step one, the flexible material film is formed on the substrate On the silicon nitride layer on the bottom.
  • a peeling step is further included; wherein, the peeling step includes peeling the flexible material film formed with the vanadium oxide film from the substrate to obtain a formation on the flexible material film Composite film with vanadium oxide film.
  • the thermal decomposition temperature of the high temperature resistant flexible material is higher than the high temperature annealing temperature in step three.
  • the high temperature resistant flexible material is a high temperature resistant resin material.
  • the high temperature resistant resin material is polyimide.
  • the thermal decomposition temperature of the polyimide is greater than 400°C.
  • the vanadium oxide precursor thin film is formed on the flexible material by a magnetron sputtering method.
  • the conditions of the magnetron sputtering are: the substrate temperature is 100-420° C., the vacuum degree is 2.5-4.0 ⁇ 10 -4 Pa, the distance between the target and the substrate is 80 mm, and the argon flow rate is 15-30 sccm , Oxygen flow rate is 0.3-2.0sccm, argon-oxygen ratio is 7.5:1-50:1, sputtering working pressure is 0.1-0.3Pa, sputtering power is 150-200W, deposition time is 15-60min.
  • the condition for performing high-temperature annealing in step three is to anneal the substrate formed with the vanadium oxide precursor thin film in a vacuum or inert environment.
  • the temperature for high-temperature annealing in step 3 is 420-480°C.
  • the annealing environment is an argon atmosphere with a vacuum of 0.1-0.3 Pa.
  • the invention also relates to a method for preparing a vanadium oxide composite film, which includes step one, preparing a substrate, and forming a silicon nitride layer on a silicon substrate; step two, placing the substrate in deionized water and anhydrous water in sequence Ultrasonic cleaning in ethanol and acetone solvents for 10 minutes and drying; Step three, prepare the substrate and form a polyimide film on the substrate; Step four, place the substrate in deionized water, Ultrasonic cleaning in absolute ethanol and acetone solvents for 10 minutes and drying; Step five: Place the cleaned substrate in a high vacuum RF magnetron sputtering device with a vacuum of 2.5 ⁇ 4.0 ⁇ 10 -4 Pa.
  • argon flow rate of 15-30sccm, oxygen flow rate of 0.3-2.0sccm, argon-oxygen ratio of 7.5:1-50:1, sputtering working pressure of 0.1-0.3Pa, sputtering
  • the power is 150-200W and the distance between the target and the substrate is 80mm, deposit 15-60min to form a vanadium oxide precursor film on the substrate;
  • the target is a metal vanadium target; step six, at 420 After annealing at -480°C for 30 min or more, the obtained vanadium oxide film is a layered polycrystalline film, and the thickness of the vanadium oxide film is 150 nm.
  • a peeling step is further included; wherein the peeling step includes peeling the polyimide film formed with a vanadium oxide film from the substrate to obtain the flexible material film A vanadium oxide composite film with a vanadium oxide film formed thereon.
  • the third step further includes uniformly applying the polyimide solution on the substrate by means of knife coating or spin coating, baking at 50-60°C for 2 hours, and then at 300-400°C Heating for 8 hours under annealing to obtain a uniform polyimide film on the silicon substrate.
  • the invention also relates to a vanadium oxide composite film formed by any one of the above methods.
  • the beneficial effect of the present invention lies in overcoming the shortcomings of the existing low-temperature technology for preparing flexible vanadium oxide.
  • a flexible polyimide-based substrate using magnetron sputtering method, low-temperature preparation of layered vanadium oxide, and then high-temperature annealing in different atmospheres to obtain a simple process and easy to control
  • the composite film preparation method laid the foundation for the preparation of flexible vanadium oxide devices.
  • the composite flexible film obtained by the preparation method of the present invention has a uniform surface, dense structure, good film formation quality, and good crystallization, and the vanadium oxide and polyimide are tightly combined and are not easy to fall off.
  • Figure 1 The overall structure of the vanadium oxide composite film
  • Figure 2 Schematic diagram of the layered vanadium oxide composite film
  • Figure 3 Scanning electron microscope image of the vanadium oxide film prepared by the method of Example 1;
  • Figure 4 Atomic force microscope image of the vanadium oxide film prepared by the method of Example 1;
  • Figure 5 Variation curve of resistance of vanadium oxide thin film prepared by the method of Example 1 with temperature
  • Figure 6 Scanning electron microscope image of the vanadium oxide film prepared by the method of Example 2;
  • Figure 7 Atomic force microscope image of the vanadium oxide film prepared by the method of Example 2;
  • Figure 8 Variation curve of resistance of vanadium oxide thin film prepared by the method of Example 2 with temperature
  • Figure 9 Scanning electron microscope image of the vanadium oxide film prepared by the method of Example 3.
  • Figure 10 Atomic force microscope image of the vanadium oxide film prepared by the method of Example 3;
  • Figure 11 Variation curve of resistance of vanadium oxide thin film prepared by the method of Example 3 with temperature
  • Figure 12 Scanning electron microscope image of the vanadium oxide film prepared by the method of Example 4.
  • Figure 13 Atomic force microscope image of the vanadium oxide film prepared by the method of Example 4.
  • Figure 14 Variation curve of resistance of vanadium oxide thin film prepared by the method of Example 4 with temperature
  • Figure 15 Scanning electron microscope image of the vanadium oxide film prepared by the method of Example 5;
  • Figure 16 Atomic force microscope image of vanadium oxide film prepared by the method of Example 5;
  • Figure 17 Variation curve of resistance of vanadium oxide thin film prepared by the method of Example 5 with temperature
  • Figure 18 Scanning electron microscope image of the vanadium oxide film prepared by the method of Example 6;
  • Figure 19 Atomic force microscope image of the vanadium oxide film prepared by the method of Example 6;
  • Figure 20 Variation curve of resistance of vanadium oxide thin film prepared by the method of Example 6 with temperature
  • Figure 21 Scanning electron microscope image of the vanadium oxide film prepared by the method of Example 7;
  • Figure 22 Atomic force microscope image of the vanadium oxide film prepared by the method of Example 7;
  • Figure 23 Variation curve of resistance of vanadium oxide thin film prepared by the method of Example 7 with temperature
  • Figure 24 Scanning electron microscope image of the vanadium oxide film prepared by the method of Example 8.
  • Figure 25 Atomic force microscope image of the vanadium oxide film prepared by the method of Example 8.
  • Figure 26 Variation curve of resistance of vanadium oxide thin film prepared by the method of Example 8 with temperature
  • Figure 27 Scanning electron microscope image of the vanadium oxide film prepared by the method of Example 9;
  • Figure 28 Atomic force microscope image of the vanadium oxide film prepared by the method of Example 9;
  • Figure 29 Variation curve of resistance of vanadium oxide thin film prepared by the method of Example 9 with temperature
  • Figure 30 Scanning electron microscope image of the vanadium oxide film prepared by the method of Example 10;
  • Figure 31 Atomic force microscope image of vanadium oxide thin film prepared by the method of Example 10;
  • Figure 32 Variation curve of resistance of vanadium oxide thin film prepared by the method of Example 10 with temperature
  • Figure 33 Scanning electron microscope image of the vanadium oxide film prepared by the method of Example 11;
  • Figure 34 Atomic force microscope image of the vanadium oxide thin film prepared by the method of Example 11;
  • Figure 35 Variation curve of resistance of vanadium oxide thin film prepared by the method of Example 11 with temperature.
  • This embodiment relates to a two-step preparation method for preparing a flexible vanadium oxide (VO x ) thin film.
  • the method mainly includes two steps of forming a vanadium oxide precursor at a low temperature on a substrate and annealing the vanadium oxide precursor at a high temperature.
  • the vanadium oxide is not limited to VO 2 and V 2 O 5 , that is, oxides including various forms of vanadium, that is, generally referred to as VO x by those skilled in the art.
  • the main steps include forming a high-temperature resistant flexible material film 12 on a substrate, and forming a substrate therefrom, the substrate can be used in a subsequent step to form a vanadium oxide film 11, that is, the flexible material on the substrate A vanadium oxide precursor film is formed thereon, and then the substrate on which the vanadium oxide precursor film is formed is further annealed at high temperature to form a composite film 1 of vanadium oxide film.
  • a vanadium oxide precursor is formed on the substrate, which can form a vanadium oxide crystal with good crystalline form during the reaction combination; then annealing at a high temperature can effectively diffuse the elements uniformly, forming a good film forming quality, and having a small surface roughness film.
  • a step of preparing a substrate is also included, and a silicon substrate is generally selected as the substrate of the composite thin film, so as to facilitate making the composite thin film directly into related devices in a terahertz detector.
  • the step of preparing the substrate further includes forming a silicon nitride layer 13 on the silicon substrate 14 to form a silicon substrate having the silicon nitride layer 13; and further thinning the flexible material film 12 is formed on the silicon nitride layer on the substrate.
