CN107815665A - A kind of titanium deoxid film and its preparation method and application - Google Patents
A kind of titanium deoxid film and its preparation method and application Download PDFInfo
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- CN107815665A CN107815665A CN201610826139.0A CN201610826139A CN107815665A CN 107815665 A CN107815665 A CN 107815665A CN 201610826139 A CN201610826139 A CN 201610826139A CN 107815665 A CN107815665 A CN 107815665A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
Abstract
The present invention relates to a kind of titanium deoxid film and its preparation method and application, it is to utilize technique for atomic layer deposition, using containing titanium precursors and oxygen-containing presoma respectively as titanium source and oxygen source, obtained after carrying out ultraviolet irradiation after the titanium deoxid film that substrate surface deposits to obtain, the titanium deoxid film is polycrystalline titanium deoxid film, and crystalline phase is pure Anatase.The present invention prepares anatase titanium dioxide film using technique for atomic layer deposition, has excellent biocompatibility, excellent anti-microbial property can be obtained after ultraviolet light irradiation.
Description
Technical field
The present invention relates to a kind of biocompatibility and the titanium deoxid film of excellent antibacterial performance and preparation method thereof and answer
With being to be related to a kind of to deposit anatase in substrate surfaces such as silicon, titanium alloy, stainless steels using technique for atomic layer deposition specifically
The method of type titanium deoxid film, belong to medical bio coating technology field.
Background technology
Due to reasons such as aging population, motion and traffic accidents, the demand of bone implant material is increasing.Titanium and its conjunction
Gold is conventional bone implant material, has good biocompatibility, chemical stability and corrosion resistance.It is reported that titanium alloy this
A little superior functions are all attributed to oxide-film (TiO existing for surface2).But the oxide thickness of self-assembling formation is too small (about 5nm),
Once being penetrated by body fluid, substrate will be caused exposed, accelerated corrosion, do harm to huamn body.Therefore, a kind of biocompatibility is studied
It is excellent, and bond strength is high, not flaky coating of titanium dioxide is significant.
The existing method for preparing titanium dioxide biological coating has：Sol-gal process, vapour deposition process, liquid-phase precipitation method, etc.
Plasma spray method etc., it is low bond strength to be present, easily peels off, is not easy accurately to control coating morphology, technological temperature high, easily causes base material
The problems such as damage.
Another requirement of bone implant material is that possess certain anti-microbial property, prevents postoperative infection.Hand is implanted into orthopaedics
In art, implant infection is to cause operative failure one of the main reasons.Wherein due in air pollution, art pollution etc. reason cause
Early postoperation infection can not be ignored.Postoperative infection not only extends the healing time of wound, damages the using effect of implant, sternly
The disability and dysfunction of limbs, or even amputation and threat to life can be also caused during weight.Therefore, it is excellent to assign titanium deoxid film
Anti-microbial property it is significant.
In order to improve the antibiotic property of coating of titanium dioxide, antiseptic such as Ag, Zn etc. can be added in the coating；It can also prepare
The coating of titanium dioxide of nonmetalloid (N, P, B etc.) doping, reduces TiO2Band gap width, improve photocatalysis antibacterial performance.
But there is the shortcomings of toxic metals Ion release, preparation technology complexity in above two method.
The content of the invention
The defects of in order to solve the problems, such as in the presence of prior art, there is provided one kind has excellent biocompatibility and antibiotic property
Film of energy and preparation method thereof.
On the one hand, it is to utilize technique for atomic layer deposition, using containing titanium precursor the invention provides a kind of titanium deoxid film
Body and oxygen-containing presoma carry out ultraviolet photograph respectively as titanium source and oxygen source after the titanium deoxid film that substrate surface deposits to obtain
Obtained after penetrating, the titanium deoxid film is polycrystalline titanium deoxid film, and crystalline phase is pure Anatase.
