CN105483631B - A kind of preparation method of nanoporous crystalline inorganic thin-film material - Google Patents

A kind of preparation method of nanoporous crystalline inorganic thin-film material Download PDF

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CN105483631B
CN105483631B CN201510952377.1A CN201510952377A CN105483631B CN 105483631 B CN105483631 B CN 105483631B CN 201510952377 A CN201510952377 A CN 201510952377A CN 105483631 B CN105483631 B CN 105483631B
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nitride
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CN105483631A (en
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郑建云
郝俊英
刘维民
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0635—Carbides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5826—Treatment with charged particles

Abstract

The invention discloses a kind of preparation method of nanoporous crystalline inorganic thin-film material, this method is in a manner that magnetron sputtering deposition and plasma etching are combined, and nanoporous crystalline inorganic film is prepared under low temperature, Template-free method and surfactant-free.Such porous membrane is nitride（Such as titanium nitride (TiN), chromium nitride (CrN), zirconium nitride (ZrN)）, oxide（Titanium oxide (TiO2), zirconium oxide (ZrO2) etc.）, carbide（Titanium carbide (TiC), zirconium carbide (ZrC) etc.）And metal（Nickel (Ni), copper (Cu) etc.）, aperture size is from 1 nm to 1000 nm and pore passage structure from vermiform to simple six side is adjustable, and porous membrane is firmly combined with base material, has high mechanical strength.Therefore, such porous membrane is suitably applied the fields such as catalysis, drug, lubrication, hydrophobic, optics.

