TWI792920B - Method for manufacturing metallic glass thin film - Google Patents

Abstract

A manufacturing method for metallic glass thin film mainly includes preparing a high power impulse magnetron sputtering system first, and then placing a zirconium target, a titanium target and a copper target in a sputtering chamber; prepare an object to be plated, and place the object to be plated in the sputtering chamber; then evacuating the sputtering chamber to form a vacuum environment in the sputtering chamber; and then venting an argon gas into the sputtering chamber; finally, the zirconium target, the titanium target and the copper target are deposited on the surface of the object to be plated to form a metallic glass thin film using a high power impulse magnetron sputtering process.

Description

Manufacturing method of metallic glass film

The invention relates to a method for manufacturing a thin film, in particular to a method for manufacturing a metallic glass thin film.

Generally speaking, zirconium-copper-based metallic glasses have better glass forming ability (GFA) than aluminum-based, nickel-based, and titanium-based metallic glasses. , hardness, corrosion resistance, and good biocompatibility have attracted many researchers to devote themselves to the development of zirconium-copper-based amorphous materials. The results show that zirconium-copper metallic glasses exhibit good glass-forming capabilities over a wide range of elemental compositions.

Many studies have also confirmed that the addition of a third element in zirconium-copper metallic glass, for example: the addition of aluminum can improve the thermal stability of the film, the addition of tantalum is beneficial to increase the hardness and Young's modulus, and the addition of tungsten can improve the thermal stability of the film. Greatly increase the hardness and increase the glass transition temperature and high temperature crystallization temperature. The addition of titanium can have higher corrosion resistance, good electrochemical stability and low cytotoxicity. The addition of nitrogen can improve the hardness of the film, and Slow down the rate of metal surface oxidation.

In the prior art, zirconium-copper-titanium metallic glass has been researched to have a wide range of glass forming capabilities. There have been literatures mentioning the advantages of this material in terms of corrosion, but studies have improved the mechanical properties or antibacterial properties of zirconium-copper-titanium metallic glass films. The literature on sexuality is very limited.

Whereas in the prior art, zirconium-copper-titanium metallic glass has been researched and proved to have a wide range of glass forming capabilities, and has higher corrosion resistance than metallic glass films of other compositions, but the mechanical properties or antibacterial properties However, there are very few researches; therefore, the main purpose of the present invention is to provide a method for manufacturing metallic glass films, which can produce metallic glass films with antibacterial effects.

In order to solve the problems of the prior art, the necessary technical means adopted by the present invention is to provide a method for manufacturing a metallic glass film, which includes the following steps (A) to (F). Step (A) is to prepare a high-power pulse magnetron sputtering system, the high-power pulse magnetron sputtering system has a sputtering chamber; step (B) is to prepare a zirconium target, a titanium target and a copper target The materials are respectively arranged in the sputtering chamber; the step (C) is to prepare an object to be plated, and place the object to be plated in the sputtering chamber; the step (D) is to exhaust the sputtering chamber, so as to A type of vacuum environment is formed in the sputtering chamber; step (E) passes an argon gas into the sputtering chamber; step (F) uses a high-power pulsed magnetron to zirconium target, titanium target and copper target Sputtering process Co-sputtering deposits a metallic glass film on the surface of the object to be plated, in which the sputtering power ratio of the zirconium target and the titanium target is 1:0.2~1, and the sputtering power of the zirconium target and the copper target The ratio is 1:0.1~0.3, the power of the titanium target is between 1kW~5kW, so that the stoichiometric ratio of the metallic glass film is Zr:Cu:Ti=30~45:20~60:5~30.

In order to solve the problems of the prior art, another necessary technical means adopted by the present invention is to provide a method for manufacturing a metallic glass film, which includes the following steps (A) to (F). Step (A) is to prepare a high-power pulse magnetron sputtering system, the high-power pulse magnetron sputtering system has a sputtering chamber; step (B) is to prepare a zirconium target, a titanium target, a copper target material and an aluminum target are respectively arranged in the sputtering chamber; step (C) is to prepare an object to be plated, and place the object to be plated in the sputtering chamber; step (D) is to carry out the sputtering chamber Evacuation, so as to form a kind of vacuum environment in the sputtering chamber; step (E) passes an argon gas into the sputtering chamber; step (F) is to combine zirconium target material, titanium target material, copper target material and aluminum The target uses a high-power pulsed magnetron sputtering process to deposit a metallic glass film on the surface of the object to be plated by co-sputtering. The sputtering power ratio of the zirconium target and the titanium target is 1:0.2, and the zirconium target and the titanium target are 1:0.2. The sputtering power ratio of the copper target is 1:0.3, the sputtering power ratio of the zirconium target and the aluminum target is 1:0.06~0.26, and the power of the titanium target is between 1kW~5kW, so as to make the chemical The metering ratio is Zr:Cu:Ti:Al=25~35:45~55:5~10:5~20.

In order to solve the problems of the prior art, another necessary technical means adopted by the present invention is to provide a method for manufacturing a metallic glass film, which includes the following steps (A) to (F). Step (A) is to prepare a high-power pulse magnetron sputtering system, the high-power pulse magnetron sputtering system has a sputtering chamber; step (B) is to prepare a zirconium target, a titanium target, a copper target material and an aluminum target are respectively arranged in the sputtering chamber; step (C) is to prepare an object to be plated, and place the object to be plated in the sputtering chamber; step (D) is to carry out the sputtering chamber Evacuation, so as to form a kind of vacuum environment in the sputtering chamber; step (E) pass an argon gas and a nitrogen gas into the sputtering chamber; step (F) is to put the zirconium target, titanium target, copper target Co-sputtering metal and aluminum targets are deposited on the surface of the object to be plated by a high-power pulse magnetron sputtering process to form a metallic glass film, in which the sputtering power ratio of zirconium targets and titanium targets is 1:0.2, zirconium The sputtering power ratio of target and copper target is 1:0.3, the sputtering power ratio of zirconium target and aluminum target is 1:0.06~0.26, and the power of titanium target is between 1kW~5kW, so as to make metallic glass The stoichiometric ratio of the film is Zr:Cu:Ti:Al:N=5~20:40~55:1~5:5~20:15~30.

