CN109536904A - A kind of doping TiO2Barrier film and preparation method thereof - Google Patents
A kind of doping TiO2Barrier film and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000010408 film Substances 0.000 claims abstract description 125
- 230000004888 barrier function Effects 0.000 claims abstract description 55
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010409 thin film Substances 0.000 claims abstract description 23
- 239000012298 atmosphere Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 238000004544 sputter deposition Methods 0.000 claims description 56
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910004337 Ti-Ni Inorganic materials 0.000 claims description 8
- 229910011209 Ti—Ni Inorganic materials 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 229910003074 TiCl4 Inorganic materials 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004062 sedimentation Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000027756 respiratory electron transport chain Effects 0.000 description 9
- 229960000935 dehydrated alcohol Drugs 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 1
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
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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
- C23C14/22—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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- 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
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic 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
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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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
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
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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
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
- C23C14/5853—Oxidation
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- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present invention relates to a kind of doping TiO2Barrier film and preparation method thereof belongs to photoelectric semiconductor material technical field.Doping TiO of the invention2The preparation method of barrier film, comprising the following steps: 1) titanium alloy thin films are prepared in substrate by physical vaporous deposition, titanium alloy thin films obtained are then subjected to thermal oxidative reaction in having oxygen atmosphere；2) film after thermal oxidative reaction in step 1) is impregnated in 80~100 DEG C of titanium tetrachloride solution to get.Doping TiO of the invention2The preparation method of barrier film, doping TiO obtained2The uniform free from flaw of barrier film, greatly reduces the porosity of film, and keeps film stronger in conjunction with substrate.Preparation method of the invention, mature easy to operate, technology stability is good, and quality of forming film is high, low in cost, has good popularization and application basis.
Description
Technical field
The present invention relates to a kind of doping TiO2Barrier film and preparation method thereof belongs to photoelectric semiconductor material technology neck
Domain.
Background technique
Nano-TiO2Material is as a kind of widely applied novel optoelectronic materials, photoelectricity of the different morphosis to material
Performance influences different.Currently, nano-TiO2Material one typical application field is the light sun of third generation novel solar battery
Pole material, primarily as light induced electron transport layer, in the absorption and reduction of the injection of light induced electron, transmission, collection and dyestuff
Electronics is compound etc. to be played an important role.But either use nano-TiO2Particle film does electron transfer layer, or with one
Tie up TiO2Nanometer rods (Guan or line) film does electron transfer layer, all there is a common problem, is exactly unable to reach very high cause
Density.In this way, in the solar battery preparation in later period, especially with the solar battery of liquid electrolyte, due to electronics
Transport layer consistency is not high, and gap is more, can not accomplish being effectively isolated for liquid electrolyte and conductive substrates, as a result will be in electricity
A part of short circuit current, i.e. battery dark current are generated in pond.The presence of dark current seriously reduces the density of photocurrent of battery, most
The photoelectric conversion performance of solar battery is influenced eventually.
To solve the above-mentioned problems, researcher is fine and close by preparing one layer between conductive substrates and electron transfer layer
Barrier film, to realize that conductive substrates are isolated with the preferable of liquid electrolyte.On the one hand fine and close barrier film plays
The effect of conductive substrates and liquid electrolyte is isolated, on the other hand plays the role of seed layer, on this basis electron transfer layer
Crystalline growth be more easier.However, due to the study on the modification for being currently mainly focused on electron transfer layer, for how to improve resistance
The research of barrier conductivity is less.
In the prior art, the Chinese invention patent that Authorization Notice No. is CN105648414B, which discloses, a kind of to be splashed using magnetic control
The method that the method for penetrating prepares nitrogenous titanium deoxid film, method is dry comprising steps of cleaning substrate, reaches 1~5 in vacuum degree
×10-3Under conditions of Pa, ion beam cleaning is carried out to substrate, then using titanium as target, magnetron sputtering forms titanium film, in nitrogen
In oxygen mix atmosphere, nitrogen-doped titanium dioxide film is made in 400~700 DEG C of 30~60min of annealing.Using the party
Titania-doped film made from method can be improved its photocatalysis effect under visible light illumination, undisclosed doping obtained
The conductivity of titanium deoxid film.
Summary of the invention
The object of the present invention is to provide a kind of doping TiO2The preparation method of barrier film, TiO obtained2Barrier layer is thin
Membrane conductivity is high.
