CN100491582C

CN100491582C - Method for forming Tio2-X film on material surface by using plasma immersion ion implantation and use thereof

Info

Publication number: CN100491582C
Application number: CNB00817704XA
Authority: CN
Inventors: 黄楠; 杨萍; 冷永祥; 陈俊英; 孙鸿; 王进; 万国江
Original assignee: Southwest Jiaotong University
Current assignee: Southwest Jiaotong University
Priority date: 1999-12-23
Filing date: 2000-12-25
Publication date: 2009-05-27
Anticipated expiration: 2020-12-25
Also published as: CN1413269A

Abstract

The present invention relates to a TiO<2-x> film-forming method on surface of material by injecting plasma and application thereof. The method includes: placing sediment film material on workbench in evacuated chamber of plasma injecting device, wherein oxygen is taken as atmosphere in the form of plasma; leading system of titanium, titanium-tantalum or titanium-niobium into said evacuated chamber by metallic arc plasma; apply a negative pulse potential of 500-50,000 Hz and 0.1-10 kV amplitude on the workbench, thereby forming TiO<2-x> films or TiO<2-x> films with Ta or Nb, wherein x is about 0-0.35. The said material is easily compatible with blood and can improve blood compatibilities obviously when taken as artificial organ and implanted into human body and contacting blood, have obvious improved blood compatibilities.

Description

Form TiO with plasm immersion ion implantation at material surface 2-xThe method of film and application thereof

The present invention relates generally to the material surface modifying technology field, specifically relate to the method that modification is carried out on inorganic materials or organic materials surface.The invention still further relates to the surface modifying method of artificial organs material.Particularly to the method for the artificial organs that contacts with blood and implant into body and the apparatus surface modification that contacts with blood.

The biocompatibility of artificial organs and weather resistance are that artificial organs is used for clinical basic assurance, and especially important cardiovascular systems artificial organs such as artificial heart, heart valve prosthesis and left ventricle service pump have higher requirement to weather resistance and blood compatibility.The white forever first-class of moral is " numerous with artificial organ present situation and future ", one artificial man's cap used in ancient times one, artificial organ, 1990,19 (3), described the present situation that artificial organs is used among the 100-102 etc., artificial heart and its weather resistance of heart valve prosthesis made from natural materials (pig, OX-heart born of the same parents), macromolecular material still can not satisfy above-mentioned requirements fully.And also have two aspect problems at present based on the heart valve prosthesis of inorganic materials such as RESEARCH OF PYROCARBON, titanium alloy, cobalt-base alloy and stainless steel: the one, blood compatibility is still good inadequately, and the 2nd, fatigue, burn into wearing and tearing and brittle rupture still may take place in the valve that such material is made behind implant into body.RESEARCH OF PYROCARBON material with best blood compatibility has been represented the highest level that is used for clinical heart valve prosthesis based on mechanical prosthetic valve, but concerning clinical requirement, its blood compatibility still is not enough height, and its toughness only is 1/100 of metal; Is PaulDidisheim at " Substitute Heart Valves-Do We Need Better Ones? ", Government News, Biomaterials Forum, 1996,18 (5), touch upon among the 15-16, be respectively 1.5-3% in artificial valvular blood coagulation of the U.S. and hemorrhage complication, need the development anticoagulation function to be better than the novel valve of the heart valve prosthesis of present clinical application, wherein new biomaterial, surface modification, new valve designs etc. are the important means that develops more excellent heart valve prosthesis; Mitamura.Y. wait the people at " Development of a Ceramic Valve ", Journal of Biomaterials Applications, 1989,4 (11), discussed the technology with physical gas-phase deposite method overlay film titanium nitride among the 33-55, pointed out that its blood compatibility and RESEARCH OF PYROCARBON are suitable on titanium heart valve prosthesis surface.At present, in the problem aspect there are two in the Artificial heart valve membrane surface modification such as cardiovascular system artificial organ material surface depositing titanium nitride, class diamond film, RESEARCH OF PYROCARBON film: the one, the improvement degree of the blood compatibility of the material after overlay film is handled is not high, compares with the Artificial heart valve mould material RESEARCH OF PYROCARBON of long-term clinical application that anticoagulation function is not significant to be improved.The 2nd, the physical essence limitation of the film synthetic method that is adopted, film is lower with high base strength.China Patent No. ZL 95111386.0 has provided the method for preparing titanium oxide/titanium nitride composite membrane with ion beam enhanced depositing method (IBED) on cardiovascular system artificial organ, this method can only realize planar, simple artificial cardiovascular organ overlay film (as the blade of heart valve prosthesis), can't be to complex-shaped, the artificial cardiovascular organ of curved surface is carried out uniform comprehensive overlay film (as the lobe frame surface of heart valve prosthesis), is only stable and the modification processing is all carried out on all surfaces that contact with blood of artificial organs, improve the assurance of artificial organs performance and security reliably.

In sum, need provide the method for a kind of inorganic materials or organic materials surface modification, to improve the blood compatibility of these materials. and then when these materials are used on the apparatus of artificial organs or implant into body, can obtain good blood compatibility.

One object of the present invention is to provide a kind of material and preparation method of material surface modifying.

Another object of the present invention is to provide a kind of material and preparation method of artificial organ surface modifying.

A further object of the present invention is to provide a kind of artificial organs that contacts with blood and implant into body and the surface modifying material and the preparation method of the apparatus that contacts with blood, can improve the blood compatibility on complex-shaped artificial organs such as artificial heart, heart valve prosthesis and left ventricular assist pump, intravascular stent etc. and apparatus surface effectively by this technology.

The present invention prepares the titanium oxide multielement film of two element films of specific titanium oxide and hydrogen, tantalum, niobium element doping by propose adopting specific technological method, and the nitride film for preparing titanium at its bottom earlier, prepare the gradient film that the nitrogen-atoms gradient descends, the Sauerstoffatom gradient increases then, to obtain to have the surface of excellent blood compatibility and height mechanical property.Method of the present invention can realize by following scheme, wherein term " workpiece " comprise natch term " artificial organs " and implant into body and with blood contacted " apparatus "; Equally, term " artificial organs " or " apparatus " also should be promoted the workpiece that is used for various fields that is interpreted as that available any inorganic materials or organic materials are made in the literary composition:

One, the TiO that synthesizes oxygen vacancy at material surface _2-xFilm and TiO _2-x/ Ti-N-O/TiN gradient film

1) TiO of oxygen vacancy _2-xFilm: workpiece (as artificial organs) is placed plasma immersion ion injection device (Plasma Immersion Ion Implantation, PIII) in the vacuum chamber, charge into oxygen with certain pressure, adopt radio frequency discharge, microwave discharge to form oxygen plasma, make the negative electrode of metal plasma source simultaneously with titanium, open the titanium metal plasma source, the titanium metal plasma body is introduced vacuum chamber, under the pulse negative voltage effect that applies on the workpiece, titanium, oxonium ion bombard and form TiO on the surface of workpiece (artificial organs) _2-xFilm.The parameter of control film performance comprises: titanium metal plasma density, titanium ion sedimentation rate, oxygen plasma volume density, oxygen pressure, pulse negative voltage repetition rate, pulse width and pulse negative voltage amplitude.

2) TiO _2-x/ Ti-N-O/TiN gradient film: the vacuum chamber that workpiece (artificial organs) is placed the plasma immersion ion injection device, charge into the nitrogen of certain pressure, adopt radio frequency discharge, microwave discharge forms nitrogen plasma, make the negative electrode of metal plasma source simultaneously with titanium, open the titanium metal plasma source, the titanium metal plasma body is introduced vacuum chamber, under the pulse negative voltage effect that applies on the workpiece, titanium, nitrogen ion bombardment also forms the TiN film on the surface of workpiece (artificial organs), lower nitrogen pressure then gradually, improve oxygen pressure, but synthetic nitrogen atom gradient descends, the transition Ti-N-O film that the Sauerstoffatom gradient increases, gaseous media aerobic after certain hour in the vacuum chamber, oxygen or oxygen plasma and titanium plasma body form TiO under the effect of pulse negative voltage _2-xFilm.The parameter of control film performance comprises: titanium metal plasma density, titanium ion sedimentation rate, nitrogen plasma density, oxygen plasma volume density, nitrogen pressure, oxygen pressure, pulse negative voltage repetition rate, pulse width and pulse negative voltage amplitude.

Utilize above-mentioned 1), 2) after method handled, workpiece surface obtained the TiO of oxygen vacancy _2-xFilm (artificial organs).Workpiece also can be handled through the vacuum annealing of certain temperature, time and vacuum tightness again, and the parameter of control annealing rear film performance comprises: annealing temperature, annealing time and vacuum tightness.

Two, at the synthetic hydrogenous titanium of material surface-oxygen film

Utilize following method can prepare the adulterated thin film of titanium oxide of protium.

Workpiece (artificial organs) is placed the vacuum chamber of plasma immersion ion injection device (PlasmaImmersion Ion Implantation is PIII), charge into oxygen with certain pressure, adopt radio frequency discharge, microwave discharge to form oxygen plasma, make the negative electrode of metal plasma source simultaneously with titanium, open the titanium metal plasma source, the titanium metal plasma body is introduced vacuum chamber, under the pulse negative voltage effect that applies on the workpiece, titanium, oxonium ion bombard and form TiO on the surface of workpiece (artificial organs) ₂Film.The parameter of control film performance comprises: titanium metal plasma density, titanium ion sedimentation rate, oxygen plasma volume density, oxygen pressure, pulse negative voltage repetition rate, pulse width and pulse negative voltage amplitude.