As mentioned above, because the manufacturing method of the metallic glass film of the present invention mainly utilizes the high-power pulse magnetron sputtering system to carry out the sputtering process, and then forms the metallic glass film by sputtering on the object to be plated, so that the metallic glass film is Its composition is antibacterial.

The specific embodiments adopted by the present invention will be further described by the following embodiments and drawings.

Please refer to the first figure. The first figure is a schematic plan view of a high-power pulsed magnetron sputtering system used in the manufacturing method of the metallic glass thin film of the present invention. As shown in the first figure, the manufacturing method of a metallic glass film provided by the first preferred embodiment of the present invention is applied to a high-power pulse magnetron sputtering system 100, and the high-power pulse magnetron sputtering system 100 has a The sputtering chamber SC is equipped with a rotating platform RT, a zirconium target ZrTG, a titanium target TiTG, a copper target CuTG and an aluminum target AlTG, a zirconium target ZrTG, a titanium target The material TiTG, the copper target material CuTG and the aluminum target material AlTG are set around the rotating platform RT as the center.

Based on the above, zirconium target ZrTG, titanium target TiTG, copper target CuTG and aluminum target AlTG are respectively electrically connected to a high-power pulsed magnetron power supply TGPS1 and a high-power pulsed magnetron power supply TGPS2 , A high-power pulse magnetron power supply TGPS3 and a high-power pulse magnetron power supply TGPS4, and the models of the high-power pulse magnetron power supply TGPS1, TGPS2, TGPS3 and TGPS4 are, for example, Hüttinger 4002 G2 or Melec SPIK 3000A .

In addition, the high-power pulsed magnetron sputtering system 100 is also provided with an argon gas supply source GC1, a nitrogen gas supply source GC2, a first mass flow controller (Mass Flow Controller) MFC1, a second mass flow controller MFC2 and a Vacuum pump assembly VA. The argon gas supply source GC1 is connected to the sputtering chamber SC through the first mass flow controller MFC1, and then the flow rate of the argon gas flowing into the sputtering chamber SC is controlled by the first mass flow controller MFC1, and the nitrogen gas supply source GC2 is It is connected to the sputtering chamber SC through the second mass flow controller MFC2, and then the flow rate of the nitrogen gas flowing into the sputtering chamber SC is controlled by the second mass flow controller MFC2.

Please continue to refer to the second figure. The second figure is a flow chart showing the steps of the manufacturing method of the metallic glass film provided by the first preferred embodiment of the present invention. As shown in the first figure and the second figure, the manufacturing method of the metallic glass film includes the following steps S101 to S108.

Step S101 is to prepare a high power pulsed magnetron sputtering system 100 with a sputtering chamber SC.

In step S102 , a zirconium (Zr) target ZrTG, a titanium (Ti) target TiTG and a copper (Cu) target CuTG are respectively placed in the sputtering chamber SC. Wherein, although in the first figure, the sputtering chamber SC is also provided with an aluminum (Al) target material AlTG, but since the aluminum target material AlTG is not needed in this embodiment, it is not necessary to set the aluminum target material AlTG in practice. , or make the high-power pulsed magnetron power supply TGPS4 electrically connected to the aluminum target AlTG not operate.

Step S103 is to prepare an object to be plated 200, and place the object to be plated 200 in the sputtering chamber SC; wherein, the object to be plated 200 is, for example, 304 stainless steel (SUS304), molybdenum rolled sheet (Molybdenum sheet) or silicon Chip (Silicon wafer), but not limited to this.

Step S104 is to evacuate the sputtering chamber SC, so as to form a type of vacuum environment in the sputtering chamber SC; wherein, the vacuum-like environment means that the air pressure is extremely low to close to vacuum. In this embodiment, high power The vacuum pump component VA used in the pulsed magnetron sputtering system 100 includes a mechanical pump and a Ruby pump. The mechanical pump can reduce the pressure in the sputtering chamber SC to a low vacuum pressure of 5×10-2torr , and the Lushi pump can reduce the pressure in the sputtering chamber SC to a high vacuum pressure of 3×10-6torr.

Step S105 is to pass an argon gas into the sputtering chamber SC; wherein, in this embodiment, only argon gas is passed into the sputtering chamber SC, and the nitrogen gas supply source GC2 is turned off and no nitrogen gas is supplied.

Step S106 is to apply an electric field in the sputtering chamber SC to dissociate the argon gas to form argon ions, and use the argon ions to bombard the object 200 to be plated; Fine dust on top.

Step S107 is to use the titanium target material TiTG to carry out ion bombardment on the object to be plated 200; wherein, to use the titanium target material TiTG to carry out ion bombardment on the object to be plated 200 is mainly used to clean the surface of the object to be plated 200 to increase the surface area of the object to be plated 200 adhesion.

Step S108 is to deposit zirconium target material ZrTG, titanium target material TiTG and copper target material CuTG on the surface of the object to be plated 200 by a high-power pulsed magnetron sputtering process to form a metallic glass film (not shown); wherein, zirconium The sputtering power ratio of target ZrTG and titanium target TiTG is 1:0.2~1, the sputtering power ratio of zirconium target ZrTG and copper target CuTG is 1:0.1~0.3, and the power of titanium target TiTG is between 1kW ~5kW, so that the stoichiometric ratio of the metallic glass film is Zr:Cu:Ti=30~45:20~60:5~30.

Based on the above, in this embodiment, the detailed process parameters of the high-power pulsed magnetron sputtering process are shown in Table 1 below.