Description

A kind of preparation method of nanoporous crystalline inorganic thin-film material
Technical field
A kind of prepare the invention belongs to technical field of preparation for inorganic material more particularly at low temperature the porous of nanoscale The method of crystalline inorganic thin-film material.
Background technology
An important branch of the porous inorganic membrane material as material science, scientific research, industrial production to us It is extremely important with daily life etc..And as people go deep into nanostructured understanding, nanoporous without Machine thin-film material brings new opportunity for the development of porous material, is concerned this field.Nanoporous inorganic thin film The aperture of material can be differed from several nanometers to hundreds of nanometers, and can be by its pore passage structure according to heterogeneity and processing method It is accurately controlled with aperture size.Nanoporous inorganic thin film material usually have bigger serface, good chemical stability, The performances such as good thermal stability, high transmittance, against weather, anticorrosive, high mechanical properties, make it thin compared to porous polymer Film possesses the excellent properties for being difficult to replace, and is used in the industries such as metallurgy, chemical industry, environmental protection, the energy, biology.Now, green, section The main trend of material technology development, function and preparation side of the people to nanoporous inorganic thin film material can, be efficiently become Method proposes more requirements, develops and prepare the vital task that nanoporous inorganic thin film material is considered as researcher.
At present, preparing the main method of nanoporous inorganic thin film material has solvent-thermal method, sol-gel method, chemical gas Xiang Fa, laser ablation method, self-assemble mould board method, organic precursor pyrolysismethod, electrochemical erosion method, hard template method, microwave method etc.. Although the nanoporous inorganic thin film material prepared using these methods has been applied in industrial production, it is still suffered from Many problems.First, the nanoporous silica-base film obtained by these methods is usually impalpable structure, is easy to and the poles such as water Property medium effect, thus hot property and hydro-thermal performance are bad.Comparatively, nanoporous non-silicon base film can have crystalline state hole Wall, it is shown that high thermal stability, but non-silicon sill is generally all worm meso-porous structure.Secondly, template legal system is used During standby nanoporous inorganic thin film, template often has stronger interaction with inorganic skeleton structure, and is difficult to remove.It is high Temperature calcining can remove surfactant, but would generally destroy nano-porous structure.Finally, the above method is preparing nanoporous Often to be used during inorganic thin film to surfactant, and its expensive price and be difficult to regenerated characteristic all for nanoporous without The preparation of machine film brings high cost burden and certain environmental pollution.Therefore, development it is a kind of low temperature, Template-free method and The method that the nanoporous inorganic thin film of crystalline state hole wall is prepared under surfactant-free is necessary, but has been also filled with challenge.
Invention content
The main object of the present invention is the mode being combined using magnetron sputtering deposition and plasma etching, low temperature, Nanoporous crystalline inorganic film is prepared under Template-free method and surfactant-free, which can be nitride（Such as nitrogen Change titanium (TiN), chromium nitride (CrN), zirconium nitride (ZrN) etc.）, oxide（Titanium oxide (TiO2), zirconium oxide (ZrO2) etc.）, carbonization Object（Titanium carbide (TiC), zirconium carbide (ZrC) etc.）And metal（Nickel (Ni), copper (Cu) etc.）, aperture size is 1 nm to 1000 Nm, thickness are 50~800 nm, and pore passage structure is adjustable, and porous membrane and base material from vermiform to simple six side It is firmly combined with.
The principle of the present invention be using magnetron sputtering glancing angle deposition technology shadow effect prepared in substrate it is loose or Then porous metal material carries out metallic film by the etching characteristic of plasma the generation of hole and the expansion in aperture Greatly, so as to obtain nano porous metal film.In addition, the characteristic being easily etched using amorphous carbon material, using magnetron sputtering It is co-deposited amorphous carbon and inorganic material（Nitride, oxide and carbide）Mode, obtain with inorganic material skeleton Then composite material passes through corresponding plasma（Nitrogen (N2), oxygen (O2) and argon gas (Ar)）It performs etching, forms nanometer Porous crystalline state inorganic thin film.
A kind of preparation method of nanoporous crystalline inorganic thin-film material, it is characterised in that be as follows：
1）Inorganic thin film is prepared using magnetron sputtering apparatus deposition, wherein, target is simple metal target, and nitride, oxygen is made Sputter gas used in compound, carbide and metallic film is followed successively by N2+Ar+CH4、O2+Ar+CH4、Ar+CH4、Ar+CH4, stagnation pressure It is 0.4~4.0 Pa, CH by force4It divides as 0~50%, N2It divides as 5~40%, O2It is 5~40% to divide, depositing ions incident angle With substrate into 0~90 °, the distance of target and substrate is 5~20 cm, and sedimentation time is 5~180 min, and initial chamber temp is 15~45 DEG C, the power for the DC power supply being applied on the target is 200~1600 W, is applied to negative in the substrate Bias and duty ratio are respectively 0~-400 V and 40~90%, at the end of deposition chamber temp at 100 DEG C hereinafter, wherein depositing It will be with loose or porous under the synergistic effect that prepared film is formed in low deposition ion incident angles and amorphous carbon Structure and the ingredient being easily etched；
2）It is carried out and etched in the film using lower temperature plasma technology, wherein nitride, oxide, carbide is made N is followed successively by with the plasma gas used in metallic film2 、O2, Ar, Ar, total pressure be 1.0~4.5 Pa, initial chamber temp It it is 15~45 DEG C, it is respectively -500~-1200 V and 40~90% to be applied to the back bias voltage of the film and duty ratio, and etching is tied During beam chamber temp at 100 DEG C hereinafter, wherein etch period for 20~180 min with etching amorphous carbon quick at low temperature Ingredient and open structure and cause inorganic thin film formed nano-porous structure.
It is titanium, chromium or zirconium that the nitride, oxide, the metallic target used in carbide thin film, which is made,.
It is nickel or copper that the metallic target used in the metallic film, which is made,.
The depositing ions incident angle is 60~90 °.
Total pressure is 1.0~3.0 Pa during the deposition.
The power of the DC power supply being applied on target is 400~800 W.
The CH during deposition4Divide is 20~40%.
In the etching process, it is respectively -800~-1200 V and 60 to be applied to the back bias voltage of the film and duty ratio ~80%.
The present invention is using relatively simple magnetron sputtering method is operated, by selecting appropriate technological parameter, in low deposition Under ion incident angles, appropriate total pressure and power can reduce the transfer ability of depositing ions, under deposition rate Drop, so as to generate loose or porous inorganic thin film under shadow effect；Adjust CH4Partial pressure can control amorphous carbon in film Content, so as to which the nanoporous crystalline inorganic film of different pore size can be prepared under low temperature plasma etching；It is born in high Under bias and appropriate duty ratio, the film is implemented to etch using lower temperature plasma technology, obtains nanoporous crystalline state Inorganic thin film；Importantly, in deposition and etching process, due to N2、O2、CH4Participation and high particle with Ar gases Ionization level can be respectively formed the nano-porous film of the nitride of crystalline state, oxide, carbide and metal.Therefore, by this hair Bright preparation method can prepare nanoporous crystalline inorganic thin-film material.
