CN115704086B - Ion homopolar sputtering coating device and method - Google Patents
Ion homopolar sputtering coating device and method Download PDFInfo
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Abstract
The invention discloses an ion homopolar sputtering coating device and method. The target material and the matrix of the ion homopolar sputtering coating device are arranged at the same pole of the cathode, and the cathode is connected with a negative voltage power supply; the device comprises: a vacuum chamber with a plasma source inside; the shell of the vacuum chamber is grounded; a sample stage as a cathode; a plasma source; a vacuum device; the cavity of the vacuum chamber is communicated with the vacuum device and the gas source; a gas source; controlling the flow of the gas source through a valve; a target material; the target material is arranged on the sample table and is in direct contact with the sample table for conducting electricity; a negative voltage power supply; the negative voltage power supply is connected with the sample stage; a servo motor; a controller; the controller controls the servo motor to rotate, the negative voltage power supply to regulate voltage, the gas source to regulate flow, the vacuum device to vacuumize and the plasma source to power. The device designs the same pole of the target material and the matrix, not only can realize the sputtering coating of the insulator, but also can simultaneously improve the sputtering yield and the deposition rate.
Description
Technical Field
The invention relates to the field of biological material surface treatment, in particular to an ion homopolar sputtering coating device and method.
Background
Ion sputter coating is an important method for preparing bioactive films. The ion sputtering coating can be used for plating various functional films, such as films with osteogenesis, vascularization, antibiosis or anticancer performances, and can also form nano structures such as quantum dots, quantum wells or superlattices. Of course, ion sputter coating has also wide industrial application. Wherein, the ion sputtering coating film can be used for preparing self-lubricating films, superhard films, superconductive films, ferroelectric films and memory alloy films commonly used in the industries of flat panel displays, solar batteries, microwave devices, machinery and the like.
In order to rapidly prepare a film with high purity, high density, uniformity, flatness and strong binding force, researchers continuously improve an ion sputtering coating device, and the method comprises the steps of changing an ion source, adjusting the relative position of a substrate and a target material, loading a magnetic field to control the movement track of ions and the like. Whereas sputtering is the bombardment of a solid surface with energetic particles (typically ions) to cause the escape of ions from the solid surface, plating is the redeposition or injection of escaping elements into the substrate surface, and therefore the sputter yield and deposition rate are key parameters for ion sputter plating.
The influencing factors of the sputtering yield mainly include: (i) The energy particles bombard the solid surface to produce various effects, such as desorption of adsorbed gas on the solid surface, deposition of atoms on the solid surface, sputtering of surface atoms, and ion implantation. (ii) the energy of the incident ions. When the energy of the incident ions is smaller than a certain value, no particles are sputtered from the surface of the cathode. That is, there is a certain sputter energy threshold. The sputtering phenomenon may occur only when the incident ion energy is greater than the sputtering threshold. (iii) incident ion angle. Sputtering yields at oblique incidence are generally greater than normal incidence. (iv) incident ion species. The larger the mass of the incident ions, the larger the sputter yield. Inert gas is often selected as the working gas in sputter coating because the inert gas does not react with the cathode target. Argon is used as a common inert gas because of its low cost. (v) target species, crystal structure and temperature. The sputter yield shows a periodic variation with the atomic number of the target. Different crystal orientations for the same single crystal have different sputter yields. When the temperature is lower than a certain critical temperature, the sputtering yield does not change obviously along with the temperature change; and when the temperature is higher than a certain critical value, the sputtering yield tends to rise sharply with the temperature rise.
The deposition rate refers to the thickness of ions sputtered from the target deposited onto the substrate per unit time. The deposition rate is proportional to the sputter yield, to the target area, and to the sputtering device characteristics. In order to increase the deposition rate, the distance between the substrate and the target should be minimized, but too close a distance may result in unstable discharge. The distance from the target to the substrate must meet the condition of stable operation of the glow discharge, i.e. at least 3 to 4 times the width of the dark area of the cathode, and is generally selected to be 5 to 10cm. Whereby atoms (or ions) sputtered from the target in the sputter coating can frequently collide with atoms (ions) of the working gas.
The current ion sputtering coating equipment for direct current diode sputtering coating has the characteristics that a target material is separated from a substrate, the target material is a cathode, and the substrate is an anode. The coating apparatus has many disadvantages such as: the discharge parameters cannot be controlled independently, the deposition rate is low, the substrate temperature is easy to rise, the target and the substrate must be good conductors, etc. The above limits the wide application of ion sputter coating apparatus and methods. Meanwhile, as the materials of the target material and the sample frame are different, the ion bombardment of the sample frame can also generate sputtering effect, so that the substrate and the target material are polluted, and the purity of the film is influenced. In view of the foregoing drawbacks and deficiencies of ion sputter coating apparatus, there is a need for an ion sputter coating apparatus and method that can increase deposition rate, avoid sample stage contamination, and be suitable for use in insulator coating.
Disclosure of Invention
In order to solve the problems, the invention provides an ion homopolar sputtering coating device and method, wherein the device is designed to have the same pole with a substrate, so that not only can the insulator sputtering coating be realized, but also the sputtering yield and the deposition rate can be simultaneously improved.
