Device for quickly and uniformly depositing thin film on inner wall of slender pipe barrel piece through pre-ionization hollow cathode tube internal discharge and using method

Abstract

The invention relates to a device for quickly and uniformly depositing a film on the inner wall of a slender pipe barrel by discharging in a pre-ionization hollow cathode tube and a use method. The method belongs to the field of surface treatment. The problems that a hollow cathode target deforms and loses efficacy, and a large-thickness film is difficult to uniformly and rapidly deposit on the inner wall of a slender pipe barrel piece are solved. The device comprises a pre-ionization device consisting of a pre-ionization power supply, a pre-ionization ion source and an anode ring, and the pre-ionization ion source, the anode ring, the hollow cathode target material, the slender pipe barrel piece and the anode rod are coaxially arranged. By arranging the pre-ionization ion source, the discharge difficulty of the hollow cathode target material is reduced, the discharge intensity of the hollow cathode target material is improved, the heat input of a port of the hollow cathode target material is reduced, the port is prevented from being deformed and invalid due to overheating, and the deposition rate of a film is further improved; the reciprocating mechanism drives the slender pipe barrel part and the discharge area of the hollow cathode target material to move relatively, so that plasma discharge in the slender pipe barrel part and uniform and rapid deposition of a large-thickness film are realized.

Description

Technical Field

[0001] The invention belongs to the field of surface treatment, and in particular relates to a device and a use method for quickly and evenly depositing a thin film on the inner wall of a slender tube by discharging in a pre-ionized hollow cathode tube. Background Art

[0002] With the progress of industrial society, the proportion of slender tubular materials in industrial production is increasing. In actual use, slender tubular parts often fail due to high temperature, friction or corrosion on the inner wall. The preparation of inner wall coating is an effective way to solve this problem. Common methods for coating the inner wall of slender tubular parts include chemical vapor deposition (CVD), electroplating, magnetron sputtering coating and cathode arc ion plating. CVD technology requires the metal material to be plated to be heated above its boiling point, so it is not suitable for temperature-sensitive substrate materials, and the ionization rate of this technology is too low. Although electroplating technology can achieve surface coating of complex structural parts, there are problems such as brittle coating, serious environmental pollution and low current utilization. PVD technology has the advantages of environmental friendliness and small restrictions on the types of coatings that can be plated. However, arc ion plating or magnetron sputtering in conventional PVD technology requires a built-in magnetic field and water cooling structure, and the volume and size of the target are limited. For slender tubular parts, it is impossible to achieve a large target-substrate distance while building the target, and discharge is extremely difficult. Also due to the limitation of the space inside the tube, after arc ion plating or magnetron sputtering, the target material is very small and the anode cannot be built in. The only way is to use a two-pole discharge method in which the target is connected to the positive electrode and the slender tube is connected to the positive electrode of the power supply, which limits the effective regulation of the plasma energy. The hollow cathode discharge method is simple to install and can perform three-stage discharge inside the slender tube. However, during the hollow cathode discharge process, the plasma is concentrated at the tube mouth, and the local plasma density and energy are very high. The narrow space inside the tube is not enough to implement water cooling and other methods to cool down the hollow cathode discharge structure, which eventually leads to local overheating, deformation and failure of the hollow cathode target port. Therefore, how to reduce the plasma energy and heat input at the port position while maintaining the port plasma density and ionization rate has become a key issue that limits the further application of this method in the field of inner wall coating of slender tubes and needs to be solved urgently. Summary of the invention

[0003] The purpose of the present invention is to solve the problem that the hollow cathode discharge coating method in a slender tube is limited by the local excessive temperature of the hollow cathode port, resulting in deformation and failure of the hollow cathode target, and the problem that conventional methods are difficult to meet the requirements of uniformly and quickly depositing a thick film on the inner wall of a slender tube, and to provide a device and a method for using the discharge in a pre-ionized hollow cathode tube to quickly and uniformly deposit a film on the inner wall of a slender tube.

