CN116988040A - Transitional film and preparation method thereof - Google Patents

Transitional film and preparation method thereof Download PDF

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Publication number
CN116988040A
CN116988040A CN202310708393.0A CN202310708393A CN116988040A CN 116988040 A CN116988040 A CN 116988040A CN 202310708393 A CN202310708393 A CN 202310708393A CN 116988040 A CN116988040 A CN 116988040A
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iron
film
film layer
transitional
silicon
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卢建宁
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
    • C23C16/14—Deposition of only one other metal element
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/16—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal carbonyl compounds
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating

Abstract

The application discloses a transitional film layer and a preparation method thereof. According to the application, the intermediate transitional film layer is introduced between the incompatible bottom film coating base material and the upper target film layer, and the problem of poor growth of the upper target film layer on the bottom film coating base material is solved by utilizing the characteristic that the transitional film layer is compatible with the bottom film coating base material and the upper target film layer, and the problem of poor growth of the silicon film when the silicon film coating is carried out on the base materials such as high aluminum, high nickel, high copper and the like in the prior art is solved.

Description

Transitional film and preparation method thereof
Technical Field
The application belongs to the field of material preparation, and particularly relates to a transitional film layer and a preparation method thereof.
Background
Chemical vapor deposition (chemical vapor deposition, CVD) is a common surface treatment method. The technology mainly uses one or more gas phase compounds or simple substances containing film elements to carry out chemical reaction on the surface of a base material (substrate) so as to generate a film. The film layer changes the physical and chemical properties of the surface of the substrate, and can provide the functions of improving hardness, enhancing acid and alkali resistance, increasing chemical inertness, changing surface conductivity, changing surface color and the like, thereby expanding the original application range of the substrate. Among the various chemical vapor deposition methods, the most basic is thermal chemical vapor deposition, i.e., thermal energy is used to cause raw material gases to pyrolyze or react with each other and deposit on the surface of a substrate, eventually forming a thin film. To reduce the reaction temperature, auxiliary means such as plasma enhancement, radio frequency enhancement, ultraviolet enhancement, radical enhancement, laser induction, etc. are also commonly employed.
The film layer with an amorphous or crystalline structure is generated by taking silicon element as a main body and one or more of hydrogen, oxygen, carbon, nitrogen, phosphorus, fluorine, chlorine and the like as objects, which are generated on the surface of a metal or ceramic substrate through chemical vapor deposition, and is one of the functional film layers which are applied at present. Because the film layer takes silicon element as a main body, the film layer can be simply called a silicon material film. The silicon material film itself or after further modification has the functions of chemical inertia, acid resistance, alkali resistance, wear resistance, surface conductivity change and the like compared with the original base material, is widely used in the fields of analytical instruments, petrochemical industry, hydrogen energy sources, aerospace, semiconductors, biochemistry and the like, and is in need in certain fields. For example, in the monitoring of Volatile Organic Compounds (VOCs) in the atmosphere, passivation of silicon films is required for all metal surfaces in contact with gas samples during sampling, storage, and analysis of the gas samples. The sampling device comprises a stainless steel sampling tank (a sigma tank), a constant-current sampler, a particulate filter, a sampling pipeline, a sampling valve and the like, and also comprises gas path components in analysis and detection devices such as a preconcentrator, a chromatograph and a mass spectrometer. In the field of chromatographic analysis, the inner surface of a stainless steel gas or liquid chromatographic column is also typically treated with a silicon material film to reduce adsorption of the analyzed target compound, thereby improving peak shape and chromatographic efficiency. In the field of hydrogen energy and semiconductors, silicon material films are often used on the inner surface of ultra-high purity material delivery pipelines to reduce metal ion contamination from metal pipelines and reduce corrosion to the pipelines.
The preparation of the silicon film is generally accomplished by a thermal chemical deposition process. For example, patent CN105112886B (an inert surface treatment technique) discloses a method of depositing a film of silicon material on a substrate. Patent CN103866262B (a preparation method of a stainless steel surface silanization treatment film) discloses a preparation method of a stainless steel surface silanization treatment film. Patent CN111220832a (an overvoltage detection sensor processing method and an overvoltage detection sensor) discloses a method of depositing amorphous silicon on the surface of a high purity silicon wafer and modifying it into silicon dioxide. The basic principle of these patents is to use silicon-containing gases such as monosilane, disilane, alkylsilane, alkoxysilane, chlorosilane, etc. to thermally decompose in a vacuum environment to obtain silicon or to deposit silicon material film with other doping elements (such as hydrogen, oxygen, carbon, etc.) on a substrate.