  • the silicon nitride layer is used as an insulating layer for subsequent device preparation, as well as for MEMS process preparation suitable for device processing. During the reaction, it only serves as a carrier for the flexible film together with the silicon wafer, and does not participate in the direct reaction.
  • a peeling step is also included.
  • the peeling step includes peeling the flexible material film 12 formed with the vanadium oxide film 11 from the substrate to obtain the vanadium oxide film 11 formed on the flexible material film 12, that is, the flexible vanadium oxide composite film.
  • the peeling step includes peeling the flexible material film 12 formed with the vanadium oxide film 11 from the substrate to obtain the vanadium oxide film 11 formed on the flexible material film 12, that is, the flexible vanadium oxide composite film.
  • a flexible vanadium oxide composite film can be obtained separately, which can be suitable for use as a separate flexible film material under different use environments and use conditions.
  • the high temperature resistant flexible material is preferably a high temperature resistant resin material, and further preferably a polyimide resin material, and the thermal decomposition temperature of the polyimide is greater than 400°C.
  • the thermal decomposition temperature of the high temperature resistant flexible material is higher than the temperature of high temperature annealing. Therefore, the vanadium oxide film 11 formed on the surface of the flexible material film 12 can be annealed under high temperature conditions, and the surface is uniform, the structure is dense, the film formation quality is good, the crystallization is good, and the vanadium oxide and polyimide Combined with a vanadium oxide composite film that is tight and not easy to fall off.
  • the vanadium oxide precursor thin film is formed on the flexible material by a magnetron sputtering method; and the condition of the magnetron sputtering is preferably that the substrate temperature is 100-400°C, Vacuum degree is 2.5 ⁇ 4.0 ⁇ 10 -4 Pa, distance between target and substrate is 80mm, argon flow rate is 15-30sccm, oxygen flow rate is 0.3-2.0sccm, argon-oxygen ratio is 7.5:1-39:1, splash The working pressure of the jet is 0.3Pa, the sputtering power is 150-200W, and the deposition time is 15-60min; wherein, the target material used is a metal vanadium target, the mass purity is ⁇ 99.99%, the purity of argon is ⁇ 99.999%, The purity of oxygen is ⁇ 99.99%. In this way, a vanadium oxide film with uniform surface, dense structure, good film formation quality, and good crystallization, and the combination of vanadium oxide and polyimide is not easy to fall
  • the high temperature annealing condition is that the vanadium oxide precursor film is annealed in a vacuum or inert environment; further preferably, in an argon atmosphere with a vacuum of 0.1-0.3 Pa, at 420- After annealing at 480°C for more than 30 min, the obtained vanadium oxide film is a layered polycrystalline film, and the thickness of the vanadium oxide film is 150 nm.
  • High-temperature annealing under vacuum or inert conditions helps to improve the quality of film formation, forming a thin film of vanadium oxide with uniform surface, dense structure, good crystallization, and not easy to fall off.
  • a specific method for preparing a vanadium oxide thin film includes: step one, preparing a substrate and forming a silicon nitride layer on a silicon substrate; step two, placing the substrate in deionized water and absolute ethanol in sequence ⁇ Using ultrasonic cleaning in acetone solvent for 10 minutes, and drying; Step three, prepare the substrate, forming a polyimide film on the substrate; Step four, place the substrate in deionized water, no Sonicate for 10 minutes in water ethanol and acetone solvent, and dry; Step five: Place the cleaned substrate in a high vacuum RF magnetron sputtering equipment with a vacuum of 2.5 ⁇ 4.0 ⁇ 10 -4 Pa.
  • the wafer temperature is 100-400°C
  • the argon flow rate is 15-30sccm
  • the oxygen flow rate is 0.3-2.0sccm
  • the argon-oxygen ratio is 7.5:1-39:1
  • the sputtering working pressure is 0.3Pa
  • the sputtering power is 150- 200W, under the condition that the distance between the target and the substrate is 80mm, deposit 15-60min to form a vanadium oxide precursor film on the substrate;
  • the target is a metal vanadium target with a mass purity of ⁇ 99.99%;
  • Step 6 After annealing at 420-480°C for more than 30 minutes, the obtained vanadium oxide film is a layered polycrystalline film, and the thickness of the vanadium oxide film is 150 nm. In this way, a vanadium oxide film with uniform surface, dense structure, good film formation quality, and good crystallization, and the combination of vanadium oxide and polyimide is not easy to fall off.
  • a peeling step is further included; wherein, the peeling step includes peeling the polyimide film formed with the vanadium oxide film from the substrate to obtain The vanadium oxide film formed on the flexible material film.
  • the peeling step includes peeling the polyimide film formed with the vanadium oxide film from the substrate to obtain The vanadium oxide film formed on the flexible material film.
  • the third step further includes uniformly applying the polyimide solution on the substrate by knife coating or spin coating, baking at 50-60°C for 2 hours, and then at 300 -Heating at 400°C for 8 hours for annealing to obtain a uniform polyimide film on the silicon substrate.
  • a polyimide film having a high thermal decomposition temperature can be obtained.
  • the thermal decomposition temperature of the polyimide film is greater than 400°C.
  • the obtained polyimide film has a dielectric constant of 3.4 and a thermal decomposition temperature of 494°C.
  • Step 1 Prepare the substrate.
  • a silicon substrate is provided, and a silicon nitride layer is formed on the silicon substrate by a plasma enhanced chemical vapor deposition method.
  • the size of the silicon substrate used is 33mm ⁇ 33mm.
  • the silicon nitride layer is used as an insulating layer for subsequent device preparation, as well as for MEMS process preparation suitable for device processing. During the reaction, the silicon nitride layer only serves as a carrier for the flexible film together with the silicon wafer, and does not participate in the direct reaction.
  • Step 2 Put the substrate in deionized water, absolute ethanol, and acetone solvents in sequence for 10 minutes, and dry them.
  • Step 3 Prepare the substrate.
  • the polyimide (PI) solution is evenly applied on the cleaned substrate by scraping or spin coating, and baked at 50-60°C for 2 hours to remove the organic components in the polyimide, After heating at a high temperature of 300-400°C for 8 hours, an imidization reaction occurs, and finally a uniform polyimide film is obtained on the substrate.
  • the obtained polyimide had a dielectric constant of 3.4 and a thermal decomposition temperature of 494°C.
  • Step 4 Place the substrate in the deionized water, absolute ethanol, and acetone solvents in sequence for 10 minutes, and dry.
  • Step five prepare a vanadium oxide precursor film.
  • the vacuum degree of sputtering work is 2.5 ⁇ 4.0 ⁇ 10 -4 Pa, metal vanadium as target, the distance between target and substrate is 80mm, argon flow rate is 15sccm, oxygen flow rate is 1.0sccm, argon-oxygen ratio is 15:1, sputtering working pressure is 0.3Pa ,
  • the sputtering power is 200W
  • the substrate temperature during growth is 300°C
  • the deposition time is 15-60min.
  • the mass purity of the metal vanadium target is 99.99%, the purity of argon is ⁇ 99.999%, and the purity of oxygen is ⁇ 99.99%.
  • the resulting vanadium oxide (VO x ) is a layered amorphous VOx thin film.
  • Step 6 Anneal at high temperature in a vacuum or argon atmosphere.
  • the gas pressure is adjusted to 0.3 Pa by introducing argon gas, and annealed at 480°C for 30 min.
  • the obtained vanadium oxide (VO x ) is a layered polycrystalline film, and the thickness of the obtained vanadium oxide (VO x ) film is 150 nm. .
  • the vanadium oxide composite film 1 obtained by this method includes a silicon substrate 14, a silicon nitride layer 13, a polyimide film 12, and a vanadium oxide film 11.
  • the vanadium oxide thin film 11 has a uniform surface, a dense structure, good film formation quality, and good crystallization, and the combination of vanadium oxide and polyimide is tight and not easy to fall off.
  • the polyimide film 12 and the silicon nitride layer 13 can be peeled from each other to form a flexible vanadium oxide composite film with a vanadium oxide film 11 formed on the surface of the flexible polyimide film 12.
  • FIG. 3 shows that the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment is manufactured by Carl Zeiss Corporation’s ZEISS Standard Scanning Electron Microscope image obtained by 55 Scanning Electron Microscope. It can be seen from the figure that the vanadium oxide film has the characteristics of layer growth, the film structure is dense, and the crystallization effect is good, and the quality of the film is high.
  • FIG. 4 shows an atomic force microscope image of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, characterized by using Agilent model AFM. It can be seen from the figure that the surface of the vanadium oxide film is flat and the surface roughness is small.
  • FIG. 5 is a graph showing the change in resistance of a vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment with a four-probe tester as a function of temperature. It can be seen from the figure that the vanadium oxide film has a temperature coefficient of resistance in the range of -2% to -3%, has a high temperature coefficient of resistance, and is similar to vanadium oxide prepared on rigid substrates such as silicon and rutile The film performance is comparable.