The present invention utilize technique for atomic layer deposition, using containing titanium precursors and oxygen-containing presoma respectively as titanium source and oxygen
Source, anatase titanium dioxide film is deposited in substrate surface.Prepare titanium deoxid film using technique for atomic layer deposition, have with
Under it is several prominent the advantages of：1) step coverage of film is good, is suitable in three-dimensional implant surfaces homogeneous film formation；2) film causes
It is close, it is high with base material bond strength, it is not easy to be penetrated by body fluid, preferably base material can be protected not corroded, prevent base material ion
Dissolution damages to human body；3) thickness of film accurately controls, favorable repeatability；4) depositing temperature is low, will not cause base
Material melts damage.Moreover, the titanium deoxid film being prepared using technique for atomic layer deposition, its crystallite dimension is in nanoscale (5
~250nm).Due to quantum size effect, titanium dioxide energy gap broadens, oxidation-reduction potential increase, the driving force of light-catalyzed reaction
Increase, its photocatalytic activity is caused to improve.Therefore the nano-titanium dioxide film that technique for atomic layer deposition obtains is through ultraviolet irradiation
Light induced electron and hole are more also easy to produce afterwards, with the O in environment2、H2The reactions such as O produce superoxide anion, hydroxyl radical free radical isoreactivity
Oxygen, active oxygen can destroy cell membrane, mitochondria, protein and the DNA of bacterium, play bactericidal effect.Using ald
The nano-titanium dioxide film that technology obtains, the advantage is that after ultraviolet irradiation, produces more active oxygen, is transferred to dark
There is certain antibiotic property after in environment, it is a kind of possible so as to be provided for the early infection of prevention orthopaedics implant surgery.Therefore, originally
Invention using technique for atomic layer deposition prepares anatase titanium dioxide film, has an excellent biocompatibility, and process is ultraviolet
Excellent anti-microbial property can be obtained after light irradiation.Moreover, the titanium deoxid film of the present invention is polycrystalline Anatase.Anatase
Than TiO2Other crystalline phases have more preferable photocatalytic activity, therefore possess higher sterilizing ability after ultraviolet irradiation.
It is preferred that the thickness of the polycrystalline titanium deoxid film is 10~200nm.
It is preferred that the base material is one kind in silicon, titanium alloy, stainless steel.
It is preferred that the titanium precursors that contain are at least one of Titanium alkoxides, titanium halide, titanium alkylamide.Preferably
TiCl4.Reason is TiCl4Have that saturated vapor pressure is suitable, sedimentation rate is high, without organic than Titanium alkoxides and titanium alkylamide
The advantages that thing remains.
It is preferred that the oxygen-containing presoma is H2O、O3、H2O2At least one of.
It is preferred that the ultraviolet light 5~200 minutes using 240~380nm of wavelength.After ultraviolet irradiation, produce more
Active oxygen, be transferred in dark surrounds after there is certain antibiotic property, so as to prevent the early stage of orthopaedics implant surgery feel
Dye.
On the other hand, present invention also offers a kind of method that titanium deoxid film is prepared using technique for atomic layer deposition,
Including：
(1) after the reative cell of atomic layer deposition apparatus is vacuumized, then the base material is placed in reative cell and it is heated to 180~
250 DEG C, preferably greater than 180 DEG C and≤250 DEG C；
(2) gaseous state is passed through into reative cell and contains 100~1000 milliseconds of titanium precursors, then the inertia with flow velocity for 100~300sccm
Gas once purges 1~7 second；
(3) 100~1000 milliseconds of the oxygen-containing presoma of gaseous state is passed through into reative cell again, is finally that 100~300sccm is lazy with flow velocity
Property gas it is secondary purging 1~7 second, complete primary depositing circulation；
(4) deposition cycles of repeat step (2)-(3) once more than control the thickness of film.The present invention passes through ald
Pure anatase phase titanium dioxide is prepared in technology.
In one preferred embodiment, the present invention uses TiCl4And H2O is deposited, and technical process is as follows：By base
After material is placed in reative cell, reative cell is vacuumized.TiCl is passed through into reative cell4, TiCl4Absorption is in substrate surface.Inertia is used again
Gas is once purged, and individual layer TiCl is left to substrate surface4Molecule.Vapor is passed through into reative cell again, with TiCl4Reaction, it is raw
Into TiO2.Reaction principle (net reaction) is as follows：TiCl4+2H2O→TiO2+4HCl..Followed in turn by the secondary purging of inert gas,
Unreacted presoma and byproduct of reaction are removed, as a circulation, film can be controlled by controlling cycle-index
Thickness.
It is preferred that the vacuum is 5~10mbr.
It is preferred that the inert gas is Ar or N2At least one of.
Another further aspect, present invention also offers a kind of titanium deoxid film answering in the reparation and alternate material of sclerous tissues
With.
The present invention has the advantages that：1) biofilm provided by the invention has excellent biocompatibility, warp
Excellent anti-microbial property can be obtained after crossing ultraviolet light irradiation；2) preparation method of the invention have simple to operate, depositing temperature is low,
Film bond strength is high, accurately control film thickness, can be uniform coated, the favorable repeatability on three-dimensional sample the advantages that.