In a first aspect, the present invention provides an ion homopolar sputter coating apparatus (which may also be referred to as an "ion sputter coating apparatus"). The target material and the matrix of the ion homopolar sputtering coating device are arranged at the same pole of the cathode, and the cathode is connected with a negative voltage power supply; the device comprises:
a vacuum chamber with a plasma source inside; the shell of the vacuum chamber is grounded;
a sample stage as a cathode; the sample table is arranged at the bottom of the vacuum chamber, is connected with a negative voltage power supply, and is driven to rotate by a servo motor;
a plasma source; the plasma source is arranged above the sample table and is connected with the controller;
a vacuum device; the cavity of the vacuum chamber is communicated with the vacuum device and the gas source;
a gas source; controlling the flow of the gas source through a valve;
a target material; the target material is arranged on the sample table and is in direct contact with the sample table for conducting electricity;
a negative voltage power supply; the negative voltage power supply is connected with the sample stage;
A servo motor; the servo motor is respectively connected with the sample table and the controller, and the servo motor drives the sample table and the target to move at a set speed under the control of the controller;
A controller; the controller controls the servo motor to rotate, the negative voltage power supply to regulate voltage, the gas source to regulate flow, the vacuum device to vacuumize and the plasma source to power.
The ion homopolar sputtering coating device adopts the homopolar sputtering coating of the target material and the matrix, has the advantages of simplified structure and simple operation, is suitable for surface treatment of metal materials, high polymer materials and inorganic nonmetallic materials, can improve the effects of sputtering yield and deposition efficiency, has high uniformity and bonding strength of the prepared film, and can solve the problem of sputtering pollution of a sample stage.
Preferably, the ion homopolar sputtering coating device further comprises an oil pump cooler for cooling the sample stage.
Preferably, the plasma source is a radio frequency plasma source or a Hall ion source; the power of the ion source is 50-2000W.
Preferably, the vacuum device comprises at least one of a mechanical pump, a Roots pump, and a molecular pump.
Preferably, the gas provided by the gas source is at least one of argon, nitrogen, hydrogen, oxygen, water vapor, carbon dioxide, acetylene, methane, and ammonia.
Preferably, a substrate is placed on the sample, the substrate being in contact with the target or the substrate being insulated from the target; preferably, an insulating layer of insulating material is provided between the substrate and the target.
Preferably, the substrate is a conductor, a semiconductor or an insulator; the material of the matrix is a high polymer material, an inorganic nonmetallic material or a metallic material with an insulating coating.
Preferably, the target is metal or alloy.
In a second aspect, the invention provides an ion homopolar sputtering coating method. The method uses the ion homopolar sputtering coating device of any one of the above to carry out ion homopolar sputtering coating. The method comprises the following steps: placing a substrate and a target above a sample stage connected with negative voltage, exciting gas by a plasma source under the action of the negative voltage to generate gas ions to bombard the target, sputtering target elements onto the surface of the substrate, and simultaneously injecting and depositing to realize film plating on the surface of the substrate.
Preferably, the background vacuum degree is 1X 10 -4～1×10-2 Pa, the gas flow rate is 1-200 sccm, the working vacuum degree is 1X 10 -2 -5X 100Pa, the ion source power is 50-2000W, the negative voltage is 0.1-50 kV, and the duty ratio is 10% -80%.
Drawings
FIG. 1 is a schematic diagram of an ion homopolar sputter coating device of the present invention;
FIG. 2 is a sputtering schematic diagram of an ion homopolar sputtering coating device;
FIG. 3 is an SEM image of a sample obtained by sputtering a Cu target on the surface of a Ge substrate, an EDS mapping spectrum of Ge element, an EDS mapping spectrum of Cu element, and an EDS mapping spectrum of superposition of two elements of Ge and Cu;
FIG. 4 is a practical photograph of a Cu target for ion sputter coating of PEEK;
FIG. 5 is a distribution of surface elements of a sample obtained by sputtering a Cu target with a vertically placed polyether-ether-ketone sheet;
FIG. 6 is a distribution of surface elements of a sample obtained by sputtering a horizontally placed polyether-ether-ketone sheet with a Cu target;
FIG. 7 shows the surface element distribution of a sample obtained by sputtering a Cu target and vertically placing a polyether-ether-ketone rod;
FIG. 8 is a surface topography of samples obtained by sputtering a horizontally placed polyether ether ketone sheet and vertically placed polyether ether ketone sheet on a Cu target;
FIG. 9 shows the surface effect (Cu atom number ratio) and theoretical sputter yield of samples obtained by sputtering PEEK with different targets;
FIG. 10 is a photograph of sample obtained by two placement modes of contact and insulation before and after sputtering;
FIG. 11 shows the Cu content of the sputtered substrate surface in both contact and insulation modes;
FIG. 12 is a graph showing the surface Cu content and theoretical calculation of samples obtained by sputtering different types of substrates with Cu targets;
FIG. 13 shows Cu element contents of the upper surface and the side surfaces of different matrixes sputtered by Cu targets;
FIG. 14 shows the Cu element content and theoretical sputter yield of Cu targets sputtering different substrates at negative biases below 1000V;
FIG. 15 shows Cu element contents and theoretical sputter rates of different matrixes sputtered by Cu targets at negative high voltage of more than 1 kV;
FIG. 16 is a graph showing the antimicrobial effect of various PEEK modified surfaces against Staphylococcus aureus;
FIG. 17 shows the antibacterial effect of various PEEK modified surfaces on E.coli;
FIG. 18a is a surface topography and EDS composition analysis of PEEK samples and ArFe samples;
FIG. 18b is a surface topography and EDS composition analysis of ArFe samples and ArFe samples;
FIG. 19 shows the elemental content of surface C, O, fe for PEEK samples, arFe samples, arFe samples, and ArFe samples;
FIG. 20 shows surface contact angles of PEEK samples, arFe samples, arFe samples, and ArFe60 samples;
FIG. 21 is a plot of surface zeta potential versus pH for PEEK samples, arFe samples, arFe samples, and ArFe samples;
FIG. 22a is a graph of adhesion morphology of MC3T3-E1 osteoblasts 1h, 4h and 24h of PEEK samples and ArFe samples;
FIG. 22b is a graph of the adhesion morphology of MC3T3-E1 osteoblasts 1h, 4h and 24h for ArFe samples and ArFe60 samples;
FIG. 23 shows the cell proliferation effect of the surface rBMSCs of PEEK, arFe, arFe, and ArFe, 60 samples.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the invention, it should be understood that the terms "center," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like indicate or are based on the orientation or positional relationship shown in the drawings, merely to facilitate describing the invention and simplify the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the invention. In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
Negative voltage refers to the voltage at a point in the overall loop relative to a reference point. In the present invention, negative voltage refers to a negative voltage that is biased relative to the grounded enclosure potential.
