CN102459702A - Protective coating, method for protecting a substrate and use for the same - Google Patents

Protective coating, method for protecting a substrate and use for the same Download PDF

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CN102459702A
CN102459702A CN2010800249315A CN201080024931A CN102459702A CN 102459702 A CN102459702 A CN 102459702A CN 2010800249315 A CN2010800249315 A CN 2010800249315A CN 201080024931 A CN201080024931 A CN 201080024931A CN 102459702 A CN102459702 A CN 102459702A
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layer
base material
hole
protective coating
influence
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M·赛康恩
L·古兹曼
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Beneq Oy
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Beneq Oy
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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
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • 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
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C16/44—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]
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications

Abstract

19 ABSTRACT A method and a protective coating for protecting a substrate (1) from effects caused by aninteraction of the substrate (1) with the environment, by depositing on the substrate (1) a first layer (3) comprising a top surface(4)oriented essentially parallel to the surface of the substrate (1). The method comprises the step of depositing a second layer (5) on the first layer (3) by exposing the first layer (3) to alter- nately repeated surface reactions of two or more dif- ferent precursors, to at least partially fill pores (7) in the first layer (3), the pores (7) opening through to the top surface(4), with the material of the second layer (5), such that the second layer (5) conforms to the shape of the surface of thepores (7). (Fig. 5)

Description

The method and the application thereof of protective coating, protection base material
Invention field
The present invention relates to coating technology.Especially, the present invention relates to protective coating and protection base material away from environment method.
Background of invention
Usually requirement of the object that in the rigorous environment condition, is utilized, for example machinery or chemoproection is so that prevent this object of environmental influence.The example of such object comprises transmitter, electronic package and the object with functional surface, like mirror or solar cell.Through on body surface, promptly applying coatings can realize the protection to object on base material.Known technology discloses the protective coating that is used for various purposes; The protection base material avoids the hard coat of mechanical influence, is used to be protected from the diffusion barrier block body (barrier) of chemical affect, thermal barrier (or thermal insulator) and electrical insulator.
Effectively protective coating usually must be thick relatively.For example, the protection feature of diffusion barrier block body, thermal barrier or electrical insulator and the proportional increase of coat-thickness with given coated material.Because this reason and other reasons, the protective coating of prior art is by the method preparation with high relatively speed of growth; Physical vaporous deposition (PVD), chemical Vapor deposition process (CVD) are perhaps based on liquid or aerocolloidal deposition method.For example, the open US2009087585 of patented claim discloses the method for utilizing PVD and the preparation of CVD method to comprise the blocking layer of titanium nitride and aluminium.
The deposition method of above-mentioned prior art and be that the coating deposited material comprises fine porosity and bubble (pin hole) as flaw by the problem of the protective coating of these methods preparation.These flaws usually are called as the residual porosity rate.These characteristics of coating possibly cause the barrier properties of coating seriously to reduce.For example hole in the chemical barrier body and bubble can make material be diffused on the base material of coating intention protection from environment through these flaws.Hole and bubble also can for example reduce the puncture threshold (threshold of breakdown) that is caused by electric field or the mechanical characteristics that makes protective coating degenerated.
Goal of the invention
The objective of the invention is to reduce the above-mentioned technical problem of prior art through being provided for protecting the application and the coating of base material away from environment method, this method.
Summary of the invention
According to the method for the invention being characteristic shown in the independent claim 1.
Structure according to the present invention is shown in the independent claim 10 being characteristic.
Application according to the present invention is shown in the claim 14 being characteristic.
The method of avoiding the influence that base material and environmental interaction cause through the first layer protection base material that comprises the upper surface that is arranged essentially parallel to substrate surface orientation in deposition on the base material according to the present invention comprises the steps: through making the first layer be exposed to the alternately repeated surface reaction of two or more different precursors (precursor) second layer to be deposited on the first layer; Material with the second layer is filled the hole in the first layer at least in part; It is the hole that opening passes to upper surface; So that the second layer is complied with the surface shape of hole; Wherein the first layer mainly is made up of titanium, aluminium and nitrogen compound, and the material of the second layer mainly is a MOX.
