CN105018928B - The film plating process of Nanosurface coating on profiled metal - Google Patents
The film plating process of Nanosurface coating on profiled metal Download PDFInfo
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- CN105018928B CN105018928B CN201410157795.7A CN201410157795A CN105018928B CN 105018928 B CN105018928 B CN 105018928B CN 201410157795 A CN201410157795 A CN 201410157795A CN 105018928 B CN105018928 B CN 105018928B
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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
- C23C16/44—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
- C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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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
- C23C16/22—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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
-
- 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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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
- C23C16/22—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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
Abstract
The film plating process for the Nanosurface coating that the present invention provides a kind of on profiled metal, comprising: 1) profiled metal is placed in vacuum cavity；Organo-metallic compound steam is imported in vacuum cavity, it is made to generate physics or chemisorption with surface；Nitrogen is passed through to remove extra organo-metallic compound；It is passed through vapor again or ozone enters vacuum cavity；It is passed through nitrogen again to take away extra unreacted vapor；To constitute a circulation and form the atomic layer of sull in metal surface；2) repeat 50 circulations, the atomic layer of sull from level to level is made to stack the oxide film layer to form 5nm densification；3) by oxysilane system fluorine carbide coating in the surface of oxide film layer, one anti-fingerprint fluorinated film layer is generated with plating through 60~150 DEG C of bakings.Thickness of coating of the invention only has 10 nanometers, does not influence product appearance, has that hardness is high, stain resistance is strong, antiacid alkali, abrasion resisting are durable persistently.
Description
Technical field
The present invention relates to a kind of metallic surface processing methods, relate in particular to a kind of nanometer on profiled metal
The film plating process and its Nanosurface coating of overlay coating, the surface treatment method make metal surface not influence appearance tactile impression
In the case where, it can achieve the surface characteristic of hydrophobic, oleophobic, anti-pollution, anti-fingerprint, low-surface-energy.
Background technique
Currently, the anti-pollution processing coating on metal is that resin class coating is in the majority, resin class coating has high thickness, and (> 1 is micro-
Rice arrive hundreds of microns), destruction product appearance (brightness that can not then retain original surface if specular surface), the low (1H of hardness
~5H), the disadvantages of stain resistance and persistence are all insufficient.In addition, having the anti-pollution processing coating on small part metal is non-resin
The problem of class coating, such as methoxy silane fluorine carbide nanometer anti-fingerprint coating, such coating is then very poor surface attachment
Power, as long as slightly wiping its effect with cloth can disappear.
In addition, other technologies are to utilize vacuum coating technology such as physical vapor deposition (such as vapor deposition or magnetron sputtering plating)
Or the mode of chemical meteorology deposition CVD plates one layer of oxide film (such as SiO with hydroxyl (- OH) on the metal surface2), so
Carry out the coating of subsequent methoxy silane fluorine carbide nanometer anti-fingerprint coating again afterwards.Although the method improves anti-fingerprint fluorination
Film is in the adhesive ability of metal surface, however above-mentioned several plated film modes can only be all applied on the product of plane, if
On special-shaped product, due to plating the limitation of membrane property, film will be unable to equably be plated on the surface of special-shaped product, and work as
The deviation of light refraction and reflection will be generated in the case where the uneven thickness of sull, so that product surface generates seven coloured silks
Light line, cause the product of general appearance part not to be available above-mentioned two classes technology coat anti-pollution processing coating.
Summary of the invention
Thickness in order to solve prior art metal surface anti-pollution layer is thick, the low, uneven coating that destroys product appearance, hardness
Even, the problems such as stain resistance and persistence are insufficient, the Nanosurface coating that the present invention provides a kind of on profiled metal
Film plating process, the coating can be equably plated on all surface on special-shaped product, and the thickness of the coating only has 10 nanometers,
Product appearance is not influenced, has that hardness is high, stain resistance is strong, antiacid alkali, abrasion resisting are durable persistently.
One of goal of the invention of the invention is to provide a kind of film plating process of Nanosurface coating on profiled metal,
This method includes forming at least one layer of oxide film layer in metal surface using atomic vapor deposition technology, then then at described
Plating at least one layer fluorine carbide thin film layer on oxide film layer.
Preferably, one layer of sull with a thickness of 1nm~1 μm.It should be noted that oxide film layer is by one
It can also be exactly individual one layer of sull, this is according to specific production requirement made of sull overlapping layer by layer
Depending on.
Film plating process for the Nanosurface coating on profiled metal of the invention, specifically comprises the following steps: step
1) profiled metal is placed in vacuum cavity；By the organo-metallic compounds steam such as trimethyl aluminium, titanium tetrachloride or diethyl zinc
It imports in 100 DEG C~300 DEG C vacuum cavities, it is made to generate physics or chemisorption with surface；Nitrogen is passed through by extra unreacted
Organo-metallic compound removal；It is passed through vapor again or ozone enters vacuum cavity, makes its organic metal with absorption surface
Compound generates chemical reaction；It is passed through nitrogen again to take away extra unreacted vapor or ozone；To constitute a circulation simultaneously
The atomic layer of one layer of sull is formed in metal surface；The organo-metallic compound is trimethyl aluminium, zirconium chloride, two
Zinc ethyl, titanium tetrachloride, hafnium tetrachloride, tantalic chloride or indium trichloride；Step 2) repeats 50 circulations, makes one layer
The atomic layer of layer sull stacks the oxide film layer to form 5nm densification；Step 3) uses vacuum vapour deposition or liquid
Cladding process is impregnated by oxysilane system fluorine carbide coating in the surface of the oxide film layer, the oxysilane system fluorine carbon
The oxysilane group of compound is reacted with the surface functionalities of oxide film layer group hydroxyl (- OH), finally through 60~150
DEG C baking keeps its reaction more complete, to obtain the anti-fingerprint fluorinated film layer of metal surface.The above are the anti-fingers of metal surface
The plating steps of line fluorinated film layer.
