CN107815665A - A kind of titanium deoxid film and its preparation method and application - Google Patents

Abstract

The invention relates to a titanium dioxide thin film and its preparation method and application. It uses atomic layer deposition technology, adopts a titanium-containing precursor and an oxygen-containing precursor as a titanium source and an oxygen source respectively, and deposits a titanium dioxide thin film on the surface of a substrate. Obtained after ultraviolet irradiation, the titanium dioxide thin film is a polycrystalline titanium dioxide thin film, and the crystal phase is pure anatase phase. The invention adopts atomic layer deposition technology to prepare anatase titanium dioxide thin film, has excellent biocompatibility, and can obtain excellent antibacterial performance after being irradiated with ultraviolet light.

Description

A kind of titanium dioxide film and its preparation method and application

technical field

The present invention relates to a titanium dioxide thin film with excellent biocompatibility and antibacterial performance and its preparation method and application, specifically, it relates to a method of depositing anatase on the surface of silicon, titanium alloy, stainless steel and other substrates by using atomic layer deposition technology. The invention relates to a method for a type titanium dioxide thin film, which belongs to the technical field of medical biological coatings.

Background technique

Bone implant materials are in increasing demand due to reasons such as population aging, sports, and traffic accidents. Titanium and its alloys are commonly used bone implant materials with good biocompatibility, chemical stability and corrosion resistance. According to reports, these superior properties of titanium alloys are all attributed to the oxide film (TiO ₂ ) existing on the surface. However, the thickness of the naturally formed oxide film is too small (about 5nm). Once it is penetrated by body fluids, it will cause the substrate to be exposed, accelerate corrosion, and cause harm to the human body. Therefore, it is of great significance to study a titanium dioxide coating with excellent biocompatibility, high bonding strength, and not easy to peel off.

The existing methods for preparing titanium dioxide bio-coatings include: sol-gel method, vapor deposition method, liquid phase precipitation method, plasma spraying method, etc., which have low bonding strength, easy peeling, difficult to accurately control the coating morphology, and high process temperature. It is easy to cause problems such as substrate damage.

Another requirement for bone implant materials is to have certain antibacterial properties to prevent postoperative infection. In orthopedic implant surgery, implant infection is one of the main causes of surgical failure. Among them, the early postoperative infection caused by air pollution, intraoperative pollution and other reasons cannot be ignored. Postoperative infection not only prolongs the healing time of the wound, impairs the effect of the implant, but also causes disability and dysfunction of the limbs, even amputation and life-threatening. Therefore, it is of great significance to endow titanium dioxide thin films with excellent antibacterial properties.

In order to improve the antibacterial properties of titanium dioxide coatings, antibacterial agents such as Ag, Zn, etc. can be added to the coatings; titanium dioxide coatings doped with non-metallic elements (N, P, B, etc.) can also be prepared to reduce the band gap of _TiO2 Width, improve photocatalytic antibacterial performance. However, the above two methods have disadvantages such as the dissolution of toxic metal ions and complicated preparation processes.

Contents of the invention

In order to solve the defects in the prior art, a film with excellent biocompatibility and antibacterial performance and a preparation method thereof are provided.

On the one hand, the present invention provides a kind of titanium dioxide thin film, is to utilize atomic layer deposition technology, adopt titanium-containing precursor and oxygen-containing precursor as titanium source and oxygen source respectively, carry out ultraviolet irradiation after depositing the obtained titanium dioxide thin film on the substrate surface Finally, the titanium dioxide thin film is a polycrystalline titanium dioxide thin film, and the crystal phase is pure anatase phase.