In the present invention, without using surfactant and template in deposition and etching process, and it need not be heated, So as to be conducive to that nanoporous crystalline inorganic film is prepared under the conditions of environmentally friendly, energy saving and lossless.
Plated film and low temperature plasma equipment of the present invention, power supply, target and gas are all extremely simple, easily operated and make With large area production can be carried out.
Nanoporous crystalline inorganic film of the present invention is well bonded with substrate, and value is 15~35 N.Together When, the hardness number of nanoporous crystalline inorganic film is 5~35 GPa.
Nanoporous crystalline inorganic thin-film material of the present invention have crystal phase structure, be able to maintain that high thermal stability and Hydrothermal stability.
Nanoporous crystalline inorganic film of the present invention has high specific surface area and mechanical strength, if in the porous membrane Surface deposited catalyst, low-surface energy substance or greasing substance can reach high catalytic performance, super-hydrophobic or super lubrication property.
Nanoporous crystalline inorganic film of the present invention can be used as catalyst, drug, hydrophobic substance, soft friction material etc. Carrier, it can also be used to the absorption etc. of optics, telecom communication, exhaust gas.
Description of the drawings
Fig. 1 is the field emission scanning electron microscope figure of nanoporous TiAlN thin film described in the embodiment of the present invention 1.
Fig. 2 is the X ray diffracting spectrum of nanoporous TiAlN thin film described in the embodiment of the present invention 1.
Fig. 3 is nanoporous TiO described in the embodiment of the present invention 22The field emission scanning electron microscope figure of film.
Fig. 4 is the field emission scanning electron microscope figure of nano porous Zr N thin film described in the embodiment of the present invention 3.
Specific embodiment
It is further illustrated the present invention below in conjunction with attached drawing and following embodiments, it should be appreciated that attached drawing and following embodiments The present invention is merely to illustrate, is not intended to limit the present invention.
Embodiment 1
Deposition：By N2, Ar and CH4Mixed gas is passed through in chamber, control total pressure, N2Partial pressure and CH4Partial pressure is respectively The distance of 1.0 Pa, 15 % and 40%, target and substrate is 10 cm, and back bias voltage and duty ratio are respectively -200 V and 70%, initially Chamber temp opens DC power supply (power is 600 W) under conditions of being maintained at 25 DEG C, sputter pure titanium target material, sedimentation time is 20 min, so as to obtain TiN and the compound nano thin-film of amorphous carbon by changing 75 ° of depositing ions incident angle.Etching： Only by N2It is passed through in chamber, total pressure is 2.0 Pa, and initial chamber temp is 40 DEG C, and back bias voltage and duty ratio are respectively -900 V and 80% will etch to prepare nanoporous TiAlN thin film by 80 min.
Using field emission scanning electron microscope to nanoporous TiAlN thin film surface（As shown in Figure 1）It observes and sends out with section Existing, the TiN skeletons of film are dendroid, and pore passage structure is vermiform, and width is 20~50 nm, and length can be more than 100 nm, hole Road depth is 100~150 nm, and film thickness is 300 nm, and TiN skeletons are well combined with substrate.Using X-ray diffractometer It is found that this nano-porous film has the TiN phases of crystalline state, as shown in Figure 2.The table of such film is found by atomic force microscope Face bumps rise and fall, and there are porous structures.It is tested by cut, the binding force of this nano-porous film and substrate is 25 N.According to Nano-indentation experiment shows that the hardness of nanoporous TiAlN thin film is 15 GPa.In contact angle test, nanoporous TiAlN thin film All shown as stronger hydrophily, contact angle is less than 20 °.
Embodiment 2
Deposition：By O2, Ar and CH4Mixed gas is passed through in chamber, controls total pressure and O2Partial pressure is respectively 1.0 Pa and 25 %, depositing ions incident angle are 80 °, and the distance of target and substrate is 12 cm, back bias voltage and duty ratio be respectively -100 V and 70%, initial chamber temp opens DC power supply (power is 800 W) under conditions of being maintained at 25 DEG C, sputter pure titanium target material, sink The product time is 60 min, CH4It is 45% to divide, and is prepared for TiO2The compound nano thin-film with amorphous carbon.Etching：Only by O2It is passed through In chamber, total pressure is 3.0 Pa, and initial chamber temp is 40 DEG C, and back bias voltage and duty ratio are respectively -900 V and 80%, will It etches to obtain nanoporous TiO by 40 min2Film.
Using field emission scanning electron microscope to nanoporous TiO2Film surface（As shown in Figure 3）It observes and sends out with section It is existing, the TiO of film2Skeleton is column, and pore passage structure is cylinder, and table circular diameter is 5~15 nm, and cylindrical duct depth is 55~150 nm, and film thickness is 250 nm, and TiO2Skeleton is well combined with substrate.Using X-ray diffractometer it is found that this nanometer Porous membrane has anatase TiO2Phase.The concave-convex surface for finding such film by atomic force microscope rises and falls, and there are porous Structure.It is tested by cut, the binding force of this nano-porous film and substrate is 20 N.Show to receive according to nano-indentation experiment Meter Duo Kong TiO2The hardness of film is 20 GPa.In contact angle test, nanoporous TiO2Film passes through short time ultraviolet lighting Superhydrophilic is shown as after penetrating, contact angle is close to 0 °.
Embodiment 3
Deposition：By N2, Ar and CH4Mixed gas is passed through in chamber, control total pressure, N2Partial pressure and CH4Partial pressure is respectively 1.0 Pa, 15 % and 40%, depositing ions incident angle are 80 °, and the distance of target and substrate is 10 cm, back bias voltage and duty ratio Respectively -200 V and 70%, initial chamber temp open DC power supply under conditions of being maintained at 25 DEG C, sputter pure zirconium target, sink The product time is 10 min, and power is 700 W, is prepared for ZrN and the compound nano thin-film of amorphous carbon.Etching：Only by N2 It is passed through in chamber, total pressure is 2.0 Pa, and initial chamber temp is 40 DEG C, and duty ratio 80%, etch period is fixed as 80 Min, back bias voltage are -1000 V, obtain nano porous Zr N thin film.
Using field emission scanning electron microscope to nano porous Zr N thin film surface（As shown in Figure 4）It observes and sends out with section Existing, the ZrN skeletons of film are rodlike, and pore passage structure is unordered, and width is 20~150 nm, and duct depth is 100~250 Nm, film thickness is 300 nm, and ZrN skeletons are well combined with substrate.Using X-ray diffractometer it is found that this nanoporous is thin Film has the ZrN phases of crystalline state.The concave-convex surface for finding such film by atomic force microscope rises and falls, and there are porous structures.It is logical It crosses cut to test, the binding force of this nano-porous film and substrate is 25 N.Nanoporous is shown according to nano-indentation experiment The hardness of ZrN films is 25 GPa.In contact angle test, nano porous Zr N thin film is all shown as stronger hydrophobicity, contact Angle is more than 90 °.
Industrial applicability：The nanoporous crystalline inorganic film of the present invention is respectively provided with different pore size size, pore passage structure And framework ingredient, cause make it have high specific surface area.Meanwhile this nano-porous film is firmly combined with substrate, there is high machine Tool intensity.Therefore, such porous membrane is suitably applied the fields such as catalysis, drug, lubrication, hydrophobic, optics.