The present disclosure provides an ion homopolar sputter coating device. The target material and the matrix of the device are arranged at the same pole of the cathode, and the cathode is connected with a negative voltage power supply. The ion homopolar sputtering coating device comprises: the device comprises a vacuum chamber, a sample table, a plasma source, a vacuum device, a gas source, a target, a negative voltage power supply, a servo motor and a controller. A plasma source is disposed in the vacuum chamber. The plasma source is a radio frequency plasma source or a hall ion source. The plasma source is placed on top of the vacuum chamber (above the sample stage). The ion source power may be 50W-2000W. The plasma source is connected with the controller. The outer shell of the vacuum chamber is grounded. The cavity of the vacuum chamber is communicated with the vacuum device and the gas source. The vacuum device includes at least one of a mechanical pump, a Roots pump, and a molecular pump. The vacuum device can control the air pressure in the cavity of the vacuum chamber to be between 1 multiplied by 10 -4～5×101 Pa. The flow of gas (source) may be controlled by a valve. The sample stage is a cathode, is connected with a negative voltage power supply, and is arranged at the bottom of the vacuum chamber. The sample stage may be driven to rotate by the servo motor. The servo motor is connected with the sample table and the controller respectively. The servo motor drives the sample table and the target to move at a set speed under the control of the controller. Therefore, the device adopts the mode that the substrate and the target are positioned at the same cathode, the sputtering yield and the deposition efficiency are improved, the target and the sample table rotate at a certain speed under the control of the servo motor, the sputtering is uniform, and the equipment is simplified.
The target is arranged on the sample table. The target material can be in direct contact with the sample stage for conduction. The target material is metal or alloy. When the device is used for ion sputtering, a substrate is placed on a target. The substrate may be in direct contact with the sample stage or may be indirectly underlying the sample stage through the spacing of the insulating layers. The substrate may be a conductor, a semiconducting insulator. Therefore, the target material has the sputtering function and can isolate the sputtering function of the sample stage, and the problem of sample stage pollution of the conventional ion sputtering coating equipment is solved. The target material is fixed on the surface of the sample table by gravity and friction, so that the replacement is convenient and the manufacture is simple. Of course, because the matrix is placed on the target, the servo motor drives the sample stage, the substrate and the target to move at a set speed under the control of the controller.
Optionally, the coating device comprises an oil pump cooler. The oil pump cooler is used for cooling the sample stage.
The basic principle of sputtering coating is that gas is subjected to glow discharge under the vacuum condition of charging gas, at the moment, gas atoms are ionized into gas ions, the gas ions are accelerated to bombard a cathode target made of a coating material under the action of an electric field force, and the target is sputtered out and deposited on the surface of a workpiece. The invention relates to an ion homopolar sputtering coating device, which is characterized in that a substrate is placed on a target, negative voltage is loaded, the target and the substrate are arranged on the same pole of a cathode, a plasma source is positioned right above the target, gas plasma is generated in atmosphere, the target is bombarded under the action of the negative voltage, and target elements are sputtered on the surface of the substrate. The substrate and the target are subjected to homopolar sputtering coating, so that the equipment is simplified, and the sputtering efficiency is high.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of the invention will be rendered by reference to the appended drawings and appended detailed description.
Fig. 1 is a schematic structural diagram of an ion sputtering coating device provided by the invention. As shown in FIG. 1, the ion homopolar sputtering coating device comprises a vacuum chamber, a gas source, a plasma source, a vacuum device, a negative voltage power supply, a sample stage, a target, a servo motor (not shown in the figure) and a controller (not shown in the figure). The sample stage is arranged at the bottom of the vacuum chamber, can be driven to rotate by the servo motor, and can be loaded with the negative voltage of the negative voltage power supply. The voltage of the negative voltage power supply is adjustable from 50kV to 100V. The vacuum chamber housing is grounded, the vacuum chamber cavity is communicated with the vacuum pump and the gas source, and the flow can be controlled through the valve. The servo motor is connected with the sample table and the controller respectively. The servo motor drives the sample table, the target (and the matrix) to move at a set speed under the control of the controller. The plasma source is a radio frequency plasma source. The plasma source is connected with the controller. The plasma source is arranged above the sample stage and is 5 cm-150 cm away from the sample stage. The target material is placed on the sample stage, can be in direct contact with the sample stage for conducting electricity, is loaded with negative voltage, and is fixed on the sample stage by gravity and friction. The (film-coated) substrate is placed on the target and is in the same pole as the target. The target may be insulated from the substrate, the insulation resulting from the substrate itself being non-conductive or by providing an insulating layer between the substrate and the target. The insulating layer may be made of an insulating material.