The present invention also provides a kind of doping TiO with high conductivity2Barrier film.
In order to achieve the goal above, doping TiO of the invention2Technical solution used by the preparation method of barrier film
It is:
A kind of doping TiO2The preparation method of barrier film, includes the following steps:
1) titanium alloy thin films are prepared in substrate by physical vaporous deposition, then there are titanium alloy thin films obtained
Thermal oxidative reaction is carried out in oxygen atmosphere；
2) film after thermal oxidative reaction in step 1) is impregnated in 80~100 DEG C of titanium tetrachloride solution, i.e.,
?.
It, can be in TiO since fluctuation of film during formation by factors such as temperature, atmosphere and pressure is influenced2
Some internal flaws, doping TiO of the invention are formed inside barrier film2The preparation method of barrier film, by by titanium
In the TiCl of heat after alloy firm thermal oxide4Solution is impregnated, and TiO can be effectively reduced or eliminate2In barrier film
The crystal defects such as defect state and surface state, doping TiO obtained2The uniform free from flaw of barrier film, greatly reduces film
Porosity, and keep film stronger in conjunction with substrate；In addition, by by the film after thermal oxide heat TiCl4Aqueous solution
It carries out impregnating the flatness that can also improve film surface.Preparation method of the invention can significantly reduce the electricity of barrier film
Resistance rate improves barrier film conductivity and increases barrier film electron transfer rate, and mature easy to operate, process stabilizing
Property it is good, quality of forming film is high, low in cost, and it is basic to have good popularization and application.
In order to obtain the titanium alloy thin films oxidation rate of rational, it is preferred that the thermal oxidative reaction be 400~
0.5~2.0h is aoxidized at 600 DEG C.
Preferably, the titanium alloy thin films are made of titanium and nickel；The mass ratio of titanium and nickel is 95~99:5~1.Titanium alloy
A small amount of nickel is adulterated in film the excessive of crystal grain to grow up in inhibiting film formation process, increase film to the benefit of visible light
With efficiency, effect is significantly improved to the photoelectric properties of film.
Preferably, the physical vaporous deposition is magnetron sputtering method.The nuclear energy that magnetron sputtering method sputters out is high,
The diffusivity of atom, further increases the compactness extent of the titanium alloy thin films tissue of deposition, and make when being conducive to improve deposition
There is stronger adhesive force between titanium alloy thin films and substrate.
Preferably, the magnetron sputtering method is magnetically controlled DC sputtering.Magnetically controlled DC sputtering is not easy to make base in sputtering process
Bottom temperature increases, and can make film due to the temperature difference between substrate and titanium alloy thin films layer after the completion to avoid magnetron sputtering
Generate crack；And for conductor, magnetically controlled DC sputtering technology is simpler, and also more easy-regulating, coating process are easy to parameter
Operation and realization.
In order to further increase the quality of titanium alloy thin films, it is preferred that the sputtering control condition of the magnetically controlled DC sputtering
Include: base reservoir temperature be 15~30 DEG C, sputtering power be 100~150W, operating air pressure be 0.5~0.6Pa, sputtering time 5
~30min.
Preferably, the target that the magnetron sputtering method uses is titanium alloy target；The titanium alloy target be nickeliferous 1%~
The Ti-Ni alloy of 5% (mass fraction).Magnetron sputtering plating is carried out using titanium alloy target to be easier to obtain the uniform titanium of ingredient
Alloy firm especially can reduce magnetically controlled DC sputtering to the uneven etching of target to titanium alloy thin films ingredient stability
It influences.
Since alloy firm oxidation rate is too fast under pure oxygen atmosphere, TiO can be made2Barrier film internal flaw increases.For
Convenient for by the control to oxidation rate reducing TiO2Defect concentration inside barrier film, it is preferred that described aerobic
Atmosphere is made of at least one of nitrogen, inert gas with oxygen；The oxygen accounts for the volume fraction for having oxygen atmosphere
20~90%.
Preferably, the titanium tetrachloride solution is the aqueous solution of titanium tetrachloride, the molar concentration of titanium tetrachloride in aqueous solution
For 0.03~0.08mol/L.The TiCl of the concentration4Aqueous solution heat treatment can effectively reduce or eliminate TiO2Barrier film
Internal defect, and have some improvement for the flatness of film surface；And concentration is too low, does not have and effectively changes
Kind effect, excessive concentration can then be easy to happen TiCl4Hydrolysis, to destroy TiO2Barrier film surface texture.