Preferably, the sull coating technique is atomic layer deposition technology, the original of the sull
Sublayer or the oxide film layer are silica (SiO2), zirconium oxide (ZrO2), aluminium oxide (Al2O3), zinc oxide (ZnO), oxygen
Change titanium (TiO2), tantalum oxide (Ta2O5), indium oxide (In2O3) or hafnium oxide (HfO2)。
Preferably, the chemical structure such as following formula (I) of the oxysilane system fluorine carbide, be fluorinated anti-pollution hydrophobic grouping with
Then group is formed for reaction；
Wherein: its chemical structure such as following formula (I-1) of the fluorination anti-pollution hydrophobic grouping:
In formula (I-1): a is 0 to 20, Y H, F, CnF2n+1Or CnH2n+1, n is positive integer, preferably n be 1~20, X be H or
It is 0~20, h is 0~20 that F, K, which are 0~20, r,；
The chemical structure for reacting then group includes following two chemical structural formula (1), formula (2):
In formula (1): n can be 1~20；
Preferably, the oxysilane system fluorine carbide is trimethoxy silane fluorine carbide, triethoxysilane fluorine carbon
Compound, trichlorosilane fluorine carbide；The trimethoxy silane fluorine carbide is perfluoro decyl trimethoxy silane or perfluor nonyl
Base trimethoxy silane；The triethoxysilane fluorine carbide is perfluoro decyl triethoxysilane；The trichlorosilane fluorine
Carbide perfluoro decyl trichlorosilane or perfluoro capryl trichlorosilane.
Preferably, the vacuum pressure of vacuum cavity described in step 1) is 0.1Torr.
Preferably, vacuum vapour deposition described in step 2) includes: the oxide for being coated with the atomic layer deposition
Profiled metal and oxysilane system fluorine carbide be placed in vacuum tank, and by oxysilane system fluorine carbide heating make its gas
Change, and be heated to 150 DEG C in vacuum tank and close the pipeline of pumping, make vacuum tank that the state of a sealing be presented, makes gasification
The plating of oxysilane system fluorine carbide is overlying on atomic layer deposition oxide surface, to form alumina silicon, titanyl silicon or zinc oxygen silicon
Structure open the pipeline of pumping after completion of the reaction and be passed through nitrogen to take extra oxysilane system fluorine carbide steam away
So that surface leaves single layer fluosilicic carbide molecule, an anti-fingerprint fluorinated film layer is generated with plating.Preferably, the vacuum tank
Vacuum pressure is less than 1Torr.
Alternatively, preferably liquid described in step 2) impregnate cladding process include: by oxysilane system fluorine carbide dissolution in
To form solution in fluorine ether solvent；The solution is applied in such a way that Typical spray, routine are smeared or routinely impregnated
The surface of the profiled metal of oxide coated with the atomic layer deposition reaches adhesional wetting, to form alumina silicon, titanyl silicon
Or the structure of zinc oxygen silicon is washed using ultrasonic wave shake after completion of the reaction and cleans remaining oxysilane system fluorine carbide, so that table
Face leaves single layer oxygroup fluosilicic carbide molecule, generates an anti-fingerprint fluorinated film layer with plating.Preferably, the weight of the solution
Concentration is 0.3~0.8wt.%, and the fluorine ether solvent is 1,1,2,2- tetra- fluoro ethyl -2,2,3,3- tetrafluoro propyl ethers.
The main action principle of film plating process of the invention is the full side of three-dimensional using atomic layer deposition technology (ALD)
The characteristic of the uniform plating in position, in the sull of the uniform one layer of nano-scale of plating in metal surface.Make sull
Surface functionalities are bonded with oxysilane class fluorine carbide, and anti-fingerprint fluorinated film strength is allowed to be bonded to metal surface, with
Achieve the effect that height is durable wear-resistant.Specifically, such as (1) is firstly, using atomic layer deposition technology (ALD) in metal
Surface growing oxide film, the sull can be one or more layers aluminium oxide Al2O3Plating is overlying on metal surface, former
Material is trimethyl aluminium Al (CH3)3And water, trimethyl aluminium and water are passed through in vacuum cavity by circulation, cavity temperature is 100 DEG C,
Make it react to each other to form aluminum oxide film, which is homogeneously applied to any product table for exposing to gas
On face.Wherein, which also can be titanium oxide (TiO2), silica (SiO2), zinc oxide (ZnO), zirconium oxide (ZrO2), oxygen
Change tantalum (Ta2O5), indium oxide (In2O3), the metal oxide that can grow up of the ALD such as hafnium oxide (HfO2).What each circulation generated
Aluminium oxide thickness is about 0.1nm.(2) then, in Al2O3Film forming procedure in, trimethyl aluminium circulation interaction is passed through cavity, when complete
After 50 circulations, in the aluminum oxide film of product surface plating about 5nm.(3) then, it is soaked using vacuum vapour deposition or liquid
The plating of trimethoxy silane fluorine carbide is overlying on the Al by bubble cladding process2O3The surface of film, through 60~150 DEG C of bakings with plating
Generate an anti-fingerprint fluorinated film layer.The atomic layer deposition technology sull can generate physics or change with metal surface
Bond is learned, and on identical the film thickness equably entire product surface of plating.The atomic layer deposition technology oxide
The chemical functional group on its surface contacted with air is hydroxyl (- OH) after film growth is complete, and the functional group is mainly as rear
The bond functional group of continuous trimethoxy silane fluorine carbide, by trimethoxy silane fluorine carbide coating on sull
Afterwards, toasted that its is accelerated to chemically react, it is final to obtain an anti-fingerprint fluorinated film layer.The thickness of the anti-fingerprint fluorinated film is about 10
Nanometer.