1) plasma hydrogenation: the workpiece (artificial organs) that the surface is covered with titanium deoxid film places the vacuum chamber of plasma immersion ion injection device (Plasma Immersion IonImplantation is PIII), charge into the hydrogen of certain pressure, the discharge generation hydrogen plasma, on workpiece, apply certain pulse or dc negative bias voltage, but the while is heated parts (artificial organs) also, utilizes the plasma hydrogenation method to form hydrogeneous thin film of titanium oxide on the artificial organs surface.The parameter of control film performance comprises: the pressure, hydrogen plasma density, Heating temperature, sparking voltage, discharging current and the hydrogen treatment time that feed hydrogen.

2) the substance hydrogen ion injects: the workpiece (artificial organs) that the surface is covered with titanium deoxid film places the vacuum chamber of plasma immersion ion injection device, charge into the hydrogen of certain pressure, adopt radio frequency discharge, microwave discharge to generate hydrogen plasma, on workpiece (artificial organs), apply the pulse negative voltage, inject hydrogen ion to workpiece surface high energy, form hydrogeneous titania surface modified layer.The parameter of controlling hydrogenous thin film of titanium oxide performance comprises: vacuum chamber hydrogen pressure, hydrogen plasma density, hydrogen ion energy, hydrogen ion implantation dosage, pulse negative high voltage repetition rate, pulse width and pulse negative voltage amplitude.

3) multiple hydrogen ion injects: the workpiece (artificial organs) that the surface is covered with titanium deoxid film places the vacuum chamber of PIII device, charge into the hydrogen of certain pressure, adopt certain method to form hydrogen plasma, under the effect of pulse negative high voltage, inject hydrogen ion to artificial organs surface high energy, after injecting certain hour, turn down voltage, using plasma immersion ion implantttion technique is injected hydrogen ion to workpiece (artificial organs) high energy under a lower high voltage pulse, after injecting certain hour, turn down voltage again, using plasma immersion ion implantttion technique is injected hydrogen ion to workpiece (artificial organs) surface under lower high voltage pulse.Repeat as this method, adopt multiple ion to inject, make hydrogen ion in thin film of titanium oxide concentration along depth of film direction uniform distribution.The parameter of controlling hydrogenous thin film of titanium oxide performance comprises: vacuum chamber hydrogen pressure, hydrogen plasma density, hydrogen plasma energy, hydrogen ion implantation dosage, pulse negative high voltage repetition rate, pulse width, pulse negative voltage amplitude, multiple ion inject the enforcement number of times and inject the enforcement time at every turn.

Workpiece (artificial organs) after utilizing aforesaid method to handle again after the vacuum annealing of certain temperature, time and vacuum tightness is handled, the hydrogeneous oxidation titanium film that availability is good.The parameter of control film performance is: annealing temperature, annealing time and vacuum tightness.

The nitride film that also can prepare titanium earlier at its bottom prepares the gradient film TiO that the nitrogen-atoms gradient descends, the Sauerstoffatom gradient increases then ₂/ Ti-N-O/TiN gradient film prepares the adulterated thin film of titanium oxide of protium top layer by above method at last.

Three, in thin film of titanium oxide, mix niobium or tantalum element

Utilize following method can prepare niobium or the adulterated thin film of titanium oxide of tantalum element.(1) with synthetic tantalum of PIII or the adulterated TiO of niobium ₂Film or TiO ₂/ Ti-N-O/TiN gradient film, can be in the following ways:

1) ion implantation mode: at first use PIII at workpiece (artificial organs) base material surface deposition TiO ₂Film or TiO ₂/ Ti-N-O/TiN gradient film is put into workpiece (artificial organs) on the vacuum chamber sample table of PIII device then.Make the negative electrode of metal plasma source with tantalum or niobium, on sample table, apply the pulse negative high voltage, open tantalum or niobium metal plasma source, tantalum or niobium metal plasma body are introduced vacuum chamber, under pulse negative high voltage effect on the workpiece, the surface of tantalum or niobium ion bombardment and injection workpiece forms niobium or the adulterated thin film of titanium oxide of tantalum.Form niobium or the adulterated TiO of tantalum ₂Film or TiO ₂/ Ti-N-O/TiN gradient film.By on sample, applying multiple pulse negative voltage from high to low, can obtain niobium or tantalum at thin film of titanium oxide or TiO ₂Uniform distribution in the/Ti-N-O/TiN gradient film.The parameter of control film performance comprises: the implantation dosage of tantalum or niobium metal plasma density, tantalum or niobium, pulse negative high voltage repetition rate, pulse width and pulse negative voltage amplitude, the change number of times of pulse negative voltage amplitude.

2) thin film deposition mode: workpiece (artificial organs) is put on the vacuum chamber sample table of PIII device.Feed oxygen with certain pressure in vacuum chamber, oxygen can be the neutral gas state in vacuum chamber, also can utilize radio frequency discharge or microwave discharge to produce oxygen plasma.On sample table, apply the pulse negative voltage, open the metal plasma source of titanium, tantalum or titanium, niobium alloy negative electrode simultaneously and introduce titanium and tantalum or titanium and niobium metal plasma body simultaneously to vacuum chamber, workpiece is under the effect of pulse negative voltage, titanium, tantalum, oxonium ion or titanium, niobium, oxonium ion bombard the surface of workpiece (artificial organs) simultaneously, form niobium or the adulterated thin film of titanium oxide of tantalum.The parameter of control film performance comprises: the atomic ratio of niobium ion or tantalum ion and titanium ion in titanium, tantalum or titanium, the niobium binary metal plasma body, titanium, tantalum or titanium, niobium binary metal plasma density, the oxygen plasma volume density, the vacuum chamber oxygen pressure, pulse negative high voltage repetition rate, pulse width, pulse negative voltage amplitude.

Also can in vacuum chamber, introduce tantalum or niobium plasma body, titanium plasma body, nitrogen plasma (or nitrogen) earlier simultaneously, contain the nitrogenize titaniferous compound film of tantalum or niobium in its layer deposition, prepare the TiO that contains tantalum or niobium that the nitrogen-atoms gradient descends, the Sauerstoffatom gradient increases then ₂/ Ti-N-O/TiN gradient film.

Utilize above-mentioned 1), 2) after two kinds of methods handled, the artificial organs surface can obtain tantalum or adulterated oxidation titanium film of niobium or TiO ₂/ Ti-N-O/TiN gradient film.Also can be again after certain temperature, time, vacuum tightness vacuum annealing to be handled with artificial organs, the parameter of control annealing rear film performance comprises: annealing temperature, annealing time and vacuum tightness.

(2) adopt synthetic niobium of magnetic controlled sputtering ion plating device or the adulterated thin film of titanium oxide of tantalum element, can be in the following ways:

1) at first adopts the alloys target of niobium-titanium or tantalum-titanium or mosaic target to make sputtering target, utilize the film coating method of this high-speed low temperature of magnetron sputtering, at artificial organs surface deposition titanium-tantalum or titanium-niobium alloy film.Apply direct current or pulse negative voltage on sputtering target, feed argon gas in vacuum chamber, form argon plasma, argon ion will bombard target, sputter target atom and be deposited on workpiece (artificial organs) surface that rotatablely moves.The parameter of control film performance comprises: the atomic ratio of niobium atom or tantalum atom in alloys target or the mosaic target, sputtering voltage (direct current or pulse), sputtering power density, Heating temperature, sputtering time, sample table bias voltage (direct current or pulse), the pressure of the gas argon that feeds in the vacuum chamber, sample table speed of rotation.

2) feed argon gas and nitrogen simultaneously in vacuum chamber, target atom that sputters and nitrogen reaction form the titanium nitride membrane that contains tantalum or niobium.The parameter of control film performance comprises: the atomic ratio of niobium atom or tantalum atom in alloys target or the mosaic target, sputtering voltage (direct current or pulse), sputtering power density, Heating temperature, sputtering time, sputtering pressure, sample table bias voltage (direct current or pulse), the gas argon that feeds in the vacuum chamber and the pressure of nitrogen can obtain to contain the titanium nitride membrane of tantalum or niobium.

To aforesaid method 1), 2) the synthetic film carries out specific oxide treatment and can obtain tantalum or the adulterated thin film of titanium oxide of niobium or titanium oxide/titanium nitride compound film.Method for oxidation can be following two kinds:

A. thermooxidizing, the workpiece (artificial organs) that is coated with titanium-tantalum or titanium-niobium alloy film is placed quartz glass tube, be heated to certain temperature, feed oxygen with certain pressure simultaneously in quartz glass tube, at this moment alloy film has just obtained tantalum or the adulterated thin film of titanium oxide of niobium through oxidation.The parameter of control film performance comprises: oxygen pressure, Heating temperature, oxidization time, niobium atom or tantalum atom percentage composition in tantalum-titanium or the niobium-titanium alloy thin films.