Fig. 2 is a schematic view of a sputtering principle of the ion sputtering coating device of the invention. The target material and the matrix of the ion homopolar sputtering coating device are arranged at the same pole of the cathode, and the cathode is connected with a negative voltage power supply. In the implementation process of sputtering coating, a substrate is in direct contact with a target, the target is loaded with negative voltage, and the surface of the target is negatively charged; when the sample table is used for placing the conductive matrix and is in direct contact with the target, the conductive matrix is negatively charged, the surface of the matrix is in equipotential with the target, generated gas ions bombard the matrix and the target under the action of the same electric field, and partial substances of the target are bombarded and sputtered on the surface of the matrix, but are easily bombarded again by the gas ions to be separated from the surface of the matrix, so that the deposition effect is poor. Particularly, when the sputtering rate of the target material is lower than that of the surface of the substrate, the target material cannot be deposited on the surface of the substrate, and the target material is polluted by the substrate element. When a semiconductor substrate, particularly an insulator substrate, is placed, the target is loaded with a negative voltage, the surface of the target is negatively charged, and the contact surface of the substrate and the target is negatively charged. Because the matrix is not conductive, the charge transportation is difficult, and the whole matrix is maintained to be electrically neutral, the other surface of the matrix is positively charged, an electric field formed by positively charging the surface of the matrix weakens or even counteracts the negatively charged target material to form an electric field, the generated gas ions bombard the surface of the target material under the action of different electric fields, the acting force bombarding the surface of the matrix is strong, the acting force bombarding the surface of the matrix is weak, and the sputtered elements of the target material can be deposited on the surface of the matrix to form a film. Therefore, the ion sputtering coating device is suitable for surface treatment of high polymer materials, inorganic nonmetallic materials and metal matrixes with insulating films. In addition, when the sample stage is provided with the conductive matrix and an insulating layer is arranged between the matrix and the target for isolation, the target is loaded with negative voltage, and the surface of the target is negatively charged. Because the insulating layer is isolated, the charge transportation is difficult, and the neutrality of the whole matrix is maintained, the other surface of the matrix is positively charged, an electric field formed by positively charging the surface of the matrix weakens or even counteracts the negatively charged target material to form an electric field, generated gas ions bombard the surface of the target material under the action of different electric fields, the acting force bombarding the surface of the matrix is strong, and sputtered elements of the target material can be deposited on the surface of the matrix to form a film. Therefore, the ion sputtering coating device is also suitable for the surface treatment of the conductive material matrix.
The ion homopolar sputtering coating method by using the ion homopolar sputtering coating device comprises the following steps: placing a substrate and a target above a sample stage connected with negative voltage, exciting gas by a plasma source under the action of the negative voltage to generate gas ions to bombard the target, sputtering target elements onto the surface of the substrate, and simultaneously injecting and depositing to realize film plating on the surface of the substrate. The film prepared by the method is uniform and smooth, high in density and firm in combination. In the method, the background vacuum degree is 1X 10 -4～1×10-2 Pa, the gas flow rate is 1-200 sccm, the working vacuum degree is 1X 10 -2 -5X 100Pa, the ion source power is 50-2000W, the negative voltage is 0.1-50 kV, and the duty ratio is 10% -80%. The method can be used for modifying the surface of biological materials and improving the biological activity and antibacterial property of the biological materials.
In the following examples, the target was a metal disc 160mm in diameter, 2mm in thickness, and >99.99% pure. The disk is made of iron (Fe), titanium (Ti), copper (Cu), magnesium (Mg), nickel (Ni) and zinc (Zn). The substrate is made of one of polyether-ether-ketone, pure titanium and pure germanium.
Example 1
The substrate is pure germanium with the thickness of 10mm multiplied by 1mm, and the surface is smooth. The ion homopolar sputtering film plating device of the invention is adopted to sputter and deposit copper ions on the surface of a pure germanium matrix. The parameters of the specific ion homopolar sputtering coating are shown in Table 1. The surface of the obtained sample was subjected to microcomponent analysis by means of a scanning electron microscope (Hitachi S4800).
TABLE 1 parameters of ion homopolar sputter coating
Fig. 3 is a mapping spectrum of SEM and EDS elements sputtered on the surface of a germanium sample using a copper target. It can be seen that the copper target is sputter deposited onto the germanium substrate surface by argon ion bombardment, in the form of particles of tens to hundreds of nanometers. The ion homopolar sputtering coating film of the invention can be used for coating the surface of semiconductor materials.
Example 2
The polyether-ether-ketone sheet with the length of 20mm multiplied by 1mm is respectively horizontally placed and vertically placed on the surface of the target material or is to be placedThe polyether-ether-ketone rod is vertically arranged on the surface of the target material. The homopolar ion sputtering film plating device of the invention is adopted to sputter and deposit copper ions on the surface of the polyether-ether-ketone group. The parameters of the specific ion homopolar sputtering coating are shown in Table 2. The placement is shown in fig. 4. The surface of the obtained sample was subjected to microcomponent analysis by a scanning electron microscope (Hitachi S2800).