Another object of the present invention is to provide a kind of using the film plating process on profiled metal coating is received
Rice overlay coating, the Nanosurface coating includes monoxide film layer and an anti-fingerprint fluorinated film layer；The nanometer table
Face coating with a thickness of 1nm~1 μm.
Preferably, the oxide film layer with a thickness of 1~5nm, the anti-fingerprint fluorinated film layer with a thickness of 5~
10nm。
Preferably, the oxide film layer is silica (SiO2), zirconium oxide (ZrO2), aluminium oxide (Al2O3), oxygen
Change zinc (ZnO), titanium oxide (TiO2), tantalum oxide (Ta2O5), indium oxide (In2O3) or hafnium oxide (HfO2)。
The beneficial effects of the present invention are: the thickness for finally obtaining the anti-fingerprint fluorinated film layer is about 10 nanometers, group
As the sull of internal layer ALD plating, outer layer is anti-fingerprint fluorinated film layer.Due between metal and sull
For the physically or chemically bond of planar, methyl-monosilane fluorine carbide again with sull with chemical bonded refractory in conjunction with, make entirely anti-
Fingerprint fluorinated film is all strong bond as link, therefore entire its mechanical strength of film all can be very good with adhesive force.Metal produces
Product can change the surface nature on its surface in the case where not influencing appearance, with 10 nanometers of the double-deck fluorinated film reach it is hydrophobic,
Oleophobic, anti-pollution, anti-fingerprint, the surface characteristic of low-surface-energy make the metal product after processing not stain, is easy to clean, hand
The easypro sliding advantage of sense.The hardness of the film is high, stain resistance is strong, anti acid alkali performance wearability is strong.
Specific embodiment
In order to further appreciate that feature and other purposes of the invention, now it is described in detail using specific embodiment
As follows, which is only used to illustrate the technical scheme of the present invention, and is not used to limit the present invention.
The anti-fingerprint dirt resistant surfaces fluorination technology of nano-scale mainly utilizes oxysilane system fluorine carbide molecule now
It carries out chemical reaction with the hydroxyl (- OH) of product surface to be combined into, due to oxysilane system fluorine carbide and surface functionalities
The anti-fingerprint dirt resistant surfaces fluorination technology of the limitation of respond, nano-scale can only be used on category of glass product so far,
Main cause is that glass surface is full of the functional group (silicone hydroxyl (- OH)) that can be reacted with oxysilane system fluorine carbide, favorably
Chemical bonded refractory is generated in the chemisorption of silane system fluorine carbide, this chemical bonded refractory provides this nanometer of anti-fingerprint dirt resistant surfaces fluorination
The adsorption ability of coating high strength makes this coating have the properties such as wear-resistant, antiacid alkali, durable.However, due to metal surface
Lack the group (such as silicone hydroxyl) that chemical reaction can be generated with oxysilane system fluorine carbide, so that oxysilane system fluorine carbide
In effectively lasting anti-fingerprint surface fluorination coating can not be formed on metal surface.
Surface and thickness is completely covered in one layer of metal surface plating using atomic layer deposition technology (ALD) in the present invention
Uniform nano-scale oxide film is spent, this sull will produce planar physical absorption or chemical bonded refractory with metal surface, and
Effective functional group (hydroxyl (- OH)) is provided in surface and oxysilane system fluorine carbide is formed and is bonded, and is fluorinated anti-fingerprint
Film strength is bonded to metal surface, achievees the effect that height is durable wear-resistant.
Atomic layer deposition technology (ALD) is the deposition technique of surface reaction, and the principle of deposition is to utilize two kinds
Above gaseous precursor is passed through in a circulating manner in the vacuum cavity to be reacted, and generates solid after so that predecessor is reacted to each other
Film, this film by can uniformly plating to all surfaces for exposing to air of object to be plated, film thickness is then followed by predecessor
The number that ring is passed through cavity is determined.The producible film of this technology includes metal, macromolecule and metal-oxide film.
I, the embodiment of oxide film layer is prepared
Embodiment I-1
The specific embodiment of atomic layer deposition technology (ALD) of the invention, to process metal product as stainless steel,
Film is aluminium oxide Al2O3For film, with trimethyl aluminium (CH3)3Al and water H2O is as its reaction raw materials.
1) stainless steel product is placed in the vacuum cavity of 100 DEG C of heating first, and vacuum cavity is extracted into vacuum state
(pressure is about 0.1Torr)；2) by trimethyl aluminium steam import vacuum cavity in, trimethyl aluminium steam by with stainless steel surface
OH group generates chemical reaction, releases methane (CH4) and form (- O-Al (CH in surface4)2)；3) nitrogen is passed through vacuum chamber
Body takes the extra trimethyl aluminium not reacted with surface away, leaves behind the trimethyl aluminium of single molecular layer on stainless steel surface；
4) it is passed through vapor again and enters vacuum cavity, the trimethyl aluminium on vapor at a touch surface will be generated rapidly with its methyl
React and generate two parts of methane (CH4), so that the structure on surface becomes (- O-Al (OH)2)；5) it is then similarly passed through nitrogen again
Gas takes away extra unreacted vapor.Above-mentioned steps 1), 2), 3), 4) He 5) be known as a circulation, a circulation will provide
One molecular layer Al of stainless steel surface2O3, the thickness of growth is about 0.1nm.6) 50 operations control Jing Guo the circulation, reaches
It has arrived to surface alumina oxide Al2O3The control of thickness recycled so that trimethyl aluminium film thickness reaches 5nm with above-mentioned 50
At film growth.
Embodiment I-2
The specific embodiment of atomic layer deposition technology (ALD) of the invention, to process metal product as stainless steel,
Film is zirconium oxide ZrO2For film, with zirconium chloride ZrCl4With water H2O is as its reaction raw materials.