Doping TiO of the invention2Technical solution used by barrier film are as follows:
It is a kind of by above-mentioned doping TiO2The preparation method of barrier film is obtained to adulterate TiO2Barrier film.
Doping TiO of the invention2Barrier film is made, the hole of uniform free from flaw and film using above-mentioned preparation method
Gap rate is low, and film is stronger in conjunction with substrate, the titanium dioxide that can be used between substrate and mesoporous titanium dioxide film
Barrier layer, obtained doping TiO2Barrier film material belongs to oxide semiconductor material, can be used as compacted zone or resistance
Barrier film is applied in semiconductor photoelectric device, such as solar battery light anode film, photocatalytic device film.
Detailed description of the invention
Fig. 1 is doping TiO of the invention2Doping TiO in the embodiment 1 of barrier film2The Flied emission of barrier film
Scanning electron microscope image；
Fig. 2 is the doping TiO in comparative example 1 of the invention2The field emission scanning electron microscope image of barrier film.
Specific embodiment
Doping TiO provided by the invention2The preparation method of barrier film, includes the following steps:
1) titanium alloy thin films are prepared in substrate by physical vaporous deposition, then there are titanium alloy thin films obtained
Thermal oxidative reaction is carried out in oxygen atmosphere；
2) film after thermal oxidative reaction in step 1) is impregnated in 80~100 DEG C of titanium tetrachloride solution, i.e.,
?.
Preferably, the substrate is conductive substrates.The conductive substrates are that surface is deposited with transparent conductive oxide film
Glass, i.e. TCO glass can be ito glass, FTO glass or AZO glass.
Preferably, the temperature of the thermal oxidative reaction is 400~600 DEG C.The time of the thermal oxidative reaction be 0.5~
2.0h。
Preferably, the time that the film after thermal oxidative reaction is impregnated in titanium tetrachloride solution is 30~60min.
Preferably, the titanium alloy thin films are made of titanium and nickel.It is further preferred that in titanium alloy thin films titanium and nickel matter
Amount is than being 95~99:1~5.
Preferably, the physical vaporous deposition is magnetron sputtering method.
Preferably, the magnetron sputtering method is magnetically controlled DC sputtering.
Control can be carried out by time, power, operating air pressure and the target-substrate distance etc. of regulation magnetron sputtering by control to mix
Miscellaneous TiO2The thickness of barrier film.Preferably, the sputtering control condition of the magnetically controlled DC sputtering includes: that sputtering power is
100~150W, operating air pressure are 0.5~0.6Pa, and sputtering time is 5~30min.The electricity used during magnetically controlled DC sputtering
Stream is not fixed with voltage, but as long as the corresponding power obtained after product is in claimed range.
The sputtering time can be more preferably 5~10min.The working gas is argon gas.Preferably, working gas
Flow is 30~50sccm.Preferably, background vacuum is controlled during magnetically controlled DC sputtering be not more than 10-4Pa.Preferably, directly
Flowing control base reservoir temperature in magnetron sputtering process is 15~30 DEG C.Preferably, during magnetically controlled DC sputtering, target-substrate distance be 60~
80mm。
Preferably, step 1) further include using direct current magnetron sputtering process in substrate before deposited titanium alloys film, to
Pre-sputtering is carried out in the target of magnetically controlled DC sputtering.The control condition of pre-sputtering can be consistent with magnetically controlled DC sputtering.It is excellent
Choosing, the time of the pre-sputtering is 10~15min.
Preferably, the target that the magnetron sputtering method uses is titanium alloy target.Alloy member in the titanium alloy target
Element is nonmetalloid and/or the metallic element in addition to titanium.The metallic element can be selected from rare earth element.It is further preferred that
The titanium alloy target can be selected from binary, ternary or multielement titanium alloy.Each alloying element accounts for the matter of the titanium alloy target
Measuring score is 1%~5%.Still more preferably, the titanium alloy target is the titanium nickel of nickeliferous 1%~5% (mass fraction)
Alloy.
Preferably, described to be made of at least one of nitrogen, inert gas with oxygen oxygen atmosphere；The oxygen accounts for institute
The volume fraction for stating oxygen atmosphere is 20~90%.