Since the film starts to grow on the surface of the substrate, the substrate surface must be suitable for film growth (or, alternatively, compatible with the film) in order to produce a uniform and dense film. However, the inventors have found in practice that not all substrates are suitable for the growth of silicon material films. Generally, the surface of metals such as iron, chromium, cobalt, manganese, and the like, and the surface of non-metals such as glass, ceramics, silicon wafers, carbon fibers, and the like are more suitable for the growth of silicon film layers, and these substrates can be called silicon film compatible substrates; pure aluminum or aluminum alloy, pure nickel or hastelloy (B series) with higher nickel content, pure copper or high copper alloy, pure silver or high silver alloy, etc., are not suitable for the growth of silicon material film layers, and these substrates may be referred to as silicon material film incompatible substrates. When the film is coated on the incompatible base material, the problems of uneven film layer, loose texture, wear resistance, easy falling off and the like can occur, so that the generated film has no practical value. For example, CN105112886B discloses a coating method, which has good effects on stainless steel, hastelloy (C and G series) with low nickel content, glass, ceramics and other materials, but on metal materials with high content of elements such as aluminum, nickel, copper, silver and the like, for example hastelloy B series alloy, the generated film has uneven color, loose texture and wear resistance. This disadvantage is probably caused by the uneven growth of the silicon film on the substrate surface due to the enrichment of the elements such as aluminum, nickel, copper, silver, etc., and the growth rate in the direction perpendicular to the substrate surface is much faster than that in the horizontal direction. This incompatibility has long been reported in some scientific literature, such as Bellangera p.et al. (2017) to report the problem of abnormal growth of polysilicon films on aluminum substrates; budini et al (2012) report that amorphous hydrogen silicate films on nickel substrates can locally crystallize resulting in layer porosity problems.
As with widely used stainless steel, incompatible substrates of silicon films such as aluminum alloys, copper alloys, silver alloys and the like, which contain higher nickel, are also materials commonly used in the manufacture of instruments and industrial equipment, and the surfaces thereof also often require film coating treatment of the silicon films. The prior art cannot effectively solve the problem of coating films on the substrates.
Disclosure of Invention
The embodiment of the application provides a transitional film and a preparation method thereof, which can solve the problem that in the prior art, a silicon film layer is not uniform on the surface of a substrate incompatible with a silicon film.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
in one aspect of the present application, a transitional film layer is provided, wherein the transitional film layer grows on a bottom coating substrate, the transitional film layer is a transitional layer between the bottom coating substrate and an upper target film layer, and the transitional film layer is an iron-based film.
According to the application, the transitional film layer is introduced, so that the surface property of the original film-coated substrate is changed, and the subsequent target film layer can be continuously deposited.
As still further aspects of the application: the thickness of the iron-based film is nano-scale.
In the application, the transition layer iron-based film bears the action of the transition layer, so that the thickness of the iron-based film is only required to be several to tens of nanometers, and the thickness of the iron-based film is increased without better effect on the film coating of the following silicon material film.
In another aspect of the present application, a method for preparing a transitional film layer is provided, comprising the steps of:
and (3) gasifying an iron-containing compound to generate iron, and depositing the iron-containing compound on the bottom coating substrate to form an iron-based film, wherein the iron-containing compound is one of anhydrous ferric chloride, pentacarbonyl iron and ferrocene.
In the application, before the gas phase reaction of the silicon material film, a gas phase metal compound is introduced, heated and decomposed to form a nano-scale iron-based overage on the surface of the workpieceAnd (3) coating, namely changing the chemical property of the surface of the substrate, so that the subsequent gas phase reaction of the silicon material film can be smoothly carried out and the film can be uniformly formed. The gas phase metal compound is heated at room temperature<Has enough vapor pressure at 300 DEG C>200 Pa) of metal compounds, e.g. iron trichloride FeCl 3 Iron pentacarbonyl Fe (CO) 5 Ferrocene, etc. These metal compounds have a vapor pressure high enough to allow them to be introduced into the reaction chamber in a gaseous state, decomposed into metals and deposited as a film.