The protective coating that protection base material according to the present invention is avoided on the base material of the influence that base material and environmental interaction cause comprises the first layer with the upper surface that is arranged essentially parallel to the substrate surface orientation.Said the first layer comprises that opening passes to the hole of upper surface.This protective coating comprises the second layer on the first layer, and the hole of the partially filled at least the first layer of the material of the said second layer is so that the second layer is complied with the surface shape of hole.The first layer mainly is made up of titanium, aluminium and nitrogen compound, and the material of the second layer mainly is a MOX.
According to the present invention, method of the present invention is used to protect base material to avoid base material and environmental chemistry effect and the influence that causes.
Under this background, " hole " is appreciated that any hollow zone in the layer, comprises hole, bubble or analogue.The hole of mentioning in this document should be understood that on the layer or the little flaw of microscopically in the layer.These flaws are layer parts of residual porosity rate, and it is to be caused by the deposition method that is used for layer.
The invention provides the simple method of preparation coating, said coating is served as the effective baffle element of substance transfer through coating, and has excellent mechanical intensity and weather resistance.Method of the present invention and coating suppress the chemical reaction that takes place between environment and the base material effectively, arrive on the substrate surface under the coating because material can not or shift through coating from the environment diffusion in addition.At least the partially filled mechanical stability that also improves coating of the first layer mesoporosity makes it more durable and improve the mechanical protection to base material.
In an embodiment of the invention, the deposition second layer comprises that the first layer is exposed to is alternately repeated basically from restricted (self-limiting) surface reaction, with through ald (ALD) the deposition second layer.In the method for the second layer at similar ALD through alternately repeated basically when restricted surface reaction deposits, even the second layer can very conformably be deposited in the very little hole or bubble, and the thickness of the second layer is very even.
In an embodiment of the invention, the influence that is caused by base material and environmental interaction is caused by chemical action.In yet another embodiment of the present invention, the influence that is caused by base material and environmental interaction is caused by electrochemical action.In another embodiment of the present invention, the influence that is caused by base material and environmental interaction is an infection.
In an embodiment of the invention, the thickness of the second layer is below 20 nanometers (nm).Through only the extremely thin second layer being deposited on the first layer, might giving coating excellent protection characteristic and still keep the functional of the following second layer simultaneously.In application, like solar cell, perhaps on the for example reflexive optical coating of optical property of very thick second layer meeting remarkably influenced layered structure, this can be very useful.
The material of the second layer mainly is a MOX.In an embodiment of the invention, the material of the second layer mainly is an aluminum oxide.In an embodiment of the invention, the deposition second layer comprises makes the first layer be exposed to trimethylaluminium and the alternately repeated surface reaction of water, with aluminum oxide layer.
In an embodiment of the invention, base material mainly is made up of metal.In an embodiment of the invention, base material comprises cutting tool, for example cutting tip.In an embodiment of the invention, base material comprises the cutting tool that contains metal.
In yet another embodiment of the present invention, chemical action is to cause the corrosive effect.Be very suitable for protecting metal base to avoid corrosion with protective coating according to the method for the invention, the coating of the first layer mesoporosity surface shape can effectively reduce water (moisture) and/or oxygen diffuses through on the coating arrival base material because the second layer is complied with.Aluminum oxide and MOX generally are the materials that water and oxygen are had good barrier properties.These materials also are very suitable for for example depositing through ALD through alternately repeated surface reaction.
The first layer mainly is made up of titanium, aluminium and nitrogen compound.In an embodiment of the invention, the first layer mainly is made up of TiAlN.In an embodiment of the invention, the first layer is mainly by Ti 1-xAl xN (0＜x＜1) forms.In an embodiment of the invention, the ratio of titanium and aluminium changes.In an embodiment of the invention, ratio is 40% aluminium and 60% titanium.In yet another embodiment of the present invention, ratio is 70% aluminium and 30% titanium.
Titanium, aluminium and nitrogen compound, TiAlN for example can be effectively used to the purpose of the hard coat of mechanical protection base material as the first layer on the base material.The second layer is applied on this first layer also and can makes the coating of this embodiment according to the present invention become for example good corrosion baffle element through the hole that blocks in the first layer.
The embodiment of the present invention of describing in the preceding text can be used with mutual arbitrary combination.Several embodiments can be combined, and forms further embodiment of the present invention.Method involved in the present invention, structure or application can comprise at least one above-described embodiment of the present invention.