Brief description of the drawings
Fig. 1 a-1d are that ald saturation time determines figure；
Fig. 2 is the XRD spectrum of film, wherein (a) is Anatase TiO prepared by embodiment 12, (b) be comparative example 1 prepare
Amorphous phase TiO2；, (c) be comparative example 2 prepare Rutile Type TiO2；
Fig. 3 is the stereoscan photograph of titanium deoxid film prepared by embodiment 1, and wherein a is film surface SEM photograph, b is thin
Film section SEM photograph；
Fig. 4 is the Anatase TiO of embodiment 12Rutile Type TiO prepared by film, comparative example 22Film and silicon substrate table
Face MC3T3-E1 cells a adhesions, b propagation, c differentiation and d mineralizations；
Fig. 5 is antibacterial effect figure of the film to Escherichia coli, and wherein a is and visible bacterium, b after silicon substrate control group effect 24h
It is the rutile membrane action prepared with comparative example 2 for visible bacterium, c after the anatase membrane action 24h that is prepared with embodiment 1
Visible bacterium after 24h；
Fig. 6 is antibacterial effect figure of the film to staphylococcus aureus, and wherein a is visible with after silicon substrate control group effect 24h
Visible bacterium, c are that the rutile prepared with comparative example 2 is thin after bacterium, b are the anatase membrane action 24h prepared with embodiment 1
Visible bacterium after film effect 24h.
Embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention is by the way of technique for atomic layer deposition and ultraviolet irradiation technology are combined so that of the present invention two
Thin film of titanium oxide is both with compatibility also with antibiotic property.The present invention using containing titanium precursors such as Titanium alkoxides, titanium halide etc. and
Oxygen-containing presoma such as H2O、O3Deng respectively as titanium source and oxygen source, using technique for atomic layer deposition in base material (for example, silicon, titanium close
Gold, stainless steel etc.) surface deposit polycrystalline titanium deoxid film.Wherein, the crystalline phase of the polycrystalline titanium deoxid film is rutile titania
Ore deposit phase.
The preparation method of the present invention has that simple to operate, depositing temperature is low, film bond strength is high, accurately controls film
Thickness, can be the uniform coated on three-dimensional sample and favorable repeatability the advantages that.
Illustrate to following exemplary the method provided by the invention that titanium deoxid film is prepared using technique for atomic layer deposition.
After base material is placed in into the reative cell of atomic layer deposition apparatus, reative cell is evacuated to 5~10mbr, and by base material
It is heated to 180~250 DEG C.
It is passed through into reative cell containing 100~1000 milliseconds of titanium precursors so that be adsorbed in substrate surface containing titanium precursors.Again
Once purged with inert gas 1~7 second, individual layer titaniferous precursor molecule is left to substrate surface.Wherein containing titanium precursors with gas
Body form is passed through in reative cell, and its flow velocity can be 100~300sccm.
Oxygen-containing 100~1000 milliseconds of presoma is passed through into reative cell again, makes it with being reacted containing titanium precursors.Followed in turn by
The secondary purging of inert gas 1~7 second, removes unreacted presoma and byproduct of reaction.Wherein oxygen-containing presoma is with gas shape
Formula is passed through in reative cell, and its flow velocity can be 100~300sccm.
The present invention can be by controlling cycle-index (100~3000 times) to control the thickness of polycrystalline titanium deoxid film
(10~200nm).Above-mentioned inert gas is chosen as Ar or N2At least one of.The above-mentioned flow velocity for being passed through inert gas can be
100~300sccm.Wherein, it is to be passed through in gaseous form in reative cell containing titanium precursors and oxygen-containing presoma, is ventilated by controlling
Time and gas flow rate control the intake containing titanium precursors and oxygen-containing presoma.Flow velocity control of the invention by controlling gas
The saturation time of ald processed.One of ALD deposition key character is exactly that the speed of growth reaches one as the reaction time changes
Individual stationary value, corresponding time are saturation time.Ald will select saturation time without special circumstances, because the time
Not reaching saturation easily causes the endless all standing of film, and the time exceedes saturation time can destroy layer by layer deposition again.
Titanium deoxid film prepared by the present invention has excellent biocompatibility, (such as can make through ultraviolet light irradiation
With 240~380nm of wavelength ultraviolet light 5~200 minutes) after possess high antibiotic property in dark surrounds, promote hard group
Knit the development repaired with alternate material.