The invention utilizes atomic layer deposition technology, adopts titanium-containing precursor and oxygen-containing precursor as titanium source and oxygen source respectively, and deposits anatase type titanium dioxide film on the surface of a base material. The use of atomic layer deposition technology to prepare titanium dioxide thin films has the following outstanding advantages: 1) The step coverage of the thin film is good, which is suitable for uniform film formation on the surface of three-dimensional implants; 2) The thin film is dense and has high bonding strength with the substrate. It is not easy to be penetrated by body fluids, and can better protect the substrate from corrosion and prevent the dissolution of substrate ions from causing harm to the human body; 3) The thickness of the film can be precisely controlled and the repeatability is good; 4) The deposition temperature is low and will not Cause substrate melting damage. Moreover, the titanium dioxide thin film prepared by atomic layer deposition technology has a grain size of nanoscale (5-250nm). Due to the quantum size effect, the energy gap of titania is widened, the redox potential is increased, and the driving force of the photocatalytic reaction is increased, leading to the improvement of its photocatalytic activity. Therefore, the nano-titanium dioxide film obtained by atomic layer deposition technology is more likely to generate photogenerated electrons and holes after ultraviolet irradiation, and react with O ₂ , H ₂ O in the environment to produce active oxygen such as superoxide anion and hydroxyl radical, which can destroy Bacterial cell membranes, mitochondria, proteins and DNA, play a bactericidal effect. The nano-titanium dioxide film obtained by atomic layer deposition technology has the advantage of producing more active oxygen after being irradiated by ultraviolet rays, and has certain antibacterial properties after being transferred to a dark environment, thus providing a means for preventing early infection in orthopedic implant surgery. possibility. Therefore, the present invention adopts the atomic layer deposition technique to prepare the anatase titanium dioxide thin film, which has excellent biocompatibility, and can obtain excellent antibacterial performance after being irradiated with ultraviolet light. Furthermore, the titanium dioxide thin film of the present invention has a polycrystalline anatase phase. Compared with other crystal phases of TiO ₂ , anatase has better photocatalytic activity, so it has higher bactericidal ability after ultraviolet irradiation.

Preferably, the polycrystalline titanium dioxide thin film has a thickness of 10-200 nm.

Preferably, the substrate is one of silicon, titanium alloy and stainless steel.

Preferably, the titanium-containing precursor is at least one of titanium alkoxide, titanium halide, and titanium alkylamide. TiCl ₄ is preferred. The reason is that compared with titanium alkoxide and titanium alkylamide, TiCl ₄ has the advantages of suitable saturated vapor pressure, high deposition rate, and no organic residue.

Preferably, the oxygen-containing precursor is at least one of H ₂ O, O ₃ , and H ₂ O ₂ .

Preferably, ultraviolet light with a wavelength of 240-380 nm is used to irradiate for 5-200 minutes. After being irradiated by ultraviolet rays, more reactive oxygen species are produced, and after being transferred to a dark environment, it has certain antibacterial properties, which can prevent early infection in orthopedic implant surgery.

On the other hand, the present invention also provides a method for preparing a titanium dioxide film by atomic layer deposition, comprising:

(1) After the reaction chamber of the atomic layer deposition equipment is evacuated, the substrate is placed in the reaction chamber and heated to 180-250°C, preferably greater than 180°C and ≤250°C;

(2) Pass the gaseous titanium-containing precursor into the reaction chamber for 100-1000 milliseconds, and then use an inert gas with a flow rate of 100-300 sccm to purge for 1-7 seconds at a time;

(3) Feed the gaseous oxygen-containing precursor into the reaction chamber for 100-1000 milliseconds, and finally use an inert gas with a flow rate of 100-300 sccm for a second purge for 1-7 seconds to complete a deposition cycle;

(4) Repeat the deposition cycle of steps (2)-(3) more than once to control the thickness of the film. The invention prepares pure anatase phase titanium dioxide through atomic layer deposition technology.

In a preferred embodiment, the present invention uses TiCl ₄ and H ₂ O for deposition, and the process is as follows: After the substrate is placed in the reaction chamber, the reaction chamber is evacuated. Feed TiCl ₄ into the reaction chamber, and TiCl ₄ is adsorbed on the surface of the substrate. Then use an inert gas to purify once, leaving a single layer of TiCl ₄ molecules on the surface of the substrate. Water vapor is then introduced into the reaction chamber to react with TiCl ₄ to generate TiO ₂ . The reaction principle (total reaction formula) is as follows: TiCl ₄ +2H ₂ O→TiO ₂ +4HCl. Then, the inert gas is used for secondary purging to remove unreacted precursors and reaction by-products. As a cycle, the thickness of the film can be controlled by controlling the number of cycles.

Preferably, the vacuum is 5-10 mbr.

Preferably, the inert gas is at least one of Ar or N ₂ .