[0004] A device for quickly and evenly depositing a thin film on the inner wall of a slender tube by discharging in a pre-ionized hollow cathode tube, comprising a pre-ionized ion source, an anode ring, a hollow cathode target, a slender tube, an anode rod, a pre-ionized power supply, a hollow cathode power supply, a bias power supply and a pre-ionized box;

[0005] One end of the pre-ionization ion source is connected to the negative output end of the pre-ionization power supply, the positive output end of the pre-ionization power supply is connected to the anode ring and one end of the hollow cathode target, the other end of the hollow cathode target is connected to the negative output end of the hollow cathode power supply, the positive output end of the hollow cathode power supply is connected to one end of the anode rod and grounded, the elongated tube is connected to the negative output end of the bias power supply, and the positive output end of the bias power supply is connected to the anode rod and grounded;

[0006] An opening is arranged on one side of the pre-ionization box, one side of the opening is connected to one end of the hollow cathode target, and the other side of the opening is an anode ring; the pre-ionization ion source, the anode ring, the opening, the hollow cathode target, the slender tube and the anode rod are coaxially arranged;

[0007] The other end of the hollow cathode target is sleeved on one end of the slender tube member, and the other end of the slender tube member is sleeved on the other end of the anode rod;

[0008] The pre-ionization ion source and the anode ring are arranged inside the pre-ionization box, and the working gas enters the pre-ionization box; the pre-ionization ion source, the anode ring and the pre-ionization box constitute a pre-ionization device.

[0009] Furthermore, it also includes a base plate, a first insulating bracket, a second insulating bracket and a reciprocating mechanism; the pre-ionization device is fixed on the base plate; the hollow cathode target is fixed on the base plate through the first insulating bracket; the anode rod is fixed on the base plate through the first insulating bracket; the slender tube is fixed on the reciprocating mechanism through the second insulating bracket; the reciprocating mechanism is arranged on the base plate; the second insulating bracket is pulled by the reciprocating mechanism to drive the slender tube to reciprocate at a uniform speed along the axial direction.

[0010] Furthermore, the hollow cathode target is made of Cr, Ti, Ta, Cu, Ni, Zn, Nb, Sn, Al, Fe, Mg or Zr;

[0011] Alternatively, it may be a nickel-chromium alloy, a nickel-aluminum alloy, a nickel-iron alloy, a nickel-vanadium alloy, a titanium-aluminum alloy, a titanium-aluminum-silicon alloy, a gold-tin alloy, a gold-palladium alloy, a molybdenum-niobium alloy, a ruthenium-chromium alloy, a boron-iron alloy or a silicon-iron alloy.

[0012] Furthermore, the pre-ionized ion source is divided into a hollow cathode pre-ionized ion source, a magnetron sputtering pre-ionized ion source or an arc pre-ionized ion source according to different discharge modes; the material of the pre-ionized ion source is Cr, Ti, Ta, Cu, Ni, Zn, Nb, Sn, Al, Fe, Mg or Zr;

[0013] Alternatively, it may be a nickel-chromium alloy, a nickel-aluminum alloy, a nickel-iron alloy, a nickel-vanadium alloy, a titanium-aluminum alloy, a titanium-aluminum-silicon alloy, a gold-tin alloy, a gold-palladium alloy, a molybdenum-niobium alloy, a ruthenium-chromium alloy, a boron-iron alloy or a silicon-iron alloy.

[0014] Furthermore, the pre-ionization power supply, hollow cathode power supply and bias power supply can all be a direct current power supply, a pulse power supply, a high voltage power supply, a radio frequency power supply, an intermediate frequency power supply or a high power pulse power supply.

