CN115029669B - Method for improving deposition efficiency by adopting liquid metal high-power pulse magnetron sputtering - Google Patents

Method for improving deposition efficiency by adopting liquid metal high-power pulse magnetron sputtering Download PDF

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CN115029669B
CN115029669B CN202210638878.2A CN202210638878A CN115029669B CN 115029669 B CN115029669 B CN 115029669B CN 202210638878 A CN202210638878 A CN 202210638878A CN 115029669 B CN115029669 B CN 115029669B
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target
sputtering
power
magnetron sputtering
deposition efficiency
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CN115029669A (en
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王浪平
孙田玮
黄新放
王小峰
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/35Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/3407Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3428Cathode assembly for sputtering apparatus, e.g. Target using liquid targets
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/3485Sputtering using pulsed power to the target

Abstract

A method for improving deposition efficiency by adopting liquid metal high-power pulse magnetron sputtering relates to a method for improving magnetron sputtering deposition efficiency. The invention aims to solve the problem of low deposition efficiency of the existing magnetron sputtering. The method comprises the following steps: 1. placing the sputtering target material into a target seat, and adjusting a gap exists between the target seat and a magnetic control target cooling base; 2. forming high-power pulse magnetron sputtering discharge by a high-power pulse magnetron power supply until the surface of the target material is melted; 3. and (5) sputtering. The invention is used for improving the deposition efficiency by adopting the liquid metal high-power pulse magnetron sputtering.