Preferably, the titanium tetrachloride solution is the aqueous solution of titanium tetrachloride.The molar concentration of titanium tetrachloride in aqueous solution
For 0.03~0.08mol/L.
Preferably, step 1) further includes cleaning the film after thermal oxidative reaction.The cleaning is to be placed in film
15~25min is ultrasonically treated in cleaning agent.The cleaning agent used that cleans is ethyl alcohol.Preferably, step 1) further include will be clear
Film after washing dries at room temperature.
Preferably, step 1) further includes that will wash after titanium alloy thin films before thermal oxidative reaction.It is described washing be by
Titanium alloy thin films are placed in 3~8min of ultrasonic treatment in detergent.The detergent is ethyl alcohol.Preferably, step 1) further include by
Titanium alloy thin films after washing are dried at room temperature.
Preferably, step 2) further includes that will be dried after film cleaning processed in titanium tetrachloride solution.
Step 2) clean the detergent used as water.It is described to be dried to dry.
Below in conjunction with specific embodiment, further description of the technical solution of the present invention.
In following embodiment, Examples 1 to 6 is doping TiO2The embodiment of the preparation method of barrier film, embodiment 7
To adulterate TiO2The embodiment of barrier film.
The purity of the pure argon used in Examples 1 to 6 is 99.99%, and the titanium alloy target of use is according to composition by phase
The metal powder answered is made after mixing using hot isostatic pressing method.
Embodiment 1
The doping TiO of the present embodiment2The preparation method of barrier film, comprising the following steps:
1) FTO glass conductive substrates and titanium alloy target are placed in the sputtering chamber of magnetron sputtering coater, will be sputtered
Chamber is evacuated to 10-4The background vacuum of Pa, is passed through pure argon, and the gas flowmeter for adjusting pure argon keeps sputtering chamber
In the sputtering operating air pressure of 0.55Pa, sputtering power is set as 120W, and adjustment target-substrate distance is 70cm, is carried out to titanium alloy target
The pre-sputtering of 15min, then uses direct current magnetron sputtering process under pre-sputtering control condition above-mentioned, and the temperature for controlling substrate is
Room temperature deposited titanium alloys film in substrate, sedimentation time 10min；Used titanium alloy target is that 3wt% nickel (Ni) mixes
Miscellaneous Ti-Ni alloy (Ti97Ni3)。
2) the Ti-Ni alloy film deposited is cleaned by ultrasonic 20min in dehydrated alcohol, and drying is placed in ceramic crucible,
It is put into high temperature sintering furnace in the mixed atmosphere that nitrogen oxygen ratio (i.e. the volume ratio of nitrogen and oxygen, similarly hereinafter) is 7:3 in 450 DEG C of heat
Aoxidize 30min.Ultrasound 5min in dehydrated alcohol is placed into after thermal oxide, later in 80 DEG C of TiCl4It is impregnated in aqueous solution
30min is finally cleaned and is dried with deionized water, obtains the TiO of Ni doping2Barrier film to get；Used TiCl4Water
The molar concentration of solution is 0.05mol/L.
Embodiment 2
The doping TiO of the present embodiment2The preparation method of barrier film, the difference with embodiment 1 are only that: in step 1)
Sedimentation time be 20min.
Embodiment 3
The doping TiO of the present embodiment2The preparation method of barrier film, the difference with embodiment 1 are only that: in step 1)
Sedimentation time be 30min.
Embodiment 4
The doping TiO of the present embodiment2The preparation method of barrier film, the difference with embodiment 1 are only that: step 1)
In, the sputtering power set is 100W, sedimentation time 5min.