10 ^-3 注入氣體(sccm) Ar(160) 沉積溫度(℃) 60 靶材功率(kW) #1 #2 #3 #4 #5 5 (Zr) 5 (Zr) 5 (Zr) 5 (Zr) 5 (Zr) 5(Ti) 4(Ti) 3(Ti) 2(Ti) 1(Ti) 0.5(Cu) 0.75(Cu) 1(Cu) 1.25(Cu) 1.5(Cu) 工作週期(%) 5 頻率(Hz) 200 平台轉速(rpm) 50 偏壓(V) -45 沉積時間(min) 50 模式 單極 Table 1: Process parameters of high-power pulsed magnetron sputtering in the first embodiment. target Zirconium, Titanium, Copper Deposition distance (mm) 90 working pressure (torr) 3

^10-3 Injection gas (sccm) Ar(160) Deposition temperature (°C) 60 Target power (kW) #1 #2 #3 #4 #5 5 (Zr) 5 (Zr) 5 (Zr) 5 (Zr) 5 (Zr) 5(Ti) 4(Ti) 3(Ti) 2(Ti) 1(Ti) 0.5(Cu) 0.75(Cu) 1(Cu) 1.25(Cu) 1.5(Cu) Working period(%) 5 Frequency (Hz) 200 Platform speed(rpm) 50 Bias voltage (V) -45 Deposition time (min) 50 model Unipolar

As mentioned above, in the first preferred embodiment of the present invention, the high-power pulse magnetron sputtering process parameters (hereinafter referred to as process parameters) of the target power of the zirconium target ZrTG, titanium target TiTG and copper target CuTG share Five groups (#1~#5), and the stoichiometric ratio of metallic glass films produced by process parameters #1~#5 are shown in Table 2 below.

Table 2: Stoichiometric ratios of the metallic glass films produced in the first embodiment. Composition Atomic ratio (at.%) Zr Cu Ti #1 Zr ₄₂ Cu ₂₅ Ti ₂₉ 41.5±2.0 25.1 ± 1.3 28.9±1.5 #2 Zr ₃₉ Cu ₃₅ Ti ₂₂ 39.0±2.0 35.4±1.8 22.3 ± 1.2 #3 _{Zr33Cu44Ti18 _ _} 33.2 ± 1.7 43.6 ± 2.2 18.4±0.9 #4 Zr ₃₂ Cu ₄₉ Ti ₁₃ 32.0±1.6 50.0±2.5 13.1±0.7 #5 Zr ₃₄ Cu ₅₄ Ti ₈ 33.9 ± 1.7 54.1 ± 2.7 7.7 ± 0.4

Table 3: Surface roughness of the metallic glass film produced in the first embodiment. #1 #2 #3 #4 #5 Ra (nm) 1.5±0.1 1.3±0.1 1.4±0.1 1.3±0.1 1.5±0.3 Rq (nm) 1.8±0.1 1.6±0.1 1.8±0.1 1.6±0.1 1.9±0.1 Rmax (nm) 10.3±0.1 9.1±0.1 9.7±0.2 9.0±0.2 11.3±0.3 Thickness(μm) 1.8 1.8 1.8 2.0 2.1

As mentioned above, the average surface roughness values of the metallic glass films with process parameters #1 to #5 are all lower than 1.5nm, showing a very smooth surface.

Table 4: Mechanical properties of the metallic glass films produced in the first embodiment. Hardness (GPa) Elastic coefficient (GPa) H/E #1 7.3±0.7 124 ± 6 0.059 #2 6.8±0.3 125 ± 4 0.054 #3 6.7±0.4 129 ± 4 0.052 #4 6.8 ± 0.5 127 ± 7 0.054 #5 6.5±0.3 123 ± 4 0.053

As mentioned above, the hardness of process parameters #1~#5 has no obvious change; since the Mohs hardness of Ti metal is 6; the Mohs hardness of Cu metal is 3, the proportion of Ti element in process parameter #1 is higher than that of Cu; process parameter # The Cu element ratio of 5 is much higher than that of Ti, so it can be inferred that the slight difference in hardness between #1 and #5 of the metallic glass film is caused by the composition of Cu and Ti. In addition, the H/E value calculated from the hardness and Young's modulus is the ability to resist plastic deformation. It can be found that the H/E value of all metallic glass films is less than 0.1, indicating that when the film is squeezed, plastic deformation will occur locally flow.

Table 5: Corrosion test data of the metallic glass film prepared in the first embodiment tested in 3.5 wt.% NaCl aqueous solution. SUS304 #1 #2 #3 #4 #5 E _corr (V) -0.232 -0.323 -0.301 -0.278 -0.296 -0.274 I _corr (A/cm ² ) 7.33×10 ^-8 9.01×10 ^-8 6.03×10 ^-8 4.19×10 ^-7 1.15×10 ^-7 1.07×10 ^-6 βa (mV) 328.19 104.93 63.85 66.51 132.28 37.72 βc (mV) 120.06 146.88 136.51 148.87 284.28 103.24 Rp (kΩ/cm ² ) 468.44 767.58 290.08 45.15 26.68 17.89

Among them, E _corr is the open circuit voltage, I _corr is the short-circuit current, βa is the Taffer slope of the anode curve, βc is the Taffer slope of the cathode curve, and R _p is the polarization resistance. In addition, it can be seen from the data in Table 4 that the metal glass film made by process parameter #1 has better anti-corrosion effect than the stainless steel (SUS304) used as the control group.

Table 6: Water contact angles of metallic glass films measured at different times. time #1 #2 #3 #4 #5 SUS304 TiN 3(s) 91.6 108.2 108.4 108.1 105.0 64.7 90.2 5(min) 88.8 107.7 102.9 103.2 102.1 41.6 87.2 10(min) 84.2 105.9 99.7 100.3 97.5 33.7 79.4 15(min) 80.0 103.6 96.1 95.9 95.8 33.5 74.9 20(min) 78.6 99.0 93.0 89.4 91.8 29.5 66.6 25(min) 74.6 94.7 90.2 88.0 87.6 23.3 63.0 30(min) 72.2 89.5 85.3 83.5 84.1 20.5 55.6

As mentioned above, the hydrophobicity of the metal glass films of all process parameters #1~#5 is better than that of the control group SUS304 and TiN, and the process parameter #2 has the best hydrophobicity, and the contact angle is still close to 90 degrees after 30 minutes , showing an extremely hydrophobic surface.

