CN109132999A - Metal oxide nano array film and preparation method thereof and the electrode comprising it, battery - Google Patents
Metal oxide nano array film and preparation method thereof and the electrode comprising it, battery Download PDFInfo
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- CN109132999A CN109132999A CN201811036158.9A CN201811036158A CN109132999A CN 109132999 A CN109132999 A CN 109132999A CN 201811036158 A CN201811036158 A CN 201811036158A CN 109132999 A CN109132999 A CN 109132999A
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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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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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
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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Abstract
The present invention provides a kind of metal oxide nano array films and preparation method thereof and the electrode comprising it, battery, it is related to field of material preparation, the preparation method of the metal oxide nano array film, using argon gas and oxygen as working gas, using metal targets as sputtering target, using magnetically controlled sputter method in substrate surface depositing metal oxide film, the metal oxide nano array is obtained；Wherein, the temperature of substrate is 0~700 DEG C, 0.9~10Pa of operating pressure in magnetron sputtering, and sputtering power is 1~6W/cm2, sputtering time is 0.5~10h.Can be alleviated using the preparation method using the metal-oxide film that existing preparation method obtains is planar structure, specific surface area is small and metals in films oxidate nano array film technical problem can not be prepared, and achievees the purpose that the metal-oxide film for preparing nano array structure.
Description
Technical field
The present invention relates to technical field of material, more particularly, to a kind of metal oxide nano array film and its system
Preparation Method and the electrode comprising it, battery.
Background technique
Metal oxide nano array film because its with small-size effect, surface and interfacial effect, quantum size effect,
Macro quanta tunnel effect and show excellent physical and chemical performance, in battery, supercapacitor, catalysis, gas sensing, electricity
The fields such as sub-information, life science and military affairs have broad application prospects.Therefore, high performance metal oxide nano array
The synthesis of film and its property Quality Research become the hot spot studied extensively at present.
Currently, existing kinds of experiments means are used to prepare metal oxide nano array film, including chemical vapor deposition
Method, hydro-thermal method, solvent-thermal method, electrodeposition process, chemical oxidization method, template etc..However, above every kind of common method is difficult to
Large area equably grows metal oxide nano array in substrate, and every kind of method is usually applicable only to a certain kind specifically
Substrate, it is difficult to expand to other substrates, narrow application range.In addition, preparing nano-array film using above-mentioned preparation method
When, it usually needs using template to prepare nano-array.
Magnetron sputtering method is one of common method of growing film material, is compared with other methods, magnetron sputtering have at
Membrane area is big, and the binding force of film and substrate is high, and form a film dense uniform, and the film of preparation is easily controllable, can be on different substrates
The advantages that film forming, therefore, magnetron sputtering method, are widely used in the research and production of thin-film material.However, being aoxidized for metal
For the preparation of object film, previous magnetron sputtering method is according to metal-oxide film to be prepared using corresponding metal oxygen
Compound prepares the metal-oxide film of plane as target, and specific surface area is limited, and the metal with bigger serface
The preparation of oxidate nano array film material is rarely reported.
Summary of the invention
The first object of the present invention is to provide a kind of metal oxide nano array film and preparation method thereof, to alleviate
It is planar structure using the metal-oxide film that existing preparation method obtains, specific surface area is small and film-form can not be prepared
Metal oxide nano array film technical problem.
The second object of the present invention is to provide a kind of using above-mentioned metal oxide nano array film as electrode active
The electrode of property material, the third object of the present invention is to provide a kind of battery, to reduce the material cost of electrode, and improves battery
Capacity.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of preparation method of metal oxide nano array film, using argon gas and oxygen as working gas, with metallic target
Material is sputtering target, using magnetically controlled sputter method in substrate surface depositing metal oxide film, obtains the metal oxide and receives
Rice array；
Wherein, in magnetron sputtering substrate temperature be 0~700 DEG C, 0.9~10Pa of operating pressure, sputtering power be 1~
6W/cm2, sputtering time is 0.5~10h.
Further, the metal in the metal targets include V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, In, Sn,
One of Sb, W or Bi or alloy including at least any of the above-described metal.