  • This example uses the same preparation method as Example 1, the only difference being the working conditions and annealing temperature of magnetron sputtering. That is, the working conditions of magnetron sputtering in Example 2 different from those in Example 1 are: argon flow rate 15 sccm, oxygen flow rate 1.0 sccm, argon-oxygen ratio 15:1, sputtering working pressure 0.3 Pa, sputtering
  • the injection power is 200W
  • the growth temperature is 200°C
  • the heat treatment annealing temperature is 420°C.
  • the remaining preparation steps and related conditions are exactly the same as those described in Example 1.
  • FIG. 6 shows that the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example is manufactured by Carl Zeiss Corporation’s ZEISS Standard Scanning Electron Microscope image obtained by 55 Scanning Electron Microscope. It can be seen from the figure that the vanadium oxide film has the characteristics of layer growth, the film structure is dense, and the crystallization effect is good, and the quality of the film is high.
  • FIG. 7 shows the atomic force microscope image of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, characterized by using Agilent model AFM. It can be seen from the figure that the surface of the vanadium oxide film is flat and the surface roughness is small.
  • FIG. 8 is a graph showing the change in resistance of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment with a four-probe tester as a function of temperature. It can be seen from the figure that the vanadium oxide thin film has a temperature coefficient of resistance of about -2% or more and has a high temperature coefficient of resistance, which is comparable to the performance of vanadium oxide thin films prepared on rigid substrates such as silicon and rutile.
  • This example uses the same preparation method as Example 1, the only difference being the working conditions and annealing temperature of magnetron sputtering. That is, in this embodiment, the working conditions of magnetron sputtering and embodiment 1 are different: the argon flow rate is 30 sccm, the oxygen flow rate is 1.0 sccm, the argon-oxygen ratio is 30:1, the sputtering working pressure is 0.3 Pa, and the sputtering The injection power is 200W, the growth temperature is 100°C, and the heat treatment annealing temperature is 450°C. The remaining preparation steps and related conditions are exactly the same as those described in Example 1.
  • the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment is manufactured by Carl Zeiss Corporation’s ZEISS Standard Scanning Electron Microscope image obtained by 55 Scanning Electron Microscope. It can be seen from the figure that the vanadium oxide film has the characteristics of layer growth, the film structure is dense, and the crystallization effect is good, and the quality of the film is high.
  • FIG. 10 shows the atomic force microscope image of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, using an Agilent model AFM. It can be seen from the figure that the surface of the vanadium oxide film is flat and the surface roughness is small.
  • FIG. 11 is a graph showing the change in resistance of a vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment with a four-probe tester as a function of temperature. It can be seen from the figure that the vanadium oxide film has a temperature coefficient of resistance in the range of about -2% to -3%, has a high temperature coefficient of resistance, and is suitable for the thermosensitive film of a terahertz detector.
  • This example uses the same preparation method as Example 1, the only difference being the working conditions and annealing temperature of magnetron sputtering. That is, in this embodiment, the working conditions of magnetron sputtering and embodiment 1 are different: argon flow rate is 15 sccm, oxygen flow rate is 2.0 sccm, argon-oxygen ratio is 7.5:1, sputtering working pressure is 0.3 Pa, sputtering The injection power is 200W, the growth temperature is 420°C, and the heat treatment annealing temperature is 480°C. The remaining preparation steps and related conditions are exactly the same as those described in Example 1.
  • FIG. 12 shows that the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example is manufactured by Carl Zeiss Corporation’s ZEISS Standard Scanning Electron Microscope image obtained by 55 Scanning Electron Microscope. It can be seen from the figure that the vanadium oxide film has the characteristics of layer growth, the film structure is dense, and the crystallization effect is good, and the quality of the film is high.
  • FIG. 13 shows an atomic force microscope image of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, characterized by an Agilent model AFM. It can be seen from the figure that the surface of the vanadium oxide film is flat and the surface roughness is small.
  • FIG. 14 is a graph showing the change in resistance of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment with a four-probe tester as a function of temperature. It can be seen from the figure that the vanadium oxide thin film has a temperature coefficient of resistance of about -2% or more and has a high temperature coefficient of resistance, which is comparable to the performance of vanadium oxide thin films prepared on rigid substrates such as silicon and rutile.
  • This example uses the same preparation method as Example 1, the only difference being the working conditions and annealing temperature of magnetron sputtering. That is, in this embodiment, the working conditions of magnetron sputtering and embodiment 1 are different: the argon flow rate is 15 sccm, the oxygen flow rate is 0.5 sccm, the argon-oxygen ratio is 30:1, the sputtering working pressure is 0.3 Pa, and the sputtering The injection power is 200W, the growth temperature is 300°C, and the heat treatment annealing temperature is 420°C. The remaining preparation steps and related conditions are exactly the same as those described in Example 1.
  • Figure 15 shows the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, which is produced by Carl Zeiss Corporation's ZEISS Standard Scanning Electron Microscope image obtained by 55 Scanning Electron Microscope. It can be seen from the figure that the vanadium oxide film has the characteristics of layer growth, the film structure is dense, and the crystallization effect is good, and the quality of the film is high.
  • FIG. 16 shows the atomic force microscope image of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, characterized by using Agilent model AFM. It can be seen from the figure that the surface of the vanadium oxide film is flat and the surface roughness is small.
  • FIG. 17 is a graph showing the change in resistance of a vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment with a four-probe tester as a function of temperature. It can be seen from the figure that the curve of the resistance of the vanadium oxide film with temperature changes, the vanadium oxide film shows a partial phase transition, and the temperature coefficient of resistance is high.
  • This example uses the same preparation method as Example 1, the only difference being the working conditions and annealing temperature of magnetron sputtering. That is, in this embodiment, the working conditions of magnetron sputtering and embodiment 1 are different: the argon flow rate is 15 sccm, the oxygen flow rate is 0.3 sccm, the argon-oxygen ratio is 50:1, the sputtering working pressure is 0.3 Pa, and the sputtering The injection power is 200W, the growth temperature is 300°C, and the heat treatment annealing temperature is 480°C. The remaining preparation steps and related conditions are exactly the same as those described in Example 1.
  • FIG. 18 shows that the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment is manufactured by ZEISS produced by Carl Zeiss Corporation. Standard Scanning Electron Microscope image obtained by 55 Scanning Electron Microscope. It can be seen from the figure that the vanadium oxide film has the characteristics of layer growth, the film structure is dense, and the crystallization effect is good, and the quality of the film is high.
  • FIG. 19 shows an atomic force microscope image of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, characterized by using Agilent model AFM. It can be seen from the figure that the surface of the vanadium oxide film is flat and the surface roughness is small.
  • FIG. 20 is a graph showing the change in resistance with temperature of a vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment using a four-probe tester.
  • the resistance of the vanadium oxide film varies with temperature.
  • the vanadium oxide film has a high temperature coefficient of resistance of -2% to -3% and is prepared on rigid substrates such as silicon and rutile. The performance of the vanadium oxide film is comparable.
  • This example uses the same preparation method as Example 1, the only difference being the working conditions and annealing temperature of magnetron sputtering. That is, in this embodiment, the working conditions of magnetron sputtering and embodiment 1 are different: the argon flow rate is 30sccm, the oxygen flow rate is 0.83sccm, the argon-oxygen ratio is 36:1, the sputtering working pressure is 0.3Pa, the sputtering The injection power is 190W, the growth temperature is 420°C, and the heat treatment annealing temperature is 480°C. The remaining preparation steps and related conditions are exactly the same as those described in Example 1.
  • FIG. 21 shows the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, which is produced by ZEISS produced by Carl Zeiss Corporation. Standard Scanning Electron Microscope image obtained by 55 Scanning Electron Microscope. It can be seen from the figure that the vanadium oxide film has the characteristics of layer growth, the film structure is dense, and the crystallization effect is good, and the quality of the film is high.
  • Fig. 22 shows an atomic force microscope image of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, characterized by using Agilent model AFM. It can be seen from the figure that the surface of the vanadium oxide film is flat and the surface roughness is small.
  • FIG. 23 is a graph showing the change in resistance of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment with a four-probe tester as a function of temperature. It can be seen from the figure that the resistance of the vanadium oxide film changes with temperature. The vanadium oxide film undergoes a phase change around 70°C, and the change drops by 2-3 orders of magnitude.
  • This example uses the same preparation method as Example 1, the only difference being the working conditions and annealing temperature of magnetron sputtering. That is, in this embodiment, the working conditions of magnetron sputtering and embodiment 1 are as follows: argon flow rate is 30sccm, oxygen flow rate is 0.93sccm, argon-oxygen ratio is 32.2:1, sputtering working pressure is 0.3Pa, sputtering The injection power is 190W, the growth temperature is 420°C, and the heat treatment annealing temperature is 480°C. The remaining preparation steps and related conditions are exactly the same as those described in Example 1.
  • FIG. 24 shows that the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment is manufactured by ZEISS produced by Carl Zeiss Corporation. Standard Scanning Electron Microscope image obtained by 55 Scanning Electron Microscope. It can be seen from the figure that the vanadium oxide film has the characteristics of layer growth, the film structure is dense, and the crystallization effect is good, and the quality of the film is high.