As still further aspects of the application: when the iron-containing compound is anhydrous ferric chloride, the method comprises the steps of:
s1, placing anhydrous ferric chloride in a closed container, and vacuumizing;
s2, heating the closed container to sublimate anhydrous ferric chloride, and introducing H 2 The carrier gas is brought to a pressure of 1 to 2 atmospheres;
S3、H 2 the carrier gas introduces ferric chloride vapor into a vacuum reaction furnace containing a bottom coating substrate, and reacts at 350-1000 ℃.
Optionally, let in H 2 The pressure of the closed vessel after the carrier gas is independently selected from 1 atmosphere, 1.2 atmospheres, 1.4 atmospheres, 1.6 atmospheres, 1.8 atmospheres, 2 atmospheres.
Alternatively, the lower limit of the reaction temperature in the vacuum reaction furnace is independently selected from 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃; the upper limit of the reaction temperature in the vacuum reaction furnace is independently selected from 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ and 1000 ℃.
In the application, the iron-based film is formed by thermal decomposition or mutual reaction of gaseous compounds containing iron. In particular by FeCl 3 Steam in NH-containing state 3 H of (2) 2 Elemental iron generated by reduction in the atmosphere is deposited on the surface of the workpiece. In addition, the closed vessel in the present application may be a stainless steel closed vessel.
As still further aspects of the application: in step S2, the H 2 The carrier gas is doped with 0.1-0.5% (v/v) NH 3 High purity H of (2) 2 ；
Preferably, the heating temperature is 200 to 250 ℃.
Alternatively, H 2 NH doped in carrier gas 3 Independently selected from 0.1%, 0.2%, 0.3%, 0.4%, 0.5%.
Alternatively, the lower limit of the heating temperature is independently selected from 200 ℃, 210 ℃, 220 ℃, 230 ℃; the upper limit of the heating temperature is independently selected from 235 ℃, 240 ℃ and 250 ℃.
In the embodiment of the application, high-purity H 2 H with purity of more than or equal to 99.999 percent 2 。
As still further aspects of the application: in the step S3, the reaction time is 2-90 min;
preferably, the reaction time is 10 to 30 minutes.
Optionally, the lower limit of the reaction time is independently selected from 2min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min; the upper limit of the reaction time is independently selected from 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min, and 90min.
As still further aspects of the application: prior to step S1, the method further comprises:
pretreating the bottom coating substrate, including degreasing, degreasing and deoxidizing;
placing the bottom coating substrate into a vacuum reaction furnace, vacuumizing, and preheating at 280-380 ℃;
preferably, the preheating temperature is 300-350 ℃.
Alternatively, the preheating temperature is independently selected from 280 ℃, 300 ℃, 320 ℃, 340 ℃, 350 ℃, 360 ℃, 380 ℃.
As still further aspects of the application: in step S1, the vacuum pumping specifically includes: vacuumizing to below 0.1Pa to remove air in the closed container, and replacing with high-purity nitrogen;
preferably, the number of high purity nitrogen substitutions is 2.
In the embodiment of the application, the high-purity nitrogen is the nitrogen with the purity more than or equal to 99.999 percent.
As still further aspects of the application: after step S3, the method further comprises:
removing excess H while maintaining the reaction temperature 2 NH produced by reaction 4 Cl and unreacted FeCl 3 。
As still further aspects of the application: the method further comprises the steps of:
and depositing an upper target film layer on the iron-based film.
The application has the beneficial effects that:
1. according to the application, the intermediate transitional film layer is introduced between the incompatible bottom film coating base material and the upper target film layer, and the problem of poor growth of the upper target film layer on the bottom film coating base material is solved by utilizing the characteristic that the transitional film layer is compatible with the bottom film coating base material and the upper target film layer, and the problem of poor growth of the silicon film when the silicon film coating is carried out on the base materials such as high aluminum, high nickel, high copper and the like in the prior art is solved.
2. The deposition process of the iron-based transition film layer and the subsequent silicon film coating process can be organically combined in a coating process. Because both are thermally chemical vapor deposited, the iron-based transitional film and the target film can be sequentially completed in the same process. Therefore, the cost of implementing the iron-based transitional film layer is limited.
3. As the target film layer-silicon material film, the application adopts a vapor deposition method, has extremely high coiling and plating property, can carry out transition layer coating on a substrate with a complex shape, can completely cover all exposed surfaces of a workpiece, and can be suitable for the workpiece which cannot be carried out by the traditional spraying process.