Further, the metal in the metal targets is Cr, Mn or Mo.
Further, when the metal targets are Cr target, the heating temperature of substrate is 300~700 DEG C, operating pressure
0.9~2Pa, sputtering power are 1~3W/cm2, sputtering time is 0.5~10h.
Further, when the metal targets are Mn target, the heating temperature of substrate is 0~50 DEG C, operating pressure 0.9
~2Pa, sputtering power are 1~3W/cm2, sputtering time is 0.5~10h.
Further, when the metal targets are Mo target, the heating temperature of substrate is 200~700 DEG C, operating pressure
0.9~2Pa, sputtering power are 1~3W/cm2, sputtering time is 0.5~10h.
Further, the substrate include stainless steel foil, aluminium foil, copper foil, silicon wafer, alumina wafer, mica sheet, sheet glass,
FTO glass, carbon cloth, carbon paper or polymer matrix film；
Preferably, the polymer matrix film is polyimide film or polyethylene film；
Preferably, the non-metal base bottom surface is equipped with metal coating.
A kind of metal oxide nano array film, is obtained using above-mentioned preparation method.
A kind of electrode, using above-mentioned metal oxide nano array film as battery active material.
A kind of battery, including above-mentioned electrode.
Compared with the prior art, the invention has the following beneficial effects:
The preparation method of metal oxide nano array film provided by the invention is using argon gas and oxygen as work gas
Body, using metal targets as sputtering target, using magnetically controlled sputter method in substrate surface depositing metal oxide film, to obtain institute
State metal oxide nano array.In the preparation method, it is sputtering target using metal targets, oxygen is passed through while being passed through argon gas
Gas, while using oxygen as working gas, metallic atom is aoxidized during metal atom sputtering to obtain metal oxide,
Metal oxide is deposited in substrate to obtain metal-oxide film in substrate surface.In the preparation method, pass through control
The temperature of substrate makes to control the dynamic process of metal oxide forming core and growth on substrate that reactive sputtering obtains
The atom or molecule of the metal oxide of deposition tend to be mutually bonded with itself, form island growth mode, thus
Metal oxide nano array film is directly prepared in substrate.
It, can be by the control of sputter temperature and sputtering power due to using sputtering technology in the preparation method
The metal-oxide film of nano array structure is prepared in different base, use scope is wide.Meanwhile the preparation method is opposite
For traditional method for preparing nano-array film, without using template, the preparation of large area, more conducively work can be carried out
The implementation of industry.Specifically, the preparation method has the advantage that
1) preparation process carries out under low pressure, the working gas being passed through be oxygen and argon gas gaseous mixture, it is low in cost and
It is nontoxic；
2) being grown in magnetron sputtering cavity for metal-oxide film carries out, using metallic target as sputtering source, woth no need to
Other special materials；
3) without using template, uniformly, adhesive force is strong for film forming, and prepared film size is only dependent upon substrate used
Area, process flow is simple, operates easy to accomplish.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the Cr obtained using the preparation method that the embodiment of the present invention 1 provides2O3The scanning electron microscope of nano-array material
Figure；
Fig. 2 is the Cr obtained using the preparation method that the embodiment of the present invention 2 provides2O3The scanning electron microscope of nano-array material
Figure；
Fig. 3 is the Mn obtained using the preparation method that the embodiment of the present invention 3 provides3O4The scanning electron microscope of nano-array material
Figure；
Fig. 4 is the Mn obtained using the preparation method that the embodiment of the present invention 4 provides3O4The scanning electron microscope of nano-array material
Figure；
Fig. 5 is the Mn obtained using the preparation method that the embodiment of the present invention 5 provides3O4The scanning electron microscope of nano-array material
Figure；
Fig. 6 is the MoO obtained using the preparation method that the embodiment of the present invention 6 provides3The scanning electron microscope of nano-array material
Figure；
Fig. 7 is the MoO obtained using the preparation method that the embodiment of the present invention 7 provides3The scanning electron microscope of nano-array material
Figure；
Fig. 8 is the Cr obtained using the preparation method that comparative example 1 provides2O3The scanning electron microscope (SEM) photograph of thin-film material；