Experiment proves：MC3T3-E1 preosteoblasts are good in the adhesion of anatase film surface, propagation, differentiation and mineralising behavior
It is good.Film has obvious antibacterial effect, antibacterial after 100min ultraviolet lights, to Escherichia coli, staphylococcus aureus
Rate reaches more than 90%.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to is interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
A：Technique for atomic layer deposition prepares anatase film
(100) single crystal silicon substrate is successively cleaned with alcohol and deionized water in ultrasonic cleaner, dries, loads
In BENEQTFS-500 atomic layer deposition apparatus reative cells.6-8mbar is evacuated to, base material is heated to 200 DEG C, carries out TiO2
Deposition.TiCl is passed through into reative cell4500 milliseconds, then the inert gas for being 200sccm with flow velocity once purges 4 seconds.Again to
500 milliseconds of vapor is passed through in reative cell, is finally the secondary purging of 200sccm inert gases 4 seconds with flow velocity, completes primary depositing
Circulation.Circulation 1500 times.After deposition terminates, it is inflated in settling chamber and recovers an atmospheric pressure, sample is taken out, is cooled down, it is standby.
Time is passed through and after Ar purge times reach certain value by precursor it can be seen from Fig. 1 a-1d, sedimentation rate reaches
To stabilization, the time is defined as ald saturation time, i.e. TiCl4/Ar/H2O/Ar=500ms/4s/500ms/4s.ALD
One of deposition key character is exactly as the reaction time changes, and the speed of growth reaches a stationary value, and the corresponding time is full
And the time.Ald should when saturated between it is lower carry out, can so realize the self-limiting growth behavior of ald, protect
Demonstrate,prove film quality.The XRD spectrum of film in Fig. 2 shown in (a)：Gained film is pure Anatase, and 2 θ=25.3 ° are right
Answer anatase (101) crystal face；Corresponding anatase (200) crystal face in 2 θ=47.7 °.
Fig. 3 is the surface a and section SEM pattern photos b of anatase film, it can be seen that film densification is homogeneous, and thickness is equal
It is even, about 120nm, base material is covered good.
B：Anatase film surface cell compatibility is tested
Cell adherence, propagation, differentiation and mineralization experiments are carried out using mouse preosteoblast MC3T3-E1.
1) cell adherence
After Si base materials (control group) and anatase film (experimental group) steam sterilizing disinfecting, 24 porocyte culture plates are carefully placed in
In.Collect the good MC3T3-E1 cells of growth conditions, after digesting and adjusting concentration of cell suspension, take 1mL cell suspensions (3 ×
103Individual cell/mL) it is planted in each hole sample surfaces.37 DEG C, 5%CO2After cultivating 4h, 8h and 12h respectively in cell culture incubator, abandon
Remove nutrient solution.0.5mL fresh mediums and 0.05mL CCK-8 solution are separately added into per hole.37 DEG C, 5%CO2Cell culture incubator
In continue cultivate 3h after, carefully each hole solution is suctioned out and added in 96 orifice plates；Each hole is measured at 450nm using ELIASA
OD values.
2) cell is bred
After Si base materials (control group) and anatase film (experimental group) steam sterilizing disinfecting, 24 porocyte culture plates are carefully placed in
In.Collect the good MC3T3-E1 cells of growth conditions, after digesting and adjusting concentration of cell suspension, take 1mL cell suspensions (1 ×
104Individual cell/mL) it is planted in each hole sample surfaces.37 DEG C, 5%CO2After cultivating 1,4 and 7 day in cell culture incubator respectively, discard
Nutrient solution.0.5mL fresh mediums and 0.05mL CCK-8 solution are separately added into per hole.37 DEG C, 5%CO2In cell culture incubator
Continue after cultivating 3h, carefully each hole solution is suctioned out and added in 96 orifice plates；The OD in each hole is measured at 450nm using ELIASA
Value.
3) cell differentiation：ALP is quantitatively detected
After Si base materials (control group) and anatase film (experimental group) steam sterilizing disinfecting, 24 porocyte culture plates are carefully placed in
In.Collect the good MC3T3-E1 cells of growth conditions, after digesting and adjusting concentration of cell suspension, take 1mL cell suspensions (1 ×
105Individual cell/mL) it is planted in each hole sample surfaces.37 DEG C, 5%CO2After cultivating 4,7 and 14 days in cell culture incubator respectively, abandon
Nutrient solution is removed, PBS is washed 2 times.300 μ L 0.1%Triton X-100 (PBS dilutions) are separately added into per hole.Inhaled repeatedly with pipette tips
After taking piping and druming sample surfaces, liquid in hole and foam are drawn to EP together and manage interior centrifuge.Prepare Chromogenic Substrate Solution and standard
Product working solution (0.5mM)；Blank control wells, standard sample wells and sample well are set using 96 orifice plates with reference to following table.The use of standard items
Amount is respectively 4,8,16,24,32 and 40 μ L；
After liquid being mixed by shaking table (50rpm/min), 37 DEG C of incubation 10min.100 μ L terminate liquids are added per hole；Utilize
ELIASA determines absorbance at 405nm.After total protein concentration is normalized, ALP quantitative results are obtained.