B. plasma oxidation, the workpiece (artificial organs) that is coated with titanium-tantalum or titanium-niobium alloy film is placed the vacuum chamber of plasma ion implantation apparatus, charge into oxygen with certain pressure, utilize radio frequency or microwave discharge to produce oxygen plasma, at this moment workpiece (artificial organs) is immersed in the oxygen plasma atmosphere, heated parts, and on workpiece, apply certain direct current or pulse negative voltage, utilize the plasma oxidation method to obtain tantalum or the adulterated thin film of titanium oxide of niobium in the workpiece surface oxidation.The parameter of control film performance comprises: oxygen pressure, and the oxygen plasma volume density, Heating temperature is applied to the negative voltage amplitude on the artificial organs, plasma oxidation time, pulse negative voltage repetition rate, pulse width, the composition of titanium-tantalum or titanium-niobium alloy film.

3) feed argon gas and oxygen simultaneously in vacuum chamber, apply the pulse negative voltage on sputtering target material, target atom that sputters and oxygen reaction form niobium or the adulterated thin film of titanium oxide of tantalum atom.The parameter of control film performance comprises: the atomic ratio of niobium atom or tantalum atom in alloys target or the mosaic target, the sputter pulsed voltage, sputtering power density, pulse-repetition, pulse width, substrate heating temperature, sputtering time, sample table pulsed bias, pulse-repetition, pulse width, the gas argon that feeds in the vacuum chamber and the pressure of oxygen, sample table speed of rotation.

Also can feed argon gas, nitrogen earlier simultaneously in vacuum chamber, nitrogen pressure constantly reduces after for some time, and feeds the ever-increasing oxygen of pressure, thus the TiO that contains tantalum or niobium that synthetic nitrogen atom gradient descends, the Sauerstoffatom gradient increases ₂/ Ti-N-O/TiN gradient film.

4) adopt Niobium Pentxoxide-titanium dioxide or tantalum pentoxide-titanium dioxide ceramic as sputtering target, feed the argon or the xenon of certain pressure in the vacuum chamber, adopt RF-wise to form argon or xenon plasma body, utilize radio-frequency sputtering at synthetic tantalum in artificial organs surface or the adulterated thin film of titanium oxide of niobium.The parameter of control film performance comprises: radio frequency power, argon or xenon-133 gas pressure, radio-frequency voltage, the sample Heating temperature, sputtering time, the composition of Niobium Pentxoxide-titanium dioxide or tantalum pentoxide-titanium dioxide ceramic target, sample table bias voltage (pulse or direct current), the sample table speed of rotation.

The present invention compared with prior art adopts the aforesaid method synthetic TiO of institute _2-xFilm and mix hydrogen, mix the thin film of titanium oxide or the TiO of tantalum or niobium ₂/ Ti-N-O/TiN gradient film, its advantage is: institute's synthetic film blood compatibility is fabulous, artificial organs to complicated shape, can realize the comprehensive modification of artificial organs, evenly reliable, can realize industrial applications, the blood compatibility of these titanyl compound films significantly is better than internationally recognized best worker's heart valve materials---the RESEARCH OF PYROCARBON of present clinical use, the modified layer easy control of components, and good reproducibility, the reliability height is with workpiece (artificial organs) surface bonding strength height.In a word, blood compatibility, erosion resistance and the abrasion resistance properties that adopts method of the present invention to handle the workpiece (artificial organs) that is obtained improved comprehensively.

The description of drawings of invention is as follows:

Fig. 1 is used plasma immersion ion implanter (PIII) the vacuum chamber synoptic diagram of the present invention;

Fig. 2 is the vacuum chamber synoptic diagram of the used rf magnetron sputtering platform of the present invention;

Fig. 3 is the used vitreosil pipe process furnace of the present invention;

Fig. 4 (a) and 4 (b) be respectively the platelet adhesion reaction situation utilized on the institute of the present invention synthetic film material and with the RESEARCH OF PYROCARBON surface on the contrast of platelet adhesion reaction situation;

Fig. 5 (a) for utilize institute of the present invention synthetic thin-film material in animal body after the heeling-in hemocyte in the adhesion situation on its surface;

Fig. 5 (b) 5 (c) is respectively the adhesion situation of RESEARCH OF PYROCARBON surface hemocyte;

Fig. 6 (a) carries out the lobe frame situation that thrombus forms on its surface after the heeling-in in animal body of the commercial heart valve prosthesis of surface modification for utilizing institute of the present invention synthetic thin-film material;

Fig. 6 (b) for the lobe frame of the heart valve prosthesis of not doing surface modification in animal body after the heeling-in thrombus in its surperficial formation situation;

Fig. 7 utilizes institute of the present invention synthetic thin-film material to carry out the contrast of the wearing character of the wearing character of the titanium Artificial heart valve mould material after the surface modification and unmodified titanium Artificial heart valve mould material.

The invention will be further described below in conjunction with accompanying drawing:

With reference to figure 1, Fig. 1 is used plasma immersion ion implanter (PIII) the vacuum chamber synoptic diagram of the present invention.This ion implanter comprises: vacuum chamber 1, negative electrode 2, cathode arc source 3, deflector coil 4, sweep coil 5, worktable 6, workpiece (artificial organs or other organic or inorganic material) 7, heater supply 8, radio-frequency power supply 9, microwave power supply 10, switch 11, direct supply 12 and high-voltage pulse power source 13.By this device, available plasm immersion ion implantation prepares oxygen vacancy TiO _2-xFilm, TiO _2-xThe adulterated thin film of titanium oxide of the thin film of titanium oxide of/Ti-N-O/TiN gradient film, hydrogen doping and niobium or tantalum element.

One, adopt the PIII method to prepare oxygen vacancy TiO _2-xFilm and TiO _2-x/ Ti-N-O/TiN gradient film

Embodiment 1: workpiece (artificial organs) 7 is put on vacuum chamber 1 worktable 6 of PIII device of Fig. 1, titanium is installed in the negative electrode in metallic cathode arc plasma source 3 as cathode material 2.Be evacuated to 1 * 10 ^-4Handkerchief, aerating oxygen in the vacuum chamber 1, open radio-frequency power supply 10 (or microwave power supply) and produce oxygen plasma, switch 11 is allocated to the pulse power 13, on worktable, apply certain pulse negative high voltage, open cathode arc source 3, open the outer magnetic deflection coil 4 of the extraction catheter in metallic cathode arc plasma source and the power supply of sweep coil 5, introduce the titanium metal plasma body to vacuum chamber, under the effect of pulse negative voltage, titanium, oxonium ion bombard the surface of workpiece (artificial organs) 7 simultaneously, can obtain thin film of titanium oxide by three kinds of implementation methods shown in the table one.The parameter of control film performance comprises: titanium metal plasma density 10 ⁸～10 ¹²Centimetre ^-3, oxygen plasma volume density 10 ⁸～10 ¹²Centimetre ^-3, titanium is at the sedimentation rate 0.1～1nm/s of workpiece surface, vacuum chamber oxygen pressure 10 ^-3～1 handkerchief, 500～50000 hertz of pulse negative high voltage repetition rates, pulse width 1～200 μ s, pulse negative voltage amplitude 0.1-10 kilovolt.

Table one

Implementation method	The titanium plasma density (centimetre ^-3)	Titanium sedimentation rate (nm/s)	The oxygen plasma volume density (centimetre ^-3)	Oxygen pressure (handkerchief)	Pulse-repetition (hertz)	Pulse width (μ s)	Pulsed voltage (kilovolt)
Implementation method	The titanium plasma density (centimetre ^-3)	Titanium sedimentation rate (nm/s)	The oxygen plasma volume density (centimetre ^-3)	Oxygen pressure (handkerchief)	Pulse-repetition (hertz)	Pulse width (μ s)	Pulsed voltage (kilovolt)	One	3×10 ⁸	0.08	5×10 ⁸	5×10 ^-3	500	20	-0.1
Two	3×10 ⁹	0.2	5×10 ⁹	1.6×10 ^-2	25000	5	-2.5	One	3×10 ⁸	0.08	5×10 ⁸	5×10 ^-3	500	20	-0.1
Two	3×10 ⁹	0.2	5×10 ⁹	1.6×10 ^-2	25000	5	-2.5	Three	3×10 ¹⁰	1	5×10 ¹⁰	6×10 ^-2	2000	100	-10

Embodiment 2: workpiece (artificial organs) 7 is put on vacuum chamber 1 worktable 6 of PIII device of Fig. 1, synthetic TiN film of fs at first is installed in titanium the negative electrode in metallic cathode arc plasma source 3 as cathode material 2.Be evacuated to 1 * 10 ^-4Handkerchief, in vacuum chamber 1, feed nitrogen, open radio-frequency power supply 10 (or microwave power supply) and produce nitrogen plasma, switch 11 is allocated to high-voltage pulse power source 13, on worktable, apply certain pulse negative voltage, open cathode arc source 3, open the outer magnetic deflection coil 4 of the extraction catheter in metallic cathode arc plasma source and the power supply of sweep coil 5, introduce the titanium metal plasma body simultaneously to vacuum chamber, artificial organs 7 is under the effect of pulse negative high voltage, titanium, the nitrogen ion bombards the surface of artificial organs simultaneously, obtains TiN film bottom, and subordinate phase lowers nitrogen pressure gradually then, improve oxygen pressure, but synthetic nitrogen atom gradient descends, the middle Ti-N-O thin film layer that the Sauerstoffatom gradient increases, an aerobic in the last phase III vacuum chamber, the titanium plasma body forms TiO _2-xThe film top layer.Can obtain TiO by three kinds of implementation methods shown in the table two _2-x/ Ti-N-O/TiN gradient film.The parameter of control film performance is: titanium metal plasma density 10 ⁸～10 ¹²Centimetre ^-3, nitrogen plasma density 10 ⁸～10 ¹²Centimetre ^-3, oxygen plasma volume density 10 ⁸～10 ¹²Centimetre ^-3, titanium is to the sedimentation rate 0.1～1nm/s on artificial organs surface, vacuum chamber nitrogen pressure 10 ^-3～1 handkerchief, vacuum chamber oxygen pressure 10 ^-3～1 handkerchief, 500～50000 hertz of pulse negative high voltage repetition rates, pulse width 1～200 μ s, 0.1～10 kilovolt of pulse negative voltage amplitude, the rate of change 10 of nitrogen pressure and oxygen pressure in the vacuum chamber ^-3Pa/ minute-10 ^-2Pa/ minute.