Fig. 9 is the Cr obtained using the preparation method that comparative example 2 provides2O3The scanning electron microscope (SEM) photograph of thin-film material；
Figure 10 is the Mn obtained using the preparation method that comparative example 3 provides3O4The scanning electron microscope (SEM) photograph of thin-film material；
Figure 11 is the Mn obtained using the preparation method that comparative example 4 provides3O4The scanning electron microscope (SEM) photograph of thin-film material；
Figure 12 is the MoO obtained using the preparation method that comparative example 5 provides3The scanning electron microscope (SEM) photograph of thin-film material；
Figure 13 is the MoO obtained using the preparation method that comparative example 6 provides3The scanning electron microscope (SEM) photograph of thin-film material.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
On the one hand, the present invention provides a kind of preparation methods of metal oxide nano array film, with argon gas and oxygen
It, using magnetically controlled sputter method in substrate surface depositing metal oxide film, is obtained for working gas using metal targets as sputtering target
To the metal oxide nano array；Wherein, the temperature of substrate is 0~700 DEG C in magnetron sputtering, operating pressure 0.9~
10Pa, sputtering power are 1~6W/cm2, sputtering time is 0.5~10h.
The preparation method of metal oxide nano array film provided by the invention is using argon gas and oxygen as work gas
Body, using metal targets as sputtering target, using magnetically controlled sputter method in substrate surface depositing metal oxide film, to obtain institute
State metal oxide nano array.In the preparation method, it is sputtering target using metal targets, oxygen is passed through while being passed through argon gas
Gas, while using oxygen as working gas, metallic atom is aoxidized during metal atom sputtering to obtain metal oxide,
Metal oxide is deposited in substrate to obtain metal-oxide film in substrate surface.In the preparation method, pass through control
The temperature of substrate makes to control the dynamic process of metal oxide forming core and growth on substrate that reactive sputtering obtains
The atom or molecule of the metal oxide of deposition tend to be mutually bonded with itself, form island growth mode, thus
Metal oxide nano array film is directly prepared in substrate.
It, can be by the control of sputter temperature and sputtering power due to using sputtering technology in the preparation method
The metal-oxide film of nano array structure is prepared in different base, use scope is wide.Meanwhile the preparation method is opposite
For traditional method for preparing nano-array film, without using template, the preparation of large area, more conducively work can be carried out
The implementation of industry.Specifically, the preparation method has the advantage that
1) preparation process carries out under low pressure, the working gas being passed through be oxygen and argon gas gaseous mixture, it is low in cost and
It is nontoxic；
2) being grown in magnetron sputtering cavity for metal-oxide film carries out, using metallic target as sputtering source, woth no need to
Other special materials；
3) without using template, uniformly, adhesive force is strong for film forming, and prepared film size is only dependent upon substrate used
Area, process flow is simple, operates easy to accomplish.
In the present invention, the typical but non-limiting temperature of substrate is, for example, 0 DEG C, 10 DEG C, 20 DEG C, 25 DEG C, 50 DEG C, 100
DEG C, 150 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C or 700 DEG C；
Typical but non-limiting operating pressure for example can be 0.9Pa, 1.5Pa, 2Pa, 3Pa, 4Pa, 5Pa, 6Pa, 7Pa, 8Pa, 9Pa
Or 10Pa；Typical but non-limiting sputtering power for example can be 1W/cm2、1.5W/cm2、2W/cm2、2.5W/cm2、3W/
cm2、3.5W/cm2、4W/cm2、4.5W/cm2、5W/cm2、5.5W/cm2Or 6W/cm2；Sputtering time for example can for 0.5h, 1h,
1.5h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h.
Preparation method provided by the invention is aoxidized by replacing the available different types of metal of different metal targets
Object nano-array film.In certain embodiments of the present invention, the metal in the metal targets include V, Cr, Mn, Fe,
One of Co, Ni, Cu, Zn, Nb, Mo, In, Sn, Sb, W or Bi or alloy including at least any of the above-described metal.The present invention
The preparation method of offer is particularly suitable for preparing chromium oxide, manganese oxide and molybdenum oxide, correspondingly, metal targets be preferably selected from Cr,
Mn and Mo.