Drawings
FIG. 1 is a flow chart of a conventional film coating process of a silicon film;
FIG. 2 is a flow chart of a film coating process of a silicon film after pretreatment of an iron film layer;
FIG. 3 is a scanning electron microscope image of a silicon film on the surface of an aluminum alloy workpiece in example 1 of the present application;
FIG. 4 is a scanning electron microscope image of a silicon film on the surface of an aluminum alloy workpiece in comparative example 1 of the present application.
Detailed Description
The present application is described in detail below with reference to examples.
Unless otherwise specified, the starting materials in the examples were purchased commercially and used without treatment; the instrument and equipment are recommended to use parameters by manufacturers.
The existing silicon film coating process flow is shown in figure 1, a workpiece is subjected to conventional surface pretreatment (degreasing, oxide layer removal and the like), then is placed into a vacuum reaction furnace, is sealed, is vacuumized to remove air in the furnace, is preheated, reaches a preset reaction temperature (between 200 and 1200 ℃), and is added with reaction gas to carry out film forming reaction. And stopping heating/maintaining the temperature after the film layer reaches the expected thickness, cooling the workpiece, starting a vacuum pump to discharge reaction residual gas, and opening the furnace to take out the workpiece after the temperature is reduced and obtaining the finished product after the quality inspection is qualified.
In order to carry out film coating of a silicon material film on an incompatible substrate, the application discloses a method, which is based on the existing film coating process flow of the silicon material film, and inserts an iron film layer modification procedure. And after the workpiece is preheated and before the vapor phase reaction of the film coating of the silicon film is carried out, carrying out an iron film layer modification procedure on the surface of the incompatible base material of the silicon film. After the modification process of the iron film layer is finished, the film coating gas-phase reaction of the silicon film is continued according to the original route. The flow chart after improvement of the application is shown in figure 2.
The application proposes that the iron-based transition film can be realized by thermal decomposition of gas phase metal compounds of iron. Among them, the gas phase metal compound of iron (under heating) may be selected from anhydrous ferric chloride, pentahydroxy iron, ferrocene, etc. In the present application, anhydrous ferric trichloride (FeCl) is the preferred 3 )。FeCl 3 Black brown solid powder at room temperature, but FeCl is heated to 150-250 DEG C 3 The saturated gaseous vapor pressure of (2) reaches the level of hundred Pa (hPa) and has a sufficient amount of FeCl 3 Sublimating into gas phase, and can be used as source of iron element for chemical vapor deposition. And the anhydrous ferric chloride has low cost, is easy to gasify and simple to operate, and the compatibility of the reduced iron simple substance transition layer is better than that of other metals.
Technical source of the applicationThe method comprises the following steps: high purity hydrogen (H) at about 200deg.C 2 ) In the atmosphere, sublimated gaseous FeCl 3 (or by FeCl) 3 Polymerized Fe 2 Cl 6 Gas) is brought into a vacuum reaction furnace at a temperature of 200 to 600 ℃. At this temperature, excess hydrogen will FeCl 3 Reduced to iron simple substance and deposited on the surface of the substrate to form a very thin iron-based film. The general chemical reaction formula of this process is:
2FeCl 3 (gas) +3H 2 (gas, excess)2Fe (solid, amorphous film) +6HCl (gas)
HCl gas and excessive H generated by reaction 2 Will be evacuated by the vacuum pump. To promote the reaction, high purity H 2 Can be doped with 0.1 to 0.5 percent (v/v) ammonia (NH) 3 ). The iron-based film only needs to change the surface property of the base material, so that the thickness of the iron-based film is only a few to tens of nanometers. The process of depositing the iron-based film may be completed in a period of several minutes to 1 hour.
Example 1
7075 aluminum alloy workpieces for experiments, which have the size of 10cm multiplied by 7cm multiplied by 48cm, are added with an iron-based film interlayer according to the method provided by the application, and then are subjected to silicon film coating, and the whole process sequentially comprises the following steps:
(1) After degreasing, the aluminum alloy workpiece is cleaned by ultrasonic wave, rinsed by pure water, and then dried at 110 ℃;
(2) The aluminum alloy workpiece is placed into a vacuum reaction furnace, vacuumized until the pressure in the furnace is less than 0.01Pa, heated, and the temperature is set to 320 ℃. At the same time of heating, high-purity nitrogen is used for replacing for 2 times, and finally vacuum pumping is carried out until the pressure in the furnace is less than 0.01Pa;
(3) After the temperature of the vacuum reaction furnace reaches 320 ℃, waiting for 20 minutes, ensuring the internal temperature of the workpiece to be uniform, and simultaneously maintaining the vacuum degree in the furnace to be less than 0.01Pa.