With above-mentioned example 1), 2) film that obtains places in the vacuum chamber of PIII device of Fig. 1 and is evacuated to 10 ^-4～10 ^-1Handkerchief is heated to 100～800 degree, is incubated 0.1～2 hour anneal.The synthetic TiO of institute _2-xThe x value of film is 0.05～0.35, and typical structure is a rutile crystal type, and film thickness is 0.05～5 μ m, and the gradient transition layer thickness of film is 10～100nm.

Table two

Two, the thin film of titanium oxide of preparation hydrogen doping:

Embodiment 3: at first workpiece (artificial organs) 7 is placed on the sample table 6 of plasma immersion ion implanter vacuum chamber 1 shown in Figure 1, adopt the process similar to embodiment 1,2 at artificial organs surface deposition titanium deoxid film or TiO ₂/ Ti-N-O/TiN gradient film, preparation parameter sees Table three, is evacuated to air pressure then less than 10 ^-3Handkerchief charges into hydrogen, and heating artificial organs 7 is allocated to action of low-voltage pulse power supply 12 to switch 11, applies-0.05～-5 kilovolt of pulsed voltage on artificial organs 7, opens radio frequency

Table three

Implementation method	The titanium plasma density (centimetre ^-3)	Titanium sedimentation rate (nm/s)	The oxygen plasma volume density (centimetre ^-3)	Oxygen pressure (handkerchief)	Pulse-repetition (hertz)	Pulse width (μ s)	Pulsed voltage (kilovolt)
Implementation method	The titanium plasma density (centimetre ^-3)	Titanium sedimentation rate (nm/s)	The oxygen plasma volume density (centimetre ^-3)	Oxygen pressure (handkerchief)	Pulse-repetition (hertz)	Pulse width (μ s)	Pulsed voltage (kilovolt)		3×10 ⁹	0.2	7×10 ⁹	2.0×10 ^-2	25000	5	-3.5

Source 9 or microwave discharge power supply 10 utilize radio frequency discharge or microwave discharge to produce hydrogen plasma, and plasma hydrogenation obtained hydrogen doping thin film of titanium oxide or TiO after 0.1～2 hour ₂/ Ti-N-O/TiN gradient film.Can obtain by four kinds of implementation methods shown in the table four

Table four

Implementation method	Hydrogen pressure (handkerchief)	Heating temperature (℃)	Apply voltage (kilovolt)	Hydrogen plasma density (centimetre ^-3)	Working current (peace)	Working hour (hour)
Implementation method	Hydrogen pressure (handkerchief)	Heating temperature (℃)	Apply voltage (kilovolt)	Hydrogen plasma density (centimetre ^-3)	Working current (peace)	Working hour (hour)	One	0.01	200	-0.2	10 ⁸	0.1	2
Two	0.1	300	-0.8	5×10 ⁹	1	1	One	0.01	200	-0.2	10 ⁸	0.1	2
Two	0.1	300	-0.8	5×10 ⁹	1	1	Three	0.8	400	-2	5×10 ¹⁰	3	0.5
Four	10	600	-3	10 ¹¹	5	0.1	Three	0.8	400	-2	5×10 ¹⁰	3	0.5

Mix the hydrogen film.The parameter of control film performance is a hydrogen pressure (10 ^-3～10 handkerchiefs), hydrogen plasma density (10 ⁸～10 ¹²Centimetre ^-3), Heating temperature (100～600 degree), sparking voltage (0.2～-5 kilovolt), discharging current (0.1～5 peace), hydrogenation time (0.1～2 hour).

Utilize the artificial organs after aforesaid method is handled to handle through vacuum annealing, vacuum tightness is 10 again ^-4～10 ^-1Handkerchief, temperature are 200～600 degree, 0.1～1 hour time, form hydrogenous oxidation titanium film or TiO ₂/ Ti-N-O/TiN gradient film, hydrogen atom content wherein are 10%～35%.

Embodiment 4: the surface is covered with titanium dioxide or TiO ₂The workpiece of/Ti-N-O/TiN gradient film (artificial organs) 7 places on the sample table 6 of plasma immersion ion implanter vacuum chamber 1 shown in Figure 1, is evacuated to air pressure less than 10 ^-4Handkerchief charges into hydrogen, and switch 11 is allocated to high-voltage pulse power source 13, on artificial organs 7, apply the pulse negative high voltage, open radio-frequency power supply 9 or microwave discharge power supply 10, utilize radio frequency discharge or microwave discharge to produce hydrogen plasma, the using plasma immersion ion injection method is to manually

Table five

Embodiment	Hydrogen pressure (handkerchief)	Pulsed voltage (kilovolt)	Pulse width (μ s)	Pulse-repetition (hertz)	Hydrogen plasma density (centimetre ^-3)	The hydrogen ion implantation dosage (atom/centimetre ²)
Embodiment	Hydrogen pressure (handkerchief)	Pulsed voltage (kilovolt)	Pulse width (μ s)	Pulse-repetition (hertz)	Hydrogen plasma density (centimetre ^-3)	The hydrogen ion implantation dosage (atom/centimetre ²)	0.001	-2	2	20000	10 ⁸	2×10 ¹⁶
	0.017	-20	5	200	2×10 ⁹	1.5×10 ¹⁷	0.001	-2	2	20000	10 ⁸	2×10 ¹⁶
	0.017	-20	5	200	2×10 ⁹	1.5×10 ¹⁷	0.3	-50	40	1000	6×10 ¹⁰	5×10 ¹⁷
Four	1	-100	200	200	10 ¹²	9×10 ¹⁷	0.3	-50	40	1000	6×10 ¹⁰	5×10 ¹⁷

Organ 7 surperficial high energy inject hydrogen ion and form hydrogenous titania surface modified layer.Can obtain hydrogenous thin film of titanium oxide or TiO by four kinds of implementation methods shown in the table five ₂/ Ti-N-O/TiN gradient film.The parameter of control film performance is a vacuum chamber hydrogen pressure 10 ^-3～10 handkerchiefs, hydrogen plasma density 10 ⁸～10 ¹²Centimetre ^-3, hydrogen ion implantation dosage 10 ¹⁵～1.2 * 10 ¹⁸Atom/centimetre ², 50～20000 hertz of pulse negative high voltage repetition rates, pulse width 1～200 μ s, 1～100 kilovolt of pulse negative voltage amplitude.Utilize the artificial organs 7 after aforesaid method is handled to adopt device shown in Figure 1 to do the vacuum annealing processing again, vacuum chamber 1 is evacuated down to 10 by method shown in the table six ^-4～10 ^-1Handkerchief is heated to 100～400 degree with sample table 6 with artificial organs 7, and vacuum annealing in 0.1～2 hour can be synthesized hydrogeneous oxidation titanium film or hydrogeneous TiO after handling ₂/ Ti-N-O/TiN gradient film, wherein hydrogen atom content is 10%～35%.

Table six

Method	Temperature ℃	Time (minute)	Vacuum tightness Pa
Method	Temperature ℃	Time (minute)	Vacuum tightness Pa	1	230	55	2×10 ^-3
2	280	65	8×10 ^-4	1	230	55	2×10 ^-3

Embodiment 5: the surface is covered with titanium deoxid film or TiO ₂The workpiece of/Ti-N-O/TiN gradient film (artificial organs) 7 places on vacuum chamber 1 sample table 6 of PIII device as shown in Figure 1, is evacuated to air pressure less than 10 ^-4Handkerchief, charge into hydrogen, switch 11 is allocated to high-voltage pulse power source 13, open radio-frequency power supply 9 or microwave discharge power supply 10, utilize radio frequency discharge or microwave discharge to produce hydrogen plasma, on artificial organs 7, apply 70～100 kilovolts of pulse negative high voltages, inject the high energy hydrogen ion with plasm immersion ion implantation to artificial organs 7, inject after 0.1～2 hour, turn down the voltage of high-voltage pulse power source 13, on artificial organs 7, apply 30～60 kilovolts of pulse negative high voltages, inject hydrogen ion to artificial organs 7.Turn down voltage again and inject, adopt multiple ion to inject, make hydrogen ion at thin film of titanium oxide or TiO as this method repetition ₂/ Ti-N-O/TiN gradient is thin