In certain embodiments of the present invention, when the metal targets are Cr target, the heating temperature of substrate is 300
~700 DEG C, 0.9~2Pa of operating pressure, sputtering power is 1~3W/cm2, sputtering time is 0.5~10h.Preferably
In, by the reasonably combined of substrate heating temperature, operating pressure, sputtering power and sputtering time, sputtering technology is made to meet Cr2O3
Forming core and growth kinetics, in Cr2O3Growth course in formed island growth mode, could substrate surface grow prepare
The Cr of nano array structure out2O3Film.
In certain embodiments of the present invention, when the metal targets are Mn target, the heating temperature of substrate is 0~
50 DEG C, 0.9~2Pa of operating pressure, sputtering power is 1~3W/cm2, sputtering time is 0.5~10h.In this embodiment,
By the reasonably combined of substrate heating temperature, operating pressure, sputtering power and sputtering time, sputtering technology is made to meet Mn3O4Shape
Core and growth kinetics, in Mn3O4Growth course in formed island growth mode, could substrate surface grow preparation cashier
The Mn of rice array structure3O4Film.
In certain embodiments of the present invention, when the metal targets are Mo target, the heating temperature of substrate is 200
~700 DEG C, 0.9~2Pa of operating pressure, sputtering power is 1~3W/cm2, sputtering time is 0.5~10h.Preferably
In, by the reasonably combined of substrate heating temperature, operating pressure, sputtering power and sputtering time, sputtering technology is made to meet MoO3
Forming core and growth kinetics, in MoO3Growth course in formed island growth mode, could substrate surface grow prepare
The MoO of nano array structure out3Film.
It is thin can to prepare different metal oxide nano arrays in different substrates for preparation method provided by the invention
Film, substrate for example can for stainless steel foil, aluminium foil, copper foil, silicon wafer, alumina wafer, mica sheet, sheet glass, FTO glass, carbon cloth,
Carbon paper or polymer matrix film；Wherein, polymer matrix film for example can be polyimide film or polyethylene film.In order to improve substrate with
The bond strength of metal oxide can prepare one layer of metal coating in non-metal base bottom surface, such as can be in silicon wafer, oxidation
Aluminium flake, mica sheet or glass sheet surface are used as substrate after plating the conductive metal layer of one layer of gold, platinum or iron.
Second aspect, the present invention provides a kind of metal oxide nano array film, the metal oxide nano arrays
Film is obtained using above-mentioned preparation method.
The third aspect, the present invention provides a kind of electrodes, using above-mentioned metal oxide nano array film as battery
Active material.The electrode includes electrode current collecting body, and electrode current collecting body surface coats the metal oxide nano array film conduct
Battery active material.
Since the microstructure of above-mentioned metal oxide nano array film is nano array structure, specific surface is larger,
The contact area that electrode material and electrolyte can be increased improves the activity and capacity of electrode material, and then improves the energy of battery
Metric density and power density.
In another aspect, the battery includes above-mentioned electrode the present invention provides a kind of battery.The battery has above-mentioned electrode
All advantages, details are not described herein.
Below in conjunction with embodiment, the present invention will be further described in detail.
Embodiment 1
The present embodiment is a kind of Cr2O3The preparation method of nano-array film, specifically includes the following steps:
(1) method for using magnetically controlled DC sputtering, uses pure Cr metallic target as target, silicon wafer is as substrate；It installs
After target and substrate, sputtering chamber is closed, sputtering chamber is evacuated to 1.0 × 10-4Pa hereinafter, substrate is heated to 450 DEG C,
It is passed through 60sccm argon gas and the oxygen of 10sccm, then gas pressure intensity in chamber is adjusted to 1Pa；
(2) sputtering power 1.4W/cm is set2, target-substrate distance 80mm, pre-sputtering 5min, to clear up the miscellaneous of target material surface
Matter, sputtering time 3h, obtains Cr on silicon wafer2O3Nano-array film.