  • FIG. 25 shows the atomic force microscope image of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, characterized by using Agilent model AFM. It can be seen from the figure that the surface of the vanadium oxide film is flat and the surface roughness is small.
  • FIG. 26 is a graph showing the change in resistance with temperature of a vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment using a four-probe tester. It can be seen from the graph that the vanadium oxide film resistance changes with temperature, and the vanadium oxide film undergoes a phase change around 75°C, and the change drops by 2-3 orders of magnitude.
  • This example uses the same preparation method as Example 1, and the only difference is the working conditions and annealing temperature of magnetron sputtering. That is, in this embodiment, the working conditions of magnetron sputtering and embodiment 1 are different: the argon flow rate is 30sccm, the oxygen flow rate is 0.88sccm, the argon-oxygen ratio is 34.1:1, the sputtering working pressure is 0.3Pa, the sputtering The injection power is 190W, the growth temperature is 420°C, and the heat treatment annealing temperature is 480°C. The remaining preparation steps and related conditions are exactly the same as those described in Example 1.
  • FIG. 27 shows that the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment is manufactured by Carl Zeiss Corporation’s ZEISS Standard Scanning Electron Microscope image obtained by 55 Scanning Electron Microscope. It can be seen from the figure that the vanadium oxide film has the characteristics of layer growth, the film structure is dense, and the crystallization effect is good, and the quality of the film is high.
  • Fig. 28 shows an atomic force microscope image of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, using an Agilent model AFM. It can be seen from the figure that the surface of the vanadium oxide film is flat and the surface roughness is small.
  • FIG. 29 is a graph showing the change in resistance with temperature of a vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment, using a four-probe tester. It can be seen from the figure that the vanadium oxide film has a temperature coefficient of resistance in the range of -2% to -3%, has a high temperature coefficient of resistance, and is similar to vanadium oxide prepared on rigid substrates such as silicon and rutile The film performance is comparable. And part of the phase change characteristic appears, the resistance drops by an order of magnitude.
  • This example uses the same preparation method as Example 1, the only difference being the working conditions and annealing temperature of magnetron sputtering. That is, in this embodiment, the working conditions of magnetron sputtering and embodiment 1 are different: the argon flow rate is 30sccm, the oxygen flow rate is 0.77sccm, the argon-oxygen ratio is 39:1, the sputtering working pressure is 0.3Pa, the sputtering The injection power is 190W, the growth temperature is 420°C, and the heat treatment annealing temperature is 480°C. The remaining preparation steps and related conditions are exactly the same as those described in Example 1.
  • FIG. 30 shows that the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment is manufactured by ZEISS produced by Carl Zeiss Corporation. Standard Scanning Electron Microscope image obtained by 55 Scanning Electron Microscope. It can be seen from the figure that the vanadium oxide film has the characteristics of layer growth, the film structure is dense, and the crystallization effect is good, and the quality of the film is high.
  • FIG. 31 shows an atomic force microscope image of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, using an Agilent model AFM. It can be seen from the figure that the surface of the vanadium oxide film is flat and the surface roughness is small.
  • FIG. 32 is a graph showing the change in resistance of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment with a four-probe tester as a function of temperature. It can be seen from the figure that the vanadium oxide film has a temperature coefficient of resistance in the range of -2% to -3%, has a high temperature coefficient of resistance, and is similar to vanadium oxide prepared on rigid substrates such as silicon and rutile The film performance is comparable.
  • This example uses the same preparation method as Example 1, the only difference being the working conditions and annealing temperature of magnetron sputtering. That is, in this embodiment, the working conditions of magnetron sputtering and embodiment 1 are different: the argon flow rate is 30sccm, the oxygen flow rate is 0.83sccm, the argon-oxygen ratio is 36:1, the sputtering working pressure is 0.1Pa, the sputtering The injection power is 190W, the growth temperature is 420°C, and the heat treatment annealing temperature is 480°C. The remaining preparation steps and related conditions are exactly the same as those described in Example 1.