Detailed Description Of The Invention
Hereinafter, through utilizing illustrative embodiments that the present invention is described in more detail, wherein with reference to accompanying drawing:
Fig. 1 is the synoptic diagram of the protective coating of prior art,
Fig. 2 to 6 schematic illustration the method for preparation according to the protective coating of one embodiment of the present invention,
Fig. 7 schematic illustration the provide protection of protective coating of prior art,
Fig. 8 a and Fig. 8 b schematic illustration according to the provide protection of the protective coating of one embodiment of the present invention,
Fig. 9 has explained ALD round-robin pulse sequence in preparing according to the protective coating of one embodiment of the present invention,
Figure 10 show the testing data measured from galvanic corrosion and
Figure 11 shows from the wear test data measured.
For for simplicity, repeating under the situation of assembly and will in following illustrative embodiments, keep item number.
The structure of Fig. 1 comprises base material 1, and the first layer 3 and the second layer 5 are arranged on base material 1.The first layer 3 is by conventional deposition method, like PVD or CVD preparation and comprise that opening passes to the hole 7 of the upper surface 4 of the first layer 3.The second layer 5 is arranged on the first layer 3, and the said second layer 5 is planar layers basically, is positioned on the hole 7 of the first layer 3; That is, the second layer 5 can not penetrate into hole 7 blocking them, and only is to cover on the upper surface 4 of the first layer 3.When being prepared by conventional PVD or CVD method, the second layer 5 also possibly comprise hole 9.
The coating that comprises the first layer 3 and the second layer 5 among Fig. 1 can not be served as the protective coating of base material 1 effectively, and two reasons are arranged.At first, the hole 7 in the first layer 3 makes the first layer 3 mechanically frangible.Secondly, the hole 9 of the hole in the first layer 37 and the second layer 5 can serve as material for example the molecular transfer (for example, diffusion) in the gas phase arrive the passage on the base material 1 through coating.This is exposed to by base material 1 and environmental chemistry or electrochemical action base material 1, for example causes base material 1 corrosive effect and the influence that causes.
Ald (ALD) is on the base material of different shape, even on the complex three-dimensional structure, deposits the well-known method of uniform thin film, and it has good conformability.In ALD, coating through alternately repeated between precursor and the surface (base material) to be coated, grow from restrictive surface reaction basically.Therefore; Growth mechanism in the ALD method is such responsive unlike the growth mechanism in other coating process to the flowing dynamics (flow dynamics) in the reaction chamber for example usually; Said flowing dynamics possibly be the source of ununiformity, especially in the coating process that depends on gas-phase reaction.In the ALD method, two or more differential responses things (precursor) with in succession, the alternative mode is introduced into reaction chamber, and precursor adsorption is in reaction chamber for example on the surface on the base material.Precursor in succession, alternative introduces and to be commonly called (precursor) pulse.
Between each precursor pulse, the cleaning phase (purging period) is arranged usually, interim in this cleaning, unnecessary precursor and sub product that inert gas flow---usually is called carrier gas---and will be for example produced by the absorption reaction of precursor pulse before clean out reaction chamber.Through repeating to comprise above-mentioned precursor pulse and the pulse sequence of the phase of cleaning several times, utilize ALD method film to grow.This sequence multiple number of times that is called as " ALD circulation " depends on target film or coating, thickness.
Be suitable for the structure through the equipment of ALD deposition material, the structure of promptly conventional ALD reactor assembly is conspicuous for the technician, therefore will no longer discuss this structure.
A series of figure from Fig. 2 to Fig. 6 have explained how on base material 1, to prepare the protective coating according to one embodiment of the present invention.Begin from Fig. 2 that naked base material 1 is shown, these a series of figure in chronological sequence order show the xsect at the coating structure of said method different steps.In Fig. 3, utilize for example PVD or CVD, base material is coated thick the first layer 3.The first layer comprises hole 7, and its opening passes to the upper surface 4 of the first layer 3.In Fig. 4, be exposed to the alternately repeated surface reaction of two or more different precursors through making base material 1, the deposition of the beginning second layer 5.In this embodiment of the present invention, ALD is used to deposit the second layer 5.