Fig. 1 is Cr obtained in the present embodiment2O3The scanning electron microscope (SEM) photograph of nano-array film, as can be seen from the figure gained
To film be by orderly Cr2O3Nanocrystal nano-array obtained from equably vertical-growth is in glass sheet substrate is thin
Film.
Embodiment 2
The present embodiment is a kind of Cr2O3The preparation method of nano-array film, specifically includes the following steps:
(1) method for using magnetically controlled DC sputtering, uses pure Cr metallic target as target, aluminium foil is as substrate；It installs
After target and substrate, sputtering chamber is closed, sputtering chamber is evacuated to 1.0 × 10-4Pa hereinafter, substrate is heated to 350 DEG C,
It is passed through 60sccm argon gas and the oxygen of 10sccm, then gas pressure intensity in chamber is adjusted to 1Pa；
(2) sputtering power 1.4W/cm is set2, target-substrate distance 80mm, pre-sputtering 5min, to clear up the miscellaneous of target material surface
Matter, sputtering time 3h obtain Cr in aluminium foil surface2O3Nano-chip arrays film.
Fig. 2 is the Cr that the present embodiment obtains2O3The scanning electron microscope (SEM) photograph of nano-array film, it is as can be seen from the figure acquired
Film be by orderly Cr2O3Nanocrystal nano-array film obtained from equably vertical-growth is in aluminum foil substrate.
Embodiment 3
The present embodiment is a kind of Mn3O4The preparation method of nano-array film, specifically includes the following steps:
(1) method for using magnetically controlled DC sputtering, uses pure Mn metallic target as target, mica sheet is as substrate；Installation
After good target and substrate, sputtering chamber is closed, sputtering chamber is evacuated to 1.0 × 10-4Pa hereinafter, be passed through 60sccm argon gas and
The oxygen of 10sccm, then gas pressure intensity in chamber is adjusted to 1Pa；
(2) sputtering power 1.4W/cm is set2, target-substrate distance 80mm, pre-sputtering 5min, to clear up the miscellaneous of target material surface
Matter sputters 3h at 25 DEG C of room temperature, Mn is directly obtained in substrate3O4Nano-chip arrays.
Fig. 3 is the Mn that the present embodiment obtains3O4The scanning electron microscope (SEM) photograph of nano-array film, as can be seen from the figure obtains
Film is by orderly Mn3O4Nanometer nano-array film obtained from equably vertical-growth is in mica sheet substrate.
Embodiment 4
The present embodiment is a kind of Mn3O4The preparation method of nano-array film, specifically includes the following steps:
(1) method for using magnetically controlled DC sputtering, uses pure Mn metallic target as target, stainless steel is as substrate；Installation
After good target and substrate, sputtering chamber is closed, sputtering chamber is evacuated to 1.0 × 10-4Pa hereinafter, be passed through 60sccm argon gas and
The oxygen of 10sccm, then gas pressure intensity in chamber is adjusted to 1Pa；
(2) sputtering power 1.4W/cm is set2, target-substrate distance 80mm, pre-sputtering 5min, to clear up the miscellaneous of target material surface
Matter sputters 3h at 25 DEG C of room temperature, Mn is directly obtained in substrate3O4Nano-array film.
Fig. 4 is the Mn that the present embodiment obtains3O4The scanning electron microscope (SEM) photograph of nano-array film, it is as can be seen from the figure acquired
Film be by orderly Mn3O4Nanocrystal nano-array film obtained from equably vertical-growth is in stainless steel base.
Embodiment 5
The present embodiment is a kind of Mn3O4The preparation method of nano-array film, specifically includes the following steps:
(1) method for using magnetically controlled DC sputtering, uses pure Mn metallic target as target, polyimides is as substrate；Peace
After installing target and substrate, sputtering chamber is closed, sputtering chamber is evacuated to 1.0 × 10-5Pa is hereinafter, be passed through 60sccm argon gas
With the oxygen of 10sccm, then gas pressure intensity in chamber adjusted to 1Pa；
(2) sputtering power 1.4W/cm is set2, target-substrate distance 80mm, pre-sputtering 5min, to clear up the miscellaneous of target material surface
Matter sputters 3h at 25 DEG C of room temperature, Mn is directly obtained in substrate3O4Nano-array film.