  • FIG. 33 shows that the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example is manufactured by Carl Zeiss Corporation’s ZEISS Standard Scanning Electron Microscope image obtained by 55 Scanning Electron Microscope. It can be seen from the figure that the vanadium oxide film has the characteristics of layer growth, the film structure is dense, and the crystallization effect is good, and the quality of the film is high.
  • FIG. 34 shows an atomic force microscope image of the vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this example, using Agilent model AFM. It can be seen from the figure that the surface of the vanadium oxide film is flat and the surface roughness is small.
  • FIG. 35 is a graph showing the change in resistance with temperature of a vanadium oxide film in the flexible vanadium oxide composite film finally obtained by the method of this embodiment using a four-probe tester. It can be seen from the figure that the vanadium oxide film has a temperature coefficient of resistance in the range of -2% to -3%, has a high temperature coefficient of resistance, and is similar to vanadium oxide prepared on rigid substrates such as silicon and rutile The film performance is comparable.
  • a high-temperature resistant polyimide film is used as a substrate, a layered grown vanadium oxide film is prepared at a low temperature, and then a vanadium oxide film based on a flexible polyimide substrate is prepared by high-temperature annealing in different atmospheres.
  • the vanadium oxide film has high crystallinity, a smooth and uniform surface, and has good thermally induced phase transition characteristics.
  • the electrical characteristics are comparable to those of a vanadium oxide film prepared directly on a rigid material such as a silicon substrate.
  • the resistance value varies widely.
  • the polyimide film is tightly bonded and not easy to fall off.
  • the two-step method involved in the present invention not only has the advantages of simple operation but also is easy to control stably; the use of high-temperature resistant flexible substrate materials has the characteristic of being compatible with silicon substrates alone and expands the range of use of vanadium oxide films.

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Abstract

一种氧化钒复合薄膜的制备方法，包括，步骤一，在衬底上形成耐高温柔性材料薄膜（12），以形成基片；步骤二，在所述基片上的所述柔性材料上形成氧化钒前驱体薄膜；步骤三，对形成有所述氧化钒前驱体薄膜的基片进行高温退火，形成具有氧化钒薄膜（11）的复合薄膜（1）。上述制备方法制备过程简单且容易控制，为柔性氧化钒器件的制备奠定了基础；同时上述制备方法获得的复合柔性薄膜表面均匀、结构致密、成膜质量好、结晶良好，且氧化钒与聚酰亚胺结合紧密，不易脱落。

Description

一种两步法制备柔性氧化钒薄膜的方法 技术领域
本发明涉及一种微电子半导体技术薄膜的制备方法，特别是一种两步法制备柔性氧化钒太赫兹探测器热敏薄膜材料的制备方法。
背景技术
太赫兹频段(0.1-10THz,1THz＝10 12Hz)是电磁波谱最后一个待开发的频谱区域，在短距离无线通信、生物传感、医疗诊断、材料特性光谱检测以及无损探测等方面均具有潜在的应用，其具有的瞬态性、低能性、相干性、穿透性以及光谱的特征吸收等独特的性能已普遍被人认识。
推动太赫兹技术进一步的发展和实际应用，我们不仅需要很好的解决可靠廉价稳定的太赫兹源，高灵敏高信噪比的太赫兹探测器，同时还需要提供很好的太赫兹波导、滤波、调制、开关、分束、偏振等新型功能器件。然而，跟微波和光波段不同，自然物质对太赫兹波缺乏有效响应，已有电子器件和光学器件均无法实现太赫兹的传输和控制。太赫兹材料和器件的缺乏严重制约了太赫兹技术向实用化方向发展，成为太赫兹领域亟待解决的关键问题之一。
目前报道的相关太赫兹探测器均为直接在硅基底上制备，器件加工难度较大：根据红外微测辐射热计微桥的“λ/4原理”，应用到太赫兹检测，如若需检测波长为100μm(3THz)，则微桥谐振腔的高度需达到25μm(注：红外探测器仅为1～2μm)，而且微桥的制造精度为0.1～1μm。目前的器件材料及加工技术(MEMS)均难以满足相关要求。
基于柔性基底的VO x太赫兹探测器，则能够避开在硅基底上使用复杂的CMOS工艺，降低制备工艺的难度，减少制造探测器的成本。但目前有关于柔性太赫兹探测器的报道极少，主要是因为要在柔性基底上制备质量好的VO x热敏薄膜，需要在高温(>400℃)下生长，而绝大多数的柔性材料不具备耐高温的性能。对柔性材料基底的VO x薄膜有几个方面的要求：1.较高的电阻温度系数；2.表面致密、均匀；3.成膜质量好，与衬底的界面结合性好。在现有的薄膜制备工艺中，使用化学凝胶溶胶法形成的VO x薄膜难以满足以上要求，而选用磁控溅射沉积法，在适当的工艺条件下制备形成的VO x薄膜，能够满足以上条件的要求。
申请号为CN201310272361.7的专利申请中公开了一种基于柔性基底的太赫兹调制器膜材料的制备方法，并具体公开了一种基于柔性基底聚酰亚胺的VO x薄膜，该薄膜是在低温下通过磁控溅射制备金属V薄膜，此后在氧气氛围内，在250～300℃温度范围内，对所述V薄膜热处理30～180s获得VO x薄膜。
上述方法属于薄膜氧化法，该薄膜是在低温下生长，且热处理温度较低，氧气氛围制备下工艺控制困难，难以生长出质量好VO x的薄膜，不适合应用在柔性太赫兹探测器上。
本发明提出一种两步法制备柔性VO x复合薄膜。第一步，通过将耐高温的聚酰亚胺PI(热分解温度为494℃)作为基底，使用磁控溅射在低温下制备氧化钒前驱体；第二步，在高温下热处理即原位退火。由本发明方法获得的复合柔性薄膜表面均匀、结构致密、成膜质量好、结晶良好，且VO x与聚酰亚胺结合紧密，不易脱落。
发明内容
针对以上现有技术存在的技术问题，本发明通过使用磁控溅射在低温下制备氧化钒前驱体，再对该前驱体进行热处理，以形成表面均匀、结构致密、成膜质量好、结晶良好、与聚酰亚胺结合紧密、不易脱落的氧化钒复合柔性薄膜。
本发明涉及一种氧化钒复合薄膜的制备方法，包括，步骤一，在衬底上形成耐高温柔性材料薄膜，以形成基片；步骤二，在所述基片上的所述柔性材料上形成氧化钒前驱体薄膜；步骤三，对形成有所述氧化钒前驱体薄膜的基片进行高温退火，形成具有氧化钒薄膜的复合薄膜。
优选为，在所述步骤一之前，还包括衬底准备步骤；其中，所述衬底为硅衬底。
优选为，所述衬底准备步骤进一步包括，在所述硅衬底上形成氮化硅层，以形成具有氮化硅层的硅衬底；步骤一中所述柔性材料薄膜形成于所述衬底上的所述氮化硅层上。
优选为，所述步骤三之后，还包括剥离步骤；其中，所述剥离步骤包括，将形成有氧化钒薄膜的所述柔性材料薄膜与所述衬底剥离，获得在所述柔性材料薄膜上形成有氧化钒薄膜的复合薄膜。
优选为，所述耐高温柔性材料的热分解温度高于步骤三中高温退火的温度。
优选为，所述耐高温柔性材料为耐高温树脂材料。
优选为，所述耐高温树脂材料为聚酰亚胺。
优选为，所述聚酰亚胺的热分解温度大于400℃。
优选为，步骤二中，通过磁控溅射方法在所述柔性材料上形成所述氧化钒前驱体薄膜。