TABLE 2 parameters of ion homopolar sputter coating
Fig. 4 is a practical photograph of a Cu target for ion sputter coating of polyetheretherketone. It can be seen that the sputtering coating range is larger and the sputtering distance is longer. Fig. 5 shows the surface element distribution of a sample obtained by sputtering a vertical placement of a polyetheretherketone sheet with a Cu target, and it is known that the Cu element increases rapidly with the height during sputtering in the vertical direction, reaches a peak at a height of 9mm, and then decreases slowly. Fig. 6 shows the distribution of surface elements of samples obtained by horizontally placing a polyetheretherketone sheet on a Cu target by sputtering, and it is known that the distribution of Cu elements is uniform when sputtering in the horizontal direction. Fig. 7 shows the distribution of surface elements of samples obtained by vertically placing polyether-ether-ketone rods on a Cu target by sputtering, and shows that the Cu element increases with the height and then slowly decreases with the sputtering height exceeding 100mm when sputtering in the vertical direction. FIG. 8 shows the surface morphology of samples obtained by sputtering a horizontally placed polyether-ether-ketone sheet and a vertically placed polyether-ether-ketone sheet on a Cu target, wherein the sputtering elements are uniformly distributed in the horizontal direction, and the surface is smooth and flat; the surface is rough in the vertical direction.
Example 3
Will beThe polyether-ether-ketone wafer is horizontally placed on the surfaces of different targets, and the ion homopolar sputtering film plating device of the invention adopts the ion sputtering deposition of different targets to the surfaces of the polyether-ether-ketone. The parameters of the specific ion homopolar sputtering coating are shown in Table 3. The surface of the obtained sample was subjected to microcomponent analysis by a scanning electron microscope (Hitachi S2800). Meanwhile, the TRIM simulation software is adopted to perform theoretical simulation on the argon ion bombarded target material, the sputtering rate is calculated, and the sputtering rate is compared with the actual sputtering effect. The nomenclature of samples obtained from the sputtering of different targets is shown in Table 4.
TABLE 3 parameters of ion homopolar sputter coating
Table 4 target and corresponding sample nomenclature
| Target material | Magnesium (Mg) | Titanium | Iron (Fe) | Copper (Cu) | Nickel (Ni) | Zinc alloy |
| Naming the name | ArMg60 | ArTi60 | ArFe60 | ArCu60 | ArNi60 | ArZn60 |
FIG. 9 shows the surface effect and theoretical sputter yield of PEEK sputtered from different targets. Different targets have different sputter deposition amounts on the surface of the polyether-ether-ketone. Wherein the content of the target element deposited on the surface of the polyether-ether-ketone is positively correlated with the sputtering rate of the surface of the target. Generally, the easier the target is to be bombarded and sputtered by argon ions, the more the sputtering deposition amount of the target on the surface of the substrate is.
Example 4
To be used forPolyether ether ketone (PEEK), pure titanium (Ti), pure magnesium (Mg) and pure Mei (Fe 2O3 @ Mg) coated with an iron oxide coating were samples. Two samples were taken and divided into two groups. One set was placed directly on the copper target surface (contact) and the other set of 20mm x10 mm x 1mm polyether ether ketone insulating sheets was placed on the copper target surface (insulating placement), as shown in fig. 10. The ion homopolar sputtering film plating device of the invention is adopted to sputter and deposit the copper target material on the surface of each substrate. The parameters of ion homopolar sputtering coating are the same as in Table 3. The surface of the obtained sample was subjected to microcomponent analysis by a scanning electron microscope (Hitachi S2800).
Fig. 11 shows the sputtered Cu element content on the substrate surface for both substrate and target contact and substrate and target insulation. It is found that when the conductive metal sample contacts the target, the deposition effect of ion sputtering is poor, and the conductive metal sample hardly contains target elements. When the surface is provided with an insulating coating or an insulator is adopted to isolate the conductive matrix from the target, the conductive matrix has good effect of depositing target elements. For a non-conductive matrix such as a high polymer material polyether-ether-ketone, the polyether-ether-ketone is directly placed on the surface of a target, and the target has a good sputtering deposition effect on the matrix under the bombardment of argon ions.
Example 5
Will beThe invention relates to a polyether ether ketone (PEEK), paper, boron Nitride (BN), germanium (Ge), graphite (C), pure magnesium (Mg), pure titanium (Ti) and nickel titanium alloy (NiTi) sample which are directly placed on the surface of a copper target, and the ion homopolar sputtering coating device is adopted to sputter and deposit the ions of the copper target on the surface of each substrate. The parameters of ion homopolar sputtering coating are the same as in Table 3. The front and side surfaces of the obtained samples were subjected to microcomponent analysis by a scanning electron microscope (Hitachi S2800). And carrying out theoretical simulation calculation on a sample bombarded by argon ions on the surface of the substrate by adopting TRIM simulation software, and referring to the actual deposition effect.
Fig. 12 shows the surface Cu element content and theoretical calculations of samples obtained by sputtering different types of substrates with Cu targets. The content of target elements deposited on the surfaces of the substrates made of different materials is different. The higher the sputtering rate of the target element on the surface of the substrate, the less target element is deposited on the surface of the substrate. In addition, the surface electric field intensity of the conductive metal matrix is higher than that of the non-conductive matrix, so that the content of target elements deposited on the surface of the conductive metal matrix is lower than that of the insulator and the semiconductor matrix.