Embodiment 5
The doping TiO of the present embodiment2The preparation method of barrier film, comprising the following steps:
1) FTO glass conductive substrates and titanium alloy target are placed in the sputtering chamber of magnetron sputtering coater, will be sputtered
Chamber is evacuated to 10-4The background vacuum of Pa, is passed through pure argon, and the gas flowmeter for adjusting pure argon keeps sputtering chamber
In the sputtering operating air pressure of 0.5Pa, sputtering power is set as 150W, and adjustment target-substrate distance is 60cm, is carried out to titanium alloy target
The pre-sputtering of 10min, then uses direct current magnetron sputtering process under pre-sputtering control condition above-mentioned, and the temperature for controlling substrate is
Room temperature deposited titanium alloys film in substrate, sedimentation time 15min；Used titanium alloy target is that 1wt% nickel (Ni) mixes
Miscellaneous Ti-Ni alloy (Ti99Ni1)。
2) the Ti-Ni alloy film deposited is cleaned by ultrasonic 15min in dehydrated alcohol, and drying is placed in ceramic crucible,
Be put into high temperature sintering furnace nitrogen oxygen than in the mixed atmosphere for 8:2 in 400 DEG C of thermal oxide 120min.It is put again after thermal oxide
Enter ultrasound 5min in dehydrated alcohol, later in 100 DEG C of TiCl460min is impregnated in aqueous solution, is finally cleaned simultaneously with deionized water
It dries, obtains the TiO of Ni doping2Barrier film to get；Used TiCl4The molar concentration of aqueous solution is 0.03mol/L.
Embodiment 6
The doping TiO of the present embodiment2The preparation method of barrier film, comprising the following steps:
1) FTO glass conductive substrates and titanium alloy target are placed in the sputtering chamber of magnetron sputtering coater, will be sputtered
Chamber is evacuated to 10-4The background vacuum of Pa, is passed through pure argon, and the gas flowmeter for adjusting pure argon keeps sputtering chamber
In the sputtering operating air pressure of 0.6Pa, sputtering power is set as 140W, and adjustment target-substrate distance is 80cm, is carried out to titanium alloy target
The pre-sputtering of 15min, then uses direct current magnetron sputtering process under pre-sputtering control condition above-mentioned, and the temperature for controlling substrate is
Room temperature deposited titanium alloys film in substrate, sedimentation time 25min；Used titanium alloy target is that 5wt% nickel (Ni) mixes
Miscellaneous Ti-Ni alloy (Ti95Ni5)。
2) the Ti-Ni alloy film deposited is cleaned by ultrasonic 25min in dehydrated alcohol, and drying is placed in ceramic crucible,
Be put into high temperature sintering furnace nitrogen oxygen than in the mixed atmosphere for 1:9 in 600 DEG C of thermal oxide 30min.It is put again after thermal oxide
Enter ultrasound 8min in dehydrated alcohol, later in 80 DEG C of TiCl460min is impregnated in aqueous solution, is finally cleaned simultaneously with deionized water
It dries, obtains the TiO of Ni doping2Barrier film to get；Used TiCl4The molar concentration of aqueous solution is 0.08mol/L.
Embodiment 7
The doping TiO of the present embodiment2Barrier film is respectively adopted the preparation method in above-described embodiment 1~6 and is made, this
Place repeats no more.
Comparative example 1
The TiO of this comparative example2The preparation method of barrier film, comprising the following steps:
1) FTO glass conductive substrates and pure titanium metal target are placed in the sputtering chamber of magnetron sputtering coater, will be splashed
It penetrates chamber and is evacuated to 10-4The background vacuum of Pa, is passed through pure argon, and the gas flowmeter for adjusting pure argon protects sputtering chamber
The sputtering operating air pressure in 0.55Pa is held, sputtering power is set as 120W, the pre-sputtering of 15min is carried out to pure titanium metal target,
Then direct current magnetron sputtering process is used under pre-sputtering control condition above-mentioned, the temperature for controlling substrate is that room temperature is sunk in substrate
The pure titanium film of product, sedimentation time 10min.
2) the pure titanium film deposited is cleaned by ultrasonic 20min in dehydrated alcohol, and drying is placed in ceramic crucible, is put into
In high temperature sintering furnace nitrogen oxygen than in the mixed atmosphere for 7:3 in 450 DEG C of thermal oxide 30min.Nothing is placed into after thermal oxide
Ultrasound 5min in water-ethanol, later in 80 DEG C of TiCl430min is impregnated in aqueous solution, is finally cleaned and is dried with deionized water,
Obtain pure TiO2Barrier film to get；Used TiCl4The molar concentration of aqueous solution is 0.05mol/L.
Comparative example 2
The TiO of this comparative example2The preparation method of barrier film, the TiO with comparative example 12The preparation method of barrier film
Difference be only that: the sputtering power set in step 1) is 100W, sedimentation time 5min.