1) stainless steel product is placed in the vacuum cavity of 300 DEG C of heating first, and vacuum cavity is extracted into vacuum state
(pressure is about 0.1Torr)；2) zirconium chloride steam is imported in vacuum cavity, zirconium chloride steam will be with stainless steel product table
The OH group in face generates chemical reaction, releases hydrochloric acid (HCl) and forms (- O-ZrCl in surface3)；3) nitrogen is passed through vacuum
Cavity takes the extra zirconium chloride not reacted with surface away, leaves behind the zirconium chloride of single molecular layer in stainless steel surface
On；4) be passed through vapor again and enter vacuum cavity, vapor at a touch surface zirconium chloride will rapidly with its chlorine official
Energy base generates reaction and generates three parts of hydrochloric acid (HCl), so that the structure on surface becomes (- O-Zr (OH)3)；5) then same
Nitrogen is passed through again to take away extra unreacted vapor.Above-mentioned steps 1), 2), 3), 4) He 5) be known as one circulation, one is followed
Ring will provide stainless steel surface one molecular layer ZrO2, the thickness of growth is about 0.06nm.6) 50 behaviour Jing Guo the circulation
It controls, has reached to zirconia surface ZrO2Thickness control so that zirconia film thickness reaches 3nm, with above-mentioned 50
A circulation completes film growth.
Embodiment I-3
The specific embodiment of atomic layer deposition technology (ALD) of the invention, to process metal product as chromium plating gold
Belong to part, film be zinc oxide ZnO film for, with diethyl zinc Zn (C2H5)2With water H2O is as its reaction raw materials.
1) chrome-plated metal product is placed in the vacuum cavity of 100 DEG C of heating first, and vacuum cavity is extracted into vacuum shape
State (pressure is about 0.1Torr)；2) diethyl zinc steam is imported in vacuum cavity, diethyl zinc steam will be produced with chrome-plated metal
The OH group on product surface generates chemical reaction, releases hydrochloric acid (HCl) and forms (- O-Zn (C in surface2H5))；3) nitrogen is led to
Enter vacuum cavity, the extra diethyl zinc not reacted with surface is taken away, leaves behind the diethyl zinc of single molecular layer stainless
In steel surface；4) be passed through vapor again and enter vacuum cavity, vapor at a touch surface diethyl zinc will rapidly with
Its ethyl is raw to react and generates ethane (C2H6), so that the structure on surface becomes (- O-Zn (OH))；5) it is then similarly passed through again
Nitrogen takes away extra unreacted vapor.Above-mentioned steps 1), 2), 3), 4) He 5) be known as a circulation, a circulation will mention
Thickness for one molecular layer ZnO of chrome-plated metal surface, growth is about 0.2nm.6) 50 operations control Jing Guo the circulation,
The control of the thickness to surface oxidation zinc ZnO is reached, so that zinc oxide films film thickness reaches 10nm, has been recycled with above-mentioned 50
At film growth.
Embodiment I-4
The specific embodiment of atomic layer deposition technology (ALD) of the invention, to process metal product as stainless steel,
Film is titanium oxide TiO2For film, with titanium tetrachloride TiCl4With water H2O is as its reaction raw materials.
1) stainless steel product is placed in the vacuum cavity of 300 DEG C of heating first, and vacuum cavity is extracted into vacuum state
(pressure is about 0.1Torr)；2) titanium tetrachloride vapors are imported in vacuum cavity, zirconium chloride steam will be with stainless steel product table
The OH group in face generates chemical reaction, releases hydrochloric acid (HCl) and forms (- O-TiCl in surface3)；3) nitrogen is passed through vacuum
Cavity takes the extra titanium tetrachloride not reacted with surface away, leaves behind the titanium tetrachloride of single molecular layer in stainless steel surface
On；4) be passed through vapor again and enter vacuum cavity, vapor at a touch surface titanium tetrachloride will rapidly with its chlorine official
Energy base generates reaction and generates three parts of hydrochloric acid (HCl), so that the structure on surface becomes (- O-Ti (OH)3)；5) then same
Nitrogen is passed through again to take away extra unreacted vapor.Above-mentioned steps 1), 2), 3), 4) He 5) be known as one circulation, one is followed
Ring will provide stainless steel surface one molecular layer TiO2, the thickness of growth is about 0.06nm.6) 50 behaviour Jing Guo the circulation
It controls, has reached to titanium oxide surface TiO2Thickness control so that zirconia film thickness reaches 3nm, with above-mentioned 50
A circulation completes film growth.
Embodiment I-5
The specific embodiment of atomic layer deposition technology (ALD) of the invention, to process metal product as stainless steel,
Film is hafnium oxide HfO2For film, with hafnium tetrachloride HfCl4With water H2O is as its reaction raw materials.
1) stainless steel product is placed in the vacuum cavity of 300 DEG C of heating first, and vacuum cavity is extracted into vacuum state
(pressure is about 0.1Torr)；2) hafnium tetrachloride steam is imported in vacuum cavity, hafnium tetrachloride steam will be with stainless steel product table
The OH group in face generates chemical reaction, releases hydrochloric acid (HCl) and forms (- O-HfCl in surface3)；3) nitrogen is passed through vacuum
Cavity takes the extra titanium tetrachloride not reacted with surface away, leaves behind the hafnium tetrachloride of single molecular layer in stainless steel surface
On；4) be passed through vapor again and enter vacuum cavity, vapor at a touch surface hafnium tetrachloride will rapidly with its chlorine official
Energy base generates reaction and generates three parts of hydrochloric acid (HCl), so that the structure on surface becomes (- O-Hf (OH)3)；5) then same
Nitrogen is passed through again to take away extra unreacted vapor.Above-mentioned steps 1), 2), 3), 4) He 5) be known as one circulation, one is followed
Ring will provide stainless steel surface one molecular layer HfO2, the thickness of growth is about 0.06nm.6) 50 behaviour Jing Guo the circulation
It controls, has reached to surface oxidation hafnium HfO2Thickness control so that zirconia film thickness reaches 3nm, with above-mentioned 50
A circulation completes film growth.
