CN116555720A - High-temperature stable TiN film and preparation method thereof - Google Patents
High-temperature stable TiN film and preparation method thereof Download PDFInfo
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- CN116555720A CN116555720A CN202310679992.4A CN202310679992A CN116555720A CN 116555720 A CN116555720 A CN 116555720A CN 202310679992 A CN202310679992 A CN 202310679992A CN 116555720 A CN116555720 A CN 116555720A
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004544 sputter deposition Methods 0.000 claims abstract description 99
- 239000000758 substrate Substances 0.000 claims abstract description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005498 polishing Methods 0.000 claims abstract description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 3
- 238000007747 plating Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- 238000005086 pumping Methods 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 230000005284 excitation Effects 0.000 claims description 10
- 229910000997 High-speed steel Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 238000005477 sputtering target Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 4
- 244000137852 Petrea volubilis Species 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
- C23C14/22—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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
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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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
-
- 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
- C23C14/0641—Nitrides
-
- 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
- C23C14/54—Controlling or regulating the coating process
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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
- C23C14/58—After-treatment
Abstract
The invention discloses a high-temperature stable TiN film and a preparation method thereof, wherein the preparation method comprises the following steps: step 1, polishing a substrate; cleaning a substrate; drying the substrate; placing the body on a central sample stage of a magnetron sputtering instrument, mounting a Ti target, a Cr target and a Si target on a target base, closing a sputtering chamber, and carrying out vacuum extraction; when the vacuum reaches the background vacuum 6.0X10 ‑4 After Pa, pre-sputtering three targets to remove impurities attached to the surfaces of the three targets; setting film sputtering parameters, opening a nitrogen valve, opening a Ti target, a Cr target and a Si target direct current power supply, and performing magnetron co-sputteringJetting, plating a TiN composite film; and taking out the film sample. The invention can greatly improve the high-temperature stability of the film.
Description
Technical Field
The invention relates to the technical field of film preparation, in particular to a high-temperature stable TiN film and a preparation method thereof.
Background
As a first hard film which is industrialized and widely used, a TiN film has peculiar optical characteristics, and meanwhile, since the resistivity of TiN is between a metal and an insulator, the forbidden band between a conduction band and a valence band is very narrow, valence electrons are not very tightly combined with atomic nuclei, in a mid-far infrared region, the interaction of free carriers and infrared light is similar to that of metal, conduction band electrons can generate in-band transition under the excitation of infrared light, and the TiN film has lower infrared emissivity, so the TiN film has the potential of being an infrared stealth film.
The TiN film is inevitably used in high temperature or oxidation environment, however, in this environment, the microstructure of the TiN film is greatly changed, so that the infrared stealth performance of the TiN film is greatly affected. The TiN film with single layer structure is rapidly oxidized into TiO with rutile structure after heat treatment at more than 500 DEG C 2 The method comprises the steps of carrying out a first treatment on the surface of the And secondly, the substrate element diffuses into the single-layer TiN film at high temperature. Defects caused by these two factors deteriorate the infrared stealth performance of TiN films. Good thermal stability and oxidation resistance under high temperature conditions are two important indexes for ensuring the surface radiation characteristics of the film with low infrared emissivity. Therefore, a method is needed to avoid the defects caused by high temperature and oxidation, and improve the high temperature stability of the TiN film, so that the application range of the TiN film is widened.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a high-temperature stable TiN film and a preparation method thereof. Doping a certain content of elements Cr and Si into the TiN film by magnetron sputtering to prepare the TiN composite film. Cr and Si in the film can not only effectively control the diffusion of the substrate element into the film at high temperature, but also can be combined with N element in the film in a covalent bond way, so that the heat stability of the film is improved. At the same time, cr or Si element in the film expands outwards at high temperatureBulk and form compact Cr with O element 2 O 3 Or SiO 2 And a mixed oxide protective layer. The formation of the oxide layer can generate volume expansion on the surface of the coating to form compressive stress, and can close cracks and gaps on the surface of the coating, which are affected by high temperature, so that the deep progress of oxidation can be effectively prevented, and the oxidation resistance of the coating is improved. The content of the doping element is critical, and the doping content of the element in the TiN film is controlled by controlling the sputtering power of the Cr and Si targets.