Table seven

Implementation method	Hydrogen pressure (handkerchief)	Pulsed voltage (kilovolt) and working hour (hour)	Pulsed voltage (kilovolt) and working hour (hour)	Pulsed voltage (kilovolt) and working hour (hour)	Pulsed voltage (kilovolt) and working hour (hour)	Pulse width (μ s)	Pulse-repetition (hertz)	Hydrogen plasma density (centimetre ^-3)	The hydrogen ion implantation dosage (atom/centimetre ²)
Implementation method	Hydrogen pressure (handkerchief)	Pulsed voltage (kilovolt) and working hour (hour)	Pulsed voltage (kilovolt) and working hour (hour)	Pulsed voltage (kilovolt) and working hour (hour)	Pulsed voltage (kilovolt) and working hour (hour)	Pulse width (μ s)	Pulse-repetition (hertz)	Hydrogen plasma density (centimetre ^-3)	The hydrogen ion implantation dosage (atom/centimetre ²)	One	2×10 ^-2	7 kilovolts 1.5 hours	18 kilovolts 2 hours			30	500	2×10 ⁸	2.1×10 ¹⁷
Two	1.7×10 ^-2	7 kilovolts 0.25 hour	15 kilovolts 0.7 hour	35 kilovolts 1 hour	55 kilovolts 1 hour	?5	250	6×10 ⁹	5.6×10 ¹⁷	One	2×10 ^-2	7 kilovolts 1.5 hours	18 kilovolts 2 hours			30	500	2×10 ⁸	2.1×10 ¹⁷
Two	1.7×10 ^-2	7 kilovolts 0.25 hour	15 kilovolts 0.7 hour	35 kilovolts 1 hour	55 kilovolts 1 hour	?5	250	6×10 ⁹	5.6×10 ¹⁷	Three	4×10 ^-2	10 kilovolts 0.05 hour	30 kilovolts 0.15 hour	60 kilovolts 0.2 hour	95 kilovolts 0.3 hour	100	50	2×10 ¹⁰	1×10 ¹⁸

Concentration can obtain hydrogeneous thin film of titanium oxide or hydrogeneous TiO by three kinds of implementation methods shown in the table seven along film thickness direction uniform distribution in the film ₂/ Ti-N-O/TiN gradient film.The parameter of controlling hydrogeneous film performance is a vacuum chamber hydrogen pressure 10 ^-2～10 ⁰Handkerchief, pulse negative high voltage repetition rate is 50～20000 hertz, the hydrogen ion implantation dosage is 10 ¹⁶～10 ¹⁸Atom/centimetre ² Hydrogen plasma density 10 ⁸～10 ¹²Centimetre ^-3, pulse width 2～200 μ s, 1～100 kilovolt of pulse negative voltage amplitude, multiple ion injects implements number of times 2～10 times, injects 0.1～2 hour enforcement time at every turn.Utilize the artificial organs 7 after aforesaid method is handled to adopt device shown in Figure 1 to do the vacuum annealing processing again, vacuum chamber 1 is evacuated down to 10 ^-4～10 ^-1Handkerchief is heated to the vacuum annealing in 0.1～2 hour of 100～400 degree with sample table 6 with artificial organs 7 and handles, and the annealing example sees Table six, and the hydrogen atom content of synthetic hydrogeneous oxidation titanium film is 10%～35%.

Three, preparation niobium or the adulterated thin film of titanium oxide of tantalum element:

(1) adopt synthetic tantalum of PIII device or the adulterated titanium deoxid film of niobium, can adopt following embodiment:

Embodiment 6: the workpiece (artificial organs) 7 that the surface has been coated with titanium deoxid film is put on vacuum chamber 1 worktable 6 of PIII device of Fig. 1, as cathode material 2, is installed in the negative electrode in metallic cathode arc plasma source 3 with tantalum or niobium.Be evacuated to 1 * 10 ^-4Handkerchief, switch 11 is allocated to high-voltage pulse power source 13, open metallic cathode arc source 3, open the outer magnetic deflection coil 4 of metallic cathode arc plasma source extraction catheter and the power supply of sweep coil 5, on work stage, apply certain pulse negative voltage, tantalum or niobium metal plasma body are introduced vacuum chamber, artificial organs 7 is under the effect of pulse negative voltage, the surface of tantalum or niobium ion bombardment and injection artificial organs 7 can obtain niobium or the adulterated thin film of titanium oxide of tantalum by three kinds of implementation methods shown in the table eight. and the parameter of control film performance is: tantalum or niobium metal plasma density 10 ⁸～10 ¹²Centimetre ^-3, the implantation dosage 10 of tantalum or niobium ¹⁵～5 * 10 ¹⁷Atom/centimetre ², 100～20000 hertz of pulse negative high voltage repetition rates, pulse width 1 μ s～200 μ s, 1～100 kilovolt of pulse negative voltage amplitude.Artificial organs through above-mentioned processing adopts device shown in Figure 1 to do the vacuum annealing processing again, and vacuum chamber 1 is evacuated down to 10 ^-4～10 ^-1Handkerchief is heated to 100～800 degree with sample table 6 with artificial organs 7, is incubated 0.1～2 hour and carries out the vacuum annealing processing.

Table eight

Implementation method	Tantalum or niobium plasma density (centimetre ^-3)	Tantalum or niobium ion implantation dosage (centimetre ^-2)	Pulse-repetition (hertz)	Pulse width (μ s)	Pulsed voltage (kilovolt)
Implementation method	Tantalum or niobium plasma density (centimetre ^-3)		Pulse-repetition (hertz)	Pulse width (μ s)	Pulsed voltage (kilovolt)	One	10 ⁸	3.5×10 ¹⁵	20	5	-20
Two	5×10 ⁹	8×10 ¹⁵	500	100	-50	One	10 ⁸	3.5×10 ¹⁵	20	5	-20
Two	5×10 ⁹	8×10 ¹⁵	500	100	-50	Three	10 ¹¹	1.5×10 ¹⁶	5000	50	-100
Four	2×10 ¹⁰	1.2×10 ¹⁵	20000	2	5	Three	10 ¹¹	1.5×10 ¹⁶	5000	50	-100

Embodiment 7: workpiece (artificial organs) 7 is put on vacuum chamber 1 worktable 6 of PIII device of Fig. 1, titanium, tantalum or titanium, niobium alloy are installed in the negative electrode in metallic cathode arc plasma source 3 as cathode material 2.Be evacuated to 1 * 10 ^-4Handkerchief, aerating oxygen in the vacuum chamber 1, open radio-frequency power supply 10 (or microwave power supply) and produce oxygen plasma, switch 11 is allocated to high-voltage pulse power source 13, on worktable, apply certain pulse negative high voltage, open cathode arc source 3, open the outer magnetic deflection coil 4 of the extraction catheter in metallic cathode arc plasma source and the power supply of sweep coil 5, introduce titanium simultaneously to vacuum chamber, tantalum (or titanium, niobium) metallic plasma, artificial organs 7 is under the effect of pulse negative high voltage, titanium, tantalum, oxonium ion (or titanium, niobium, oxonium ion) bombards the surface of artificial organs 7 simultaneously, can obtain the adulterated thin film of titanium oxide of tantalum (or niobium) by three kinds of implementation methods shown in the table nine.The parameter of control film performance comprises: the atomic ratio of niobium atom or tantalum atom and titanium is 0.5:100～10:100 in the composition of titanium, tantalum or titanium, niobium binary metal cathode material, titanium, tantalum or titanium, niobium binary metal plasma density 10 ⁸～10 ¹²Centimetre ^-3, oxygen plasma volume density 10 ⁸～10 ¹²Centimetre ^-3, vacuum chamber oxygen pressure 10 ^-3～10 handkerchiefs, 100～20000 hertz of pulse negative high voltage repetition rates, pulse width 1～200 μ s, 0.1～20 kilovolt of pulse negative voltage amplitude.

Table nine

Implementation method	Alloy cathode composition tantalum or niobium atom content	Metal ion sedimentation rate (nm/s)	The metal plasma volume density (centimetre ^-3)	The oxygen plasma volume density (centimetre ^-3)	Oxygen pressure (handkerchief)	Pulse-repetition (hertz)	Pulse width (μ s)	Pulsed voltage (kilovolt)
Implementation method	Alloy cathode composition tantalum or niobium atom content	Metal ion sedimentation rate (nm/s)	The metal plasma volume density (centimetre ^-3)	The oxygen plasma volume density (centimetre ^-3)	Oxygen pressure (handkerchief)	Pulse-repetition (hertz)	Pulse width (μ s)	Pulsed voltage (kilovolt)	One	0.8％	0.08	1×10 ⁹	2×10 ⁹	1.1×10 ^-2	10000	10	-0.5
Two	3％	0.2	6×10 ⁹	1×10 ¹⁰	2.0×10 ^-2	20000	2	-3	One	0.8％	0.08	1×10 ⁹	2×10 ⁹	1.1×10 ^-2	10000	10	-0.5
Two	3％	0.2	6×10 ⁹	1×10 ¹⁰	2.0×10 ^-2	20000	2	-3	Three	8％	1	2×10 ¹⁰	3.5×10 ¹⁰	7×10 ^-2	50	200	-10

Be evacuated to 10 in the vacuum chamber of the PIII device that tantalum that aforesaid method is obtained or the adulterated thin film of titanium oxide of niobium place Fig. 1 ^-4～10 ^-1Handkerchief is heated to the vacuum annealing processing that 100～800 degree carried out 0.1～2 hour.

(2) adopt the magnetic controlled sputtering ion plating mode to prepare titania-doped film, referring to Fig. 2.