Table 7: Comparison of roughness, water contact angle and antibacterial rate of SUS304, metallic glass film and TiN film. AR for E. coli Ra (nm) R (max) WCA (deg.) SUS304 140 (68%) 3.24 35 64.72 #1 Zr ₄₂ Cu ₂₅ Ti ₂₉ 78 (82%) 1.48 10.31 91.59 #2 Zr ₃₉ Cu ₃₅ Ti ₂₂ 63 (85%) 1.25 5.89 108.15 #3 _{Zr33Cu44Ti18 _ _} 60 (86%) 1.43 9.74 108.40 #4 Zr ₃₂ Cu ₄₉ Ti ₁₃ 73 (83%) 1.29 8.97 108.06 #5 Zr ₃₄ Cu ₅₄ Ti ₈ 97 (78%) 1.49 11.29 105.04 TiN Ti ₄₉ N ₅₁ 188 (58%) 7.44 40.10 90.18

As mentioned above, the metallic glass film has better antibacterial ability than the 304 stainless steel and TiN film without any coating, and the best antibacterial rate of process parameter #3 is 86%. The metallic glass film is mainly based on the following two antibacterial mechanisms And it has antibacterial properties: (1) Physically, the metallic glass film has a smooth surface and good hydrophobicity, which can improve the original rough surface of 304 stainless steel, effectively reduce bacterial adhesion and finally reduce the number of colonies of E. coli. (2) In terms of chemistry, the copper ions of the copper-containing metallic glass film have an antibacterial effect. If bacteria adhere to the surface, the copper ions will be released from the surface and interact with the cell membrane, and the cell must leak solutes to degrade the plastid of DNA. , resulting in the inability of bacteria to reproduce.

Please continue to refer to the third figure, the third figure is a flow chart showing the manufacturing method of the metallic glass film provided by the first preferred embodiment of the present invention, wherein the detailed preparation steps of the object to be plated are involved. As shown in the second and third figures, the above step S103 may further include the following steps S1031 to S1036.

Step S1031 is to prepare the object to be plated 200, step S1032 is to remove the grease attached to the object to be plated 200, step S1033 is to clean the object to be plated 200 with pure water, step S1034 is to dry the object to be plated 200, and step S1035 is to dry the object to be plated 200. The object to be plated 200 is placed in an oven for drying, and step S1036 is to place the object to be plated 200 in the sputtering chamber SC within an effective time limit.

Based on the above, when the object to be plated 200 is 304 stainless steel or molybdenum rolled sheet, step S1032 is, for example, firstly subject the object to be plated 200 to ultrasonic vibration for 300 seconds with an alkaline solution to make the surface of the object to be plated 200 Remove the grease, and then put the object to be plated 200 into the pure water tank for 10 seconds of ultrasonic vibration, and in the process of ultrasonic vibration, the temperature of the alkaline solution and pure water are maintained at 60 °C; however, when the When the coating 200 is a silicon wafer. Step S1032 is, for example, using ethanol to wipe and remove the grease on the surface of the object 200 to be plated. In step S1034, for example, when the object 200 to be plated is taken out from the above-mentioned pure water tank, the object 200 to be plated is blown dry by means of spraying air from an air gun. Step S1035 is, for example, putting the dried object 200 into an oven preheated at 70° C. and drying it in the oven for 10 minutes to ensure that no moisture remains on the surface of the object 200 . The effective time limit in step S1036 is, for example, 1 hour, mainly to prevent the object to be plated 200 from being left in an open environment for a long time after leaving the oven and being polluted.

Please continue to refer to the fourth figure. The fourth figure is a flow chart showing the steps of the method for manufacturing the metallic glass film provided by the second preferred embodiment of the present invention. As shown in the first figure to the fourth figure, the manufacturing method of a metallic glass film provided by the second preferred embodiment of the present invention is also applied to the above-mentioned high-power pulse magnetron sputtering system 100, and the second preferred The manufacturing method of the metallic glass thin film of the embodiment includes the following steps S201 to S208.

Step S201 is to prepare a high power pulsed magnetron sputtering system 100 with a sputtering chamber SC.

In step S202 , a zirconium target ZrTG, a titanium target TiTG, a copper target CuTG and an aluminum target AlTG are respectively placed in the sputtering chamber SC.

Step S203 is to prepare an object to be plated 200, and place the object to be plated 200 in the sputtering chamber SC; wherein, step S203 can also be further subdivided into steps S1031 to S1036 as shown in the third figure in practice .

Step S204 is to evacuate the sputtering chamber SC to form a kind of vacuum environment in the sputtering chamber SC.

Step S205 is to pass an argon gas into the sputtering chamber SC.

Step S206 is to apply an electric field in the sputtering chamber SC to dissociate the argon gas to form argon ions, and bombard the object to be plated with the argon ions.

Step S207 is to use the titanium target to bombard the object to be plated with ions.

Step S208 is to deposit zirconium target material ZrTG, titanium target material TiTG material, copper target material CuTG material and aluminum target material AlTG material on the surface of the object to be plated 200 by a high-power pulsed magnetron sputtering process to form a metallic glass film (not shown in the figure) ); Among them, the sputtering power ratio of the zirconium target ZrTG and the titanium target TiTG is 1:0.2, the sputtering power ratio of the zirconium target ZrTG and the copper target CuTG is 1:0.3, the zirconium target ZrTG and the aluminum target The sputtering power ratio of AlTG is 1:0.06~0.26, and the power of the titanium target TiTG is between 1kW~5kW, so that the stoichiometric ratio of the metallic glass film is Zr:Cu:Ti:Al=25~35:45~55 :5~10: 5~20.

Based on the above, in this embodiment, the detailed process conditions of the high-power pulsed magnetron sputtering process are shown in Table 8 below.

10 ^-3 注入氣體(sccm) Ar(160) 沉積溫度(℃) 60 靶材功率(kW) #6 #7 #8 #9 #10 5 (Zr) 5 (Zr) 5 (Zr) 5 (Zr) 5 (Zr) 1(Ti) 1(Ti) 1(Ti) 1(Ti) 1(Ti) 1.5(Cu) 1.5(Cu) 1.5(Cu) 1.5(Cu) 1.5(Cu) 0.3(Al) 0.5(Al) 0.8(Al) 1(Al) 1.3(Al) 工作週期(%) 5 頻率(Hz) 200 平台轉速(rpm) 50 偏壓(V) -45 沉積時間(min) 50 模式 單極 Table 8: Process parameters of high-power pulse magnetron sputtering in the second embodiment. target Zirconium, Titanium, Copper, Aluminum Deposition distance (mm) 90 working pressure (torr) 3