The invention is realized by adopting the following technical scheme:
a preparation method of a high-temperature stable TiN film comprises the following steps:
step 1, mechanically polishing a substrate by using sand paper, and polishing until the surface has no obvious scratches and is a mirror surface;
step 2, immersing the substrate obtained in the step 1 into an ethanol solution for ultrasonic excitation, and immersing into deionized water for ultrasonic cleaning;
step 3, wiping the surface of the substrate obtained in the step 2, and then drying the substrate;
step 4, placing the substrate obtained in the step 3 on a central sample stage of a magnetron sputtering instrument, mounting a Ti target, a Cr target and a Si target on a target base, closing a sputtering chamber, and carrying out vacuum extraction after confirming that each link is correct;
step 5, when the vacuum in step 4 reaches the background vacuum of 6.0X10 -4 After Pa, opening an argon valve, introducing argon, then respectively opening a Ti target, a Cr target and a Si target direct current power supply, and pre-sputtering three targets to remove impurities attached to the surfaces of the three targets;
step 6, after the pre-sputtering in the step 5 is finished, setting film sputtering parameters, opening a nitrogen valve, opening a Ti target, a Cr target and a Si target direct current power supply, performing magnetron co-sputtering, and plating a TiN composite film;
and 7, after the sputtering in the step 6 is finished, turning off the direct current power supply of the Ti target, the Cr target and the Si target, opening a vacuum valve, and taking out the film sample.
The invention is further improved in that in step 1, the substrate material is made of high-speed steel or stainless steel metal material with the size of 15.0x15.0x1.0 mm, and the high-speed steel or stainless steel is respectively polished by sand paper from coarse to fine, and then polished.
The invention is further improved in that the ultrasonic excitation time of the ethanol solution in the step 2 is 5-20 min, and the ultrasonic cleaning time of deionized water is 10-30 min.
The invention is further improved in that the drying temperature of the substrate in the step 3 is 60-100 ℃ and the drying time is 50-100 min.
The invention is further improved in that the purities of the Ti target, the Cr target and the Si target in the step 4 are 99.999 percent, when the Ti target, the Cr target and the Si target are arranged on the target base, the angles of the three targets are all 45 degrees and are obliquely arranged, the distance between the substrate and the sputtering target is adjusted to be 40-60 mm, and the targets are not biased; when vacuum is pumped, the mechanical pump and the pre-pumping valve are firstly opened to carry out low vacuum pumping, when the air pressure in the sputtering chamber is lower than 0.5Pa, the pre-pumping valve is closed, and the backing valve, the molecular pump and the gate valve and the high vacuum pumping are sequentially opened.
A further improvement of the invention is that in step 5 when the vacuum in step 4 reaches the background vacuum of 6.0X10 -4 After Pa, before the Ti target, the Cr target and the Si target are driven, a substrate baffle is opened to protect the substrate material from being polluted by pre-sputtering atoms, the flow of pre-sputtering argon is 20-60 sccm, the sputtering air pressure is 0.1-0.5 Pa, the sputtering power is 50-200W, and the sputtering time is 20-60 min.
The invention is further improved in that after the pre-sputtering in the step 6 is finished, the substrate baffle is closed, the sputtering parameters of the TiN composite film are set, the nitrogen flow is 1-8 sccm, the sputtering power of the Ti target is 80-200W, the sputtering power of the Al target is 30-60W, the sputtering power of the Si target is 30-60W, the co-sputtering deposition time is 10-40 min, and the substrate temperature is room temperature.
The invention is further improved in that the sputtering film thickness of the TiN composite film in the step 7 is 0.4-1 mu m.
The high-temperature stable TiN film is prepared by adopting the preparation method of the high-temperature stable TiN film.
The invention has at least the following beneficial technical effects:
1. the invention relates to a high-temperature stable TiN film and a preparation method thereof. The method adopts magnetron co-sputtering, and Cr and Si elements with the content less than 10% are doped into the TiN film by controlling the power of a Cr target and a Si target, so as to prepare the TiN composite film. The Cr and Si elements in the film can not only control the diffusion of the base metal element into the film at high temperature, but also form a compact oxide protection layer with the O element to prevent the deep oxidation, thereby greatly improving the high-temperature stability of the film.
2. The invention relates to a high-temperature stable TiN film and a preparation method thereof. The prepared film is oxidized at 500-800 ℃ and has compact surface and no gaps, and the oxide protective layer is formed on the surface of the film, so that the high-temperature oxidation of the film can be further hindered. The film and the metal matrix are combined well without gaps, and the limit is well defined, which indicates that the metal element of the matrix does not diffuse into the film at high temperature.