Fig. 5 is the Mn that the present embodiment obtains3O4The scanning electron microscope (SEM) photograph of nano-array film, it can be seen that obtained film
It is by orderly Mn3O4Nanocrystal nano-array film obtained from equably vertical-growth is on polyimide substrate.
Embodiment 6
The present embodiment is a kind of MoO3The preparation method of nano-array film, specifically includes the following steps:
(1) method for using magnetically controlled DC sputtering, uses pure Mo metallic target as target, silicon wafer is as substrate；It installs
After target and substrate, sputtering chamber is closed, sputtering chamber is evacuated to 1.0 × 10-4Pa hereinafter, substrate is heated to 400 DEG C,
It is passed through 60sccm argon gas and the oxygen of 10sccm, then gas pressure intensity in chamber is adjusted to 1Pa；
(2) sputtering power 1.4W/cm is set2, target-substrate distance 80mm, pre-sputtering 5min, to clear up the miscellaneous of target material surface
Matter sputters 3h at room temperature, MoO is directly obtained in substrate3Nano-array film.
Fig. 6 is the MoO that the present embodiment obtains3The scanning electron microscope (SEM) photograph of nano-array film, it can be seen from the figure that acquired
Film be by orderly MoO3Nanocrystal nano-array obtained from equably vertical-growth is on polyimide substrate is thin
Film.
Embodiment 7
The present embodiment is a kind of MoO3The preparation method of nano-array film, specifically includes the following steps:
(1) method for using rf magnetron sputtering, uses pure Mo metallic target as target, stainless steel is as substrate；Installation
After good target and substrate, sputtering chamber is closed, sputtering chamber is evacuated to 1.0 × 10-4Pa is hereinafter, be heated to 300 for substrate
DEG C, it is passed through 60sccm argon gas and the oxygen of 10sccm, then gas pressure intensity in chamber is adjusted to 1Pa；
(2) rf sputtering power 3W/cm is set2, target-substrate distance 80mm, pre-sputtering 5min, to clear up the impurity of target material surface,
3h is sputtered at room temperature, and MoO is directly obtained in substrate3Nano-chip arrays.
Fig. 7 is the MoO that the embodiment of the present invention 7 obtains3The scanning electron microscope (SEM) photograph of nano-array film, it can be seen from the figure that
Obtained film is by orderly MoO3Nanocrystal nanometer battle array obtained from equably vertical-growth is in stainless steel base
Column film.
Comparative example 1
This comparative example is a kind of Cr2O3The preparation method of film, compared with Example 1 the difference is that, in this comparative example
Substrate heating temperature be 800 DEG C, remaining is all the same with embodiment 1.
Fig. 8 is the Cr that this comparative example obtains2O3The scanning electron microscope (SEM) photograph of film, as can be seen from the figure obtained film be
Nano array structure is not present in planar structure.
Comparative example 2
This comparative example is a kind of Cr2O3The preparation method of film, compared with Example 1 the difference is that, in this comparative example
Substrate heating temperature be 200 DEG C, remaining is all the same with embodiment 1.
Fig. 9 is the Cr that this comparative example obtains2O3The scanning electron microscope (SEM) photograph of film, as can be seen from the figure obtained film be
Nano array structure is not present in planar structure.
Comparative example 3
This comparative example is a kind of Mn3O4The preparation method of film, compared with Example 3 the difference is that, in this comparative example
Substrate temperature be 400 DEG C, remaining is all the same with embodiment 3.
Figure 10 is the Mn that this comparative example obtains3O4The scanning electron microscope (SEM) photograph of film, as can be seen from the figure obtained film be
Nano array structure is not present in planar structure.
Comparative example 4
This comparative example is a kind of Mn3O4The preparation method of film, compared with Example 3 the difference is that, in this comparative example
Substrate temperature be 80 DEG C, remaining is all the same with embodiment 3.