As Fig. 2, the synoptic diagram of the vacuum chamber of the rf magnetron sputtering platform that the present invention shown in it is used.Can prepare titania-doped film with the magnetic controlled sputtering ion plating mode by this sputtering unit.The magnetic control platform of Fig. 2 comprises: worktable (sample table) 6, workpiece (artificial organs or other organic or inorganic material) 7, pulse or radio-frequency power supply 14, direct supply 15, target platform 16, transfer lever 17, gas cylinder 18 and grid bias power supply 19.

Embodiment 8: at first niobium-titanium or tantalum-titanium alloy target or mosaic target are contained on the target platform 16 of magnetron sputtering equipment, workpiece (artificial organs) 7 is placed on the sample table 6, and vacuum chamber is evacuated to 1 * 10 ^-4Handkerchief, heating artificial organs 7 is opened gas cylinder 18, feeds argon gas to vacuum chamber, argon pressure is 0.01～10 handkerchief, transfer lever 17 is allocated to the pulse power 14 or direct supply 15, on target platform 16, adds a direct current or pulse negative voltage, form argon plasma, under the negative voltage effect, argon ion bombardment titanium-niobium or titanium-tantalum target, generation titanium, niobium atom or titanium, tantalum atom are deposited on the artificial organs 7, form alloy firm.In order to improve film quality, in the deposition process, open grid bias power supply 19, on sample table 6, apply certain direct current or pulsed negative bias.With the film coating method of this high-speed low temperature of magnetron sputtering, can obtain titanium-tantalum or titanium-niobium alloy film by four kinds of implementation methods shown in the table ten.

Table ten

Implementation method	The atom content of tantalum or niobium in the target	Sputter pulsed voltage (volt)	Sputter volts DS (volt)	Average power density (W/ cm ²)	Pulse width (microsecond)	Pulse-repetition (hertz)	Heating temperature (degree)	Sputtering time (hour)	Argon pressure (handkerchief)	Sample table bias voltage (volt)	Sample pulse-repetition (hertz)	Sample pulse width (μ s)
Implementation method	The atom content of tantalum or niobium in the target	Sputter pulsed voltage (volt)	Sputter volts DS (volt)	Average power density (W/ cm ²)	Pulse width (microsecond)	Pulse-repetition (hertz)	Heating temperature (degree)	Sputtering time (hour)	Argon pressure (handkerchief)	Sample table bias voltage (volt)	Sample pulse-repetition (hertz)	Sample pulse width (μ s)	One	1％	-400	2	5	40000	200	1.5	0.1	-100	10000	2
Two	3％	-600		3	10	20000	300	0.8	0.2	-300	20000	10	One	1％	-400	2	5	40000	200	1.5	0.1	-100	10000	2
Two	3％	-600		3	10	20000	300	0.8	0.2	-300	20000	10	Three	8％	-1000	6	50	5000	500	0.1	1	-3000	40000	5
Five	3％		-500	12			250	0.6	0.2	-500	8000	20	Three	8％	-1000	6	50	5000	500	0.1	1	-3000	40000	5

The parameter of control alloy firm performance comprises: the ratio of niobium atom or tantalum atom and titanium atom is alloys target or the mosaic target of 0.5:100～10:100, volts DS-300～-1000V, sputtering voltage pulsewidth 1～100 μ s, 5000～50000 hertz of sputtering voltage pulse-repetitioies, sputter pulsed voltage-300～-1000V, 1～15 watt/centimetre of average power density ², sample Heating temperature 100～500 degree, sputtering time 0.1～2 hour, sputtering pressure 0.01～10 handkerchief, sample table direct-current biasing 0～-3000 volt, sample table pulsed bias 0～-5000V, 1000～50000 hertz of frequencies, pulsewidth 1～100 μ s.

Then the synthetic alloy firm is carried out thermal oxidative treatment or plasma oxidation can obtain tantalum or the adulterated thin film of titanium oxide of niobium, Fig. 3 is the used vitreosil pipe synoptic diagram of the present invention.This Fig. 3 illustrates the used vitreosil pipe process furnace of the present invention, and its purposes is to handle as thermal oxidative treatment and plasma oxidation.The heating of this vitreosil pipe comprises: the wherein workpiece of Fang Zhiing (sample) 7, vacuum system 20, electric furnace 21, inflation system 22 and silica tube 23, and its mode of operation is respectively:

A. thermal oxidative treatment: the artificial organs 7 that will be coated with titanium-tantalum or titanium-niobium alloy film places vitreosil Glass tubing 23, opens vacuum system power supply 20, is evacuated to 1 * 10 ^-3Handkerchief is opened furnace power 21, heating, vacuum quartz glass tube to 400～900 degree, open inflation system 22, in quartz glass tube 23, feed the oxygen of 0.1～10 handkerchief, thermooxidizing 10 minutes～2 hours, at this moment alloy film has just obtained tantalum or the adulterated thin film of titanium oxide of niobium through oxidation.

B. plasma oxidation is handled: the artificial organs 7 that will be coated with titanium-tantalum or titanium-niobium alloy film places on the sample table 6 of plasma apparatus shown in Figure 1, is evacuated to 1 * 10 ^-4Handkerchief, charge into oxygen, open radio-frequency power supply 9 (or microwave power supply 10) and produce oxygen plasma, at this moment artificial organs 7 is immersed in the oxygen plasma atmosphere, heating artificial organs 7, open action of low-voltage pulse power supply 12, on artificial organs 7, apply certain pulse negative voltage, utilize plasma oxidation process to obtain tantalum or the adulterated titanium deoxid film of niobium by three kinds of method for oxidation shown in the table ten one.The parameter of control film performance is oxygen pressure 0.01～10 handkerchief, oxygen plasma volume density 10 ⁸～10 ¹²Centimetre ^-3, Heating temperature 100～600 degree, 0.2～3 kilovolt of pulse negative voltage amplitude, 5 minutes～2 hours plasma oxidation time, 1000～20000 hertz of pulse negative high voltage repetition rates, pulse width 2～200 μ s.

Table ten one

Implementation method	Oxygen pressure (handkerchief)	The oxygen plasma volume density (centimetre ^-3)	Heating temperature (degree)	Pulse negative voltage (kilovolt)	Time (hour)	Repetition rate (hertz)	Pulse width (μ s)
Implementation method	Oxygen pressure (handkerchief)	The oxygen plasma volume density (centimetre ^-3)	Heating temperature (degree)	Pulse negative voltage (kilovolt)	Time (hour)	Repetition rate (hertz)	Pulse width (μ s)	One	0.01	10 ⁸	200	-0.2	2	5000	100
Two	0.2	3×10 ⁹	400	-2	0.5	20000	2	One	0.01	10 ⁸	200	-0.2	2	5000	100
Two	0.2	3×10 ⁹	400	-2	0.5	20000	2	Three	2	10 ¹¹	600	-3	0.05	2000	20

Embodiment 9: at first obtain to contain the titanium nitride membrane of niobium or tantalum, form niobium or the adulterated thin film of titanium oxide of tantalum through oxidized surface again.Niobium-titanium or tantalum-titanium alloy target or mosaic target are contained on the target platform 16 of magnetron sputtering equipment, and artificial organs 7 is placed on the sample table 6, and vacuum chamber is evacuated to 1 * 10 ^-4Handkerchief, heating artificial organs 7, open gas cylinder group 18, feed argon gas and nitrogen, transfer lever 17 is allocated to the pulse power 14 or galvanic current 15 to vacuum chamber, on target platform 16, add certain pulse or negative direct current high voltage, form argon, nitrogen plasma, under the negative voltage effect, argon ion bombardment titanium-niobium or titanium-tantalum target, generation titanium, niobium atom or titanium, tantalum atom are deposited on the artificial organs 7, and combine the titanium nitride membrane that formation contains niobium or tantalum with nitrogen-atoms.In order to improve film quality, in the deposition process, open grid bias power supply 19, on sample table 6, apply certain pulse or dc negative bias voltage.Can obtain the titanium nitride membrane that contains tantalum or contain niobium by implementation method shown in the table ten two, 13.The parameter of control film performance comprises: niobium atom

Table ten two

Implementation method	The atom content of tantalum or niobium in the target composition	Sputtering voltage (volt)	Sputtering power density (watt/centimetre ²)	Heating temperature (degree)	Sputtering time (hour)	Argon pressure (handkerchief)	Nitrogen pressure (handkerchief)	Sample table bias voltage (volt)
Implementation method		Sputtering voltage (volt)	Sputtering power density (watt/centimetre ²)	Heating temperature (degree)	Sputtering time (hour)	Argon pressure (handkerchief)	Nitrogen pressure (handkerchief)	Sample table bias voltage (volt)	One	0.5％	-300	3	200	1	0.8	0.8	-200
Two	3％	-600	4	300	0.8	0.5	0.4	-300	One	0.5％	-300	3	200	1	0.8	0.8	-200
Two	3％	-600	4	300	0.8	0.5	0.4	-300	Three	10％	-1000	8	500	0.2	0.3	0.2	-600

Table ten three

Implementation method	The atom content of tantalum or niobium in the target composition	Pulse sputtering voltage (volt)	Sputtering power density (watt/centimetre ²)	Pulse-repetition (hertz)	Pulse width (μ s)	Sputtering time (hour)	Argon pressure (handkerchief)	Nitrogen pressure (handkerchief)	Sample table pulse amplitude (volt)	Pulse width (μ s)	Pulse-repetition (hertz)	Heating temperature (degree)
Implementation method		Pulse sputtering voltage (volt)	Sputtering power density (watt/centimetre ²)	Pulse-repetition (hertz)	Pulse width (μ s)	Sputtering time (hour)	Argon pressure (handkerchief)	Nitrogen pressure (handkerchief)	Sample table pulse amplitude (volt)	Pulse width (μ s)	Pulse-repetition (hertz)	Heating temperature (degree)	One	1.5％	-400	3	10000	20	1	0.8	0.8	-1000	5	5000	350
Two	3％	-600	5	40000	2	0.8	0.5	0.4	-4000	2	8000	300	One	1.5％	-400	3	10000	20	1	0.8	0.8	-1000	5	5000	350

Or the ratio of tantalum atom and titanium atom is alloys target or the mosaic target of 0.5:100～10:100, sputtering voltage-100～-1000V, sputtering current 0.05～10 peace, sample Heating temperature 100～500 degree, sputtering time 0.1～2 hour, sputtering pressure 0.1～2 handkerchief, sample table direct-current biasing 0～-1000 volt, pulsed bias 0～-5000 volt, pulse width 1～200 μ s, 5000～50000 hertz of frequencies.To surface deposition contain the artificial organs oxide treatment of the titanium nitride membrane of tantalum or niobium, can obtain niobium or tantalum doped titanium oxide film.