3. The invention relates to a high-temperature stable TiN film and a preparation method thereof. The prepared film is oxidized at 500-800 ℃, and compared with an unoxidized TiN composite film, the infrared emissivity of the film is not greatly changed, which proves that the method provided by the invention can effectively improve the high-temperature stability of the film and prevent the film from deteriorating under high-temperature oxidation.
Drawings
FIG. 1 is an XRD pattern of a film prepared in accordance with the present invention;
FIG. 2 is a surface and side SEM image of a film prepared according to the present invention after oxidation at 700 ℃;
FIG. 3 is a graph of infrared emissivity of a film prepared in accordance with the present invention before and after oxidation at 700 ℃.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
The invention provides a high-temperature stable TiN film and a preparation method thereof, which are implemented according to the following steps:
step 1, polishing high-speed steel or stainless steel matrixes with the sizes of 15.0 multiplied by 1.0mm by abrasive paper from coarse to fine respectively, and then polishing;
step 2, immersing the substrate obtained in the step 1 into an ethanol solution for ultrasonic excitation for 5-20 min, and immersing into deionized water for ultrasonic cleaning for 10-30 min;
step 3, wiping the surface of the substrate obtained in the step 2 with special lens paper for a microscope, and drying in a blast drying oven at 60-100 ℃ for 50-100 min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, respectively mounting three targets with purity of 99.999% Ti target, cr target and Si target on a target base, wherein the angles of the three targets are 45 degrees, the distance between the substrate and the sputtering target is adjusted to be 40-60 mm, no bias voltage is applied to the targets, closing a sputtering chamber, after confirming that each link is correct, firstly opening a mechanical pump and a pre-pumping valve, carrying out low vacuum pumping, and when the air pressure in the sputtering chamber is lower than 0.5Pa, closing the pre-pumping valve, sequentially opening a backing valve, a molecular pump and a gate valve, and carrying out high vacuum pumping;
step 5, when the vacuum in step 4 reaches the background vacuum of 6.0X10 -4 Setting the argon flow to be 20-60 sccm after Pa, the sputtering air pressure to be 0.1-0.5 Pa, the sputtering power of the Ti target, the Cr target and the Si target to be 50-200W, opening a base body baffle, opening an argon valve to be filled with argon, opening a direct current power supply of the Ti target, the Cr target and the Si target, and pre-sputtering the Ti target, the Cr target and the Si target for 20-60 min to remove impurities attached to the surfaces of the Ti target, the Cr target and the Si target;
step 6, setting the nitrogen flow to be 1-8 sccm, the Ti target sputtering power to be 80-200W, the Cr target sputtering power to be 30-60W, the Si target sputtering power to be 30-60W, the total sputtering deposition time to be 10-40 min after the pre-sputtering in the step 5 is finished, closing a substrate temperature to be room temperature, opening a nitrogen valve to be filled with nitrogen, opening a Ti target, a Cr target and a Si target direct current power supply, and performing reactive magnetron total sputtering to plate a TiN composite film;
and 7, after the sputtering in the step 6 is finished, turning off the direct current power supply of the Ti target, the Cr target and the Si target, opening a vacuum valve, and taking out the film sample.
Example 1
Step 1, polishing high-speed steel or stainless steel matrixes with the sizes of 15.0 multiplied by 1.0mm by abrasive paper from coarse to fine respectively, and then polishing;
step 2, immersing the substrate obtained in the step 1 into an ethanol solution for ultrasonic excitation for 20min, and immersing into deionized water for ultrasonic cleaning for 30min;
step 3, wiping the surface of the substrate obtained in the step 2 with special lens paper for a microscope, and drying the substrate in a blast drying oven at 80 ℃ for 60min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, respectively mounting three targets with purity of 99.999% Ti target, cr target and Si target on a target base, wherein the angles of the three targets are 45 degrees, the distance between the substrate and the sputtering target is adjusted to be 45mm, the targets are not biased, a sputtering chamber is closed, after confirming that each link is correct, a mechanical pump and a pre-pumping valve are firstly opened, low vacuum pumping is carried out, when the air pressure in the sputtering chamber is lower than 0.5Pa, the pre-pumping valve is closed, and a backing valve, a molecular pump and a gate valve are sequentially opened, and high vacuum pumping is carried out;
step 5, when the vacuum in step 4 reaches the background vacuum of 6.0X10 -4 Setting the argon flow to be 40sccm after Pa, the sputtering air pressure to be 0.3Pa, the sputtering power of the Ti target, the Cr target and the Si target to be 100W, opening a base body baffle, opening an argon valve to be filled with argon, opening a direct current power supply of the Ti target, the Cr target and the Si target, and pre-sputtering the Ti target, the Cr target and the Si target for 20min to remove impurities attached to the surfaces of the Ti target, the Cr target and the Si target;
step 6, setting the nitrogen flow as 4sccm, the Ti target sputtering power as 150W, the Cr target sputtering power as 30W, the Si target sputtering power as 30W, the co-sputtering deposition time as 20min, the substrate temperature as room temperature, closing the substrate baffle, opening the nitrogen valve to introduce nitrogen, opening the Ti target, the Cr target and the Si target direct current power supply, and performing reactive magnetron co-sputtering to plate the TiN composite film;
and 7, after the sputtering in the step 6 is finished, turning off the direct current power supply of the Ti target, the Cr target and the Si target, opening a vacuum valve, and taking out the film sample.
