A modification method for nickel oxide film

Abstract

The present invention relates to a modification treatment method for a nickel oxide film, the modification treatment method comprising the following steps: subjecting the nickel oxide film to a heating treatment and a post-annealing treatment in sequence, and cooling the nickel oxide film to room temperature with a furnace to obtain a modified nickel oxide film; the heating treatment comprises a first heating section and a second heating section in sequence. The present invention subjects the nickel oxide film to a two-stage heating treatment and a post-annealing treatment, so that the nickel oxide film is recrystallized after high-temperature annealing, thereby improving its crystallinity and compactness, and further improving its corrosion resistance.

Description

Technical Field

[0001] The invention relates to the technical field of sputtering coating, and in particular to a modification treatment method for a nickel oxide film. Background Art

[0002] Sputtering coating refers to the plasma generated by rarefied gas in abnormal glow discharge bombarding the cathode target surface under the action of electric field, sputtering out the molecules, atoms, ions and electrons on the target surface. The sputtered particles have a certain kinetic energy and are ejected toward the substrate surface in a certain direction, forming a coating film on the substrate surface. Among them, nickel oxide film has excellent comprehensive properties and is widely used in the field of target preparation.

[0003] At present, the widely used method for preparing nickel oxide thin films is magnetron sputtering, which is mainly divided into direct magnetron sputtering, reactive magnetron sputtering, ion beam enhanced magnetron sputtering and rotating target magnetron sputtering. The direct magnetron sputtering method is to place a nickel oxide target in a vacuum chamber, and excite the plasma formed by the gas by applying a high-frequency electric field or a direct current electric field, so that the nickel oxide target is sputtered into powder and deposited on the surface of the substrate to form a nickel oxide film; the reactive magnetron sputtering method is based on the direct magnetron sputtering method, and a layer of metal aluminum film is covered on the surface of the nickel oxide target, and reactive gases such as oxygen are added at the same time, so that the metal aluminum reacts with oxygen to form aluminum oxide, and the aluminum oxide reacts with nickel oxide to form a nickel oxide film; the ion beam enhanced magnetron sputtering method is based on the direct magnetron sputtering method, and a high-energy ion beam is bombarded on the surface of the nickel oxide target to enhance the reactivity of the surface of the nickel oxide target, thereby obtaining a better nickel oxide film; the rotating target magnetron sputtering method is based on the direct magnetron sputtering method, and the nickel oxide target is set as a rotating target. Under the action of reactive gases such as oxygen, a more uniform and denser nickel oxide film can be obtained.

[0004] CN 114163139A discloses a method for preparing a two-layer composite nickel oxide film with different structures, comprising the following steps: washing and drying an FTO glass sheet; performing magnetron sputtering on the washed FTO glass sheet by a DC magnetron sputtering method to obtain a layer of magnetron sputtered nickel oxide film on the conductive surface of the FTO glass sheet; adding nickel salt and terephthalic acid into a beaker, then adding N,N-dimethylformamide, stirring, then adding deionized water and continuing to stir to obtain a precursor solution, transferring the precursor into a reactor, then vertically placing the magnetron sputtered FTO glass sheet into the reactor, washing the surface of the film layer after hydrothermal reaction, removing residual impurities, and drying to obtain NiO.

[0005] CN 105970171A discloses a method for preparing a flexible rare earth oxide film by magnetron sputtering, comprising the following steps: a: selecting a 4N rare earth metal target; b: using a liquid PDMS precursor as a substrate; c: evacuating, introducing argon gas, and pre-sputtering to clean the target surface; d: heating a heating table to a temperature required for depositing a thin film and keeping the temperature; e: introducing a mixed gas, applying sputtering power, controlling the gas flow, and starting to coat the substrate surface for 1 hour; f: maintaining a constant temperature for 3 hours, and obtaining a flexible film when the temperature drops to room temperature.

[0006] The preparation method disclosed in the above invention adopts different magnetron sputtering methods to prepare nickel oxide thin films. However, during the preparation process of nickel oxide thin films, the physical and chemical properties of the target surface will change over time, and the crystal structure and orientation of the nickel oxide thin films are also affected by the preparation conditions. Therefore, the crystal structure and orientation of the nickel oxide thin films are not stable, and the density and uniformity of the nickel oxide thin films need to be improved.