(4) Preparing iron film reaction gas: weigh 2g FeCl 3 Powder was charged into a stainless steel sealed container (FeCl) having a volume of about 1L 3 Steam generator) is provided. The container is placed in the middle of the tubular heating furnace, and an air inlet pipe and an air outlet pipe are respectively arranged at two sides of the container. The air in the vessel was evacuated using a vacuum system and replaced 2 times with nitrogen. Heating a stainless steel sealed container to 200 ℃ by a tube furnace, and introducing 0.3% (v/v) NH doped into the container 3 High purity H of (2) 2 To about one atmosphere.
(5) Introducing the aluminum alloy workpiece to be coated with 0.3% NH into a vacuum reaction furnace 3 And pass through FeCl 3 High purity H of closed container 2 . The inflow flow rate is controlled to be about 200mL/min, and the equilibrium pressure in the vacuum reaction furnace is about 5kPa to 20 kPa.
(6) The reaction is kept warm for 15 minutes, and then a vacuum system is started to remove redundant H 2 ，NH 3 Generated NH 4 Cl is discharged.
(7) And (5) replacing the iron film layer with high-purity nitrogen for 2 times, and finishing the pretreatment of the iron film layer.
(8) The vacuum reaction furnace temperature is increased to the silicon film coating temperature, and conventional silicon film coating is performed according to the steps in fig. 2.
After the whole process is finished, the 7075 aluminum alloy workpiece is uniformly plated with a thin iridescent silicon film, and a scanning electron microscope image is shown in fig. 3. The Auger electron spectrum test result shows that the thickness of the uppermost silicon material is about 140nm, the thickness of the intermediate iron film is about 26nm, and the thickness is 7075 aluminum alloy substrate.
Example 2
The Monel 400 nickel-copper alloy workpiece has the size of 16cm multiplied by 5cm multiplied by 28cm, and according to the method provided by the application, an iron-based film interlayer is added, and then a silicon film is coated. The processing process sequentially comprises the following steps:
(1) Ultrasonic cleaning of nickel-copper alloy workpiece, rinsing with pure water, and drying at 110 ℃;
(2) The nickel-copper alloy workpiece is placed into a vacuum reaction furnace, vacuumized until the pressure in the furnace is less than 0.01Pa, heated, and the temperature is set to 320 ℃. At the same time of heating, high-purity nitrogen is used for replacing for 2 times, and finally vacuum pumping is carried out until the pressure in the furnace is less than 0.01Pa;
(3) After the temperature of the vacuum reaction furnace reaches 320 ℃, waiting for 20 minutes, ensuring the internal temperature of the workpiece to be uniform, and simultaneously maintaining the vacuum degree in the furnace to be less than 0.01Pa.
(4) Preparing iron film reaction gas: weigh 3g FeCl 3 Powder, filled into a stainless steel sealed container having a volume of about 1L. The container is placed in the middle of the tubular heating furnace, and an air inlet pipeline and an air outlet pipeline are respectively arranged at two sides of the container. The air in the vessel was evacuated using a vacuum system and replaced 2 times with nitrogen. After heating the stainless steel sealed vessel to 200℃with a tube furnace, 0.3% (v/v) NH was added at a flow rate of 200mL/min 3 High purity H of (2) 2 To about one atmosphere.
(5) Introducing 0.3% NH into the reaction furnace 3 And pass through FeCl 3 High purity H of closed container 2 . The inflow flow rate is controlled to be about 200mL/min, and the equilibrium pressure in the vacuum reaction furnace is about 5kPa to 20 kPa.
(6) The reaction is carried out for 30 minutes with heat preservation, and then a vacuum system is started to carry out redundant H 2 ，NH 3 Generated NH 4 Cl is discharged.
(7) And (5) replacing the iron film layer with high-purity nitrogen for 2 times, and finishing the pretreatment of the iron film layer.
(8) The vacuum reaction furnace temperature is increased to the silicon film coating temperature, silicon-containing gas is used for chemical decomposition deposition film formation, and conventional silicon film coating is carried out according to the steps in fig. 2.