Experimental example 1
Detect doping TiO obtained in Examples 1 to 6 respectively using field emission scanning electron microscope2Barrier film and comparison
TiO obtained in example 1~22The surface topography of barrier film, wherein doping TiO obtained in embodiment 12Barrier film
Shape appearance figure is shown in Fig. 1, TiO obtained in comparative example 12The surface topography of barrier film is shown in Fig. 2.As the result is shown:
TiO is adulterated using Ni made from preparation method of the invention in Examples 1 to 62The grain diameter of barrier film
About 30~100nm adulterates TiO2Barrier film thickness about 250nm, and adulterate TiO2Barrier film dense uniform is without splitting
Line, porosity is extremely low, and about 8.3%.And pure TiO obtained in comparative example 1~22The grain diameter of barrier film is about 100
~200nm, pure TiO2Barrier film thickness about 300nm, film surface compactness is poor and has micro-crack, porosity also compared with
Height reaches 28.6%.
According to doping TiO obtained in Examples 1 to 62The surface topography of barrier film is it is found that using system of the invention
The TiO of the doping of Ni made from Preparation Method2The grain diameter of barrier film is increased slightly with the extension of sputtering sedimentation time, thin
Film thickness increases obvious.But with the extension of sputtering sedimentation time, film compactness decreases, and micro-crack gradually increases, hole
Gap rate is also gradually increased.
Experimental example 2
Doping TiO obtained in above-described embodiment 1~6 is detected respectively2Barrier film is with pure made from comparative example 1~2
TiO2Resistivity, conductivity and the electron transfer rate of barrier film, the results are shown in Table 1.
Resistivity, conductivity and the electron transfer rate of film obtained in 1 Examples 1 to 6 of table and comparative example 1~2
By data in table 1 it is found that doping TiO of the invention2The pure TiO of barrier film compared to the prior art2Barrier layer
Film has many advantages, such as that resistivity is low, conductivity is high, electron transfer rate is big, and the improvement of these performances is the longevity for improving electronics
Life extends electronics transportation range and further increases the photoelectric properties of film and haves laid a good foundation.
Claims (10)
1. a kind of doping TiO2The preparation method of barrier film, characterized by the following steps:
1) titanium alloy thin films are prepared in substrate by physical vaporous deposition, titanium alloy thin films obtained is then being had into oxygen
Thermal oxidative reaction is carried out in atmosphere；
2) film after thermal oxidative reaction in step 1) is impregnated in 80~100 DEG C of titanium tetrachloride solution to get.
2. doping TiO according to claim 12The preparation method of barrier film, it is characterised in that: the thermal oxide is anti-
It should be 0.5~2.0h of oxidation at 400~600 DEG C.
3. doping TiO according to claim 12The preparation method of barrier film, it is characterised in that: the titanium alloy is thin
Film is made of titanium and nickel；The mass ratio of titanium and nickel is 95~99:5~1.
4. doping TiO according to any one of claims 1 to 32The preparation method of barrier film, it is characterised in that:
The physical vaporous deposition is magnetron sputtering method.
5. doping TiO according to claim 42The preparation method of barrier film, it is characterised in that: the magnetron sputtering
Method is magnetically controlled DC sputtering.
6. doping TiO according to claim 52The preparation method of barrier film, it is characterised in that: the direct magnetic control
The sputtering control condition of sputtering include: base reservoir temperature be 15~30 DEG C, sputtering power be 100~150W, operating air pressure be 0.5~
0.6Pa, sputtering time are 5~30min.
7. doping TiO according to claim 42The preparation method of barrier film, it is characterised in that: the magnetron sputtering
The target that method uses is titanium alloy target；The titanium alloy target is the Ti-Ni alloy of nickeliferous 1%~5% (mass fraction).
8. doping TiO according to claim 12The preparation method of barrier film, it is characterised in that: described to have oxygen atmosphere
It is made of at least one of nitrogen, inert gas with oxygen；The oxygen account for the volume fraction for having oxygen atmosphere be 20~
90%.
9. doping TiO according to claim 12The preparation method of barrier film, it is characterised in that: the titanium tetrachloride
Solution is the aqueous solution of titanium tetrachloride, and the molar concentration of titanium tetrachloride is 0.03~0.08mol/L in aqueous solution.
10. one kind is by doping TiO described in claim 12The preparation method of barrier film is obtained to adulterate TiO2Barrier layer is thin
Film.
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