[0007] In view of the shortcomings of the prior art, it is necessary to provide a modification method for the nickel oxide film to have good crystallinity, high density and good corrosion resistance. Summary of the invention

[0008] The purpose of the present invention is to provide a modification method for a nickel oxide film, by subjecting the nickel oxide film to a temperature increase treatment and a post-annealing treatment, so that the nickel oxide film is recrystallized, thereby improving the crystallinity and density of the nickel oxide film, and further improving its corrosion resistance.

[0009] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0010] The present invention provides a modification method for a nickel oxide film, the modification method comprising the following steps:

[0011] The nickel oxide film is subjected to a heating treatment and a post-annealing treatment in sequence, and then cooled to room temperature in the furnace to obtain a modified nickel oxide film;

[0012] The temperature rising process includes a first temperature rising stage and a second temperature rising stage which are performed sequentially.

[0013] The modification method provided by the present invention subjects the nickel oxide film to a two-stage heating treatment and a post-annealing treatment, so that the nickel oxide film is recrystallized by high-temperature post-annealing, thereby improving its crystallinity and density, and further improving its corrosion resistance; the obtained modified nickel oxide film also has better thermal stability and can maintain stable performance in a high temperature environment.

[0014] Preferably, the nickel oxide film is obtained by magnetron sputtering.

[0015] Preferably, the magnetron sputtering treatment method includes any one of direct magnetron sputtering, reactive magnetron sputtering, ion beam enhanced magnetron sputtering or rotating target magnetron sputtering, or a combination of at least two of them. Typical but non-limiting combinations include a combination of direct magnetron sputtering and reactive magnetron sputtering, a combination of direct magnetron sputtering and ion beam enhanced magnetron sputtering, or a combination of direct magnetron sputtering and rotating target magnetron sputtering.

[0016] Preferably, the nickel oxide film is placed in a ark before the temperature increase treatment.

[0017] Preferably, the temperature raising treatment is carried out in a muffle furnace.

[0018] The first temperature rising stage is from room temperature to 340-360°C, for example, 340°C, 345°C, 350°C, 355°C or 360°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0019] Preferably, the heating rate of the first heating section is 5-10°C / min, for example, it can be 5°C / min, 6°C / min, 7°C / min, 8°C / min or 10°C / min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0020] The second temperature rising stage is from 340-360°C to 890-910°C.

[0021] The end point of the temperature rise is 890-910°C, for example, it can be 890°C, 895°C, 900°C, 905°C or 910°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0022] Preferably, the heating rate of the second heating stage is 14-16°C / min, for example, 14°C / min, 15°C / min or 16°C / min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0023] The temperature rise treatment is set to a first temperature rise stage and a second temperature rise stage performed sequentially, and different temperature rise rates can be controlled so that the internal crystal structure of the nickel oxide film presents a gradient level change, further enhancing the crystallinity and density of the modified nickel oxide film obtained by the subsequent post-annealing treatment.

[0024] Preferably, the post-annealing treatment time is 8.8-9.2 h, for example, 8.8 h, 8.9 h, 9 h, 9.1 h or 9.2 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0025] The post-annealing treatment time is within a limited range, which can effectively improve the crystallinity and density of the nickel oxide film. If the time is too long or too short, it will have an adverse effect on the crystallization performance of the nickel oxide film.

[0026] Preferably, the post annealing treatment is performed in an air atmosphere.

[0027] The air atmosphere can promote the oxidation of nickel oxide film and the growth of oxide during the annealing process, which is beneficial to improving the quality and grain size of the film; in addition, air has good heat transfer and thermal stability and is suitable for high-temperature annealing treatment.

[0028] Preferably, the modified nickel oxide film is a polycrystalline structure.

[0029] The grain size of the modified nickel oxide film is 30-50 nm, for example, 30 nm, 35 nm, 40 nm, 45 nm or 50 nm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0030] The crystallinity and grain size of the modified nickel oxide film are obtained by measuring the crystal diffraction pattern of the modified nickel oxide film using an XRD device, calculating the FWMH value of the crystal orientation peak, and further calculating and processing.