After the whole process is finished, the nickel-copper alloy workpiece is uniformly plated with a silvery white silicon film. The Auger electron spectrum test result shows that the thickness of the surface silicon material film is about 220nm, the thickness of the lower iron film is about 43nm, and the lower iron film is a Monel 400 nickel-copper alloy substrate.
Comparative example 1
The 7075 aluminum alloy workpiece for experiments is directly coated with the film with the size of 10cm multiplied by 7cm multiplied by 48cm according to the prior silicon film coating method, the film layer is uneven or gray spots appear in the film layer after multiple attempts, and a scanning electron microscope chart is shown in figure 4.
Comparative example 2
The Monel 400 nickel-copper alloy workpiece has the size of 16cm multiplied by 5cm multiplied by 28cm, and is coated according to the existing silicon material film method (chemical decomposition deposition film is carried out by using silicon-containing gas), so that the effect is not ideal, and the phenomena of loose film layer, non-uniformity and color spots appear.
Comparative example 3
The Monel 400 nickel-copper alloy workpiece has the size of 16cm multiplied by 5cm multiplied by 28cm, and is coated according to the existing silicon material film method (chemical decomposition deposition film is carried out by using silicon-containing gas), so that the effect is not ideal, and the phenomena of loose film layer, non-uniformity and color spots appear.
Comparative example 4
The Monel 400 nickel-copper alloy workpiece has the size of 16cm multiplied by 5cm multiplied by 28cm, and is coated according to the existing silicon material film method (chemical decomposition deposition film is carried out by using silicon-containing gas), so that the effect is not ideal, and the phenomena of loose film layer, non-uniformity and color spots appear.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (10)

1. The transition film layer is characterized in that the transition film layer grows on a bottom coating substrate, the transition film layer is a transition layer between the bottom coating substrate and an upper target film layer, and the transition film layer is an iron-based film.
2. The transitional film layer of claim 1, wherein the iron-based film has a thickness on the order of nanometers.
3. The method for preparing a transitional film layer according to claim 1, comprising the steps of:
and (3) gasifying an iron-containing compound to generate iron, and depositing the iron-containing compound on the bottom coating substrate to form an iron-based film, wherein the iron-containing compound is one of anhydrous ferric chloride, pentacarbonyl iron and ferrocene.
4. A method of preparing a transitional film according to claim 3, wherein when the iron-containing compound is anhydrous ferric chloride, the method comprises the steps of:
s1, placing anhydrous ferric chloride in a closed container, and vacuumizing;
s2, heating the closed container to sublimate anhydrous ferric chloride, and introducing H 2 The carrier gas is brought to a pressure of 1 to 2 atmospheres;
S3、H 2 the carrier gas introduces ferric chloride vapor into a vacuum reaction furnace containing a bottom coating substrate, and reacts at 350-1000 ℃.
5. The method of claim 4, wherein in step S2, the H is selected from the group consisting of 2 The carrier gas is doped with 0.1-0.5% (v/v) NH 3 High purity H of (2) 2 ；
Preferably, the heating temperature is 200 to 250 ℃.
6. The method of producing a transitional film according to claim 4, wherein in step S3, the reaction time is 2 to 90 minutes;
preferably, the reaction time is 10 to 30 minutes.
7. The method of preparing a transitional film layer according to claim 4, wherein prior to step S1, the method further comprises:
pretreating the bottom coating substrate, including degreasing, degreasing and deoxidizing;
placing the bottom coating substrate into a vacuum reaction furnace, vacuumizing, and preheating at 280-380 ℃;
preferably, the preheating temperature is 300-350 ℃.
8. The method of claim 4, wherein in step S1, the step of evacuating specifically comprises: vacuumizing to below 0.1Pa to remove air in the closed container, and replacing with high-purity nitrogen;
preferably, the number of high purity nitrogen substitutions is 2.
9. The method of preparing a transitional film layer according to claim 4, wherein after step S3, the method further comprises:
removing excess H while maintaining the reaction temperature 2 NH produced by reaction 4 Cl and unreacted FeCl 3 。
10. The method of preparing a transitional film layer according to claim 9, further comprising:
an upper target film layer is deposited on the iron-based film by thermal chemical vapor deposition.
CN202310708393.0A 2023-06-14 2023-06-14 Transitional film and preparation method thereof Pending CN116988040A (en)

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