Description

Method for improving deposition efficiency by adopting liquid metal high-power pulse magnetron sputtering
Technical Field
The invention relates to a method for improving the magnetron sputtering deposition efficiency.
Background
Compared with an electrochemical method, physical vapor deposition methods such as magnetron sputtering and the like are more and more widely applied in the field of coating at present because the process is pollution-free. However, the deposition rate of physical vapor deposition methods can only reach the order of microns per hour compared to electrochemical methods, which is about one order of magnitude lower than electrochemical deposition methods, resulting in much lower production efficiency than electrochemical methods. Thus, even today, where environmental requirements are so stringent, electrochemical deposition processes remain an irreplaceable technique for producing parts in high demand.
In the magnetron sputtering process, in order to prevent the target from being overheated and melted, the heat of Ar ions bombarding the target needs to be taken away by adopting a forced water cooling method. Therefore, most of energy is converted into heat during magnetron sputtering, and the energy utilization rate is low, resulting in low sputtering efficiency.
Disclosure of Invention
The invention aims to solve the problem of low deposition efficiency of the existing magnetron sputtering, and further provides a method for improving the deposition efficiency by adopting liquid metal high-power pulse magnetron sputtering.
A method for improving deposition efficiency by adopting liquid metal high-power pulse magnetron sputtering is carried out according to the following steps:
1. placing the sputtering target into a target seat, adjusting a gap between the target seat and a magnetron target cooling base, and placing a substrate on a sample table and hanging the substrate at a position of 100-200 mm right above the sputtering target;
2. vacuumizing a vacuum chamber, introducing Ar gas to ensure that the air pressure in the vacuum chamber is 0.1 Pa-10 Pa, forming high-power pulse magnetron sputtering discharge through a high-power pulse magnetron power supply under the conditions that the discharge voltage amplitude is 0.5 kW-2.0 kW, the discharge power is 0.7 kW-2.5 kW, the frequency is 0.6 kHz-10 kHz and the pulse width is 10 mu s-1000 mu s, melting the surface of a target, and adjusting the discharge voltage amplitude to maintain the discharge power to be 0.7 kW-2.5 kW until the target is melted to 70% -100%, thereby obtaining a liquid target;
3. sputtering is carried out under the conditions that the discharge power is 0.7 kW-2.5 kW, the frequency is 0.6 kHz-10 kHz, the pulse width is 10 mu s-1000 mu s and the liquid target material is adopted, and the method for improving the deposition efficiency by adopting the liquid metal high-power pulse magnetron sputtering is completed.
The beneficial effects of the invention are as follows:
the invention provides a method for improving deposition efficiency by adopting liquid metal high-power pulse magnetron sputtering. The method takes away the heat generated in the sputtering process of the target material without water cooling, but melts the target material by utilizing the sputtering heating effect, and the discharge power is increased along with the increase of discharge voltage and current, the ionization degree of plasma on the surface of the target material is increased, and Ar + Ion bombardment is enhanced, melting is started first at the place with the highest Ar plasma density, under the melting condition, a large amount of metal atoms are generated due to metal evaporation, the metal atoms are ionized in a large amount by using high-power pulse magnetron discharge, and then the self-sputtering effect of the metal atoms is utilized to maintain the local melting of the target. The process greatly improves the utilization rate of the thermal effect of the magnetron sputtering process. In addition, due to the large amount of evaporation of metal atoms, the number of metal atoms or ions formed is significantly increased compared to a single sputtering process, and a high deposition efficiency can be obtained.
Drawings
FIG. 1 is a photograph showing the melting process of the target in the first step of the embodiment, wherein a is that the target is not melted, b is that the target begins to melt, and c is that the target is completely melted;
FIG. 2 is a graph showing the discharge voltage-current curve of the liquid Al target in the first example and the solid Al target in the comparative experiment at 820W discharge power, (a) is the discharge voltage, (b) is the discharge current, 1 is the solid Al target in the comparative experiment, and 2 is the liquid Al target in the first example;
FIG. 3 is a diagram of a real object after deposition, (a) a liquid target sputtering 30min pure Al film in example one, and (b) a solid target sputtering 30min pure Al film in comparative experiment;
FIG. 4 is a schematic illustration of a sputtering target loaded into a molybdenum crucible and having a gap with a magnetron target cooling pedestal according to one embodiment.
Detailed Description
The first embodiment is as follows: the method for improving the deposition efficiency by adopting the high-power pulse magnetron sputtering of the liquid metal in the embodiment comprises the following steps of:
1. placing the sputtering target into a target seat, adjusting a gap between the target seat and a magnetron target cooling base, and placing a substrate on a sample table and hanging the substrate at a position of 100-200 mm right above the sputtering target;
2. vacuumizing a vacuum chamber, introducing Ar gas to ensure that the air pressure in the vacuum chamber is 0.1 Pa-10 Pa, forming high-power pulse magnetron sputtering discharge through a high-power pulse magnetron power supply under the conditions that the discharge voltage amplitude is 0.5 kW-2.0 kW, the discharge power is 0.7 kW-2.5 kW, the frequency is 0.6 kHz-10 kHz and the pulse width is 10 mu s-1000 mu s, melting the surface of a target, and adjusting the discharge voltage amplitude to maintain the discharge power to be 0.7 kW-2.5 kW until the target is melted to 70% -100%, thereby obtaining a liquid target;
3. sputtering is carried out under the conditions that the discharge power is 0.7 kW-2.5 kW, the frequency is 0.6 kHz-10 kHz, the pulse width is 10 mu s-1000 mu s and the liquid target material is adopted, and the method for improving the deposition efficiency by adopting the liquid metal high-power pulse magnetron sputtering is completed.
In the specific embodiment, the sputtering target is placed in the target seat, and a certain gap is reserved between the target seat and the magnetron target cooling base in order to ensure that heat formed by the target is not taken away by cooling water.
In this embodiment, when the target surface melts, the discharge voltage will obviously drop due to the self-sputtering effect, and adjustment is needed to maintain the discharge power unchanged, so as to ensure that the target surface is always in a melted state.
The beneficial effects of this embodiment are:
the embodiment provides a method for improving deposition efficiency by adopting liquid metal high-power pulse magnetron sputtering. The method takes away the heat generated in the sputtering process of the target material without water cooling, but melts the target material by utilizing the sputtering heating effect, and the discharge power is increased along with the increase of discharge voltage and current, the ionization degree of plasma on the surface of the target material is increased, and Ar + Ion bombardment is enhanced, melting is started first at the place with the highest Ar plasma density, under the melting condition, a large amount of metal atoms are generated due to metal evaporation, the metal atoms are ionized in a large amount by using high-power pulse magnetron discharge, and then the self-sputtering effect of the metal atoms is utilized to maintain the local melting of the target. The process greatly improves the utilization rate of the thermal effect of the magnetron sputtering process. In addition, due to the large amount of evaporation of metal atoms, the number of metal atoms or ions formed is significantly increased compared to a single sputtering process, and a high deposition efficiency can be obtained.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the sputtering target material in the first step is an Al target, a Cu target or a Cr target. The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the gap width in the first step is 1 mm-20 mm. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: step one, placing a sputtering target into a target seat, specifically, placing a sputtering target material into a crucible, and then placing the crucible with the sputtering target material into the target seat; the crucible is internally provided with a rectangular groove for holding a target. The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the crucible is made of molybdenum, graphite or tungsten. The other embodiments are the same as those of the first to fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: the substrate in the first step is quartz glass sheet, silicon wafer or 316L stainless steel. The other embodiments are the same as those of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: in the second step, the vacuum chamber is vacuumized to 1 multiplied by 10 -2 Pa or below. The other embodiments are the same as those of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: and in the second step, ar gas with the pressure of 10-200 sccm is introduced so that the air pressure in the vacuum chamber is 0.1-10 Pa. The other is the same as in embodiments one to seven.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: in the second step, the air pressure in the vacuum chamber is between 0.5Pa and 10Pa, and under the conditions that the discharge voltage amplitude is between 0.5kV and 1.2kV, the discharge power is between 0.8kW and 1.5kW, the frequency is between 0.6kHz and 10kHz and the pulse width is between 300 mu s and 1000 mu s, high-power pulse magnetron sputtering discharge is formed through a high-power pulse magnetron power supply, and the surface of the target is melted. The others are the same as in embodiments one to eight.
Detailed description ten: this embodiment differs from one of the embodiments one to nine in that: and step three, sputtering under the conditions that the discharge power is 0.8 kW-1.5 kW, the frequency is 0.6 kHz-10 kHz, and the pulse width is 300 mu s-1000 mu s. The others are the same as in embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
embodiment one, specifically described with reference to fig. 4:
a method for improving deposition efficiency by adopting liquid metal high-power pulse magnetron sputtering is carried out according to the following steps:
1. loading a sputtering target into a molybdenum crucible, then placing the molybdenum crucible with the sputtering target into a target seat, adjusting a gap between the target seat and a magnetron target cooling base to be 3mm in width, and placing a substrate on a sample table and hanging the substrate at a position 150mm above the sputtering target;
a rectangular groove is formed in the molybdenum crucible and used for containing a target;
2. the vacuum chamber was evacuated to 8X 10 -3 Under Pa, introducing Ar gas of 100sccm to ensure that the air pressure in a vacuum chamber is 0.5Pa, forming high-power pulse magnetron sputtering discharge through a high-power pulse magnetron power supply under the conditions that the discharge voltage amplitude is 0.5 kV-1.2 kV, the discharge power is 820W, the frequency is 600Hz and the pulse width is 300 mu s, melting the surface of a target material, and adjusting the discharge voltage amplitude to maintain the discharge power to be 820W until the target material is melted to 100%, thereby obtaining a liquid target material;
3. sputtering is carried out for 30min under the conditions of 820W of discharge power, 600Hz of frequency, 300 mu s of pulse width and liquid target material, and the method for improving the deposition efficiency by adopting liquid metal high-power pulse magnetron sputtering is completed.
And in the first step, the sputtering target material is an Al target. The substrate in the first step is a quartz glass sheet.
Comparison experiment:
1. directly placing a sputtering target into a target seat, canceling a molybdenum crucible, adjusting the target seat to be in direct contact with a magnetron target cooling base without a gap, placing a substrate on a sample table and hanging the substrate at a position 150mm right above the sputtering target;
2. sputtering a solid Al target by adopting a high-power pulse magnetron sputtering technology, and sputtering for 30min under the conditions that the discharge power is 820W, the frequency is 600Hz, the pulse width is 300 mu s and the solid target material is adopted;
the sputtering target in the first step is an Al target. The substrate in the first step is a quartz glass sheet.
In the first embodiment, the target is placed in the molybdenum base, and the molybdenum base is separated from the cooling system by the stainless steel bracket with the thickness of 3mm, so that heat applied to the surface of the target cannot be effectively transferred to the cooling system in the discharging process, the target begins to melt after the heat is accumulated to a certain degree, the discharge power is maintained by adjusting the discharge voltage amplitude, the target is completely melted, and the heat conduction between the target and the cooling system can be better isolated due to the low heat conductivity and better electric conductivity of molybdenum, so that the heat applied to the surface of the target cannot be dissipated through the cooling system, and finally the target is melted; in the comparative experiment, the target material is closely attached to the cooling system, and the molybdenum crucible is not arranged, so that heat generated in the discharging process can be effectively transferred to the cooling system, and therefore, the heat cannot be accumulated, and the target material cannot be melted.
FIG. 1 is a photograph showing the melting process of the target in the first step of the embodiment, wherein a is that the target is not melted, b is that the target begins to melt, and c is that the target is completely melted; from the figure, the target begins to melt first where the Ar plasma density is highest, as shown in figure b. After the target surface begins to melt locally, the heat is continuously conducted to the rest positions of the target surface and Ar + The ions continuously sputter the target surface causing heat to build up, eventually causing the target surface to fully melt, as shown in figure c.
FIG. 2 is a graph showing the discharge voltage-current curve of the liquid Al target in the first example and the solid Al target in the comparative experiment at 820W discharge power, (a) is the discharge voltage, (b) is the discharge current, 1 is the solid Al target in the comparative experiment, and 2 is the liquid Al target in the first example; as can be seen from the figure, when sputtering a solid Al target, the metal ion content of the target in the plasma is relatively small, and sputtering is mainly maintained by means of ionization of Ar gas discharge, and the ionization energy of gas atoms is high, so that a high discharge voltage is required to ionize Ar gas and maintain discharge. Sputtering of liquid Al targets, due to evaporation of liquid metal ions and Ar + The ion sputtering liquid metal, the self-sputtering effect of the target is obviously enhanced, the content of metal particles in the plasma is obviously increased, the ionization energy of metal atoms is lower, so that a large number of metal atoms can be ionized only by lower discharge voltage, the discharge voltage is obviously reduced on the premise of unchanged discharge power, as shown in figure 2 (a), and the discharge peak current is increased,as shown in fig. 2 (b), the oscilloscope signal source 1 detects a discharge current, and the signal source 2 detects a discharge voltage.
FIG. 3 is a diagram of a real object after deposition, (a) a liquid target sputtering 30min pure Al film in example one, and (b) a solid target sputtering 30min pure Al film in comparative experiment; the deposition rate of the metal film is also improved because the discharge waveform changes significantly after the target is melted, accompanied by the evaporation of the liquid metal. FIG. 3 shows a physical diagram of a pure Al film deposited by sputtering a liquid target and a solid target under the same discharge power, and the deposition rate can be calculated by subtracting the mass of the quartz plate before coating from the weight obtained after weighing by a high-precision balance weighing test and dividing the mass difference by the product of the surface area of the quartz plate and the Al density. The final measurement shows that the liquid target deposition rate is 2.3 μm/h and the solid target deposition rate is 1.3 μm/h. From the measurement results, it can be seen that the liquid target deposition rate is 1.77 times that of the solid target deposition rate.