In yet another aspect, the present invention also provides an application of a titanium dioxide film in hard tissue repair and replacement materials.

The present invention has the following beneficial effects: 1) the biofilm provided by the present invention has excellent biocompatibility, and can obtain excellent antibacterial properties after being irradiated with ultraviolet light; 2) the preparation method of the present invention has the advantages of simple operation and low deposition temperature , High film bonding strength, precise control of film thickness, uniform coating on three-dimensional samples, good repeatability, etc.

Description of drawings

Figures 1a-1d are diagrams for determining the saturation time of atomic layer deposition;

Fig. 2 is the XRD pattern of film, wherein (a) is the anatase phase TiO ₂ prepared in Example 1, (b) is the amorphous phase TiO ₂ prepared in Comparative Example 1; and (c) is prepared in Comparative Example 2 Rutile phase TiO ₂ ;

Fig. 3 is the scanning electron micrograph of the titanium dioxide thin film prepared in embodiment 1, wherein a is the SEM photo of the film surface, and b is the SEM photo of the film cross section;

Fig. 4 is the anatase phase _TiO2 film of embodiment 1, the rutile phase _TiO2 film prepared by comparative example 2 and silicon substrate surface MC3T3-E1 cell a adhesion, b proliferation, c differentiation and d mineralization situation;

Fig. 5 is the antibacterial effect figure of film to escherichia coli, and wherein a is the visible bacteria after 24h with the silicon substrate control group, b is the visible bacteria with the anatase film prepared in Example 1 after 24h, and c is with the comparative example 2 Bacteria can be seen after the prepared rutile film acts for 24 hours;

Fig. 6 is the antibacterial effect figure of film to Staphylococcus aureus, and wherein a is the visible bacteria after 24h with the silicon substrate control group, b is the visible bacteria with the anatase film prepared in Example 1 after 24h, and c is the visible bacteria with the anatase film prepared in Example 1. Bacteria can be seen after the rutile film prepared in Comparative Example 2 has been treated for 24 hours.

Detailed ways

The present invention will be further described below through the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, not to limit the present invention.

The present invention adopts the combination of atomic layer deposition technology and ultraviolet irradiation technology, so that the titanium dioxide thin film of the present invention has both compatibility and antibacterial properties. The present invention adopts titanium-containing precursors such as titanium alkoxides, titanium halides, etc. and oxygen-containing precursors such as H ₂ O, O ₃ etc. as titanium source and oxygen source respectively, and utilizes atomic layer deposition technology on substrates (for example, silicon, Titanium alloy, stainless steel, etc.) deposited polycrystalline titanium dioxide film on the surface. Wherein, the crystal phase of the polycrystalline titanium dioxide film is anatase phase.

The preparation method of the invention has the advantages of simple operation, low deposition temperature, high film bonding strength, precise control of film thickness, uniform coating on three-dimensional samples, good repeatability, and the like.

The method for preparing a titanium dioxide thin film by atomic layer deposition technology provided by the present invention is exemplarily described below.

After the substrate is placed in the reaction chamber of the atomic layer deposition equipment, the reaction chamber is evacuated to 5-10 mbr, and the substrate is heated to 180-250° C.

The titanium-containing precursor is passed into the reaction chamber for 100-1000 milliseconds, so that the titanium-containing precursor is adsorbed on the surface of the substrate. Then purging with an inert gas for 1 to 7 seconds to leave a single layer of titanium-containing precursor molecules on the surface of the substrate. Wherein the titanium-containing precursor is passed into the reaction chamber in the form of gas, and the flow rate may be 100-300 sccm.

Then feed the oxygen-containing precursor into the reaction chamber for 100-1000 milliseconds to make it react with the titanium-containing precursor. Then, an inert gas is used for a second purging for 1 to 7 seconds to remove unreacted precursors and reaction by-products. Wherein the oxygen-containing precursor is passed into the reaction chamber in the form of gas, and the flow rate may be 100-300 sccm.