4) cell mineralising：Alizarin red staining quantitatively detects
After Si base materials (control group) and anatase film (experimental group) steam sterilizing disinfecting, 24 porocyte culture plates are carefully placed in
In.Collect the good MC3T3-E1 cells of growth conditions, after digesting and adjusting concentration of cell suspension, take 1mL cell suspensions (1 ×
105Individual cell/mL) it is planted in each hole sample surfaces.37 DEG C, 5%CO2After cultivating 4,7 and 14 days in cell culture incubator respectively, abandon
Nutrient solution is removed, PBS is washed 2 times.The paraformaldehyde solutions of 1mL 4%, 4 DEG C of incubation 15min are separately added into per hole；Abandoning supernatant,
After PBS is washed 3 times, 500 μ L alizarin red dye liquors are added per hole, are incubated at room temperature 20min；Abandoning supernatant, after PBS is washed 3 times, often
Hole adds 500 μ L10% cetylpyridinium chloride solution, is incubated at room temperature 15min.OD is determined at 590nm using ELIASA
Value.
As seen from Figure 4, MC3T3-E1 preosteoblasts are in the adhesion of anatase film surface, propagation, differentiation and mineralising
Ability is significantly better than that Si base material control groups, it was demonstrated that anatase film has preferable cell compatibility.
C：The antibiotic property experiment of anatase film
Using the anti-microbial property of colony counting method detection material：Using Escherichia coli, staphylococcus aureus as experiment strain.
Before inoculation, Si base materials (control group) are sterilized 5 minutes using ultraviolet sterilization lamp, and anatase film (experimental group) uses wavelength 254nm
Ultraviolet light irradiation 100 minutes.Take strain to be inoculated in Liquid Culture primary surface, 37 DEG C of cultures in vibration culture oven, turn per 12h
Connect once, experiment is using the Fresh bacterial after continuous switching twice；Bacterium solution is diluted to 10 using PBS6CFU/ml.Si base materials and
100 μ l bacterium solutions, 37 DEG C of insulation 24h are respectively added dropwise in anatase film surface.Sample is put into the test tube equipped with 9.9ml PBS respectively
In, vibrate 1 minute, carry out 10-2Dilution, respectively takes 0.1ml to be inoculated on fluid nutrient medium, cultivates 24h.
Fig. 5 b, Fig. 6 b are antibacterial effect figure of the anatase film to Escherichia coli, staphylococcus aureus respectively, with compareing
Group Fig. 5 a compare with Fig. 6 b, and anatase film has obvious antibacterial effect, and antibiotic rate reaches more than 90%.
Embodiment 2
Technique for atomic layer deposition prepares anatase film
Base material is used as using titanium alloy thick Φ 10mm × 2mm, successively with alcohol and deionized water in ultrasonic cleaner clearly
Wash, dry, load in BENEQ TFS-500 atomic layer deposition apparatus reative cells.6-8mbar is evacuated to, base material is heated to
200 DEG C, carry out TiO2Deposition.TiCl is passed through into reative cell4500 milliseconds, then with flow velocity be 200sccm inert gas once
Purging 4 seconds.500 milliseconds of vapor is passed through into reative cell again, is finally the secondary purging of 200sccm inert gases 4 seconds with flow velocity,
Complete primary depositing circulation.Circulation 800 times.After deposition terminates, it is inflated in settling chamber and recovers an atmospheric pressure, obtain anatase
The titanium alloy sample of phase film covering.
Comparative example 1
Technique for atomic layer deposition prepares amorphous TiO2Film
(100) single crystal silicon substrate is successively cleaned with alcohol and deionized water in ultrasonic cleaner, dries, loads BENEQ
In TFS-500 atomic layer deposition apparatus reative cells.6-8mbar is evacuated to, base material is heated to 150 DEG C, carries out TiO2Deposition.