Embodiment I-6
The specific embodiment of atomic layer deposition technology (ALD) of the invention, to process metal product as stainless steel,
Film is tantalum oxide (Ta2O5) for film, with tantalic chloride TaCl5With water H2O is as its reaction raw materials.
1) stainless steel product is placed in the vacuum cavity of 300 DEG C of heating first, and vacuum cavity is extracted into vacuum state
(pressure is about 0.1Torr)；2) tantalic chloride steam is imported in vacuum cavity, tantalic chloride steam will be with stainless steel product table
The OH group in face generates chemical reaction, releases hydrochloric acid (HCl) and forms (- O-TaCl in surface4)；3) nitrogen is passed through vacuum
Cavity takes the extra tantalic chloride not reacted with surface away, leaves behind the tantalic chloride of single molecular layer in stainless steel surface
On；4) be passed through vapor again and enter vacuum cavity, vapor at a touch surface tantalic chloride will rapidly with its chlorine official
Energy base generates reaction and generates four parts of hydrochloric acid (HCl), so that the structure on surface becomes (- O-Ta (OH)3)；5) then same
Nitrogen is passed through again to take away extra unreacted vapor.Above-mentioned steps 1), 2), 3), 4) He 5) be known as one circulation, one is followed
Ring will provide stainless steel surface one molecular layer Ta2O5, the thickness of growth is about 0.03nm.6) 50 behaviour Jing Guo the circulation
It controls, has reached to surface oxidation tantalum Ta2O5Thickness control so that zirconia film thickness reaches 1.5nm, with above-mentioned
50 circulations complete film growth.
Embodiment I-7
The specific embodiment of atomic layer deposition technology (ALD) of the invention, to process metal product as stainless steel,
Film is indium oxide (In2O3) for film, with indium trichloride InCl3With water H2O is as its reaction raw materials.
1) stainless steel product is placed in the vacuum cavity of 300 DEG C of heating first, and vacuum cavity is extracted into vacuum state
(pressure is about 0.1Torr)；2) indium trichloride steam is imported in vacuum cavity, indium trichloride steam will be with stainless steel product table
The OH group in face generates chemical reaction, releases hydrochloric acid (HCl) and forms (- O-InCl in surface2)；3) nitrogen is passed through vacuum
Cavity takes the extra indium trichloride not reacted with surface away, leaves behind the indium trichloride of single molecular layer in stainless steel surface
On；4) be passed through vapor again and enter vacuum cavity, vapor at a touch surface indium trichloride will rapidly with its chlorine official
Energy base generates reaction and generates two parts of hydrochloric acid (HCl), so that the structure on surface becomes (- O-In (OH)2)；5) then same
Nitrogen is passed through again to take away extra unreacted vapor.Above-mentioned steps 1), 2), 3), 4) He 5) be known as one circulation, one is followed
Ring will provide stainless steel surface one molecular layer In2O3, the thickness of growth is about 0.03nm.6) 50 behaviour Jing Guo the circulation
It controls, has reached to surface oxidation tantalum Ta2O5Thickness control so that indium oxide film thickness reaches 1.5nm, with above-mentioned
50 circulations complete film growth.
II, the embodiment for preparing anti-fingerprint fluorinated film layer
Embodiment II-1
Finally, being impregnated and being applied using vacuum vapour deposition or liquid after completing the growth of atomic layer deposition aluminum oxide film
Method is covered again for the 1H of low-surface-energy, 1H, 2H, 2H perfluoro decyl triethoxysilane, chemical structural formula such as chemical formula (A), plating
It is layed onto the surface of the aluminum oxide film of atomic layer deposition, makes 1H, 1H, 2H, the oxygroup of 2H perfluoro decyl triethoxysilane
Silane group is reacted with the hydroxyl (- OH) of aluminum oxide film layer, is sloughed ethyl alcohol and is formed alumina silicon (Al-O-Si-....)
Chemical structure.Finally toasting 3 hours through 100 DEG C keeps its reaction more complete, forms the anti-fingerprint fluorinated film layer of about 5nm.This
Outside, the specific experiment step operation that vacuum vapour deposition and liquid as described below impregnate cladding process is referred to.
Embodiment II-2
Finally, being impregnated and being applied using vacuum vapour deposition or liquid after completing the growth of atomic layer deposition thin film of titanium oxide
Method is covered again for the trimethoxy silane fluorine carbide of low-surface-energy, and chemical structural formula such as chemical formula (B) is plated to atomic layer gas
The mutually surface of the thin film of titanium oxide of deposition, makes the methoxy silane groups and thin film of titanium oxide of trimethoxy silane system fluorine carbide
The hydroxyl (- OH) of layer is reacted, and the chemical structure that methanol forms titanyl silicon (Ti-O-Si-....) is sloughed.Finally through 150 DEG C
Baking keeps its reaction more complete in 1.5 hours, forms the anti-fingerprint fluorinated film layer of about 10nm.In addition, referring to as described below
Vacuum vapour deposition and liquid impregnate cladding process specific experiment step operation.
Embodiment II-3
Finally, being impregnated and being applied using vacuum vapour deposition or liquid after completing the growth of atomic layer deposition silicon oxide film
Method is covered again for the 1H of low-surface-energy, 1H, 2H, and 2H perfluoro decyl trichlorosilane, chemical structural formula such as chemical formula (C) is plated to
The surface of the silicon oxide film of atomic layer deposition, makes 1H, 1H, 2H, the chlorosilane group of 2H perfluoro decyl trichlorosilane with
The hydroxyl (- OH) of silicon oxide film layer is reacted, and dehydrochlorination forms the chemical structure of silicon oxygen silicon (Si-O-Si-....).
Finally toasting 2 hours through 60 DEG C keeps its reaction more complete, forms the anti-fingerprint fluorinated film layer of about 5nm.In addition, refer to as
The lower vacuum vapour deposition and liquid impregnate the specific experiment step operation of cladding process.