Claims (8)

1. a kind of preparation method of nanoporous crystalline inorganic thin-film material, it is characterised in that be as follows：
1）Inorganic thin film is prepared using magnetron sputtering apparatus deposition, wherein, target be simple metal target, be made nitride, oxide, Sputter gas used in carbide and metallic film is followed successively by N2+Ar+CH4、O2+Ar+CH4、Ar+CH4、Ar+CH4, total pressure is 0.4~4.0 Pa, CH4It divides as 0~50%, N2It divides as 5~40%, O2It is 5~40% to divide, depositing ions incident angle and base Into 0~90 °, the distance of target and substrate is 5~20 cm at bottom, and sedimentation time is 5~180 min, initial chamber temp for 15~ 45 DEG C, the power for being applied to DC power supply on the target is 200~1600 W, the back bias voltage being applied in the substrate Be respectively 0~-400 V and 40~90% with duty ratio, at the end of deposition chamber temp at 100 DEG C hereinafter, wherein depositing made It will be with loose or porous structure under the synergistic effect that standby film is formed in low deposition ion incident angles and amorphous carbon And the ingredient being easily etched；
2）It is carried out and etched in the film using lower temperature plasma technology, wherein nitride, oxide, carbide and gold is made Belong to the plasma gas used in film and be followed successively by N2 、O2, Ar, Ar, total pressure be 1.0~4.5 Pa, initial chamber temp be 15 ~45 DEG C, the back bias voltage and duty ratio for being applied to the film are respectively -500~-1200 V and 40~90%, at the end of etching Chamber temp is at 100 DEG C hereinafter, wherein etch period is 20~180 min with etching amorphous carbon ingredient quick at low temperature With open structure so that inorganic thin film forms nano-porous structure.
2. preparation method as described in claim 1, it is characterised in that the nitride, oxide, carbide thin film institute is made Metallic target is titanium, chromium or zirconium.
3. preparation method as described in claim 1, it is characterised in that be made the metallic target used in the metallic film for nickel or Copper.
4. preparation method as described in claim 1, it is characterised in that the depositing ions incident angle is 60~90 °.
5. preparation method as described in claim 1, it is characterised in that total pressure is 1.0~3.0 Pa during the deposition.
6. preparation method as described in claim 1, it is characterised in that the power of the DC power supply being applied on target is 400~800 W.
7. preparation method as described in claim 1, it is characterised in that the CH during deposition4Divide is 20~40%.
8. preparation method as described in claim 1, it is characterised in that in the etching process, be applied to the negative bias of the film Pressure and duty ratio are respectively -800~-1200 V and 60~80%.
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The plasma nitriding treatment of TiN/TiCN multilayer films;Jianyun Zheng等;《Applied Surface Science》;20131231;第268卷;第195–203页 *
TiN/TiCN multilayer films modified by argon plasma treatment;Jianyun Zheng等;《Applied Surface Science》;20131231;第280卷;第764–771页 *

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