优选为，所述磁控溅射的条件为：基片温度为100-420℃，真空度为2.5～4.0×10 -4Pa，靶材与基片距离为80mm，氩气流量为15-30sccm，氧气流量为0.3-2.0sccm，氩氧比为7.5:1-50:1，溅射工作气压为0.1-0.3Pa，溅射功率为150-200W，沉积时间为15-60min。
优选为，步骤三中进行高温退火的条件为，在真空或惰性环境中对形成有所述氧化钒前驱体薄膜的基片进行退火。
优选为，步骤三中进行高温退火的温度为，在420-480℃。
优选为，所述退火的环境为，真空度为0.1-0.3Pa的氩气氛围。
本发明还涉及一种氧化钒复合薄膜的制备方法，包括，步骤一，准备衬底，在硅基底上形成氮化硅层；步骤二，将所述衬底依次放入去离子水、无水乙醇、丙酮溶剂中分别超声清洗10分钟，并烘干；步骤三，准备基片，在所述衬底上形成聚酰亚胺薄膜；步骤四，将所述基片依次放入去离子水、无水乙醇、丙酮溶剂中分别超声清洗10分钟，并烘干；步骤五，将清洗好的基片置于真空度为2.5～4.0×10 -4Pa的高真空射频磁控溅射设备里，在基片温度为100-420℃、氩气流量为15-30sccm、氧气流量为0.3-2.0sccm、氩氧比为7.5:1-50:1、溅射工作气压为0.1-0.3Pa、溅射功率为150-200W、靶材与基片距离为80mm的条件下，沉积15-60min，以在所述基片上形成氧化钒前驱体薄膜；所述靶材为金属钒靶；步骤六，在420-480℃退火30min以上，获得的氧化钒薄膜为层状多晶的薄膜，所述氧化钒薄膜厚度为150nm。
优选为，所述步骤六之后，还包括剥离步骤；其中，所述剥离步骤包括，将形成有氧化钒薄膜的所述聚酰亚胺薄膜与所述衬底剥离，获得在所述柔性材料薄膜上形成有氧化钒薄膜的氧化钒复合薄膜。
优选为，所述步骤三还包括，将聚酰亚胺溶液用刮涂或旋涂的方法均匀涂抹在所述衬底上，在50-60℃下烘烤2小时，然后在300-400℃下加热8小时进行退火，在硅基底上得 到均匀的聚酰亚胺薄膜。
本发明还涉及一种通过以上任一种方法制备形成的氧化钒复合薄膜。
与现有技术相比，本发明的有益效果在于，克服了现有低温制备柔性氧化钒技术的不足。提供了一种基于柔性聚酰亚胺为基底，采用磁控溅射方法，低温制备层状生长的氧化钒，再在不同气氛环境中进行高温退火，获得了一种过程简单且易稳定控制的复合薄膜制备方法，为柔性氧化钒器件的制备奠定了基础。由本发明制备方法获得的复合柔性薄膜表面均匀、结构致密、成膜质量好、结晶良好，且氧化钒与聚酰亚胺结合紧密，不易脱落。
附图说明
附图1：氧化钒复合薄膜整体结构图；
附图2：氧化钒复合薄膜分层示意图；
附图3：实施例1方法制备的氧化钒薄膜扫描电子显微镜图；
附图4：实施例1方法制备的氧化钒薄膜原子力显微镜图；
附图5：实施例1方法制备的氧化钒薄膜电阻随温度变化曲线图；
附图6：实施例2方法制备的氧化钒薄膜扫描电子显微镜图；
附图7：实施例2方法制备的氧化钒薄膜原子力显微镜图；
附图8：实施例2方法制备的氧化钒薄膜电阻随温度变化曲线图；
附图9：实施例3方法制备的氧化钒薄膜扫描电子显微镜图；
附图10：实施例3方法制备的氧化钒薄膜原子力显微镜图；
附图11：实施例3方法制备的氧化钒薄膜电阻随温度变化曲线图；
附图12：实施例4方法制备的氧化钒薄膜扫描电子显微镜图；
附图13：实施例4方法制备的氧化钒薄膜原子力显微镜图；
附图14：实施例4方法制备的氧化钒薄膜电阻随温度变化曲线图；
附图15：实施例5方法制备的氧化钒薄膜扫描电子显微镜图；
附图16：实施例5方法制备的氧化钒薄膜原子力显微镜图；
附图17：实施例5方法制备的氧化钒薄膜电阻随温度变化曲线图；
附图18：实施例6方法制备的氧化钒薄膜扫描电子显微镜图；
附图19：实施例6方法制备的氧化钒薄膜原子力显微镜图；
附图20：实施例6方法制备的氧化钒薄膜电阻随温度变化曲线图；
附图21：实施例7方法制备的氧化钒薄膜扫描电子显微镜图；
附图22：实施例7方法制备的氧化钒薄膜原子力显微镜图；
附图23：实施例7方法制备的氧化钒薄膜电阻随温度变化曲线图；
附图24：实施例8方法制备的氧化钒薄膜扫描电子显微镜图；
附图25：实施例8方法制备的氧化钒薄膜原子力显微镜图；
附图26：实施例8方法制备的氧化钒薄膜电阻随温度变化曲线图；
附图27：实施例9方法制备的氧化钒薄膜扫描电子显微镜图；
附图28：实施例9方法制备的氧化钒薄膜原子力显微镜图；
附图29：实施例9方法制备的氧化钒薄膜电阻随温度变化曲线图；
附图30：实施例10方法制备的氧化钒薄膜扫描电子显微镜图；
附图31：实施例10方法制备的氧化钒薄膜原子力显微镜图；
附图32：实施例10方法制备的氧化钒薄膜电阻随温度变化曲线图；
附图33：实施例11方法制备的氧化钒薄膜扫描电子显微镜图；
附图34：实施例11方法制备的氧化钒薄膜原子力显微镜图；
附图35：实施例11方法制备的氧化钒薄膜电阻随温度变化曲线图。
具体实施方式
本实施方式涉及的一种制备柔性氧化钒(VO x)薄膜的两步制备方法，该方法主要包括在基片上低温形成氧化钒前驱体以及对所述氧化钒前驱体进行高温退火两步骤。其中，所述氧化钒不仅限于VO 2、V 2O 5，即包括各种形式的钒的氧化物，即通常被本领域技术人员记做VO x。
主要步骤包括，在衬底上形成耐高温柔性材料薄膜12，并以此形成基片，所述基片能够用于后续步骤中形成氧化钒薄膜11，即在所述基片上的所述柔性材料上形成氧化钒前驱体薄膜，然后进一步对形成有所述氧化钒前驱体薄膜的基片进行高温退火，以形成氧化钒薄膜的复合薄膜1。先在基片上形成氧化钒前驱体，能够在反应结合时形成结晶形态好的氧化钒晶体；然后在高温下退火，则能够有效的使元素均匀扩散，形成成膜质量好，表面粗糙度小的薄膜。
在一些实施例中，还包括准备衬底的步骤，通常选用硅衬底作为所述复合薄膜的衬底，以方便将所述复合薄膜直接制作成太赫兹探测器中的相关器件。
在一些实施例中，准备衬底的步骤进一步包括，在所述硅衬底14上形成氮化硅层13，以形成具有氮化硅层13的硅衬底；并进一步将所述柔性材料薄膜12形成于所述衬底上的所述氮化硅层上。氮化硅层用于之后器件制备的绝缘层，以及适用于器件加工中的MEMS工艺制备。在反应过程中，仅与硅片一同作为柔性薄膜的载体，不参与直接反应。
在一些实施例中，还包括剥离步骤。其中，所述剥离步骤包括，将形成有氧化钒薄膜11的所述柔性材料薄膜12与所述衬底剥离，获得在所述柔性材料薄膜12上形成的氧化钒薄膜11，即柔性氧化钒复合薄膜。通过此步骤，可以单独获得柔性的氧化钒复合薄膜，能够适于在不同使用环境和使用条件下作为单独的柔性薄膜材料使用。
在一些实施例中，所述耐高温柔性材料优选为耐高温树脂材料，并进一步优选为聚酰亚胺树脂材料，且所述聚酰亚胺的热分解温度大于400℃。优选为，所述耐高温柔性材料的热分解温度高于高温退火的温度。由此使得形成在所述柔性材料薄膜12表面的氧化钒薄膜11能够在高温的条件下进行退火，并形成表面均匀、结构致密、成膜质量好、结晶良好，且氧化钒与聚酰亚胺结合紧密不易脱落的氧化钒复合薄膜。
在一些实施例中，通过磁控溅射方法在所述柔性材料上形成所述氧化钒前驱体薄膜；且所述磁控溅射的条件优选为，所述基片温度为100-400℃，真空度为2.5～4.0×10 -4Pa，靶材与基片距离为80mm，氩气流量为15-30sccm，氧气流量为0.3-2.0sccm，氩氧比为7.5:1-39:1，溅射工作气压为0.3Pa，溅射功率为150-200W，沉积时间为15-60min；其中，所使用的所述靶材为金属钒靶，质量纯度≥99.99％，氩气的纯度≥99.999％，氧气的纯度≥99.99％。以此获得表面均匀、结构致密、成膜质量好、结晶良好，且氧化钒与聚酰亚胺结合紧密不易脱落的氧化钒薄膜。
在一些实施例中，高温退火的条件为，在真空或惰性环境中对所述氧化钒前驱体薄膜进行退火；进一步优选为，在真空度为0.1-0.3Pa的氩气氛围中，在420-480℃退火30min以上，获得的氧化钒薄膜为层状多晶的薄膜，所述氧化钒薄膜厚度为150nm。在真空或惰性条件下进行高温退火，有助于提高成膜质量，形成表面均匀、结构致密、结晶良好、不易脱落的氧化钒薄膜。
在一些实施例中，具体的氧化钒薄膜制备方法包括，步骤一，准备衬底，在硅基底上形成氮化硅层；步骤二，将所述衬底依次放入去离子水、无水乙醇、丙酮溶剂中分别超声 清洗10分钟，并烘干；步骤三，准备基片，在所述衬底上形成聚酰亚胺薄膜；步骤四，将所述基片依次放入去离子水、无水乙醇、丙酮溶剂中分别超声10分钟，并烘干；步骤五，将清洗好的基片置于真空度为2.5～4.0×10 -4Pa的高真空射频磁控溅射设备里，在基片温度为100-400℃、氩气流量为15-30sccm、氧气流量为0.3-2.0sccm、氩氧比为7.5:1-39:1、溅射工作气压为0.3Pa、溅射功率为150-200W、靶材与基片距离为80mm的条件下，沉积15-60min，以在所述基片上形成氧化钒前驱体薄膜；所述靶材为质量纯度≥99.99％的金属钒靶；步骤六，在420-480℃退火30min以上，获得的氧化钒薄膜为层状多晶的薄膜，所述氧化钒薄膜厚度为150nm。以此获得表面均匀、结构致密、成膜质量好、结晶良好，且氧化钒与聚酰亚胺结合紧密不易脱落的氧化钒薄膜。
在一些实施例中，在所述步骤六之后，还包括剥离步骤；其中，所述剥离步骤包括，将形成有氧化钒薄膜的所述聚酰亚胺薄膜与所述衬底剥离，获得在所述柔性材料薄膜上形成的氧化钒薄膜。通过此步骤，可以单独获得柔性的氧化钒复合薄膜，能够适于在不同使用环境和使用条件下作为单独的柔性薄膜材料使用。
在一些实施例中，所述步骤三还包括，将聚酰亚胺溶液用刮涂或旋涂的方法均匀涂抹在所述衬底上，在50-60℃下烘烤2小时，然后在300-400℃下加热8小时进行退火，在硅基底上得到均匀的聚酰亚胺薄膜。通过此步骤，可以获得具有高热分解温度的聚酰亚胺薄膜，优选为，所述聚酰亚胺薄膜的热分解温度大于400℃。优选为，所得的聚酰亚胺薄膜的介电常数为3.4，热分解温度为494℃。
实施例1
本实施例涉及的氧化钒复合薄膜的制备方法具体如下：
步骤一，准备衬底。提供硅基底，并在所述硅基底上通过等离子体增强化学气相沉积法形成氮化硅层。其中所用的硅基底尺寸为33mm×33mm。氮化硅层用于之后器件制备的绝缘层，以及适用于器件加工中的MEMS工艺制备。在反应过程中，氮化硅层仅与硅片一同作为柔性薄膜的载体，不参与直接反应。
步骤二，将所述衬底依次放入去离子水、无水乙醇、丙酮溶剂中分别超声清洗10分钟，并烘干。
步骤三，准备基片。将聚酰亚胺(PI)溶液用刮涂或旋涂的方法均匀涂抹在清洗干净的所述衬底上，在50-60℃下烘烤2小时，除去聚酰亚胺中的有机成分，再在高温300-400℃下加热8小时，发生亚胺化反应，最终在所述基底上得到均匀的聚酰亚胺薄膜。所得的聚酰亚胺介电常数为3.4，热分解温度为494℃。
步骤四，将所述基片依次放入去离子水、无水乙醇、丙酮溶剂中分别超声10分钟，并烘干。