Embodiment II-4
Finally, being impregnated and being applied using vacuum vapour deposition or liquid after completing the growth of atomic layer deposition zinc-oxide film
Method is covered again for the trimethoxy silane fluorine carbide of low-surface-energy, and chemical structural formula such as chemical formula (D) is plated to atomic layer gas
The mutually surface of the zinc-oxide film of deposition makes the methoxy silane groups and zinc oxide films film layer of trimethoxy silane fluorine carbide
Hydroxyl (- OH) reacted, slough methanol formed zinc oxygen silicon (Zn-O-Si-....) chemical structure.Finally toasted through 80 DEG C
Make within 3 hours its reaction more complete, forms the anti-fingerprint fluorinated film layer of about 12nm.In addition, referring to vacuum as described below
Vapour deposition method and liquid impregnate the specific experiment step operation of cladding process.
Embodiment II-5
Finally, being impregnated and being applied using vacuum vapour deposition or liquid after completing the growth of atomic layer deposition tantalum oxide films
Method is covered again for the 1H of low-surface-energy, 1H, 2H, 2H perfluoro decyl trimethoxy silane, chemical structural formula such as chemical formula (E), plating
It is layed onto the surface of the tantalum oxide films of atomic layer deposition, makes 1H, 1H, 2H, the methyl of 2H perfluoro decyl trimethoxy silane
Silane group is reacted with the hydroxyl (- OH) of tantalum oxide films layer, is sloughed methanol and is formed tantalum oxygen silicon (Ta-O-Si-....)
Chemical structure.Finally toasting 1.5 hours through 100 DEG C keeps its reaction more complete, forms the anti-fingerprint fluorinated film layer of about 5nm.
In addition, referring to the specific experiment step operation that vacuum vapour deposition and liquid as described below impregnate cladding process.
Embodiment II-6
Finally, being impregnated and being applied using vacuum vapour deposition or liquid after completing the growth of atomic layer deposition indium oxide film
Method is covered again for the 1H of low-surface-energy, 1H, 2H, and 2H perfluoro capryl trichlorosilane, chemical structural formula such as chemical formula (F) is plated to
The surface of the indium oxide film of atomic layer deposition, makes 1H, 1H, 2H, the chlorosilane group of 2H perfluoro capryl trichlorosilane with
The hydroxyl (- OH) of indium oxide film layer is reacted, and dehydrochlorination forms the chemical structure of indium oxygen silicon (In-O-Si-....).
Finally toasting 1.5 hours through 100 DEG C keeps its reaction more complete, forms the anti-fingerprint fluorinated film layer of about 4nm.In addition, please join
See that vacuum vapour deposition and liquid as described below impregnate the specific experiment step operation of cladding process.
Embodiment II-7
Finally, being impregnated and being applied using vacuum vapour deposition or liquid after completing the growth of atomic layer deposition hafnia film
Method is covered again for the 1H of low-surface-energy, 1H, 2H, 2H perfluor nonyl trimethoxy silane, chemical structural formula such as chemical formula (G), plating
It is layed onto the surface of the hafnia film of atomic layer deposition, makes 1H, 1H, 2H, the methyl of 2H perfluor nonyl trimethoxy silane
Silane group is reacted with the hydroxyl (- OH) of tantalum oxide films layer, is sloughed methanol and is formed hafnium oxygen silicon (Hf-O-Si-....)
Chemical structure.Finally toasting 1.5 hours through 100 DEG C keeps its reaction more complete, forms the anti-fingerprint fluorinated film layer of about 5nm.
In addition, referring to the specific experiment step operation that vacuum vapour deposition and liquid as described below impregnate cladding process.
The vacuum vapour deposition specific experiment step operation is as follows:
It will complete stainless steel product and the oxysilane system of above-described embodiment (I-1, I-2, I-3, I-4, I-5, I-6, I-7)
Fluorine carbide is placed in vacuum tank, and the pressure in vacuum tank is evacuated to 1torr hereinafter, again by oxysilane system fluorine carbide
It is vaporized with electron beam or electric-heating-wire-heating, while vacuum tank is heated to 150 DEG C and closes the pipeline of pumping, allow vacuum tank
A sealing is presented and is full of the state of oxysilane system fluorine carbide steam, when oxysilane system fluorine carbide contact to product
The hydroxyl (- OH) on surface can generate chemical bonded refractory, form the chemical structure of alumina silicon (Al-O-Si-....).When the hydroxyl on surface
After base (- OH) has been reacted, extra oxysilane system fluorine carbide will be unable to carry out surface attachment again, and finally open pumping
Extra oxysilane system fluorine carbide steam is taken away, surface is made to leave the monolayer silicon that single layer is bonded to surface by the pipeline of gas
Fluorine carbide molecule is the plating for completing entire anti-fingerprint fluorinated film layer.
The liquid impregnates the operation of cladding process specific experiment:
By oxysilane system fluorine carbide dissolution in fluorine ether solvent, adjusting its weight concentration is 0.8% or so, then
Liquid Typical spray, the conventional mode smeared or routinely impregnated are applied to and complete above-described embodiment (I-1, I-2, I-3, I-
4, I-5, I-6, I-7) product surface, as long as bedewing its surface, during adhesional wetting, as the feelings of vapor deposition
Condition is general, and the hydroxyl (- OH) of oxysilane system fluorine carbide contact to product surface in solution can generate chemical bonded refractory, shape
At the chemical structure of alumina silicon (Al-O-Si-....), and the oxysilane system fluorine carbide of extra no chemical bonded refractory can remain on
Surface, ultrasonic wave shake can be used to be cleaned completely for this remaining methoxy silane system fluorine carbide, and have chemistry with surface
The oxysilane system fluorine carbide of bond will not then be removed during clean, finally leave single layer oxygroup silicon on the surface
Fluorine carbide completes the plating of entire anti-fingerprint fluorinated film layer.