The invention can control the thickness (10-200nm) of the polycrystalline titanium dioxide film by controlling the number of cycles (100-3000 times). The above-mentioned inert gas may be at least one of Ar or N ₂ . The flow rate of the above-mentioned introduction of the inert gas may be 100-300 sccm. Wherein, the titanium-containing precursor and the oxygen-containing precursor are passed into the reaction chamber in the form of gas, and the feeding amount of the titanium-containing precursor and the oxygen-containing precursor is controlled by controlling the gas flow time and the gas flow rate. The invention controls the saturation time of atomic layer deposition by controlling the gas flow rate. One of the important characteristics of ALD deposition is that as the reaction time changes, the growth rate reaches a stable value, and the corresponding time is the saturation time. The saturation time must be selected for atomic layer deposition without special circumstances, because if the time does not reach saturation, it will easily lead to incomplete coverage of the film, and if the time exceeds the saturation time, the layer-by-layer deposition will be destroyed.

The titanium dioxide film prepared by the present invention has excellent biocompatibility, and has high antibacterial properties in a dark environment after being irradiated with ultraviolet light (for example, ultraviolet light with a wavelength of 240-380nm can be used for 5-200 minutes), and promotes the antimicrobial properties of hard tissues. Development of restoration and replacement materials.

The experiments proved that: MC3T3-E1 pre-osteoblasts adhered, proliferated, differentiated and mineralized well on the surface of the anatase film. After the film is irradiated with ultraviolet light for 100 minutes, it has obvious antibacterial effect on Escherichia coli and Staphylococcus aureus, and the antibacterial rate reaches more than 90%.

Examples are given below to describe the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention, and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art according to the above contents of the present invention all belong to the present invention scope of protection. The specific process parameters and the like in the following examples are only an example of the appropriate range, that is, those skilled in the art can make a selection within the appropriate range through the description herein, and are not limited to the specific values exemplified below.

Example 1

A: Anatase thin film prepared by atomic layer deposition technology

The (100) single crystal silicon substrate was cleaned successively with alcohol and deionized water in an ultrasonic cleaner, dried, and loaded into the reaction chamber of BENEQTFS-500 atomic layer deposition equipment. Evacuate to 6-8mbar, heat the substrate to 200°C for _TiO2 deposition. TiCl ₄ was introduced into the reaction chamber for 500 milliseconds, and then purged once with an inert gas at a flow rate of 200 sccm for 4 seconds. Water vapor was then introduced into the reaction chamber for 500 milliseconds, and finally an inert gas with a flow rate of 200 sccm was purged for 4 seconds to complete a deposition cycle. Cycle 1500 times. After the deposition is completed, the deposition chamber is inflated to restore an atmospheric pressure, and the sample is taken out, cooled, and set aside.

It can be seen from Fig. 1a-1d that the deposition rate reaches a stable value after the time of precursor introduction and Ar purge time reaches a certain value, and this time is determined as the saturation time of atomic layer deposition, namely TiCl ₄ /Ar/H ₂ O/ Ar=500ms/4s/500ms/4s. One of the important characteristics of ALD deposition is that as the reaction time changes, the growth rate reaches a stable value, and the corresponding time is the saturation time. Atomic layer deposition should be carried out under the saturation time, which can realize the self-limited growth behavior of atomic layer deposition and ensure the film quality. It can be seen from the XRD pattern of the film shown in (a) in Figure 2: the obtained film is a pure anatase phase, 2θ=25.3° corresponds to the anatase (101) crystal plane; 2θ=47.7° corresponds to the anatase (200) Planes.

Figure 3 is the surface a and cross-sectional SEM topography photo b of the anatase film. It can be seen that the film is dense and uniform, with a uniform thickness of about 120nm and good coverage on the substrate.

B: Cytocompatibility experiment on anatase film surface

Mouse preosteoblast MC3T3-E1 was used for cell adhesion, proliferation, differentiation and mineralization experiments.

1) Cell adhesion

After the Si substrate (control group) and the anatase film (experimental group) were steam sterilized, they were carefully placed in a 24-well cell culture plate. Collect MC3T3-E1 cells in good growth state, digest and adjust the concentration of the cell suspension, and plant 1 mL of the cell suspension (3×10 ³ cells/mL) on the sample surface of each well. After culturing for 4 hours, 8 hours, and 12 hours in a cell culture incubator at 37° C. and 5% CO ₂ , the culture medium was discarded. Add 0.5mL fresh culture medium and 0.05mL CCK-8 solution to each well respectively. After continuing to culture in a 37° C., 5% CO ₂ cell culture incubator for 3 hours, the solution in each well was carefully aspirated and added to a 96-well plate; the OD value of each well was measured at 450 nm with a microplate reader.