[0031] As a preferred technical solution of the modification treatment method described in the present invention, the modification treatment method comprises the following steps:

[0032] The nickel oxide film obtained by magnetron sputtering is placed in an ark, and then subjected to a heating treatment in a muffle furnace, a post-annealing treatment in an air atmosphere for 8.8-9.2 hours, and then cooled to room temperature with the furnace to obtain a polycrystalline modified nickel oxide film with a grain size of 30-50 nm;

[0033] The temperature rise treatment includes a first temperature rise section and a second temperature rise section which are performed sequentially; the first temperature rise section is a temperature rise from room temperature to 340-360°C at a temperature rise rate of 5-10°C / min; the second temperature rise section is a temperature rise from 340-360°C to 890-910°C at a temperature rise rate of 14-16°C / min.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] The modification treatment method provided by the present invention subjects the nickel oxide film to two-stage heating treatment and post-annealing treatment, so that the nickel oxide film is recrystallized by high-temperature post-annealing, thereby improving its crystallinity and density, and further improving its corrosion resistance, with a corrosion rate as low as 1%; the modification treatment method is simple to operate, low in cost, and can prepare high-quality nickel oxide films to meet the needs of different fields. DETAILED DESCRIPTION

[0036] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0037] Example 1

[0038] This embodiment provides a modification method for a nickel oxide thin film, the modification method comprising the following steps:

[0039] The nickel oxide film obtained by magnetron sputtering was placed in an ark, and then subjected to a heating treatment in a muffle furnace, a post-annealing treatment in an air atmosphere for 9 hours, and then cooled to room temperature with the furnace to obtain a polycrystalline modified nickel oxide film;

[0040] The temperature rise treatment includes a first temperature rise section and a second temperature rise section which are performed sequentially; the first temperature rise section is from room temperature to 350°C at a temperature rise rate of 7°C / min; the second temperature rise section is from 350°C to 900°C at a temperature rise rate of 15°C / min.

[0041] Example 2

[0042] This embodiment provides a modification method for a nickel oxide thin film, the modification method comprising the following steps:

[0043] The nickel oxide film obtained by magnetron sputtering was placed in an ark, and then subjected to a heating treatment in a muffle furnace, a post-annealing treatment in an air atmosphere for 8.8 hours, and then cooled to room temperature with the furnace to obtain a polycrystalline modified nickel oxide film;

[0044] The temperature rise treatment includes a first temperature rise section and a second temperature rise section which are performed sequentially; the first temperature rise section is from room temperature to 340°C at a temperature rise rate of 5°C / min; the second temperature rise section is from 340°C to 890°C at a temperature rise rate of 14°C / min.

[0045] Example 3

[0046] This embodiment provides a modification method for a nickel oxide thin film, the modification method comprising the following steps:

[0047] The nickel oxide film obtained by magnetron sputtering was placed in an ark, and then subjected to a heating treatment in a muffle furnace, a post-annealing treatment in an air atmosphere for 9.2 hours, and then cooled to room temperature with the furnace to obtain a polycrystalline modified nickel oxide film;

[0048] The temperature rise treatment includes a first temperature rise section and a second temperature rise section which are performed sequentially; the first temperature rise section is from room temperature to 360°C at a temperature rise rate of 10°C / min; the second temperature rise section is from 360°C to 910°C at a temperature rise rate of 16°C / min.

[0049] Example 4

[0050] This embodiment provides a modification treatment method for a nickel oxide film, which is different from Embodiment 1 in that the end point of the second heating stage is adjusted to 650° C., and the rest is the same as Embodiment 1.

[0051] Example 5

[0052] This embodiment provides a modification treatment method for a nickel oxide film, which is different from Embodiment 1 in that the end point of the second heating stage is adjusted to 1050° C., and the rest is the same as Embodiment 1.

[0053] Example 6

[0054] This embodiment provides a modification treatment method for a nickel oxide film, which is different from Embodiment 1 in that the time of the post-annealing treatment is adjusted to 7 hours, and the rest is the same as Embodiment 1.

[0055] Example 7

[0056] This embodiment provides a modification treatment method for a nickel oxide film, which is different from Embodiment 1 in that the time of the post-annealing treatment is adjusted to 9.5 hours, and the rest is the same as Embodiment 1.

[0057] Example 8

[0058] This embodiment provides a modification treatment method for a nickel oxide thin film, which is different from Embodiment 1 in that the post-annealing treatment is performed in an argon atmosphere, and the rest is the same as Embodiment 1.

[0059] Comparative Example 1

[0060] This comparative example provides a modification treatment method for a nickel oxide film, which differs from Example 1 in that the temperature rise treatment is a single temperature rise stage, and the temperature is raised to 900° C. at a heating rate of 15° C. / min, and the rest is the same as Example 1.