^10-3 Injection gas (sccm) Ar(160) Deposition temperature (°C) 60 Target power (kW) #6 #7 #8 #9 #10 5 (Zr) 5 (Zr) 5 (Zr) 5 (Zr) 5 (Zr) 1(Ti) 1(Ti) 1(Ti) 1(Ti) 1(Ti) 1.5(Cu) 1.5(Cu) 1.5(Cu) 1.5(Cu) 1.5(Cu) 0.3(Al) 0.5(Al) 0.8(Al) 1(Al) 1.3 (Al) Working period(%) 5 Frequency (Hz) 200 Platform speed(rpm) 50 Bias voltage (V) -45 Deposition time (min) 50 model Unipolar

As mentioned above, in the second preferred embodiment of the present invention, there are five sets of process parameters #6~# for controlling the target power of the zirconium target ZrTG, titanium target TiTG, copper target CuTG and aluminum target AlTG 10, and the stoichiometric ratios of the metallic glass films produced by these five sets of process parameters #6~#10 are shown in Table 9 below.

Table 9: Stoichiometric ratios of the metallic glass films produced in the second embodiment. Composition Atomic ratio (at.%) Zr Cu Ti al #6 Zr ₃₀ Cu ₅₃ Ti ₈ Al ₆ 30.3±0.2 52.7±0.4 7.6±0.1 6.1±0.1 #7 Zr ₃₂ Cu ₄₈ Ti ₇ Al ₁₀ 31.7±0.5 47.6±0.5 7.2±0.1 10.0±0.1 #8 Zr ₃₀ Cu ₄₇ Ti ₇ Al ₁₄ 29.7±0.1 47.5±0.1 6.8±0.2 14.4±0.1 #9 Zr ₂₉ Cu ₄₅ Ti ₇ Al ₁₇ 29.1±0.1 45.6±0.2 6.5±0.1 16.6±0.2 #10 Zr ₂₇ Cu ₄₇ Ti ₇ Al ₁₈ 26.9±0.4 46.6±0.5 6.6±0.1 18.3±0.4

Table 10: Surface roughness of the metallic glass film produced in the second embodiment. #6 #7 #8 #9 #10 Ra (nm) 0.7±0.1 1.1±0.1 1.1±0.1 1.1±0.1 1.2±0.1 Rq (nm) 0.9±0.1 1.3±0.1 1.3±0.1 1.5±0.1 1.5±0.1 Rmax (nm) 7.1±0.1 9.1±0.1 10.2±0.1 15.5±0.2 10.6±0.2 Thickness(μm) 1.6 1.6 1.6 1.7 1.7

As mentioned above, the average surface roughness values of the metal glass films with process parameters #6~#10 are all lower than 1.2nm, which is better than the roughness of the metal glass films with process parameters #1~#5 in the first embodiment ( From 1.3 to 1.5nm), it can be seen that the average surface roughness of the metallic glass film can be reduced after the addition of Al element.

Table 11: Mechanical properties of the metallic glass films produced in the second embodiment. Hardness (GPa) Elastic coefficient (GPa) H/E #6 6.2 ± 0.4 121 ± 4 0.051 #7 6.2 ± 0.4 119 ± 4 0.052 #8 6.3 ± 0.2 119 ± 3 0.053 #9 6.4±0.2 118 ± 2 0.054 #10 6.5±0.3 121 ± 5 0.054

As mentioned above, the hardness of the metallic glass films with process parameters #6 to #10 has no significant change, which is basically the same as the hardness of the metallic glass films with process parameters #1 to #5 in the first embodiment.

Table 12: Water contact angles of metallic glass films measured at different times. time #6 #7 #8 #9 #10 3(s) 112.3 114.3 116.5 104.6 122.8 5(min) 107.7 114.1 109.6 102.5 118.9 10(min) 101.7 108.5 105.0 93.1 113.4 15(min) 96.8 107.5 99.8 90.4 110.1 20(min) 89.2 105.3 92.5 87.4 107.7 25(min) 88.1 101.9 84.6 80.0 106.7 30(min) 84.4 98.1 74.7 72.1 104.2

As mentioned above, the hydrophobicity of metallic glass films with process parameters #6~#10 is better than SUS304 and TiN, and the metallic glass film with process parameter #10 has the best hydrophobicity, and the contact angle is close to 104.19 degrees after 30 minutes. Hydrophobicity is better than that of the metallic glass film not doped with Al in the above-mentioned first embodiment (process parameter #1~#5).

Table 13: Comparison of roughness, water contact angle and antibacterial rate of SUS304, metallic glass film and TiN film. AR for E. coli Ra (nm) R (max) WCA (deg.) SUS304 140 (68%) 3.24 35 64.72 #6 Zr ₃₀ Cu ₅₂ Ti ₇ Al ₆ 70 (84%) 0.7 7.1 112.3 #7 Zr ₃₂ Cu ₄₈ Ti ₇ Al ₁₀ 77 (82%) 1.1 9.1 114.3 #8 Zr ₃₀ Cu ₄₇ Ti ₇ Al ₁₄ 53 (88%) 1.1 10.2 116.5 #9 Zr ₂₉ Cu ₄₅ Ti ₆ Al ₁₆ 70 (84%) 1.1 15.5 104.6 #10 Zr ₂₇ Cu ₄₇ Ti ₆ Al ₁₈ 5(99%) 1.2 10.6 122.8

As mentioned above, the antimicrobial rate of the metallic glass film of process parameter #10 is the best at 99%. Among them, the antimicrobial mechanism of the metallic glass film of this embodiment (process parameter #6~#10) is mainly through the smooth surface With good hydrophobicity to effectively reduce bacterial adhesion and ultimately reduce the number of E. coli colonies, and because copper ions themselves have antibacterial effects, the presence of aluminum nanoparticles can also attack and kill microbial cells, even copper ions and aluminum ions The release of the bacteria interacts with the cell membrane, causing the bacteria to be killed and unable to reproduce.

Please continue to refer to the fifth figure. The fifth figure is a flow chart showing the steps of the method for manufacturing the metallic glass film according to the third preferred embodiment of the present invention. As shown in the first figure to the fifth figure, the manufacturing method of a metallic glass film provided by the third preferred embodiment of the present invention is also applied to the above-mentioned high-power pulse magnetron sputtering system 100, and the third preferred The manufacturing method of the metallic glass thin film of the embodiment includes the following steps S301 to S308.