步骤五，制备氧化钒前驱体薄膜。将清洗好的基片置于真空度为2.5～4.0×10 -4Pa的高真空射频磁控溅射设备里，以氧气与氩气的混合气体作为工作气体，溅射工作的真空度为2.5～4.0×10 -4Pa，金属钒作为靶材，靶材与基片距离为80mm，氩气流量为15sccm，氧气流量为1.0sccm，氩氧比为15:1，溅射工作气压为0.3Pa，溅射功率为200W，生长时基片温度为300℃，沉积时间为15-60min。其中，金属钒靶质量纯度为99.99％，氩气的纯度≥99.999％，氧气的纯度≥99.99％。所得的氧化钒(VO x)为层状非晶的VOx薄膜。
步骤六，在真空或氩气氛围中高温退火。将气体压强，通过通入氩气，调整为0.3Pa，在480℃左右退火30min，获得的氧化钒(VO x)为层状多晶的薄膜，得到的氧化钒(VO x)薄膜厚度为150nm。
参见附图1和2可知，由此方法获得的氧化钒复合薄膜1包括硅基底14、氮化硅层13、 聚酰亚胺薄膜12以及氧化钒薄膜11。所述氧化钒薄膜11表面均匀，结构致密，成膜质量好，结晶良好，且氧化钒与聚酰亚胺结合紧密，不易脱落。其中，所述聚酰亚胺薄膜12可以与所述氮化硅层13之间相互剥离，以形成在柔性聚酰亚胺薄膜12表面上形成有氧化钒薄膜11的柔性氧化钒复合薄膜。
图3所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，在Carl Zeiss Corporation公司产的ZEISS
Figure PCTCN2019123451-appb-000001
55型号的扫描电镜获得的标准的扫描电子显微镜图。从图中可以看出，所述氧化钒薄膜具备层状生长的特性，薄膜结构致密，且结晶效果好，薄膜的质量高。
图4所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用Agilent型号的AFM表征的原子力显微镜图。从图中可以看出，所述氧化钒薄膜表面平整，表面粗糙度小。
图5所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用四探针测试仪测试的电阻随温度变化曲线图。从图中可以看出，所述氧化钒薄膜的电阻温度系数约在-2％～-3％的范围内，具有较高的电阻温度系数，与在硅、金红石等刚性基底上制备的氧化钒薄膜性能相当。
实施例2
本实施例与实施例1使用相同的制备方法，其区别仅在于磁控溅射的工作条件及退火温度。即，在实施例2中磁控溅射与实施例1不同的工作条件为：氩气流量为15sccm，氧气流量为1.0sccm，氩氧比为15:1，溅射工作气压为0.3Pa，溅射功率为200W，生长温度为200℃，热处理退火温度420℃。其余的制备步骤及相关条件与实施例1中所记载的完全相同。
图6所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，在Carl Zeiss Corporation公司产的ZEISS
Figure PCTCN2019123451-appb-000002
55型号的扫描电镜获得的标准的扫描电子显微镜图。从图中可以看出，所述氧化钒薄膜具备层状生长的特性，薄膜结构致密，且结晶效果好，薄膜的质量高。
图7所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用Agilent型号的AFM表征的原子力显微镜图。从图中可以看出，所述氧化钒薄膜表面平整，表面粗糙度小。
图8所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用四探针测试仪测试的电阻随温度变化曲线图。从图中可以看出，所述氧化钒薄膜的电阻温度系数约在-2％以上，具有较高的电阻温度系数，与在硅、金红石等刚性基底上制备的氧化钒薄膜性能相当。
实施例3
本实施例与实施例1使用相同的制备方法，其区别仅在于磁控溅射的工作条件及退火温度。即，在本实施例中磁控溅射与实施例1不同的工作条件为：氩气流量为30sccm，氧气流量为1.0sccm，氩氧比为30:1，溅射工作气压为0.3Pa，溅射功率为200W，生长温度为100℃，热处理退火温度450℃。其余的制备步骤及相关条件与实施例1中所记载的完全相同。
图9所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，在Carl Zeiss Corporation公司产的ZEISS
Figure PCTCN2019123451-appb-000003
55型号的扫描电镜获得的标准的扫描电子显微镜图。从图中可以看出，所述氧化钒薄膜具备层状生长的特性，薄膜结构致密，且结晶效果好，薄膜的质量高。
图10所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用Agilent型号的AFM表征的原子力显微镜图。从图中可以看出，所述氧化钒薄膜表面平整，表面粗糙度小。
图11所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用四探针测试仪测试的电阻随温度变化曲线图。从图中可以看出，所述氧化钒薄膜的电阻温度系数约在-2％～-3％的范围内，具有较高的电阻温度系数，适用于太赫兹探测器的热敏薄膜。
实施例4
本实施例与实施例1使用相同的制备方法，其区别仅在于磁控溅射的工作条件及退火温度。即，在本实施例中磁控溅射与实施例1不同的工作条件为：氩气流量为15sccm，氧气流量为2.0sccm，氩氧比为7.5:1，溅射工作气压为0.3Pa，溅射功率为200W，生长温度为420℃，热处理退火温度480℃。其余的制备步骤及相关条件与实施例1中所记载的完全相同。
图12所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，在Carl Zeiss Corporation公司产的ZEISS
Figure PCTCN2019123451-appb-000004
55型号的扫描电镜获得的标准的扫描电子显微镜图。从图中可以看出，所述氧化钒薄膜具备层状生长的特性，薄膜结构致密，且结晶效果好，薄膜的质量高。
图13所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用Agilent型号的AFM表征的原子力显微镜图。从图中可以看出，所述氧化钒薄膜表面平整，表面粗糙度小。
图14所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用四探针测试仪测试的电阻随温度变化曲线图。从图中可以看出，所述氧化钒薄膜的电阻温度系数约在-2％以上，具有较高的电阻温度系数，与在硅、金红石等刚性基底上制备的氧化钒薄膜性能相当。
实施例5
本实施例与实施例1使用相同的制备方法，其区别仅在于磁控溅射的工作条件及退火温度。即，在本实施例中磁控溅射与实施例1不同的工作条件为：氩气流量为15sccm，氧气流量为0.5sccm，氩氧比为30:1，溅射工作气压为0.3Pa，溅射功率为200W，生长温度为300℃，热处理退火温度420℃。其余的制备步骤及相关条件与实施例1中所记载的完全相同。
图15所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，在Carl Zeiss Corporation公司产的ZEISS
Figure PCTCN2019123451-appb-000005
55型号的扫描电镜获得的标准的扫描电子显微镜图。从图中可以看出，所述氧化钒薄膜具备层状生长的特性，薄膜结构致密，且结晶效果好，薄膜的质量高。
图16所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用Agilent型号的AFM表征的原子力显微镜图。从图中可以看出，所述氧化钒薄膜表面平整，表面粗糙度小。
图17所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用四探针测试仪测试的电阻随温度变化曲线图。从图中可以看出，所述氧化钒薄膜电阻随温度变化的曲线，所述氧化钒薄膜出现了部分相变的情况，电阻温度系数高。
实施例6
本实施例与实施例1使用相同的制备方法，其区别仅在于磁控溅射的工作条件及退火温度。即，在本实施例中磁控溅射与实施例1不同的工作条件为：氩气流量为15sccm，氧气流量为0.3sccm，氩氧比为50:1，溅射工作气压为0.3Pa，溅射功率为200W，生长温度为300℃，热处理退火温度480℃。其余的制备步骤及相关条件与实施例1中所记载的完全相同。
图18所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，在Carl Zeiss Corporation公司产的ZEISS
Figure PCTCN2019123451-appb-000006
55型号的扫描电镜获得的标准的扫描电子显微镜图。从图中可以看出，所述氧化钒薄膜具备层状生长的特性，薄膜结构致密，且结晶效果好，薄膜的质量高。
图19所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用Agilent型号的AFM表征的原子力显微镜图。从图中可以看出，所述氧化钒薄膜表面平整，表面粗糙度小。
图20所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用四探针测试仪测试的电阻随温度变化曲线图。从图中可以看出，所述氧化钒薄膜电阻随温度变化的曲线，所述氧化钒薄膜具有-2％～-3％，较高的电阻温度系数，与在硅、金红石等刚性基底上制备的氧化钒薄膜性能相当。
实施例7
本实施例与实施例1使用相同的制备方法，其区别仅在于磁控溅射的工作条件及退火温度。即，在本实施例中磁控溅射与实施例1不同的工作条件为：氩气流量为30sccm，氧气流量为0.83sccm，氩氧比为36:1，溅射工作气压为0.3Pa，溅射功率为190W，生长温度为420℃，热处理退火温度480℃。其余的制备步骤及相关条件与实施例1中所记载的完全相同。
图21所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，在Carl Zeiss Corporation公司产的ZEISS
Figure PCTCN2019123451-appb-000007
55型号的扫描电镜获得的标准的扫描电子显微镜图。从图中可以看出，所述氧化钒薄膜具备层状生长的特性，薄膜结构致密，且结晶效果好，薄膜的质量高。
图22所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用Agilent型号的AFM表征的原子力显微镜图。从图中可以看出，所述氧化钒薄膜表面平整，表面粗糙度小。
图23所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用四探针测试仪测试的电阻随温度变化曲线图。从图中可以看出，所述氧化钒薄膜电阻随温度变化的曲线，所述氧化钒薄膜在70℃附近出现相变，变化下降达2-3个数量级。