Embodiment 10: obtain niobium or the adulterated thin film of titanium oxide of tantalum with pulse sputter mode, embodiment is at first being contained in niobium-titanium or tantalum-titanium alloy target or mosaic target on the target platform 16 of magnetron sputtering equipment, artificial organs 7 is placed on the sample table 6, and vacuum chamber is evacuated to 1 * 10 ^-4Handkerchief, heating artificial organs 7 is opened gas cylinder group 18, feed argon gas and oxygen to vacuum chamber, argon pressure is 0.01～10 handkerchief, and oxygen pressure is 0.01～10 handkerchief, and transfer lever 17 is allocated to the pulse power 14, on target platform 16, add certain pulse negative high voltage, form argon, oxygen plasma, under the negative voltage effect, argon ion bombardment titanium-niobium or titanium-tantalum target, generation titanium, niobium atom or titanium, tantalum atom are deposited on the artificial organs 7, and combine the thin film of titanium oxide that formation contains niobium or tantalum with Sauerstoffatom.In order to improve film quality, in the deposition process, open grid bias power supply 19, on sample table 6, apply pulsed negative bias.Can obtain containing the thin film of titanium oxide of tantalum or niobium by three kinds of implementation methods shown in the table ten four.The control film

Table ten four

Implementation method	The atom content of tantalum or niobium in the target composition	Sputter pulsed voltage (volt)	Sputter mean power (watt/centimetre ²)	Heating temperature (degree)	Sputtering time (hour)	Argon pressure (handkerchief)	Oxygen pressure (handkerchief)	Sample table pulsed bias (volt)	Sample table pulse-repetition (hertz)	Sample table pulse width (μ s)
Implementation method		Sputter pulsed voltage (volt)	Sputter mean power (watt/centimetre ²)	Heating temperature (degree)	Sputtering time (hour)	Argon pressure (handkerchief)	Oxygen pressure (handkerchief)	Sample table pulsed bias (volt)	Sample table pulse-repetition (hertz)	Sample table pulse width (μ s)	One	0.5％	-300	2	100	1.5	1	0.5	-3000	50000	2
Two	3％	-600	5	300	0.8	1.5	1	-1000	5000	100	One	0.5％	-300	2	100	1.5	1	0.5	-3000	50000	2
Two	3％	-600	5	300	0.8	1.5	1	-1000	5000	100	Three	10％	-1000	8	500	0.2	2	2	-300	100	500

The parameter of performance comprises: the ratio of niobium atom or tantalum atom and titanium atom is alloys target or the mosaic target of 0.5:100～10:100, put on the pulsed voltage-300 of target～-1000V, 10000～50000 hertz of frequencies, pulse width 1-60 μ s, 1-15 watt/centimetre of sputtering power density ², sample Heating temperature 20～500 degree, sputtering time 0.1～2 hour, argon pressure 0.01～2 handkerchief, oxygen pressure 0.01～2 handkerchief, sample table pulsed bias 0～-5000 volt, pulse width 1-100 μ s, 5000～50000 hertz of frequencies, 1～100 rev/min of sample table speed of rotation.

Embodiment 11: adopt Niobium Pentxoxide-titanium dioxide or tantalum pentoxide-titanium dioxide ceramic target, utilize the radio-frequency sputtering mode to prepare niobium or tantalum doped titanium oxide film, Niobium Pentxoxide-titanium dioxide or tantalum pentoxide-titanium dioxide ceramic target is placed on the target platform 16 of magnetron sputtering equipment, artificial organs 7 is placed on the sample table 6, is evacuated to 1 * 10 ^-4Handkerchief, heating artificial organs 7, open gas cylinder 18, feed argon gas, argon pressure is 0.01～10 handkerchief, transfer lever 17 is allocated to radio-frequency power supply 14, on target platform 16, add certain radio-frequency voltage, form argon plasma, argon ion bombardment Niobium Pentxoxide-titanium dioxide or tantalum pentoxide-titanium dioxide ceramic target, generation titanium, niobium, Sauerstoffatom or titanium, tantalum, Sauerstoffatom are deposited on the artificial organs 7, synthetic tantalum or the adulterated thin film of titanium oxide of niobium.In order to improve film quality, in the deposition process, open grid bias power supply 19, on sample table 6, apply certain negative bias.Can sputter at synthetic tantalum in artificial organs surface or the adulterated thin film of titanium oxide of niobium by three kinds of implementation method utilizations shown in the table ten five.The parameter of control film performance is: 1～10 watt/cm of radio frequency power ², air pressure 10 ^-2～10 handkerchiefs, sample Heating temperature are 100～600 degree, sputtering time 0.1～3 hour.

Table ten five

Implementation method	Tantalum pentoxide or Niobium Pentxoxide molecule content in the target	Heating temperature (degree)	Radio frequency power (W)	Gaseous tension (handkerchief)	Sputtering time (hour)	Sample table bias voltage (volt)
Implementation method		Heating temperature (degree)	Radio frequency power (W)	Gaseous tension (handkerchief)	Sputtering time (hour)	Sample table bias voltage (volt)	One	0.3％	200	200	5	2	0
Two	1.5％	400	800	0.5	1	-300	One	0.3％	200	200	5	2	0
Two	1.5％	400	800	0.5	1	-300	Three	5％	600	2500	0.05	0.5	-500

As Fig. 4 (a) with (b), wherein illustrate respectively with platelet adhesion reaction situation on the method for the present invention institute synthetic thin-film material and RESEARCH OF PYROCARBON surface platelet adhesion reaction situation.In Fig. 4 (a) and 4 (b), white particle represents to stick to the thrombocyte on the material.Comparison diagram 4 (a) and 4 (b) can find that the platelet counts on Fig. 4 (a) obviously is less than the platelet counts of Fig. 4 (b), and this shows that its blood compatibility of material of the present invention of Fig. 4 (a) obviously is better than the blood compatibility of the RESEARCH OF PYROCARBON material of Fig. 4 (b).

Fig. 5 (a) for the inventive method synthetic thin-film material in animal body after the heeling-in hemocyte in the adhesion situation on surface, and Fig. 5 (b) and 5 (c) expression RESEARCH OF PYROCARBON surface hemocyte adhesion situation.Experimental result among the figure (photo) is in experimental animal dog body, is the tantalum doped Ti O of titanium with matrix ₂The test piece of film and the test piece of contrast RESEARCH OF PYROCARBON are suspended on two weeks in same the dog right atrium, this dog is handled without any anticoagulant during implanting, and dog is taken out sample with anesthesia surgery under the normal existence situation after two weeks, the surface is behind critical point drying, and is observable under electron microscope.As seen from the figure, the red blood corpuscle with the inventive method synthetic thin-film material surface has only very a spot of form to maintain the original state does not have any thrombosis.And the red blood corpuscle that can see the RESEARCH OF PYROCARBON surface in Fig. 5 (b) is destroyed, and gross distortion takes place.Can see among Fig. 5 (c) and form serious thrombus.

Fig. 6 (a) and (b) be respectively with institute of the present invention synthetic thin-film material carry out situation that thrombus behind the lobe frame animal in-vivo embed of commercial heart valve prosthesis of surface modification forms on the surface and with the lobe frame animal in-vivo embed of the heart valve prosthesis of surface modification not after thrombus form the contrast of situation on the surface.

Experiment condition: animal: dog, sample: the heart valve prosthesis lobe ring of institute of the present invention synthetic film surface modification and not the heart valve prosthesis lobe ring of surface modification hang in the dog right atrium, animal is handled without any anticoagulant during the implantation, dog is under the normal existence situation after three months, and sample is taken out in anesthesia and operation.

Fig. 6 (a): through the lobe frame of the heart valve prosthesis of institute of the present invention synthetic thin-film material modification thrombosis situation after the heeling-in in animal body.Fig. 6 (b) not the heart valve prosthesis of surface modification the lobe frame in animal body after the heeling-in thrombus form situation on the surface.As seen through the lobe frame of the heart valve prosthesis of institute of the present invention synthetic thin-film material surface modification in animal body after the heeling-in its surface thrombosis is seldom arranged, and coated whole lobe ring at the lobe frame surface thrombus of the heart valve prosthesis of surface modification not.