Fig. 4 has schematically shown the second layer 5 and how to have deposited to conformability in the hole 7 of the first layer 3.This is the result of the growth mechanism of the second layer 5, and this growth mechanism is controlled by (or gasiform) precursor of vaporization and the surface reaction that deposits between the body structure surface of this layer.Because the first layer 3 is porous, the passage in the hole 7 of the upper surface 4 that therefore can exist precursor molecule to transfer to be starkly lower than the first layer 3.These passages are not shown in the drawings.Therefore, opposite with conventional deposition method, the material of the second layer 5 can penetrate in the vesicular structure of the first layer 3 well, and the hole 7 in filling and the obstruction the first layer 3.Along with the second layer 5 continued growths, some holes 7 in the first layer 3 can be filled by the material of the second layer 5 fully.This schematically explains through Fig. 5 and Fig. 6.
The material that penetrates into the second layer 5 of the first layer 3 holes 7 can increase the weather resistance of the first layer 3, is filled because cause the first layer 3 frangible spaces.In addition, the barrier properties of the first layer 3 is improved significantly because the material of the second layer 5 block or closed material in the first layer 3 for example the molecule in the gas phase can or shift the passage that arrives on the base materials 1 through the first layer 3 in addition from the environment diffusion.Therefore, the coating that illustrates provides good machinery and chemoproection for base material 1 surprisingly, and simultaneously can be as for example corroding baffle element and hard coat.
In the protective coating of prior art, the second layer 5 rests on above the hole 7, and only covers hole 7 and support the first layer 3 from its surface.This is illustrated in Fig. 7.On the contrary, can good protection be provided to base material 1,, also therefrom reinforce the first layer 3 because the second layer 5 penetrates into hole 7 even the second layer 5 is extremely thin according to the protective coating structure of embodiment of the present invention and the method that prepare protective coating.
According to the size of hole 7,, grow on all faces of hole 7 that (Fig. 8 a) because comply with the sedimentary second layer 5 even the thin second layer 5 also can fill up hole 7.Along with the second layer 5 continued growths, the settling of on all faces of hole 7, growing finally merges, and (Fig. 8 b) closed in hole 7 intermediary spaces.This has stopped (perhaps blocking) that molecule can shift the possible molecular channel of (for example, diffusion).Referring to Fig. 7, Fig. 8 a and Fig. 8 b, therefore can understand, in order to realize identical barrier effect, when using the protective coating of embodiment of the present invention, the thin second layer 5 of protective coating of on porous the first layer 3, comparing prior art is enough.In addition; Alternately repeated according to two or more different precursors of embodiment of the present invention at the second layer 5 through depending on, maybe be from the method for restrictive surface reaction and under the sedimentary situation, the second layer 5 itself has less residual porosity rate (less hole 9) than the layer in the protective coating of prior art.This has further reduced molecular diffusion and has passed through the possibility according to the protective coating of embodiment of the present invention.Especially, the ALD method can produce the layer that is substantially free of hole 9 (for example, being substantially free of bubble or residual porosity rate).
Embodiment
Through at first being coated in the protective coating for preparing on the M2 steel substrate 1 according to one embodiment of the present invention through PVD titanium-aluminium-nitride (TiAlN) the first layer 3 that 2 microns (μ m) is thick.This coating method is conventional PVD method, and can easily be repeated by the technician.
Subsequently, the M2 steel substrate 1 that the surface is had a TiAlN the first layer 3 is inserted in the reaction chamber of widely used P400ALD instrument (from Finland Beneq Oy).After the reaction chamber pump is low to moderate the pressure of about 1 millibar (mbar), base material 1 is heated to 300 ℃ temperature.After this, base material alternately is exposed to the trimethylaluminium (TMA) of vaporization and the deionized water of vaporization.Between each precursor exposed, the cleaning phase in application 1 second was to clean out reaction chamber with nitrogen with for example unnecessary precursor and byproduct of reaction.The ALD circulation has been shown among Fig. 9, and it is made up of following: be exposed to TMA0.5 second, next use nitrogen purge 1 second (P1), next be exposed to de-ionized H 2In 0.5 second of O, next clean 1 second (P2) again with nitrogen.Basically from restricted surface reaction, this ALD circulation is repeated 40 times through alternately repeated, with growth 4 nanometers (nm) aluminum oxide (Al on titanium-aluminium-nitride (TiAlN) PVD-settled layer 2O 3).Above-mentioned ALD method is widely used, and can easily be optimized to different ALD instruments according to present disclosure by the technician.