Here, the chemical structure such as following formula (I) of used oxysilane system fluorine carbide present invention as described above:
Oxysilane system its chemical structure of fluorine carbide can be divided into two parts, and first part is fluorination anti-pollution water delivery base
Group, the second part are reaction then group.
It is fluorinated the structure such as following formula (I-1) of anti-pollution hydrophobic group:
Wherein: a is that 0 to 20, Y can be H, F, CnF2n+1Or CnH2n+1, n is positive integer, preferably n be 1~20, X can be H or
It is 0~20, h is 0~20 that F, K, which are 0~20, r,.This group major function is special using fluorine atom or the low-surface-energy of hydrocarbon molecules
Property, achieve the effect that anti-pollution water delivery.
React then group part possible structure such as following formula (1), formula (2):
Wherein: n can be 1~20 in structure (1).
Aluminium oxide Al will be arrived on oxysilane system fluorine carbide2O3When the metal surface of plating, vacuum available vapor deposition or liquid
Oxysilane system fluorine carbide is covered in the aluminium oxide Al full of hydroxyl (- OH) by the mode for impregnating coating2O3Surface, later simultaneously
60~150 DEG C of bakings are granted, when oxysilane system fluorine carbide touches hydroxyl (- OH), chemical reaction will be generated therebetween, with
For structure (1), after reaction, oxyalkyl-OCnH2n+1It will become alcohols C in conjunction with the hydrogen H atom of hydroxyl (- OH)nH2n+ 1OH leaves surface, and remaining group then forms chemical bonded refractory with surface, and chemical reaction is as shown below.
Via the metal surface that the oxide and oxysilane system fluorine carbide of atomic layer deposition are covered, surface
Surface can will will receive low-surface-energy fluorinated groups influence, so that the surface of whole surface is reduced, so reach it is hydrophobic,
The surface nature of oleophobic, anti-pollution.Additionally due to surface, aluminium oxide are all connect by chemical bonded refractory with oxysilane system fluorine carbide
It is attached, so the anti-solvent ability of film, antiacid alkali ability and its mechanical strength have splendid performance.
The present invention is thin by using atomic layer deposition technology uniformly plating one layer of oxide in metal product surface
Film allows oxysilane fluorine carbide with chemical bond using this sull as the following layer of oxysilane fluorine carbide
Knot is attached in metal surface, it is made to have the film strength of height.
Performance test
By being fluorinated to anti-fingerprint prepared by the oxide film layer as prepared by embodiment I-4 and embodiment II-2
Film layer carries out contact angle test, abrasion test, synthetic perspiration, resistance to detergent, acidproof, alkaline-resisting, Qiang Guang, high temperature and humidity, hot water
Performance test, obtain following experimental result, (referring to table 1).
Table 1
Above test data illustrates Nanosurface coating on metal of the invention, and engineering properties, resists anti-chemical capacity
Solvent power, high-temperature resistance all have splendid performance, improve many deficiencies of existing metal nano anti-pollution coating completely.This
It also demonstrates again that this film is to carry out adsorption with chemical bonded refractory outside, can be only achieved so excellent physics and chemical property.
In the present invention, the film of metal surface is overlying on as aluminium oxide Al using atomic layer deposition gaseous techniques (ALD) plating2O3
Film.However the aluminium oxide Al2O3Film also can be titanium oxide (TiO2), silica (SiO2), zinc oxide (ZnO), zirconium oxide
(ZrO2), indium oxide (In2O3), tantalum oxide (Ta2O5), the film that can grow up of the technique for atomic layer deposition such as hafnium oxide (HfO2).Oxygen
Change titanium (TiO2) use titanium tetrachloride (TiCl4) and water carry out film growth under 300 degree of vacuum of temperature；Silica (SiO2) make
With silicon tetrachloride (SiCl4) and water carry out film growth under 300 degree of vacuum of temperature；Zinc oxide (ZnO) uses diethyl zinc (Zn
(C2H5)2) and water carry out film growth under 100 degree of vacuum of temperature；Zirconium oxide (ZrO2) use zirconium chloride (ZrCl4) and water exist
Film growth is carried out under 300 degree of vacuum of temperature；Indium oxide (In2O3) use indium trichloride (InCl3) and water it is true in 300 degree of temperature
Sky is lower to carry out film growth；Tantalum oxide (Ta2O5) use tantalic chloride (TaCl5) and water carry out film under 300 degree of vacuum of temperature
Growth；Hafnium oxide (HfO2) uses hafnium tetrachloride (HfCl4) and water carry out film growth under 300 degree of vacuum of temperature.
It should be noted that foregoing invention content and specific embodiment are intended to prove technical solution provided by the present invention
Practical application should not be construed as limiting the scope of the present invention.Those skilled in the art are in spirit and principles of the present invention
It is interior, when can various modifications may be made, equivalent replacement or improve.Protection scope of the present invention is subject to the appended claims.
Claims (8)
1. a kind of film plating process of the Nanosurface coating on profiled metal, which is characterized in that the film plating process includes
At least one layer of oxide film layer, the thickness of the oxide film layer are formed in metal surface using atomic vapor deposition technology
For 1~5nm, the then plating at least one layer anti-fingerprint fluorine carbide thin film layer on the oxide film layer；The anti-finger
Line fluorine carbide thin film layer with a thickness of 5~10nm, the fluorine carbide is trimethoxy silane fluorine carbide, triethoxysilicane
Alkane fluorine carbide, trichlorosilane fluorine carbide；The trimethoxy silane fluorine carbide be perfluoro decyl trimethoxy silane or
Perfluor nonyl trimethoxy silane；The triethoxysilane fluorine carbide is perfluoro decyl triethoxysilane；The trichlorine
Silane fluorine carbide is perfluoro decyl trichlorosilane or perfluoro capryl trichlorosilane.