Fig. 7 is the contrast of the wearing character of the wearing character of carrying out the titanium Artificial heart valve mould material after the surface modification with institute of the present invention synthetic thin-film material and unmodified titanium Artificial heart valve mould material.As seen, the wearing character of the titanium Artificial heart valve mould material after institute of the present invention synthetic thin-film material carries out surface modification is much better than unmodified titanium Artificial heart valve mould material.

In sum, the product that obviously is better than prior art with its blood compatibility of method synthetic material film of the present invention and mechanical abrasive wear resistance.The applicant proposes claims for this reason.In the mode of specific embodiment the present invention is described, in fact, the present invention is not limited thereto embodiment.Any those of ordinary skills can be to implementation method correct of the present invention, and these to revise all should be in the scope of the invention.

Claims

1. one kind is carried out the method for comprehensive surface modification to the surface that comprises inorganic materials or organic materials, it is characterized in that with the synthetic TiO of plasm immersion ion implantation _2-x/ Ti-N-O/TiN gradient film, step wherein comprises:

(a) feed nitrogen in vacuum chamber, nitrogen is present in the vacuum chamber with neutral gas or plasmoid;

(b) with the metal arc plasma mode titanium plasma body is introduced vacuum chamber, make titanium, nitrogen ion bombard the surface of described material simultaneously, obtain TiN film bottom;

(c) with about 1 * 10 ^-3-1 * 10 ^-2Handkerchief/minute speed lower nitrogen pressure, and with 1 * 10 ^-3-1 * 10 ^-2Handkerchief/minute speed increase the pressure of oxygen, but like this synthetic nitrogen atom gradient descend, the Ti-N-O middle layer of Sauerstoffatom gradient increase;

(d) make the plasma body that only has oxygen and titanium in the vacuum chamber again, form TiO with the titanium plasma body _2-xFilm top layer, wherein x=0-0.35.

2. method as claimed in claim 1 is characterized in that nitrogen gas pressure is about 10 ^-3-1 handkerchief, if nitrogen exists with plasmoid, density is 10 ⁸-10 ¹²Centimetre ^-3

3. method as claimed in claim 1 is characterized in that the pressure of oxygen is about 10 ^-3-1 handkerchief, if oxygen exists with plasmoid, density is 10 ⁸-10 ¹²Centimetre ^-3

4. method as claimed in claim 1 is characterized in that described titanium metal plasma density is about 10 ⁸-10 ¹²Centimetre ^-3

5. an artificial organs surface is characterized in that described surface is to make with the method for claim 1.

6. in the implant into body and the surface of the apparatus that contacts with blood is characterized in that described surface is to make with the method for claim 1.

7. method as claimed in claim 1 is characterized in that also comprising step:

(e) be atmosphere with hydrogen, in vacuum chamber, feed hydrogen, and form hydrogen plasma;

(f) press the discharging current of about 0.1-5 peace with pact-0.2--5 Kilovolt Direct Current, or 5000～50000 hertz of frequencies, pulse width 1-200 μ s, average about 0.1-5 pulsed voltage of pacifying, making alive on described material;

(g) under 100～600 degrees centigrade environment, with described material hydrogenase 10 .1-2 hour, at TiO ₂The TiO of/Ti-N-O/TiN gradient film ₂Film is mixed hydrogen in the top layer,

(h) be about 10 at about 200-400 degree centigrade, vacuum tightness ^-4-10 ^-1Under the environment of handkerchief, with described material vacuum annealing about 0.1-1 hour.

8. method as claimed in claim 7 is characterized in that on described material hydrogen atom content is about 10%-35% in the formed film.

9. method as claimed in claim 8 is characterized in that on described material hydrogen atom content is 20% in the formed film.

10. method as claimed in claim 7 is characterized in that the hydrogen pressure that feeds is about 10 in step (e) ^-3-10 handkerchiefs, the density of its plasma body is about 10 ⁸-10 ¹²Centimetre ^-3

11. an artificial organs surface is characterized in that described surface is to make with the method for claim 7.

12. in the implant into body and with the surface of the contacted apparatus of blood, it is characterized in that described surface is to make with the method for claim 7.

13. method as claimed in claim 1 is characterized in that also comprising step:

(f) the about 50-20000 hertz of frequency, amplitude are about the 1-100 kilovolt, pulse width is that the negative voltage pulse of 1-200 μ s is added on the described material, forms hydrogen doping oxidation titanium film;

(g) be about 10 at about 100-400 degree centigrade, vacuum tightness ^-4-10 ^-1Under the environment of handkerchief, about 0.1-2 hour vacuum annealing is handled.

14., it is characterized in that on the described material that hydrogen atom content is about 10%-35% in the formed film as the method for claim 13.

15., it is characterized in that on the described material that hydrogen atom content is 20% in the formed film as the method for claim 14.

16., it is characterized in that the hydrogen pressure that feeds is about 10 in step (e) as the method for claim 13 ^-3-10 handkerchiefs, hydrogen plasma density are 10 ⁸-10 ¹²Centimetre ^-3, the hydrogen ion implantation dosage is 10 ¹⁵-1.2 * 10 ⁸Atom/centimetre ²

17. a human organs surface is characterized in that described surface is to make with the method for claim 13.

18. in the implant into body and with the surface of the contacted apparatus of blood, it is characterized in that described surface is to make with the method for claim 13.

19., it is characterized in that also comprising as the method for claim 13:

Repeating step (e), (f) and (g) 2-10 time, and when each the repetition, turn down the amplitude of added described negative voltage pulse in the described step (f) successively, mix the hydroxide titanium film thereby form, hydrogen is along depth of film direction uniform distribution, and protium content is about 10%-35%.

20., it is characterized in that protium content is 20% as the method for claim 19.

21., it is characterized in that the hydrogen pressure that feeds in the step (e) is about 10 as the method for claim 19 ^-2-10 handkerchiefs, hydrogen plasma density are 10 ⁸-10 ¹²Centimetre ^-3, the hydrogen ion implantation dosage is 10 ¹⁶-10 ¹⁸Atom/centimetre ²

22. an artificial organs surface is characterized in that described surface is to make with the method for claim 19.

23. in the implant into body and with the surface of the contacted apparatus of blood, it is characterized in that described surface is to make with the method for claim 19.

24. method as claimed in claim 1 is characterized in that also comprising step:

(e) with metallic cathode arc plasma mode tantalum or niobium ion are injected into TiO _2-xIn/Ti-N-O/TiN the film;

(f) on described thin-film material, add the about 100-20000 hertz of frequency, amplitude is about-the 1--100 kilovolt, the high pressure negative pulse of pulse width 1 μ s～200 μ s;

(g) be 10 at 100-800 degree centigrade, vacuum tightness ^-4-10 ^-1Under the environment of handkerchief vacuum annealing 0.1-2 hour.

25., it is characterized in that the density of metallic plasma in the described step (e) is 10 as the method for claim 24 ⁸-10 ¹²Centimetre ^-3, the implantation dosage of described tantalum or niobium is about 10 ¹⁵-5 * 10 ¹⁷Atom/centimetre ²

26. method as claim 24, it is characterized in that the tantalum of titanium, tantalum or titanium, niobium binary metal plasma body in described step (e) or the ion of niobium and the ratio of titanium ion are about 0.5:100-10:100, the atomic ratio of tantalum or niobium and titanium is about 0.5:100-10:100 in formed niobium or the tantalum doped titanium oxide film.

27. an artificial organs surface is characterized in that described surface is to make with the method for claim 24.

28. in the implant into body and with the surface of the contacted apparatus of blood, it is characterized in that described surface is to make with the method for claim 24.

29. method as claimed in claim 1, its feature also is when carrying out step (b), with the metal arc plasma mode titanium, tantalum or titanium, niobium plasma body are introduced vacuum chamber, make titanium, tantalum, nitrogen ion or titanium, niobium, nitrogen ion bombard the surface of described material simultaneously; When carrying out step (d), make the plasma body and the oxygen of the plasma body that only has titanium, tantalum in the vacuum chamber and oxygen or titanium, niobium, oxygen is neutral gas or plasmoid, thereby forms the TiO that contains tantalum or contain niobium _2-x/ Ti-N-O/TiN film, wherein x=0-0.35.

30., it is characterized in that nitrogen gas pressure is about 10 as the method for claim 29 ^-3-1 handkerchief, if nitrogen exists with plasmoid, density is 10 ⁸-10 ¹²Centimetre ^-3

31., it is characterized in that the pressure of oxygen is about 10 as the method for claim 29 ^-3-1 handkerchief, if oxygen exists with plasma mode, its density is about 10 ⁸-10 ¹²Centimetre ^-3

32., it is characterized in that titanium-tantalum or the titanium-niobium metal plasma density of introducing vacuum chamber are about 10 as the method for claim 29 ⁸-10 ¹²Centimetre ^-3, the ionic ratio of tantalum ion or niobium ion and titanium is 0.5:100～10:100 in titanium, tantalum or titanium, the niobium metal plasma body.

33. as the method for claim 29, it is characterized in that applying the negative voltage pulse that frequency is the 100-20000 hertz to sample table, its pulse voltage amplitude is at the 0.1-20 kilovolt; Pulse width 1～200 μ s.

34. an artificial organs surface is characterized in that described surface is to make with the method for claim 29.

35. in the implant into body and with the surface of the contacted apparatus of blood, it is characterized in that described surface is to make with the method for claim 29.