The Al of TiAlN the first layer 3 through will having M2 steel substrate 1, PVD-growth and thin ALD-growth 2O 3The exemplary configurations of the second layer 5 is introduced the corrosive water solution (0.15M) of NaCl, the barrier properties of this structure of electro-chemical test.Will be according to the corrosion of the exemplary configurations of embodiment of the present invention and the Al that on the TiAlN the first layer 3 of PVD-growth, does not have the ALD-growth 2O 3The corrosion of the other same structure of the second layer 5 and naked M2 steel substrate 1 are compared.Figure 10 shows the galvanic corrosion of these three kinds of structures and measures the result.The graphic representation of Figure 10 shows the electromotive force " E " of three kinds of test structures with respect to the battery circuit density " i " of electrochemical cell.The potential reference Ag/AgCl reference battery of test structure.
Can observe from Figure 10, the erosion rate of naked M2 steel substrate 1 (M2) is apparently higher than the erosion rate of the structure (M2+TiAlN) of the TiAlN the first layer 3 that on M2 steel substrate 1, has the PVD-growth.Graphic representation shows that the protective coating (M2+TiAlN+ALD) according to embodiment of the present invention on base material 1 obviously causes minimum erosion rate.In addition, can observe the passivation region (passivation zone) of embodiment of the present invention, battery circuit is not as the function of electromotive force and considerable change in this passivation region.The width of this passivation region is about 550mV.Therefore, further compare, add the Al of thin ALD-growth with " M2+TiAlN "-structure 2O 3The second layer 5 has obviously reduced erosion rate.
The TiAlN coating can generally be used for cutting industry, and wherein these coatings show and can use than the elevated operating temperature and the therefore characteristic of higher cutting speed in feet per minute.In the TiAlN coating, erosion resistance is owing at high temperature appear at lip-deep Al segregation (Al-segregation) in the cutting process.When the TiAlN layer being coated with Al according to one embodiment of the present invention 2O 3During layer, need not wait for that this nature Al segregation occurs.Figure 11 shows the result of the wear test mensuration of utilizing two kinds of different coating.One of coating only has the TiAlN the first layer, and another coating has according to embodiment of the present invention and is coated with Al 2O 3The TiAlN the first layer of the second layer.Utilize the tribometer of ball-dish structure to carry out wear test.Utilize constant sliding velocity (0.5cm/s), and under the condition of metal to-metal contact and mild wear, carry out this test.The time length of this test is restricted to 30 minutes, and this equals the sliding distance of 900m.The counterpart that uses (counterpart) is wolfram varbide pin (pin) (diameter 3.2mm), and the load of using is F n=3.3N.The transmitter that uses allows the load of application and the high-acruracy survey (reaching 1.2mN) of tangential force, produces friction co-efficient value.
Can observe from the data of Figure 11, the frictional coefficient original stable of coating that only has the TiAlN the first layer and is tending towards rising to 0.6 after 1400s about 0.2.In addition, can observe, compare the Al on the TiAlN the first layer with TiAlN the first layer only from the data of Figure 11 2O 3The second layer is provided at the other advantage of having stablized frictional coefficient when beginning to carry out wear test.The other advantage of stable frictional coefficient realizes under the situation that does not change the total wear-resisting behavior of coating structure (general wear behavior).That is Al, 2O 3The second layer is filled the hole or the cavity of the first layer, thereby improves erosion resistance.
Except above embodiment is disclosed, for various coated materials, natural other precursor that has many ALD of being suitable for.According to present disclosure, the precursor that is suitable for through synthetic this material of ALD is conspicuous with corresponding chemistry and method for the technician, under this background, is not listed.The chemistry of different ALD methods can find in open #US2005277780 of for example patented claim and US2004043149, and it is added among this paper as a reference.Many examples of material that have known ALD method are arranged.These materials include but not limited to hafnium oxide, aluminum oxide, titanium oxide, tantalum oxide, niobium oxides, zinc oxide, titanium nitride, tantalum nitride, platinum or the like.Many combinations of above-mentioned materials also can be through the ALD deposition, even in single method.According to present disclosure, the technician can easily carry out the for example method of the various materials of combination in the nanometer laminate layers.According to present disclosure, processing parameter in the ALD method such as temperature and pressure also can easily change and be optimized to specific deposition material and in order to adapt to for example special substrate material by the technician.