2. film plating process according to claim 1, which is characterized in that the Nanosurface coating with a thickness of the μ of 1nm~1
m。
3. a kind of film plating process of the Nanosurface coating on profiled metal, which is characterized in that the film plating process includes
Following steps:
Profiled metal is placed in vacuum cavity by step 1)；Organo-metallic compound steam is imported into 100 DEG C~300 DEG C vacuum chambers
In body, it is made to generate physics or chemisorption with surface；Nitrogen is passed through to remove extra unreacted organo-metallic compound；Again
It is passed through vapor or ozone enters vacuum cavity, the organo-metallic compound of itself and absorption surface is made to generate chemical reaction；Lead to again
Enter nitrogen to take away extra unreacted vapor or ozone, to constitute a circulation and form one layer of oxide in metal surface
The atomic layer of film；Wherein, the organo-metallic compound is trimethyl aluminium, zirconium chloride, diethyl zinc, titanium tetrachloride, four
Hafnium chloride, tantalic chloride or indium trichloride；
Step 2) repeats 50 circulations, and the atomic layer of sull from level to level is made to stack to form fine and close oxide
Film layer, the oxide film layer with a thickness of 1~5nm；And
Step 3) impregnates cladding process for oxysilane system fluorine carbide coating in the oxide using vacuum vapour deposition or liquid
The surface of film layer, the oxysilane group of the oxysilane system fluorine carbide is by the surface official with the oxide film layer
Energy group hydroxy is reacted, and finally keeps its reaction more complete through 60~150 DEG C of bakings, to obtain the anti-fingerprint of metal surface
Fluorine carbide thin film layer, the anti-fingerprint fluorine carbide thin film layer with a thickness of 5~10nm；The oxysilane system fluorine carbide
For trimethoxy silane fluorine carbide, triethoxysilane fluorine carbide, trichlorosilane fluorine carbide；The trimethoxy silane
Fluorine carbide is perfluoro decyl trimethoxy silane or perfluor nonyl trimethoxy silane；The triethoxysilane fluorine carbide
For perfluoro decyl triethoxysilane；The trichlorosilane fluorine carbide is perfluoro decyl trichlorosilane or perfluoro capryl trichlorine silicon
Alkane.
4. film plating process according to claim 3, which is characterized in that the oxide film layer is silica (SiO2), oxygen
Change zirconium (ZrO2), aluminium oxide (Al2O3), zinc oxide (ZnO), titanium oxide (TiO2 ), tantalum oxide (Ta2O5), indium oxide (In2O3) or
Hafnium oxide (HfO2) at least one.
5. film plating process according to claim 3, which is characterized in that the vacuum pressure of vacuum cavity described in step 1) is
0.1Torr。
6. film plating process according to claim 3, which is characterized in that vacuum vapour deposition described in step 3) includes: that will apply
The profiled metal and oxysilane system fluorine carbide for being covered with the oxide of the atomic layer deposition are placed in vacuum tank, and
The heating of oxysilane system fluorine carbide is vaporized, and is heated to 150 DEG C in vacuum tank and closes the pipeline of pumping, makes vacuum
The state of a sealing is presented in slot, and the oxysilane system fluorine carbide plating of gasification is made to be overlying on atomic layer deposition oxide table
It after completion of the reaction, opens the pipeline of pumping to form the structure of alumina silicon, titanyl silicon or zinc oxygen silicon and is passed through nitrogen to take out in face
Walking extra oxysilane system fluorine carbide steam makes surface leave single layer fluosilicic carbide molecule, generates primary antibody with plating and refers to
Line fluorinated film layer；The vacuum pressure of the vacuum tank is less than 1Torr.
7. film plating process according to claim 3, which is characterized in that liquid described in step 3) impregnates cladding process and includes:
By oxysilane system fluorine carbide dissolution to form solution in fluorine ether solvent；Using Typical spray, conventional smearing or routine
The mode of immersion reaches the surface for the profiled metal that the solution is applied to the oxide coated with the atomic layer deposition
To adhesional wetting, to form the structure of alumina silicon, titanyl silicon or zinc oxygen silicon, after completion of the reaction, washed using ultrasonic wave shake by remaining oxygen
Base silane system fluorine carbide is cleaned, so that surface leaves single layer oxygroup fluosilicic carbide molecule, generates an anti-fingerprint fluorine with plating
Carbide thin film layer.
8. film plating process according to claim 7, which is characterized in that the weight concentration of the solution be 0.3~
0.8wt.%, the fluorine ether solvent are 1,1,2,2- tetra- fluoro ethyl -2,2,3,3- tetrafluoro propyl ethers.
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| CN115948721B (en) * | 2023-03-15 | 2023-05-30 | 杭州幄肯新材料科技有限公司 | Method for preparing tantalum carbide coating by CVD method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1780727A (en) * | 2003-03-31 | 2006-05-31 | 美国平达系统公司 | Conformal coatings for micro-optical elements |
| CN101768740A (en) * | 2008-12-31 | 2010-07-07 | 兆震实业股份有限公司 | Method for processing surface of touch control element |
| CN103434203A (en) * | 2013-07-17 | 2013-12-11 | 北京东明兴业科技有限公司 | Anti-fingerprint film and preparation method thereof |
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| US20050008784A1 (en) * | 2003-06-27 | 2005-01-13 | 3M Innovative Properties Company | Removal and replacement of antisoiling coatings |
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| CN1780727A (en) * | 2003-03-31 | 2006-05-31 | 美国平达系统公司 | Conformal coatings for micro-optical elements |
| CN101768740A (en) * | 2008-12-31 | 2010-07-07 | 兆震实业股份有限公司 | Method for processing surface of touch control element |
| CN103434203A (en) * | 2013-07-17 | 2013-12-11 | 北京东明兴业科技有限公司 | Anti-fingerprint film and preparation method thereof |
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