Example 2
Step 1, polishing high-speed steel or stainless steel matrixes with the sizes of 15.0 multiplied by 1.0mm by abrasive paper from coarse to fine respectively, and then polishing;
step 2, immersing the substrate obtained in the step 1 into an ethanol solution for ultrasonic excitation for 20min, and immersing into deionized water for ultrasonic cleaning for 30min;
step 3, wiping the surface of the substrate obtained in the step 2 with special lens paper for a microscope, and drying the substrate in a blast drying oven at 80 ℃ for 60min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, respectively mounting three targets with purity of 99.999% Ti target, cr target and Si target on a target base, wherein the angles of the three targets are 45 degrees, the distance between the substrate and the sputtering target is adjusted to be 45mm, the targets are not biased, a sputtering chamber is closed, after confirming that each link is correct, a mechanical pump and a pre-pumping valve are firstly opened, low vacuum pumping is carried out, when the air pressure in the sputtering chamber is lower than 0.5Pa, the pre-pumping valve is closed, and a backing valve, a molecular pump and a gate valve are sequentially opened, and high vacuum pumping is carried out;
step 5, when the vacuum in step 4 reaches the background vacuum of 6.0X10 -4 Setting the argon flow to be 40sccm after Pa, the sputtering air pressure to be 0.3Pa, the sputtering power of the Ti target, the Cr target and the Si target to be 100W, opening a base body baffle, opening an argon valve to be filled with argon, opening a direct current power supply of the Ti target, the Cr target and the Si target, and pre-sputtering the Ti target, the Cr target and the Si target for 20min to remove impurities attached to the surfaces of the Ti target, the Cr target and the Si target;
step 6, setting the nitrogen flow to be 4sccm, the Ti target sputtering power to be 150W, the Cr target sputtering power to be 40W, the Si target sputtering power to be 40W, the total sputtering deposition time to be 20min, the substrate temperature to be room temperature, closing a base baffle, opening a nitrogen valve to be filled with nitrogen, opening a Ti target, a Cr target and a Si target direct current power supply, and performing reactive magnetron total sputtering to plate a TiN composite film;
and 7, after the sputtering in the step 6 is finished, turning off the direct current power supply of the Ti target, the Cr target and the Si target, opening a vacuum valve, and taking out the film sample.