Only as an example, be deposited under 150 ℃-500 ℃ the base material temperature and in pressure is the reaction environment of 0.1 millibar-100 millibar scope usually by the sedimentary many materials of hot ALD method.Plasma body enhanced (Plasma-enhanced) ALD method also can be considered, and its depositing temperature depositing temperature in the specific heat ALD method potentially is much lower.For some deposition material, also have hot ALD method, wherein basically from restrictive surface reaction---characteristic of ALD---below 100 ℃ in addition the temperature that approaches room temperature (25 ℃) just can realize.These examples of material comprise aluminum oxide (Al 2O 3) and titanium oxide (TiO 2).Through these methods, can not keep pyritous base material 1, for example prepare protective coating on some polymeric substrates 1 according to embodiment of the present invention.
As those skilled in the art institute clearly, the present invention is not limited to the embodiment of above description, but said embodiment can freely change within the scope of the claims.

Claims (16)

1. protect the method for the influence that said base material (1) avoids being caused by said base material (1) and environmental interaction through go up the first layer (3) that deposition comprises the upper surface (4) that is arranged essentially parallel to said base material (1) surface orientation at base material (1), it is characterized in that said method comprising the steps of:
Through making said the first layer (3) be exposed to the alternately repeated surface reaction of two or more different precursors the second layer (5) is deposited on the said the first layer (3); To fill the hole (7) in the said the first layer (3) at least in part with the material of the said second layer (5); Said hole (7) opening passes to said upper surface (4); So that the said second layer (5) is complied with the surface shape of said hole (7); And it is characterized in that said the first layer (3) mainly is made up of titanium, aluminium and nitrogen compound, and the material of the said second layer (5) mainly is a MOX.
2. the described method of claim 1 is characterized in that depositing the said second layer (5) and comprises that said the first layer (3) is exposed to is alternately repeated basically from restricted surface reaction, to deposit the said second layer (5) through ald (ALD).
3. each described method among the claim 1-2 is characterized in that being caused by chemical action by the influence that said base material (1) and environmental interaction cause.
4. each described method among the claim 1-3 is characterized in that being caused by electrochemical action by the influence that said base material (1) and environmental interaction cause.
5. each described method among the claim 1-4 is characterized in that the influence that is caused by said base material (1) and environmental interaction is an infection.
6. each described method among the claim 1-5, the thickness that it is characterized in that the said second layer (5) is below 20 nanometers (nm).
7. each described method among the claim 1-6 is characterized in that depositing the said second layer (5) and comprises and make said the first layer (3) be exposed to trimethylaluminium and the alternately repeated surface reaction of water, with aluminum oxide layer.
8. each described method among the claim 1-7 is characterized in that said base material (1) mainly is made up of metal.
9. each described method among the claim 1-8 is characterized in that said base material (1) comprises parting tool.
10. the protective coating on the base material (1); Be used to protect base material (1) to avoid the influence that causes with environmental interaction by said base material (1); Said protective coating comprises the first layer (3) with the upper surface (4) that is arranged essentially parallel to said base material (1) surface orientation; It is characterized in that said the first layer (3) comprises the hole (7) that opening passes to said upper surface (4); Said protective coating comprises the second layer (5) on the said the first layer (3), and the material of the said second layer (5) is filled the said hole (7) of said the first layer (3) at least in part, so that the said second layer (5) is complied with the surface shape of said hole (7); And it is characterized in that said the first layer (3) mainly is made up of titanium, aluminium and nitrogen compound, and the material of the said second layer (5) mainly is a MOX.
11. the described structure of claim 10, the thickness that it is characterized in that the said second layer (5) are below 20 nanometers (nm).
12. each described structure among the claim 10-11 is characterized in that said base material (1) mainly is made up of metal.
13. each described structure among the claim 10-12 is characterized in that said base material (1) comprises parting tool.
14. the application of the method for the influence that the described protection base material of claim 1 (1) is avoided being caused by said base material (1) and environmental chemistry effect.
15. the described application of claim 14 is characterized in that said chemical action is electrochemical action.
16. each described application among the claim 14-15 is characterized in that said chemical action is to cause the corrosive effect.
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