Claims (4)

1. A method for improving deposition efficiency by adopting liquid metal high-power pulse magnetron sputtering is characterized by comprising the following steps:
1. placing a sputtering target material into a target seat, adjusting a gap between the target seat and a magnetron target cooling base, and placing a substrate on a sample table and hanging the substrate at a position 100 mm-200 mm right above the sputtering target material;
the gap width is 1 mm-20 mm; the sputtering target material is an Al target;
step one, placing a sputtering target into a target seat, specifically, placing a sputtering target material into a crucible, and then placing the crucible with the sputtering target material into the target seat; a rectangular groove is formed in the crucible and used for containing a target; the crucible is made of molybdenum, graphite or tungsten;
2. vacuumizing a vacuum chamber, introducing Ar gas to enable the air pressure in the vacuum chamber to be 0.5Pa, forming high-power pulse magnetron sputtering discharge through a high-power pulse magnetron power supply under the conditions that the discharge voltage amplitude is 0.5 kV-1.2 kV, the discharge power is 820W, the frequency is 600Hz and the pulse width is 300 mu s, melting the surface of a target, and adjusting the discharge voltage amplitude to maintain the discharge power to be 820W until the target is melted to 100%, so as to obtain a liquid target;
3. sputtering is carried out under the conditions that the discharge power is 820W, the frequency is 600Hz, the pulse width is 300 mu s and the liquid target is adopted, and the method for improving the deposition efficiency by adopting the liquid metal high-power pulse magnetron sputtering is completed.
2. The method for improving deposition efficiency by high-power pulsed magnetron sputtering of liquid metal according to claim 1, wherein the substrate in the first step is a quartz glass plate, a silicon wafer or 316L stainless steel.
3. The method for improving deposition efficiency by high-power pulsed magnetron sputtering of liquid metal according to claim 1, wherein in step two, the vacuum chamber is evacuated to 1X 10 -2 Pa or below.
4. The method for improving deposition efficiency by liquid metal high-power pulse magnetron sputtering according to claim 1, wherein in the second step, 10 sccm-200 sccm of Ar gas is introduced so that the air pressure in the vacuum chamber is 0.1 Pa-10 Pa.
CN202210638878.2A 2022-06-07 2022-06-07 Method for improving deposition efficiency by adopting liquid metal high-power pulse magnetron sputtering Active CN115029669B (en)

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CN109996904A (en) * 2016-08-03 2019-07-09 西格玛锂业有限公司 The method for forming metal lithium coating

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