Example 3
Step 1, polishing high-speed steel or stainless steel matrixes with the sizes of 15.0 multiplied by 1.0mm by abrasive paper from coarse to fine respectively, and then polishing;
step 2, immersing the substrate obtained in the step 1 into an ethanol solution for ultrasonic excitation for 20min, and immersing into deionized water for ultrasonic cleaning for 30min;
step 3, wiping the surface of the substrate obtained in the step 2 with special lens paper for a microscope, and drying the substrate in a blast drying oven at 80 ℃ for 60min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, respectively mounting three targets with purity of 99.999% Ti target, cr target and Si target on a target base, wherein the angles of the three targets are 45 degrees, the distance between the substrate and the sputtering target is adjusted to be 45mm, the targets are not biased, a sputtering chamber is closed, after confirming that each link is correct, a mechanical pump and a pre-pumping valve are firstly opened, low vacuum pumping is carried out, when the air pressure in the sputtering chamber is lower than 0.5Pa, the pre-pumping valve is closed, and a backing valve, a molecular pump and a gate valve are sequentially opened, and high vacuum pumping is carried out;
step 5, when the vacuum in the step 4 reaches the background vacuum of 6.0X10-4 Pa, setting the flow rate of argon to 40sccm, setting the sputtering pressure to 0.3Pa, setting the sputtering power of the Ti target, the Cr target and the Si target to 100W, opening a base body baffle, opening an argon valve, introducing argon, opening a Ti target, a Cr target and a Si target direct current power supply, and pre-sputtering the Ti target, the Cr target and the Si target for 20min to remove impurities attached to the surfaces of the Ti target, the Cr target and the Si target;
step 6, setting the nitrogen flow to be 4sccm, the Ti target sputtering power to be 150W, the Cr target sputtering power to be 50W, the Si target sputtering power to be 50W, the total sputtering deposition time to be 20min, the substrate temperature to be room temperature, closing a base baffle, opening a nitrogen valve to be introduced with nitrogen, opening a Ti target, a Cr target and a Si target direct current power supply, and performing reactive magnetron total sputtering to plate a TiN composite film;
and 7, after the sputtering in the step 6 is finished, turning off the direct current power supply of the Ti target, the Cr target and the Si target, opening a vacuum valve, and taking out the film sample.
Example 4
Step 1, polishing high-speed steel or stainless steel matrixes with the sizes of 15.0 multiplied by 1.0mm by abrasive paper from coarse to fine respectively, and then polishing;
step 2, immersing the substrate obtained in the step 1 into an ethanol solution for ultrasonic excitation for 20min, and immersing into deionized water for ultrasonic cleaning for 30min;
step 3, wiping the surface of the substrate obtained in the step 2 with special lens paper for a microscope, and drying the substrate in a blast drying oven at 80 ℃ for 60min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, respectively mounting three targets with purity of 99.999% Ti target, cr target and Si target on a target base, wherein the angles of the three targets are 45 degrees, the distance between the substrate and the sputtering target is adjusted to be 45mm, the targets are not biased, a sputtering chamber is closed, after confirming that each link is correct, a mechanical pump and a pre-pumping valve are firstly opened, low vacuum pumping is carried out, when the air pressure in the sputtering chamber is lower than 0.5Pa, the pre-pumping valve is closed, and a backing valve, a molecular pump and a gate valve are sequentially opened, and high vacuum pumping is carried out;
step 5, when the vacuum in step 4 reaches the background vacuum of 6.0X10 -4 Setting the argon flow to be 40sccm after Pa, the sputtering air pressure to be 0.3Pa, the sputtering power of the Ti target, the Cr target and the Si target to be 100W, opening a base body baffle, opening an argon valve to be filled with argon, opening a direct current power supply of the Ti target, the Cr target and the Si target, and pre-sputtering the Ti target, the Cr target and the Si target for 20min to remove impurities attached to the surfaces of the Ti target, the Cr target and the Si target;
step 6, setting the nitrogen flow as 4sccm, the Ti target sputtering power as 200W, the Cr target sputtering power as 30W, the Si target sputtering power as 30W, the co-sputtering deposition time as 20min, the substrate temperature as room temperature, closing the substrate baffle, opening the nitrogen valve to introduce nitrogen, opening the Ti target, the Cr target and the Si target direct current power supply, and performing reactive magnetron co-sputtering to plate the TiN composite film;
and 7, after the sputtering in the step 6 is finished, turning off the direct current power supply of the Ti target, the Cr target and the Si target, opening a vacuum valve, and taking out the film sample.
As shown in figure 1, the XRD pattern of the high-temperature stable TiN film prepared by the method of the invention has less contents of two elements of doped Cr and Si, and only a large amount of TiN main crystal phases are detected in the film, which indicates that the TiN film is successfully prepared.
As shown in a SEM surface morphology graph of the high-temperature stable TiN film prepared by the method, after the film is oxidized at 700 ℃, the surface of the film is very compact and void-free, and a plurality of tiny aggregated particles are found on the surface of the film, and the particles are detected to be oxide particles, so that an oxide layer with a certain thickness is formed on the surface of the film, which is beneficial to isolating the further contact of the external air and the film and effectively improving the oxidation resistance of the film. In addition, after the prepared film is oxidized at 700 ℃, the film and the metal matrix are combined well without gaps, the introduction of Cr and Si elements is demonstrated, the diffusion of the matrix metal elements into the film at high temperature is prevented, and the film keeps good stability.