Figure 11 is the Mn that this comparative example obtains3O4The scanning electron microscope (SEM) photograph of film, as can be seen from the figure obtained film be
Nano array structure is not present in planar structure.
Comparative example 5
This comparative example is a kind of MoO3The preparation method of film, compared with Example 6 the difference is that, in this comparative example
Substrate heating temperature be 750 DEG C, remaining is all the same with embodiment 6.
Figure 12 is the MoO that this comparative example obtains3The scanning electron microscope (SEM) photograph of film, as can be seen from the figure obtained film be
Nano array structure is not present in planar structure.
Comparative example 6
This comparative example is a kind of MoO3The preparation method of film, compared with Example 6 the difference is that, in this comparative example
Substrate heating temperature be 150 DEG C, remaining is all the same with embodiment 6.
Figure 13 is the MoO that this comparative example obtains3The scanning electron microscope (SEM) photograph of film, as can be seen from the figure obtained film be
Nano array structure is not present in planar structure.
It can be seen that from the scanning electron microscope (SEM) photograph in embodiment and comparative example and only utilize preparation side provided by the invention
Method obtains the film of nano array structure even if base reservoir temperature, operating pressure, sputtering power and sputtering time cooperate.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of metal oxide nano array film, which is characterized in that using argon gas and oxygen as working gas,
Using metal targets as sputtering target, using magnetically controlled sputter method in substrate surface depositing metal oxide film, the metal is obtained
Oxidate nano array；
Wherein, the temperature of substrate is 0~700 DEG C, 0.9~10Pa of operating pressure in magnetron sputtering, and sputtering power is 1~6W/cm2,
Sputtering time is 0.5~10h.
2. preparation method according to claim 1, which is characterized in that the metal in the metal targets include V, Cr, Mn,
One of Fe, Co, Ni, Cu, Zn, Nb, Mo, In, Sn, Sb, W or Bi or alloy including at least any of the above-described metal.
3. preparation method according to claim 2, which is characterized in that the metal in the metal targets is Cr, Mn or Mo.
4. preparation method according to claim 3, which is characterized in that when the metal targets are Cr target, substrate
Heating temperature is 300~700 DEG C, 0.9~2Pa of operating pressure, and sputtering power is 1~3W/cm2, sputtering time is 0.5~10h.
5. preparation method according to claim 3, which is characterized in that when the metal targets are Mn target, substrate
Heating temperature is 0~50 DEG C, 0.9~2Pa of operating pressure, and sputtering power is 1~3W/cm2, sputtering time is 0.5~10h.
6. preparation method according to claim 3, which is characterized in that when the metal targets are Mo target, substrate
Heating temperature is 200~700 DEG C, 0.9~2Pa of operating pressure, and sputtering power is 1~3W/cm2, sputtering time is 0.5~10h.
7. preparation method according to claim 1-6, which is characterized in that the substrate includes stainless steel foil, aluminium
Foil, copper foil, silicon wafer, alumina wafer, mica sheet, sheet glass, FTO glass, carbon cloth, carbon paper or polymer matrix film；
Preferably, the polymer matrix film is polyimide film or polyethylene film；
Preferably, the non-metal base bottom surface is equipped with metal coating.
8. a kind of metal oxide nano array film, which is characterized in that utilize the described in any item preparation sides claim 1-7
Method obtains.
9. a kind of electrode, which is characterized in that living using metal oxide nano array film according to any one of claims 8 as battery
Property material.
10. a kind of battery, which is characterized in that including electrode as claimed in claim 9.
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| CN114931948A (en) * | 2022-03-25 | 2022-08-23 | 山东大学 | Potassium intercalation molybdenum oxide nano array material and preparation method and application thereof |
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| CN114931948B (en) * | 2022-03-25 | 2023-04-07 | 山东大学 | Potassium intercalation molybdenum oxide nano array material and preparation method and application thereof |
| CN114824286A (en) * | 2022-05-09 | 2022-07-29 | 广东工业大学 | Al-V alloy film substrate material for sodium metal battery and preparation method and application thereof |
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