Step S301 is to prepare a high power pulsed magnetron sputtering system 100 with a sputtering chamber SC.

In step S302 , a zirconium target ZrTG, a titanium target TiTG, a copper target CuTG and an aluminum target AlTG are respectively placed in the sputtering chamber SC.

Step S303 is to prepare an object to be plated 200, and place the object to be plated 200 in the sputtering chamber SC; wherein, step S303 can also be further subdivided into steps S1031 to S1036 as shown in the third figure in practice .

Step S304 is to evacuate the sputtering chamber SC to form a kind of vacuum environment in the sputtering chamber SC.

Step S305 is to pass an argon gas and a nitrogen gas into the sputtering chamber SC. Wherein, the nitrogen gas is passed into the sputtering chamber SC at a flow rate of 5 sccm to 25 sccm.

Step S306 is to apply an electric field in the sputtering chamber SC to dissociate the argon gas to form argon ions, and bombard the object to be plated with the argon ions.

Step S307 is to use the titanium target to bombard the object to be plated with ions.

Step S308 is to deposit zirconium target material ZrTG, titanium target material TiTG material, copper target material CuTG material and aluminum target material AlTG material on the surface of the object to be plated 200 by a high-power pulsed magnetron sputtering process to form a metallic glass film (not shown in the figure) ); Among them, the sputtering power ratio of the zirconium target ZrTG and the titanium target TiTG is 1:0.2, the sputtering power ratio of the zirconium target ZrTG and the copper target CuTG is 1:0.3, the zirconium target ZrTG and the aluminum target The sputtering power ratio of AlTG is 1:0.06~0.26, and the power of the titanium target TiTG is between 1kW~5kW, so that the stoichiometric ratio of the metallic glass film is Zr:Cu:Ti:Al:N=5~20:40 ~55:1~5:5~20:15~30.

Based on the above, in this embodiment, the detailed process conditions of the high-power pulsed magnetron sputtering process are shown in Table 14 below.

10 ^-3 注入氣體(sccm) #11 #12 #13 #14 #15 Ar(160) N ₂(5) N ₂10) N ₂(15) N ₂(20) N ₂(25) 沉積溫度(℃) 60 靶材功率(kW) 5 (Zr)、1(Ti)、1.5(Cu)、1.3(Al) 工作週期(%) 5 頻率(Hz) 200 平台轉速(rpm) 50 偏壓(V) -45 沉積時間(min) 50 模式 單極 Table 14: Process parameters of high-power pulsed magnetron sputtering in the third embodiment. target Zirconium, Titanium, Copper, Aluminum Deposition distance (mm) 90 working pressure (torr) 3

^10-3 Injection gas (sccm) #11 #12 #13 #14 #15 Ar(160) N ₂ (5) N ₂ 10) N ₂ (15) N ₂ (20) N ₂ (25) Deposition temperature (°C) 60 Target power (kW) 5 (Zr), 1 (Ti), 1.5 (Cu), 1.3 (Al) Working period(%) 5 Frequency (Hz) 200 Platform speed(rpm) 50 Bias voltage (V) -45 Deposition time (min) 50 model Unipolar

As mentioned above, in the third preferred embodiment of the present invention, there are five sets of process parameters #11~# for controlling the target power of the zirconium target ZrTG, titanium target TiTG, copper target CuTG and aluminum target AlTG 15, and the stoichiometric ratios of the metallic glass films produced by these five groups are shown in Table 15 below.

Table 15: Stoichiometric ratios of the metallic glass films produced in the third embodiment. Composition Atomic ratio (at.%) Zr Cu Ti al N #11 Zr ₂₀ Cu ₄₁ Ti ₃ Al ₁₆ N ₁₈ 20.0±0.2 41.5±0.7 2.6±0.1 15.5±0.2 17.7±0.9 #12 Zr ₁₆ Cu ₄₂ Ti ₂ Al ₁₄ N ₂₃ 15.9±0.4 41.8±0.5 2.4±0.1 14.9±0.2 23.3±1.1 #13 Zr ₁₀ Cu ₄₆ Ti ₂ Al ₁₁ N ₂₆ 10.1±0.2 46.1±0.3 1.8±0.2 10.6±0.1 25.5±0.6 #14 Zr ₁₀ Cu ₅₂ Ti ₂ Al ₈ N ₂₄ 9.7±0.3 51.7±0.8 2.3±0.1 7.8±0.1 23.7±1.1 #15 Zr ₉ Cu ₅₃ Ti ₂ Al ₆ N ₂₃ 9.3±0.2 53.3±0.2 2.4±0.1 6.4±0.1 22.7±0.4

Table 16: Surface roughness of the metallic glass film produced in the third embodiment. #11 #12 #13 #14 #15 Ra (nm) 4.2±0.1 2.1±0.1 3.2±0.1 2.2±0.1 1.4±0.1 Rq (nm) 5.3±0.1 2.6±0.1 4.0±0.1 2.8±0.1 1.7±0.1 Rmax (nm) 38.7±0.3 20.6±0.2 32.1±0.2 33.6±0.3 13.6±0.1 Thickness(μm) 1.6 1.4 1.3 1.2 1.1

As mentioned above, the average surface roughness of the metal glass films with process parameters #11~#15 is between 1.4-4.2nm, and the roughness is higher than that of the metal glass film of the second embodiment without nitrogen gas, showing After adding N element, it will affect the surface roughness of the film.

Table 17: Mechanical properties of the metallic glass films produced in the third embodiment. Hardness (GPa) Elastic coefficient (GPa) H/E #11 Zr ₂₀ Cu ₄₁ Ti ₃ Al ₁₆ N ₁₈ 7.3±0.7 167 ± 9 #12 Zr ₁₆ Cu ₄₂ Ti ₂ Al ₁₄ N ₂₃ 7.6±0.4 177 ± 8 #13 Zr ₁₀ Cu ₄₆ Ti ₂ Al ₁₁ N ₂₆ 7.4±0.3 163 ± 6 #14 Zr ₁₀ Cu ₅₂ Ti ₂ Al ₈ N ₂₄ 6.5±0.2 154 ± 5 #15 Zr ₂₀ Cu ₄₁ Ti ₃ Al ₁₆ N ₁₈ 6.5±0.2 152 ± 6

As mentioned above, the hardness of the process parameters #11~#18 has no significant change, which is basically the same as the hardness of the metallic glass film (process parameters #6~#10) of the second embodiment above. Compared with the metallic glass films (#6~#10) that did not react with nitrogen gas in the second embodiment, the hardness of the metallic glass films #11~#15 increased from 6.5 GPa to 7.6 GPa, an increase of about 1GPa. After reaching 20sccm and the ratio of nitrogen to argon is 12.5%, nitrogen no longer has an effect on the hardness of the film.