Fig. 13 shows Cu element contents of upper and side surfaces of different substrates sputtered by Cu targets. The sputtering element content on the side of the substrate was higher than on the front of the substrate.
Example 6
Will beThe polyether ether ketone (PEEK), pure magnesium (Mg) and pure titanium (Ti) samples are directly placed on the surfaces of copper targets, and the ion homopolar sputtering coating device is adopted to sputter and deposit the ions of the copper targets on the surfaces of all matrixes under different negative loading voltages. The parameters of ion homopolar sputtering coating are shown in the table. The surface of the obtained sample was subjected to microcomponent analysis by a scanning electron microscope (Hitachi S2800). And carrying out theoretical simulation calculation on the sputtering rate of the Cu target bombarded by the argon ions with different energies by adopting TRIM simulation software, and referring to the actual deposition effect.
TABLE 5 parameters of ion homopolar sputter coating
FIG. 14 shows the Cu element content and the theoretical sputter yield of Cu targets sputtered from different substrates at negative biases of 1000V or less. FIG. 15 shows the Cu element content and the theoretical sputter yield of Cu targets sputtered at negative high voltages of 1kV or more for different substrates. The voltage is increased, the sputtering rate is increased, and the content of target elements deposited on the surface of the substrate by sputtering is increased. When the voltage is too high, the insulator breaks down into a conductor, and the content of target elements deposited by surface sputtering is reduced.
The formula of influencing factors of the sputtering rate of the target material is shown in vacuum coating principle and technology (main edition of square Ying Cui, scientific press):
wherein: y is the sputtering rate, α is the parameter, M 1 is the incident ion mass, M 2 is the target atomic mass, E is the incident ion energy, and U s is the target surface free energy.
The influence formula of the deposition rate of target elements deposited on the surface of the substrate:
Q＝C(jT-jS)Aθγ
Wherein: q is the deposition rate, C is the device characteristic parameter, j T is the target ion current density, j S is the sample ion current density, A is the target area, and θ is the sputtering atomic angular distribution.
From examples 1-6, it can be summarized that:
Sample conductivity affects sample ion current density j S: the better the sample insulation, the smaller j S, the less sputtered elements;
Sample orientation affects sputter atomic angle distribution θ: the sputtering element content of the side surface is higher than that of the front surface;
sample height affects device characteristic parameter C: the height is increased, and the content of sputtering elements is increased and then decreased;
the target species affects the target surface free energy Us and the target atomic mass M 2: the free energy and atomic mass of the surfaces of different targets are different;
The magnitude of the negative voltage affects the incident ion energy E, the target ion current density j T: the higher the negative voltage, the greater E, j T, the higher the sputtered element content, but the negative voltage too high voltage can breakdown the sample, resulting in an increase in j S.
Example 7
Staphylococcus aureus (Staphylococcus aureus, S.aureus, ATCC 25923) and Escherichia coli (ESCHERICHIA COLI, E.coli, ATCC 25922) were selected, and the antibacterial properties of the polyether-ether-ketone material obtained by modification in example 3 were evaluated by antibacterial experiments. The method comprises the following specific steps: 1) Placing a sample sterilized by using ethanol with the volume fraction of 75% in a culture plate, sucking 60 mu L of bacterial liquid with the density of 10 6 cfu/mL, inoculating the bacterial liquid on the surface of the sample, keeping the humidity to be more than 90%, and placing the sample in an anaerobic incubator at 36.5 ℃ for culturing for 24 hours; 2) Adding 0.5mL of physiological saline containing AlamarBlueTM% dye solution by mass percent into a sample, placing a culture plate into an incubator for culturing for 2 hours, taking out 100 mu L of dye solution from each hole, and placing into a 96-well plate; 3) Absorbance values at 560nm and 590nm wavelengths were measured for each well using a microplate reader (BIO-TEK, ELX 800). The greater the fluorescence intensity, the greater the bacterial count. The relative bacterial number can be calculated by subtracting the fluorescence intensity of the blank control from the fluorescence intensity of the experimental group, and the antibacterial rate can be calculated according to the following formula:
antibacterial ratio= (a-B)/a×100%. Wherein A is the relative bacterial number of the control group sample, and B is the relative bacterial number of the experimental group sample.
FIGS. 16 and 17 show the bacterial count of the surface cultures of Staphylococcus aureus and Escherichia coli, respectively, on unmodified samples and polyether ether ketone obtained by modification in example 3, and the corresponding statistical results. As can be seen from fig. 16 and 17: the Zn, mg, ni, cu target material modified sample has fewer bacteria on the surface, the antibacterial rate reaches more than 80 percent, and particularly the antibacterial rate of the Zn and Cu target material modified sample is close to 100 percent. The Fe target material modified polyether-ether-ketone surface has no obvious antibacterial effect on two bacteria. The ion homopolar sputtering coating device has wide application prospect in the preparation of polyether-ether-ketone biological antibacterial coatings.
Example 8
Will beThe polyether-ether-ketone wafer is horizontally placed on the surface of an iron target, and the ion homopolar sputtering coating device is adopted to sputter and deposit iron ions on the surface of a polyether-ether-ketone substrate. The ion homopolar sputtering coating film is shown in Table 6. The surface of the obtained sample was subjected to microcomponent analysis by a scanning electron microscope (Hitachi S2800). Sample designations for different sputtering durations are shown in table 7.