[0061] Comparative Example 2

[0062] This comparative example provides a nickel oxide film, which is not subjected to a temperature increase treatment and a post-annealing treatment.

[0063] The modified nickel oxide films obtained by the modification treatment methods provided in Examples 1-8 and Comparative Example 1, and the nickel oxide film provided in Comparative Example 2 were subjected to crystal size analysis using X-ray diffraction, and the results obtained are shown in Table 1; a corrosion resistance test was performed: the samples were immersed in an acid-base solution, the test solution included hydrochloric acid and sodium hydroxide, and the corrosion rate of the samples was tested. The results obtained are shown in Table 1.

[0064] Table 1

[0065] Grain size (nm) Corrosion rate (%) Example 1 50 1.0 Example 2 30 2.5 Example 3 42 3.0 Example 4 15 6.0 Example 5 80 0.7 Example 6 35 2.3 Example 7 60 0.9 Example 8 25 2.1 Comparative Example 1 30 2.5 Comparative Example 2 5 15.0

[0066] It can be concluded from Table 1 that the modified nickel oxide film obtained by the modification treatment method provided by the present invention has good crystallinity and corrosion resistance; from the comparison between Example 1 and Example 4, it can be seen that since the end temperature of the second heating stage is too low, the grain growth rate will be affected, resulting in the grain size cannot be effectively optimized and increased, the crystallinity and density of the obtained modified nickel oxide film are reduced, and the corrosion rate is also increased; from the comparison between Example 1 and Example 5, it can be seen that since the end temperature of the second heating stage is too high, the grain growth rate will be accelerated, resulting in a significant increase in the grain size, which may cause changes in the film performance; in addition, too high a temperature will also cause changes in the grain morphology, such as from spherical to plate-like, which will have an adverse effect on the performance of the film, and the number of defects such as dislocations and vacancies inside the crystal in the obtained modified nickel oxide film will increase, which will further reduce the conductivity and chemical stability of the film;

[0067] From the comparison between Example 1 and Example 6, it can be seen that since the time of the post-annealing treatment is too short, the grain growth rate will be affected, resulting in the inability to effectively optimize and increase the grain size; from the comparison between Example 1 and Example 7, it can be seen that since the time of the post-annealing treatment is too long, the growth rate of the grains is too fast, which will lead to excessive grain size or uneven grain growth, thereby affecting the physical, chemical and electrical properties of the film; in addition, too long annealing time will also lead to an increase in the degree of oxidation on the surface of the film, thereby affecting the chemical composition and structural properties of the film; from the comparison between Example 1 and Example 8, it can be seen that since the atmosphere of the post-annealing treatment is argon gas, the oxide on the surface of the nickel oxide film can be reduced at high temperature, thereby reducing the content of the oxide, which is not conducive to improving the quality and grain size of the film;

[0068] By comparing Example 1 with Comparative Example 1, it can be seen that since the temperature rise treatment is adjusted to a single temperature rise stage, the crystallinity and density of the nickel oxide film are reduced; by comparing Example 1 with Comparative Example 2, it can be seen that the grain size of the nickel oxide film that has not undergone temperature rise treatment and post-annealing treatment is too small, and the corrosion rate is greatly increased.

[0069] In summary, the modification method provided by the present invention subjects the nickel oxide film to a two-stage heating treatment and a post-annealing treatment, so that the nickel oxide film is recrystallized by high-temperature post-annealing, thereby improving its crystallinity and density, and further improving its corrosion resistance, with a corrosion rate as low as 1%; the modification method is simple to operate, low in cost, and can prepare high-quality nickel oxide films to meet the needs of different fields.

[0070] The above description is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention are within the protection scope and disclosure scope of the present invention.

Claims

1. A method for modifying a nickel oxide film, characterized in that: The modification treatment method comprises the following steps: The nickel oxide film obtained by magnetron sputtering was placed in an ark, and then subjected to a heating treatment in a muffle furnace, a post-annealing treatment in an air atmosphere for 9 hours, and then cooled to room temperature with the furnace to obtain a polycrystalline modified nickel oxide film with a grain size of 50 nm; The temperature rise treatment includes a first temperature rise section and a second temperature rise section which are performed sequentially; the first temperature rise section is from room temperature to 350°C at a temperature rise rate of 7°C / min; the second temperature rise section is from 350°C to 900°C at a temperature rise rate of 15°C / min.