Table 18: Water contact angles of metallic glass films measured at different times. time #11 #12 #13 #14 #15 3(s) 115.9 109.6 109.2 107.9 97.9 5(min) 113.0 102.9 99.0 107.2 96.6 10(min) 110.4 99.0 92.7 103.6 95.1 15(min) 107.9 89.9 90.9 101.5 91.5 20(min) 106.5 86.9 84.5 97.0 86.9 25(min) 101.9 76.9 72.1 95.2 86.4 30(min) 98.5 73.2 71.1 90.0 81.8

As mentioned above, #11 metallic glass film has the best hydrophobicity, the contact angle is close to 98.5° after 30 minutes, and the contact angle value of #11~#15 metallic glass film measured in three seconds is 115.9° to 97.9°, so they are all hydrophobic materials.

Table 19: Comparison of roughness, water contact angle and antibacterial rate of SUS304, metallic glass film and TiN film. AR for E. coli Ra (nm) R (max) WCA (deg.) SUS304 140 (68%) 3.24 35 64.72 #11 Zr ₂₀ Cu ₄₁ Ti ₃ Al ₁₆ N ₁₈ 206 (85.5%) 4.2 38.7 115.9 #12 Zr ₁₆ Cu ₄₂ Ti ₂ Al ₁₄ N ₂₃ 78 (94.5%) 2.1 20.6 109.6 #13 Zr ₁₀ Cu ₄₆ Ti ₂ Al ₁₁ N ₂₆ 9 (99.3%) 3.2 32.1 109.2 #14 Zr ₁₀ Cu ₅₂ Ti ₂ Al ₈ N ₂₄ 4 (99.7%) 2.2 33.6 107.9 #15 Zr ₉ Cu ₅₃ Ti ₂ Al ₆ N ₂₃ <1 (99.9%) 1.4 13.6 97.9

As mentioned above, the AR of #11 metallic glass film is 85.5%. The reason may be that the Rmax is larger, and E. coli has a greater chance to adhere to the surface with larger fluctuations. The culture results of the metal glass film of #12 found that 78 colonies remained, but it still had excellent antimicrobial effect, with an AR value of 94.5%. The antimicrobial rate of #13, #14 and #15 metallic glass films is above 99.3%, especially #15 metallic glass film did not find any E. coli colonies survived on the agar after 40 hours of cultivation.

In practice, when observed through an electron microscope, it will be found that the surface of the metallic glass films #13, #14 and #15 will have a columnar structure, and the columnar structure will help the release of metal ions , and then relatively enhance the antibacterial effect.

To sum up, the manufacturing method of the metallic glass thin film of the present invention mainly uses a high-power pulse magnetron sputtering system to carry out a high-power pulse magnetron sputtering process, so that metals such as zirconium, titanium and copper are deposited on the surface of the object to be plated. Metallic glass film is deposited and formed, and the stoichiometric ratio of the metallic glass film can be controlled in the range of Zr:Cu:Ti=30~45:20~60:5~30 through the condition control of the high-power pulsed magnetron sputtering process In this way, the metal glass film has better antibacterial properties.

Based on the above, the manufacturing method of the metallic glass film of the present invention can further utilize a high-power pulsed magnetron sputtering system to deposit metals such as zirconium, titanium, copper and aluminum on the surface of the object to be plated to form a metallic glass film, and make the metallic glass film The stoichiometric ratio of the metallic glass film is controlled within the range of Zr:Cu:Ti:Al=25~35:45~55:5~10:5~20, so as to further enhance the antibacterial property through the release of aluminum ions. In addition, the manufacturing method of the metallic glass thin film of the present invention can further utilize the high-power pulse magnetron sputtering system to deposit metals such as zirconium, titanium, copper and aluminum on the surface of the object to be plated to form a metallic glass thin film. The way of nitrogen gas is introduced, and the stoichiometric ratio of the metallic glass film is controlled within the range of Zr:Cu:Ti:Al:N=5~20:40~55:1~5:5~20:15~30, and When the nitrogen-argon ratio is lower than 6.2%, a columnar structure can be formed on the surface of the metal glass film, which is conducive to the release of metal ions and relatively improves the antibacterial effect.

Through the above detailed description of the preferred embodiments, it is hoped that the characteristics and spirit of the present invention can be described more clearly, and the scope of the present invention is not limited by the preferred embodiments disclosed above. On the contrary, the intention is to cover various changes and equivalent arrangements within the scope of the patent application for the present invention.

100: High power pulse magnetron sputtering system 200: object to be plated SC: sputtering chamber RT: Rotating Platform ZrTG: Zirconium target TiTG: Titanium target CuTG: copper target AlTG: aluminum target TGPS1, TGPS2, TGPS3, TGPS4: high power pulse magnetron power supply GC1: Argon supply source GC2: Nitrogen supply source MFC1: First mass flow controller MFC2: Second mass flow controller VA: vacuum pump assembly S101-S108,S1031-S1036,S201-S208,S301-S308: steps

The first figure shows a schematic plan view of a high-power pulsed magnetron sputtering system used in the manufacturing method of the metallic glass thin film of the present invention; The second figure is a flow chart showing the steps of the manufacturing method of the metallic glass film provided by the first preferred embodiment of the present invention; The 3rd figure shows the manufacturing method of the metallic glass thin film provided by the first preferred embodiment of the present invention, wherein the detailed preparation steps of the relevant object to be plated is a flow chart of the steps; The fourth figure is a flow chart showing the steps of the manufacturing method of the metallic glass film provided by the second preferred embodiment of the present invention; and The fifth figure is a flow chart showing the steps of the manufacturing method of the metallic glass film provided by the third preferred embodiment of the present invention.