2) Cell proliferation

After the Si substrate (control group) and the anatase film (experimental group) were steam sterilized, they were carefully placed in a 24-well cell culture plate. MC3T3-E1 cells in good growth state were collected, digested and adjusted the concentration of the cell suspension, and 1 mL of the cell suspension (1×10 ⁴ cells/mL) was planted on the sample surface of each well. After culturing in a 37°C, 5% CO ₂ cell incubator for 1, 4, and 7 days, the culture medium was discarded. Add 0.5mL fresh culture medium and 0.05mL CCK-8 solution to each well respectively. After continuing to culture in a 37° C., 5% CO ₂ cell culture incubator for 3 hours, the solution in each well was carefully aspirated and added to a 96-well plate; the OD value of each well was measured at 450 nm with a microplate reader.

3) Cell differentiation: ALP quantitative detection

After the Si substrate (control group) and the anatase film (experimental group) were steam sterilized, they were carefully placed in a 24-well cell culture plate. MC3T3-E1 cells in good growth state were collected, digested and adjusted the concentration of the cell suspension, and 1 mL of the cell suspension (1×10 ⁵ cells/mL) was planted on the sample surface of each well. After culturing in a 37°C, 5% CO ₂ cell incubator for 4, 7, and 14 days, the culture medium was discarded and washed twice with PBS. Add 300 μL of 0.1% Triton X-100 (diluted in PBS) to each well. After repeatedly sucking and blowing the surface of the sample with the tip of the pipette, suck the liquid and foam in the hole together into the EP tube for centrifugation. Prepare chromogenic substrate solution and standard working solution (0.5mM); refer to the table below and use 96-well plate to set blank control wells, standard wells and sample wells. The volumes of standard products are 4, 8, 16, 24, 32 and 40 μL respectively;

After mixing the liquid with a shaker (50 rpm/min), incubate at 37° C. for 10 min. Add 100 μL of stop solution to each well; measure the absorbance at 405 nm using a microplate reader. After normalizing the total protein concentration, ALP quantification results were obtained.

4) Cell mineralization: Alizarin red staining quantitative detection

After the Si substrate (control group) and the anatase film (experimental group) were steam sterilized, they were carefully placed in a 24-well cell culture plate. MC3T3-E1 cells in good growth state were collected, digested and adjusted the concentration of the cell suspension, and 1 mL of the cell suspension (1×10 ⁵ cells/mL) was planted on the sample surface of each well. After culturing in a 37°C, 5% CO ₂ cell incubator for 4, 7, and 14 days, the culture medium was discarded and washed twice with PBS. Add 1mL 4% paraformaldehyde solution to each well, incubate at 4°C for 15min; discard the supernatant, wash with PBS three times, add 500μL Alizarin Red staining solution to each well, and incubate at room temperature for 20min; discard the supernatant, PBS After washing 3 times, 500 μL of 10% cetylpyridinium chloride solution was added to each well and incubated at room temperature for 15 min. The OD value was measured at 590 nm using a microplate reader.

It can be seen from Figure 4 that the adhesion, proliferation, differentiation and mineralization abilities of MC3T3-E1 preosteoblasts on the surface of the anatase film were significantly better than those of the Si substrate control group, proving that the anatase film has better cell compatibility.

C: Antibacterial experiment of anatase thin film

The antibacterial performance of the material was detected by plate counting method: Escherichia coli and Staphylococcus aureus were used as the strains used in the test. Before inoculation, the Si substrate (control group) was sterilized by ultraviolet sterilizing lamp for 5 minutes, and the anatase film (experimental group) was irradiated by ultraviolet light with a wavelength of 254 nm for 100 minutes. The bacteria were inoculated on the surface of the liquid medium, cultured in a shaking incubator at 37°C, and transferred every 12 hours. The test used fresh bacteria after two consecutive transfers; the bacterial solution was diluted to 10 ⁶ CFU/ml with PBS. 100 μl of bacterial solution was added dropwise to the surface of Si substrate and anatase film, and kept at 37°C for 24h. The samples were respectively put into test tubes containing 9.9ml of PBS, shaken for 1 minute, diluted ^10-2 , 0.1ml each was inoculated on the liquid medium, and incubated for 24h.