实施例8
本实施例与实施例1使用相同的制备方法，其区别仅在于磁控溅射的工作条件及退火温度。即，在本实施例中磁控溅射与实施例1不同的工作条件为：氩气流量为30sccm，氧气流量为0.93sccm，氩氧比为32.2:1，溅射工作气压为0.3Pa，溅射功率为190W，生长温度为420℃，热处理退火温度480℃。其余的制备步骤及相关条件与实施例1中所记载的完全相同。
图24所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，在Carl Zeiss Corporation公司产的ZEISS
Figure PCTCN2019123451-appb-000008
55型号的扫描电镜获得的标准的扫描电子显微镜图。从图中可以看出，所述氧化钒薄膜具备层状生长的特性，薄膜结构致密，且结晶效果好，薄膜的质量高。
图25所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用Agilent型号的AFM表征的原子力显微镜图。从图中可以看出，所述氧化钒薄膜表面平整，表面粗糙度小。
图26所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用四探针测试仪测试的电阻随温度变化曲线图。从图中可以看出，所述氧化钒薄膜电阻随温度变化的曲线，所述氧化钒薄膜在75℃附近出现相变，变化下降达2-3个数量级。
实施例9
本实施例与实施例1使用相同的制备方法，其区别仅在于磁控溅射的工作条件及退火温度。即，在本实施例中磁控溅射与实施例1不同的工作条件为：氩气流量为30sccm，氧气流量为0.88sccm，氩氧比为34.1:1，溅射工作气压为0.3Pa，溅射功率为190W，生长温度为420℃，热处理退火温度480℃。其余的制备步骤及相关条件与实施例1中所记载的完全相同。
图27所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，在Carl Zeiss Corporation公司产的ZEISS
Figure PCTCN2019123451-appb-000009
55型号的扫描电镜获得的标准的扫描电子显微镜图。从图中可以看出，所述氧化钒薄膜具备层状生长的特性，薄膜结构致密，且结晶效果好，薄膜的质量高。
图28所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用Agilent型号的AFM表征的原子力显微镜图。从图中可以看出，所述氧化钒薄膜表面平整，表面粗糙度小。
图29所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用四探针测试仪测试的电阻随温度变化曲线图。从图中可以看出，所述氧化钒薄膜的电阻温度系数约在-2％～-3％的范围内，具有较高的电阻温度系数，与在硅、金红石等刚性基底上制备的氧化钒薄膜性能相当。且出现部分相变特性，电阻下降1个数量级。
实施例10
本实施例与实施例1使用相同的制备方法，其区别仅在于磁控溅射的工作条件及退火温度。即，在本实施例中磁控溅射与实施例1不同的工作条件为：氩气流量为30sccm，氧气流量为0.77sccm，氩氧比为39:1，溅射工作气压为0.3Pa，溅射功率为190W，生长温度为420℃，热处理退火温度480℃。其余的制备步骤及相关条件与实施例1中所记载的完全相同。
图30所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，在Carl Zeiss Corporation公司产的ZEISS
Figure PCTCN2019123451-appb-000010
55型号的扫描电镜获得的标准的扫描电子显微镜图。从图中可以看出，所述氧化钒薄膜具备层状生长的特性，薄膜结构致密，且结晶效果好，薄膜的质量高。
图31所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用Agilent型号的AFM表征的原子力显微镜图。从图中可以看出，所述氧化钒薄膜表面平整，表面粗糙度小。
图32所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用四探针测试仪测试的电阻随温度变化曲线图。从图中可以看出，所述氧化钒薄膜的电阻温度系数约在-2％～-3％的范围内，具有较高的电阻温度系数，与在硅、金红石等刚性基底上制备的氧化钒薄膜性能相当。
实施例11
本实施例与实施例1使用相同的制备方法，其区别仅在于磁控溅射的工作条件及退火温度。即，在本实施例中磁控溅射与实施例1不同的工作条件为：氩气流量为30sccm，氧气流量为0.83sccm，氩氧比为36:1，溅射工作气压为0.1Pa，溅射功率为190W，生长温度为420℃，热处理退火温度480℃。其余的制备步骤及相关条件与实施例1中所记载的完全相同。
图33所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，在Carl Zeiss Corporation公司产的ZEISS
Figure PCTCN2019123451-appb-000011
55型号的扫描电镜获得的标准的扫描电子显微镜图。从图中可以看出，所述氧化钒薄膜具备层状生长的特性，薄膜结构致密，且结晶效果好，薄膜的质量高。
图34所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用Agilent的型号的AFM表征的原子力显微镜图。从图中可以看出，所述氧化钒薄膜表面平整，表面粗糙度小。
图35所示为，本实施例方法最终获得的柔性氧化钒复合薄膜中的氧化钒薄膜，使用四探针测试仪测试的电阻随温度变化曲线图。从图中可以看出，所述氧化钒薄膜的电阻温度系数约在-2％～-3％的范围内，具有较高的电阻温度系数，与在硅、金红石等刚性基底上制备的氧化钒薄膜性能相当。
本发明选用耐高温聚酰亚胺薄膜作为基底，低温制备层状生长的氧化钒薄膜，再通过不同气氛环境中的高温退火，制备得到基于聚酰亚胺柔性基底的氧化钒薄膜。所述氧化钒薄膜结晶度高，表面光滑均匀，具有良好的热致相变特性，电学特性与直接在硅基底等刚性材料制备的氧化钒薄膜相当，电阻值变化范围大，且氧化钒薄膜与聚酰亚胺薄膜结合紧密，不易脱落。本发明涉及的两步法既具备简单操作的优点又易于稳定控制；使用耐高温柔性基底材料，具备单独使用与硅基底的兼容特点，扩展了氧化钒薄膜的使用范围。
上面所述的只是说明本发明的一些实施方式，由于对相同技术领域的普通技术人员来说很容易在此基础上进行若干修改和改动，因此本说明书并非是要将本发明局限在所示和所述的具体结构、方法步骤、工艺流程、适用范围内，故凡是所有可能被利用的相应修改及等同物，均属于本发明所申请的专利范围。

Claims (18)

  1. 一种氧化钒复合薄膜的制备方法，包括，
    步骤一，在衬底上形成耐高温柔性材料薄膜，以形成基片；
    步骤二，在所述基片上的所述柔性材料上形成氧化钒前驱体薄膜；
    步骤三，对形成有所述氧化钒前驱体薄膜的基片进行高温退火，形成具有氧化钒薄膜的复合薄膜。
  2. 如权利要求1所述的方法，其特征在于，在所述步骤一之前，还包括衬底准备步骤；其中，所述衬底为硅衬底。
  3. 如权利要求2所述的方法，其特征在于，所述衬底准备步骤进一步包括，在所述硅衬底上形成氮化硅层，以形成具有氮化硅层的硅衬底；步骤一中所述柔性材料薄膜形成于所述衬底上的所述氮化硅层上。
  4. 如权利要求1所述的方法，其特征在于，所述步骤三之后，还包括剥离步骤；其中，所述剥离步骤包括，将形成有氧化钒薄膜的所述柔性材料薄膜与所述衬底剥离，获得在所述柔性材料薄膜上形成有氧化钒薄膜的复合薄膜。
  5. 如权利要求1所述的方法，其特征在于，所述耐高温柔性材料的热分解温度高于步骤三中高温退火的温度。
  6. 如权利要求5所述的方法，其特征在于，所述耐高温柔性材料为耐高温树脂材料。
  7. 如权利要求6所述的方法，其特征在于，所述耐高温树脂材料为聚酰亚胺。
  8. 如权利要求7所述的方法，其特征在于，所述聚酰亚胺的热分解温度大于400℃。
  9. 如权利要求1-8中任一项所述的方法，其特征在于，步骤二中，通过磁控溅射方法在所述柔性材料上形成所述氧化钒前驱体薄膜。
  10. 如权利要求9所述的方法，其特征在于，所述磁控溅射的条件为：基片温度为100-420℃，真空度为2.5～4.0×10 -4Pa，靶材与基片距离为80mm，氩气流量为15-30sccm，氧气流量为0.3-2.0sccm，氩氧比为7.5:1-50:1，溅射工作气压为0.1-0.3Pa，溅射功率为150-200W，沉积时间为15-60min。
  11. 如权利要求1-10中任一项所述的方法，其特征在于，步骤三中进行高温退火的条件为，在真空或惰性环境中对形成有所述氧化钒前驱体薄膜的基片进行退火。
  12. 如权利要求1-10中任一项所述的方法，其特征在于，步骤三中进行高温退火的温度为，在420-480℃。
  13. 如权利要求11或12所述的方法，其特征在于，所述退火的环境为，真空度为0.1-0.3Pa的氩气氛围。
  14. 一种氧化钒复合薄膜的制备方法，包括，
    步骤一，准备衬底，在硅基底上形成氮化硅层；
    步骤二，将所述衬底依次放入去离子水、无水乙醇、丙酮溶剂中分别超声清洗10分钟，并烘干；
    步骤三，准备基片，在所述衬底上形成聚酰亚胺薄膜；
    步骤四，将所述基片依次放入去离子水、无水乙醇、丙酮溶剂中分别超声清洗10分钟， 并烘干；
    步骤五，将清洗好的基片置于真空度为2.5～4.0×10 -4Pa的高真空射频磁控溅射设备里，在基片温度为100-420℃、氩气流量为15-30sccm、氧气流量为0.3-2.0sccm、氩氧比为7.5:1-50:1、溅射工作气压为0.1-0.3Pa、溅射功率为150-200W、靶材与基片距离为80mm的条件下，沉积15-60min，以在所述基片上形成氧化钒前驱体薄膜；所述靶材为金属钒靶；
    步骤六，在420-480℃退火30min以上，获得的氧化钒薄膜为层状多晶的薄膜。
  15. 如权利要求14所述的方法，其特征在于，所述步骤六之后，还包括剥离步骤；其中，所述剥离步骤包括，将形成有氧化钒薄膜的所述聚酰亚胺薄膜与所述衬底剥离，获得在所述柔性材料薄膜上形成有氧化钒薄膜的氧化钒复合薄膜。
  16. 如权利要求14或15所述的方法，其特征在于，所述步骤三还包括，将聚酰亚胺溶液用刮涂或旋涂的方法均匀涂抹在所述衬底上，在50-60℃下烘烤2小时，然后在300-400℃下加热8小时进行退火，在硅基底上得到均匀的聚酰亚胺薄膜。
  17. 一种通过权利要求1-16中任一项所述的方法制备形成的氧化钒复合薄膜。
  18. 如权利要求17所述的氧化钒复合薄膜，其特征在于所述薄膜的厚度为150nm。
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