S101-S108: Steps

Claims (10)

A method for manufacturing a metallic glass film, comprising: (A) preparing a high-power pulse magnetron sputtering system, the high-power pulse magnetron sputtering system has a sputtering chamber; (B) a zirconium target, a A titanium target and a copper target are respectively arranged in the sputtering chamber; (C) preparing an object to be plated, and placing the object to be plated in the sputtering chamber; (D) sputtering the sputtering chamber The chamber is pumped so that the pressure in the sputtering chamber is greater than 0 torr and lower than 5×10 ^-2 torr; (E) passing an argon gas into the sputtering chamber; and (F) the zirconium target material, the titanium target, and the copper target are deposited on the surface of the object to be plated by a high-power pulsed magnetron sputtering process to form a metallic glass film, wherein the sputtering power ratio of the zirconium target to the titanium target is 1:0.2~1, the sputtering power ratio of the zirconium target and the copper target is 1:0.1~0.3, the power of the titanium target is between 1kW~5kW, so that the stoichiometric ratio of the metallic glass film It is Zr: Cu: Ti=30~45:20~60:5~30. The manufacturing method of the metallic glass thin film as claimed in item 1, wherein, step (C) further comprises the following steps: (C1) preparing the object to be plated; (C2) removing the grease attached to the object to be plated; (C3 ) cleaning the object to be plated with pure water; (C4) drying the object to be plated; (C5) placing the object to be plated in an oven for drying; and (C6) placing the object to be plated in the sputtering chamber within an effective time limit. The method for manufacturing a metallic glass thin film according to Claim 1, wherein step (F) further includes the following steps: (F1) applying an electric field in the sputtering chamber to dissociate the argon gas to form an argon ion, and using the Bombarding the object to be plated with argon ions; (F2) ion bombarding the object to be plated with the titanium target; and (F3) using the high-power pulsed magnetic The controlled sputtering process deposits and forms the metallic glass film on the surface of the object to be plated. A method for manufacturing a metallic glass film, comprising: (A) preparing a high-power pulse magnetron sputtering system, the high-power pulse magnetron sputtering system has a sputtering chamber; (B) a zirconium target, a A titanium target material, a copper target material and an aluminum target material are respectively arranged in the sputtering chamber; (C) preparing an object to be plated, and placing the object to be plated in the sputtering chamber; (D) The sputtering chamber is pumped so that the pressure in the sputtering chamber is greater than 0 torr and lower than 5×10 ^-2 torr; (E) passing an argon gas into the sputtering chamber; and (F ) Depositing the zirconium target, the titanium target, the copper target and the aluminum target on the surface of the object to be plated by a high-power pulsed magnetron sputtering process, wherein the zirconium target The sputtering power ratio to the titanium target is 1:0.2, the sputtering power ratio between the zirconium target and the copper target is 1:0.3, and the sputtering power ratio between the zirconium target and the aluminum target is 1 : 0.06~0.26, the power of the titanium target is between 1kW~5kW, so that the stoichiometric ratio of the metallic glass film is Zr:Cu:Ti:Al=25~35:45~55:5~10:5~ 20. The manufacturing method of the metallic glass film as described in Claim 4, wherein, step (C) further comprises the following steps: (C1) preparing the object to be plated; (C2) removing the grease attached to the object to be plated; (C3 ) cleaning the object to be plated with pure water; (C4) drying the object to be plated; (C5) placing the object to be plated in an oven for drying; and (C6) placing the object to be plated within an effective time limit in the sputtering chamber. The method for manufacturing a metallic glass thin film according to claim 4, wherein step (F) further includes the following steps: (F1) applying an electric field in the sputtering chamber to dissociate the argon gas to form an argon ion, and using the Bombarding the object to be plated with argon ions; (F2) ion bombarding the object to be plated with the titanium target; and (F3) using the high-power pulsed magnetic The controlled sputtering process deposits and forms on the surface of the object to be plated The metallic glass film. A method for manufacturing a metallic glass film, comprising: (A) preparing a high-power pulse magnetron sputtering system, the high-power pulse magnetron sputtering system has a sputtering chamber; (B) a zirconium target, a A titanium target material, a copper target material and an aluminum target material are respectively arranged in the sputtering chamber; (C) preparing an object to be plated, and placing the object to be plated in the sputtering chamber; (D) Evacuating the sputtering chamber so that the pressure in the sputtering chamber is greater than 0 torr and lower than 5×10 ^-2 torr; (E) passing an argon gas and a nitrogen gas into the sputtering chamber; and (F) depositing the zirconium target, the titanium target, the copper target and the aluminum target on the surface of the object to be plated by a high-power pulsed magnetron sputtering process, wherein the The sputtering power ratio between the zirconium target and the titanium target is 1:0.2, the sputtering power ratio between the zirconium target and the copper target is 1:0.3, and the sputtering power ratio between the zirconium target and the aluminum target The ratio is 1:0.26, the power of the titanium target is between 1kW~5kW, so that the stoichiometric ratio of the metallic glass film is Zr:Cu:Ti:Al:N=5~20:40~55:1~5 : 5~20: 15~30. The method for manufacturing a metallic glass film as claimed in claim 7, wherein step (C) further comprises the following steps: (C1) preparing the object to be plated; (C2) Remove the grease attached to the object to be plated; (C3) Clean the object to be plated with pure water; (C4) Dry the object to be plated; (C5) Place the object to be plated to dry in an oven and (C6) placing the object to be plated in the sputtering chamber within an effective time limit. The method for manufacturing a metallic glass thin film according to Claim 7, wherein step (F) further includes the following steps: (F1) applying an electric field in the sputtering chamber to dissociate the argon gas to form argon ions, and use the Bombarding the object to be plated with argon ions; (F2) ion bombarding the object to be plated with the titanium target; and (F3) using the high-power pulsed magnetic The controlled sputtering process deposits and forms the metallic glass film on the surface of the object to be plated. The manufacturing method of the metallic glass thin film as claimed in claim 7, wherein step (E) is to pass the nitrogen gas at a flow rate of 5 sccm to 25 sccm.

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