Figure 5b and Figure 6b are the antibacterial effects of anatase film on Escherichia coli and Staphylococcus aureus, respectively. Compared with the control group Figure 5a and Figure 6b, the anatase film has obvious antibacterial effect, and the antibacterial rate reaches 90% above.

Example 2

Preparation of Anatase Thin Films by Atomic Layer Deposition

A Φ10mm×2mm thick titanium alloy was used as the base material, which was cleaned with alcohol and deionized water in an ultrasonic cleaner, dried, and loaded into the reaction chamber of BENEQ TFS-500 atomic layer deposition equipment. Evacuate to 6-8mbar, heat the substrate to 200°C for _TiO2 deposition. TiCl ₄ was introduced into the reaction chamber for 500 milliseconds, and then purged once with an inert gas at a flow rate of 200 sccm for 4 seconds. Then water vapor was introduced into the reaction chamber for 500 milliseconds, and finally an inert gas with a flow rate of 200 sccm was purged for 4 seconds to complete a deposition cycle. Cycle 800 times. After the deposition, the deposition chamber was inflated to return to an atmospheric pressure to obtain a titanium alloy sample covered with an anatase phase film.

Comparative example 1

Preparation of Amorphous TiO ₂ Thin Films by Atomic Layer Deposition

The (100) single crystal silicon substrate was cleaned successively with alcohol and deionized water in an ultrasonic cleaner, dried, and loaded into the reaction chamber of BENEQTFS-500 atomic layer deposition equipment. Evacuate to 6-8mbar and heat the substrate to 150°C for _TiO2 deposition. TiCl ₄ was introduced into the reaction chamber for 500 milliseconds, and then purged once with an inert gas at a flow rate of 200 sccm for 4 seconds. Then water vapor was introduced into the reaction chamber for 500 milliseconds, and finally an inert gas with a flow rate of 200 sccm was purged for 4 seconds to complete a deposition cycle. Loop 500 times. After the deposition is completed, the deposition chamber is inflated to restore an atmospheric pressure, and the sample is taken out, cooled, and set aside.

It can be seen from the XRD spectrum of the thin film shown in Fig. 2(b): the obtained thin film is an amorphous phase. It shows that pure anatase phase _TiO2 film cannot be obtained by deposition at 150 °C.

Comparative example 2

A: Atomic layer deposition technology combined with subsequent annealing process to prepare rutile thin films

The atomic layer deposition method and parameters are the same as those in Example 1, except that the obtained anatase film is annealed at 1000° C. for 1 hour in the atmosphere, and the anatase phase is completely transformed into a rutile phase to obtain a pure rutile phase film. The surface morphology and grain size of the film did not change significantly after annealing.

It can be seen from the XRD spectrum of the film shown in (c) in Figure 2: the obtained film is a pure rutile phase, 2θ=27.38° corresponds to the rutile (110) crystal plane; 2θ=57.3° corresponds to the rutile (220) crystal plane.

B: Cytocompatibility experiment on the surface of rutile film

It can be seen from Figure 4 that the adhesion, proliferation, differentiation and mineralization of MC3T3-E1 pre-osteoblasts on the surface of the rutile film are better than those of the Si substrate control group, but not as good as the anatase film. It is proved that the anatase film has better cell compatibility than the rutile film.

C: Antibacterial experiment of rutile film

The obtained rutile film (comparative example 2) was also irradiated with ultraviolet light with a wavelength of 254nm for 100 minutes to conduct an antibacterial test. Figure 5c and Figure 6c are the antibacterial effects of the rutile film prepared in Comparative Example 2 on Escherichia coli and Staphylococcus aureus, respectively. It can be seen that the rutile film has certain antibacterial properties, but the antibacterial properties are relatively low. It is further proved that the anatase film has better antibacterial properties than the rutile film.

Claims (10)

1. 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. 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. 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. 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. 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. 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.
7. 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. 8. according to the method for claim 7, it is characterised in that the vacuum is 5~10mbr.
9. 9. the method according to claim 7 or 8, it is characterised in that the inert gas is Ar or/and N₂。
10. 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.