TiCl is passed through into reative cell4500 milliseconds, then the inert gas for being 200sccm with flow velocity once purges 4 seconds.Again to reative cell
500 milliseconds of vapor is inside passed through, is finally the secondary purging of 200sccm inert gases 4 seconds with flow velocity, completes primary depositing circulation.
Circulation 500 times.After deposition terminates, it is inflated in settling chamber and recovers an atmospheric pressure, sample is taken out, is cooled down, it is standby.
From the XRD spectrum of the film shown in Fig. 2 (b)：Gained film is amorphous phase.Illustrate to deposit nothing at 150 DEG C
Method obtains pure Anatase TiO2Film.
Comparative example 2
A：Technique for atomic layer deposition combination subsequent annealing process prepares rutile film
Atomic layer deposition method and parameter are with embodiment 1, and difference is by gained anatase film at 1000 DEG C, air
Anneal 1h in atmosphere, and Anatase is completely transformed into Rutile Type, obtains pure rutile phase film.The surface shape of annealing rear film
Looks and crystallite dimension are without significant change.
The XRD spectrum of film in Fig. 2 shown in (c)：Gained film is pure rutile phase, 2 θ=27.38 ° correspondences
Rutile (110) crystal face；Corresponding rutile (220) crystal face in 2 θ=57.3 °.
B：Rutile film surface cell compatibility is tested
From fig. 4, it can be seen that MC3T3-E1 preosteoblasts are excellent in the adhesion of rutile film surface, propagation, differentiation and mineralization ability
In Si base material control groups, but not as good as anatase film.Prove that anatase film has more preferable cell phase than rutile film
Capacitive.
C：The antibiotic property experiment of rutile film
Wavelength 254nm ultraviolet light irradiation is equally used gained rutile film (comparative example 2) to carry out antibiotic property after 100 minutes
Experiment.Fig. 5 c, Fig. 6 c are that rutile film prepared by comparative example 2 is imitated to the antibacterial of Escherichia coli, staphylococcus aureus respectively
Fruit is schemed, it is seen then that rutile film has certain antibiotic property, but antibiotic property is relatively low.Further prove anatase film than gold
Red stone film has more preferable anti-microbial property.
Claims (10)
- A kind of 1. titanium deoxid film, it is characterised in that be to utilize technique for atomic layer deposition, using containing titanium precursors and it is oxygen-containing before Body is driven respectively as titanium source and oxygen source, is obtained after carrying out ultraviolet irradiation after the titanium deoxid film that substrate surface deposits to obtain, The titanium deoxid film is polycrystalline titanium deoxid film, and crystalline phase is pure Anatase.
- 2. titanium deoxid film according to claim 1, it is characterised in that the titanium precursors that contain are Titanium alkoxides, titanium halogen At least one of compound, titanium alkylamide, preferably TiCl4。
- 3. titanium deoxid film according to claim 1 or 2, it is characterised in that the oxygen-containing presoma is H2O、O3、H2O2 At least one of.
- 4. according to the titanium deoxid film any one of claim 1-3, it is characterised in that more crystal titanium dioxides are thin The thickness of film is 10~200nm.
- 5. according to the titanium deoxid film any one of claim 1-4, it is characterised in that the base material is silicon, titanium conjunction One kind in gold, stainless steel.
- 6. according to the titanium deoxid film any one of claim 1-5, it is characterised in that use 240~380nm of wavelength Ultraviolet light 5~200 minutes.
- A kind of 7. method that titanium deoxid film is prepared using technique for atomic layer deposition, it is characterised in that including：（1）After the reative cell of atomic layer deposition apparatus is vacuumized, then the base material is placed in reative cell and it is heated to 180~ 250℃；（2）Gaseous state is passed through into reative cell and contains 100~1000 milliseconds of titanium precursors, then the inertia with flow velocity for 100~300sccm Gas once purges 1~7 second；（3）100~1000 milliseconds of the oxygen-containing presoma of gaseous state is passed through into reative cell again, is finally that 100~300sccm is lazy with flow velocity Property gas it is secondary purging 1~7 second, complete primary depositing circulation；（4）Repeat step（2）-（3）Deposition cycle once more than control the thickness of film.
- 8. according to the method for claim 7, it is characterised in that the vacuum is 5~10mbr.
- 9. the method according to claim 7 or 8, it is characterised in that the inert gas is Ar or/and N2。
- 10. a kind of titanium deoxid film as any one of claim 1-6 is preparing the reparation of sclerous tissues with replacing material Application in material.
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