TABLE 6 parameters of ion homopolar sputter coating
TABLE 7 sample naming for different sputtering durations
Fig. 18a is a surface topography and EDS composition analysis of PEEK and ArFe samples, and fig. 18b is a surface topography and EDS composition analysis of ArFe and ArFe60 samples. Fig. 19 shows the elemental content of surface C, O, fe for PEEK, arFe, arFe, and ArFe samples. The surface elements of the sample obtained by injecting PEEK through Fe sputtering are uniformly distributed, the main component is iron oxide, and the appearance of the oxide film is compact.
Example 9
The surface wettability of the samples obtained in example 8 was tested using a static water contact angle tester (Automatic Contact ANGLE METER Model SL200B, solon information technology co., ltd, china). 2. Mu.L of ultrapure water was suspended drop-wise onto the sample surface by means of a syringe, and a photograph of the drop was taken using a machine self-contained imaging system and the contact angle size was analyzed. Three measurements were averaged over the sample.
Fig. 20 shows the surface contact angles of PEEK, arFe, arFe, and ArFe samples. The surface contact angles of PEEK samples were approximately 90 °, arFe, arFe30, and ArFe60 samples were approximately 20 °, approaching the super-hydrophilic state. The Fe ion sputtering injection is performed on the PEEK material surface to introduce iron element, so that the hydrophilicity of the material surface is increased.
Example 10
The surface zeta potential of the polyetheretherketone material before and after modification of example 8 was characterized using a zeta potential tester (Anton Parr, austria). The specific method comprises the following steps: the pH of the potassium chloride (KCl) solution was adjusted using 0.01M hydrochloric acid (HCl) and 0.01M sodium hydroxide (NaOH). The KCl solution was run under pressure along the sample surface at the time of the test. The relative movement of ions in the diffusion layer was calculated according to the Helmholtz-smolichowski formula to obtain the zeta potential value:
Zeta potential in the formula, dU/dP represents the slope of flow potential/pressure, eta, epsilon 0, epsilon and K represent electrolyte viscosity, vacuum dielectric constant, dielectric permittivity and conductivity, respectively. The Zeta potential (ζ) is automatically calculated by the instrument. The average value of zeta potential was found by taking four measurement data.
FIG. 21 is a plot of surface zeta potential versus pH for PEEK samples, arFe samples, arFe samples, and ArFe samples. At ph=7.4, the surface zeta potential values of PEEK, arFe15, arFe, and ArFe60 samples were about-86 mV, -50mV, -43mV, and-41 mV, respectively, showing an upward trend in the surface zeta potential of the sample at ph=7.4 after Fe ion sputter deposition.
Example 11
MC3T3-E1 osteoblasts are selected, and in-vitro cell culture experiments are adopted to evaluate the cell compatibility of the polyether-ether-ketone material obtained through modification treatment in the embodiment 8. Observing the morphology of the cells on the surface of the material by using SEM, the experimental procedure was as follows: 1) Placing a sample sterilized by using 75% ethanol with a volume fraction into a 24-well culture plate, and dropwise adding 1mL of MC3T3-E1 cell suspension with a density of 5X 104 cells/mL into each well; 2) Placing the cell culture plate into a cell culture box with the volume fraction of 5% CO 2 and the saturated humidity, and incubating at 36.5 ℃ for 18 hours; 3) Sucking the cell culture solution, cleaning the surface of the sample with PBS, transferring the sample into a new 24-well plate, and placing the sample into an incubator for continuous culture; 4) After 1, 4 and 7 days of cell culture, the samples were taken out, fixed with glutaraldehyde with a mass fraction of 2% at room temperature for 24 hours, and washed three times with PBS; 5) Dehydration of the immobilized cells with gradient alcohol (30%, 50%, 75%, 90%, 95% and 100%); 6) The samples were sequentially placed in mixed solutions of alcohol and Hexamethyldisilazane (HMDS) in different ratios (alcohol: hmds=2:1, 1:1, 1:2, and 100% HMDS), for 10min each. After the sample was sprayed with gold, the cell morphology on the sample surface was observed by SEM.
Fig. 22a is a graph showing the adhesion profiles of MC3T3-E1 osteoblasts 1h, 4h and 24h of PEEK sample and ArFe sample, and fig. 22b is a graph showing the adhesion profiles of MC3T3-E1 osteoblasts 1h, 4h and 24h of ArFe sample and ArFe60 sample. It can be seen that: MC3T3-E1 has a faster adhesion rate on the surface of the modified sample, and a large number of cells adhere to the surface of the sample at 1h. And the cell pseudopodia of the modified sample is more stretched, the morphology is more spread, and the modified sample is shown to have better cell compatibility.