As shown in FIG. 3, the infrared emissivity of the high-temperature stable TiN film prepared by the method is 0.3-0.4 compared with the infrared emissivity of the TiN composite film which is not subjected to high-temperature oxidation after the film is oxidized at 700 ℃, which shows that the method provided by the invention can effectively improve the high-temperature stability of the film and prevent the film from deteriorating under high-temperature oxidation.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (9)
1. The preparation method of the high-temperature stable TiN film is characterized by comprising the following steps:
step 1, mechanically polishing a substrate by using sand paper, and polishing until the surface has no obvious scratches and is a mirror surface;
step 2, immersing the substrate obtained in the step 1 into an ethanol solution for ultrasonic excitation, and immersing into deionized water for ultrasonic cleaning;
step 3, wiping the surface of the substrate obtained in the step 2, and then drying the substrate;
step 4, placing the substrate obtained in the step 3 on a central sample stage of a magnetron sputtering instrument, mounting a Ti target, a Cr target and a Si target on a target base, closing a sputtering chamber, and carrying out vacuum extraction after confirming that each link is correct;
step 5, when the vacuum in step 4 reaches the background vacuum of 6.0X10 -4 After Pa, opening an argon valve, introducing argon, then respectively opening a Ti target, a Cr target and a Si target direct current power supply, and pre-sputtering three targets to remove impurities attached to the surfaces of the three targets;
step 6, after the pre-sputtering in the step 5 is finished, setting film sputtering parameters, opening a nitrogen valve, opening a Ti target, a Cr target and a Si target direct current power supply, performing magnetron co-sputtering, and plating a TiN composite film;
and 7, after the sputtering in the step 6 is finished, turning off the direct current power supply of the Ti target, the Cr target and the Si target, opening a vacuum valve, and taking out the film sample.
2. The method for preparing a high temperature stable TiN film according to claim 1, wherein in step 1, the base material is made of a high-speed steel or stainless steel metal material having a size of 15.0 x 1.0mm, and the high-speed steel or stainless steel is polished with sandpaper from coarse to fine, respectively, and then polished.
3. The method for preparing a high-temperature stable TiN film according to claim 1, wherein the ultrasonic excitation time of the ethanol solution in the step 2 is 5-20 min, and the ultrasonic cleaning time of deionized water is 10-30 min.
4. The method for preparing a high temperature stable TiN film according to claim 1, wherein the substrate in step 3 is dried at 60-100 ℃ for 50-100 min.
5. The method for preparing a high temperature stable TiN film according to claim 1, wherein in the step 4, the purities of Ti target, cr target and Si target are 99.999%, when the Ti target, cr target and Si target are arranged on the target base, the three targets are all placed at 45 degrees in an inclined manner, the distance between the substrate and the sputtering target is adjusted to be 40-60 mm, and no bias voltage is applied to the targets; when vacuum is pumped, the mechanical pump and the pre-pumping valve are firstly opened to carry out low vacuum pumping, when the air pressure in the sputtering chamber is lower than 0.5Pa, the pre-pumping valve is closed, and the backing valve, the molecular pump and the gate valve and the high vacuum pumping are sequentially opened.
6. The method for preparing a high temperature stable TiN film according to claim 1, wherein in step 5, when the vacuum in step 4 reaches the background vacuum of 6.0X10 × -4 After Pa, before the Ti target, the Cr target and the Si target are driven, a substrate baffle is opened to protect the substrate material from being polluted by pre-sputtering atoms, the flow of pre-sputtering argon is 20-60 sccm, the sputtering air pressure is 0.1-0.5 Pa, the sputtering power is 50-200W, and the sputtering time is 20-60 min.
7. The method for preparing a high-temperature stable TiN film according to claim 1, wherein after the pre-sputtering in the step 6 is finished, a substrate baffle is closed, a TiN composite film sputtering parameter is set, the nitrogen flow is 1-8 sccm, the Ti target sputtering power is 80-200W, the Al target sputtering power is 30-60W, the Si target sputtering power is 30-60W, the co-sputtering deposition time is 10-40 min, and the substrate temperature is room temperature.
8. The method for producing a high-temperature stable TiN film according to claim 1, wherein the TiN composite film sputtering film thickness in step 7 is 0.4 to 1 μm.
9. A high temperature stable TiN film prepared by the method of any one of claims 1 to 8.
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