Example 12
The cell compatibility of the polyetheretherketone material obtained by the modification treatment of the above example 8 was evaluated by using rBMSCs rat spinal mesenchymal stem cell in vitro culture experiments. Proliferation of cells on the surface of the material was detected using AlamarBlueTM (AbD serotec Ltd, UK) kit. The method comprises the following steps: 1) Placing a sample sterilized by using 75% ethanol by volume fraction into a 24-well culture plate, and dripping 1mL of rBMSCs cell suspension with the density of 2X 10 4 cells/mL into each well; 2) Placing the cell culture plate into a cell culture box with 5% CO 2 saturated humidity by volume fraction, and incubating at 36.5 ℃ for 24 hours; 3) Sucking the cell culture solution, cleaning the surface of the sample with PBS, transferring the sample into a new 24-well plate, and placing the sample into an incubator for continuous culture; 4) After 1, 4 and 7 days of cell culture, the original culture solution is sucked, new culture solution containing AlamarBlueTM dye solution with the mass fraction of 10% is added, the culture plate is placed in an incubator for 2 hours, and 100 mu L of culture solution is taken out from each hole and placed in a 96-well plate; 5) Absorbance values at 560nm and 590nm wavelengths were measured for each well using a microplate reader (BIO-TEK, ELX 800). The greater the fluorescence intensity, the greater the cell number. The relative cell number can be calculated by subtracting the fluorescence intensity of the blank from the fluorescence intensity of the experimental group.
FIG. 23 shows the cell proliferation effect of the surface rBMSCs of PEEK, arFe, arFe, and ArFe, 60 samples. It can be seen that: the surface proliferation condition of rBMSCs cells on the polyether-ether-ketone obtained by the modification treatment of the embodiment 8 is obviously better than that of unmodified samples, which shows that the modified samples have no obvious cytotoxicity and can promote the proliferation of mesenchymal stem cells.
In conclusion, the ion homopolar sputtering coating device and the ion homopolar sputtering coating method are simple and easy to control, the mode that the substrate and the target are positioned at the same cathode is adopted, the sputtering yield and the deposition efficiency can be improved, sputtering elements are uniformly distributed, equipment is simplified, meanwhile, the good sputtering effect on the surfaces of semiconductors and insulators, particularly high polymer materials is achieved, particularly, the sputtering can be achieved on the surfaces of complex substrates with large length-diameter ratio, porous structures and the like, and the prepared film has high compactness and bonding strength. When the metal target material with biological activity and antibacterial property is adopted, the surface of the high polymer medical material can be endowed with good biological activity and antibacterial property, and the high polymer medical material has good application effect and prospect in the aspect of biological material surface modification.
Claims (11)
1. The ion homopolar sputtering coating device is characterized in that a target material and a substrate of the ion homopolar sputtering coating device are arranged on the same pole of a cathode, and the cathode is connected with a negative voltage power supply; the device comprises:
a vacuum chamber with a plasma source inside; the shell of the vacuum chamber is grounded;
a sample stage as a cathode; the sample table is arranged at the bottom of the vacuum chamber, is connected with a negative voltage power supply, and is driven to rotate by a servo motor;
a plasma source; the plasma source is arranged above the sample table and is connected with the controller;
a vacuum device; the cavity of the vacuum chamber is communicated with the vacuum device and the gas source;
a gas source; controlling the flow of the gas source through a valve;
a target material; the target material is arranged on the sample table and is in direct contact with the sample table for conducting electricity;
a negative voltage power supply; the negative voltage power supply is connected with the sample stage;
A servo motor; the servo motor is respectively connected with the sample table and the controller, and the servo motor drives the sample table and the target to move at a set speed under the control of the controller;
A controller; the controller controls the servo motor to rotate, the negative voltage power supply to regulate voltage, the gas source to regulate flow, the vacuum device to vacuumize and the plasma source to power.
2. The ion homopolar sputter coating apparatus of claim 1 further comprising an oil pump cooler for cooling the sample stage.
3. The ion homopolar sputter coating apparatus of claim 1 wherein the plasma source is a radio frequency plasma source or a hall ion source; the power of the ion source is 50-2000W.
4. The ion homopolar sputter coating apparatus of claim 1, wherein the vacuum apparatus comprises at least one of a mechanical pump, a Roots pump, and a molecular pump.
5. The ion homopolar sputter coating apparatus of claim 1, wherein the gas provided by the gas source is at least one of argon, nitrogen, hydrogen, oxygen, water vapor, carbon dioxide, acetylene, methane, and ammonia.
6. The ion homopolar sputter coating apparatus of claim 1, wherein a substrate is placed on the sample, the substrate being in contact with the target or the substrate being insulated from the target.
7. The ion homopolar sputter coating apparatus as recited in claim 6 wherein an insulating layer of insulating material is disposed between the substrate and the target.
8. The ion homopolar sputter coating device of claim 6, wherein the substrate is a conductor, a semiconductor, an insulator; the material of the matrix is a high polymer material, an inorganic nonmetallic material or a metallic material with an insulating coating.
9. The ion homopolar sputter coating apparatus as recited in any one of claims 1-8 wherein the target is a metal or alloy.
10. An ion homopolar sputter coating method characterized by using the ion homopolar sputter coating device as defined in any one of claims 1 to 9, comprising: placing a substrate and a target above a sample stage connected with negative voltage, exciting gas by a plasma source under the action of the negative voltage to generate gas ions to bombard the target, sputtering target elements onto the surface of the substrate, and simultaneously injecting and depositing to realize film plating on the surface of the substrate.
11. The method of claim 10, wherein the background vacuum is 1x 10 -4～1×10-2 Pa, the gas flow rate is 1-200 sccm, the working vacuum is 1x 10 -2 -5 x 100 Pa, the ion source power is 50-2000W, the negative voltage is 0.1-50 kV, and the duty cycle is 10% -80%.
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