[0015] The method for using the above-mentioned device for quickly and uniformly depositing a thin film on the inner wall of a slender tube by discharging in a pre-ionized hollow cathode tube is implemented by the following steps:

[0016] 1. Self-glow cleaning of the inner wall of slender tubes:

[0017] The vacuum chamber is evacuated, and the working gas enters the pre-ionization box, and the vacuum chamber pressure is maintained at 0.1-50 Pa. The positive output end of the bias power supply is connected to the anode rod and grounded, and the negative output end is connected to the slender tube member. The voltage of the bias power supply is controlled to be -50--2000V, and the duty cycle is 5%-100%. The plasma generated by the hollow cathode discharge effect is used to self-glow clean the inner surface of the slender tube member to obtain the slender tube member after self-glow cleaning;

[0018] 2. Hollow cathode enhanced glow cleaning of the inner wall of slender tubes:

[0019] The vacuum chamber pressure is maintained at 0.1-50 Pa, the negative output end of the pre-ionization power supply is connected to the pre-ionization ion source, the positive output end is connected to the anode ring and one end of the hollow cathode target, the other end of the hollow cathode target is connected to the negative output end of the hollow cathode power supply, the positive output end of the hollow cathode power supply is connected to one end of the anode rod and grounded, the slender tube after self-glow cleaning is connected to the negative output end of the bias power supply, the positive output end of the bias power supply is connected to the anode rod and grounded, the voltage of the pre-ionization power supply is controlled to be 400-2000V, and the peak current 0.1~100A, duty cycle 0.1%~100%, the working gas is ionized by a pre-ionization ion source, and then transported to the hollow cathode target, the voltage of the hollow cathode power supply is 400~2000V, the peak current is 0.1~100A, the duty cycle is 0.1%~100%, the bias power supply voltage is -50~-2000V, the duty cycle is 5%~100%, the working gas is further ionized by the hollow cathode target, and hollow cathode enhanced glow cleaning is performed to obtain a slender tube after hollow cathode enhanced glow cleaning;

[0020] 3. Deposition on the inner wall of tube and barrel:

[0021] The negative output end of the pre-ionization power supply is connected to the pre-ionization ion source, the positive output end is connected to the anode ring and one end of the hollow cathode target, the other end of the hollow cathode target is connected to the negative output end of the hollow cathode power supply, the positive output end of the hollow cathode power supply is connected to the anode rod, and the negative output end of the bias power supply is connected to the slender tube after the hollow cathode enhanced glow cleaning, the positive output end of the bias power supply is grounded, the vacuum chamber pressure is maintained at 0.1-50Pa, the voltage of the pre-ionization power supply is controlled to be 400-2000V, and the peak current is The current is 0.1-100A, the duty cycle is 0.1%-100%, the voltage of the hollow cathode power supply is 400-2000V, the peak current is 0.1-100A, the duty cycle is 0.1%-100%, the voltage of the bias power supply is -0.1-500V, the duty cycle is 5%-100%, the working gas is ionized by a pre-ionization ion source, and then further ionized by a hollow cathode target material, hollow cathode coating is performed, and a thin film is uniformly deposited on the inner wall of a slender tube, thus completing the method for using the device.

[0022] Furthermore, the working gas in step 1 is argon, helium, neon, krypton, xenon, radon, oxygen, nitrogen, hydrogen, methane, hydrogen sulfide, ammonia, Ar+O 2 、Ar+N 2 、Ar+H 2 , O 2 +N 2 , O 2 +CH 4 , Ar+He or Ar+Xe; when the working gas is a mixed gas, the two are mixed in any ratio.

[0023] Furthermore, the self-glow cleaning time in step 1 is 15 minutes to 600 minutes.

[0024] Furthermore, the time for the hollow cathode enhanced glow cleaning in step 2 is 15 min to 600 min.

[0025] Furthermore, the time for hollow cathode coating in step three is 10 min to 600 min.

[0026] Principles and beneficial effects of the present invention:

[0027] 1. The present invention effectively reduces the difficulty of hollow cathode discharge by using an external pre-ionized ion source during the hollow cathode discharge coating process. At the same time, the reciprocating mechanism pulls and drives the slender tube to reciprocate axially at a uniform speed, which facilitates uniform coating of the film at various locations of the slender tube.

[0028] 2. The present invention successfully realizes plasma discharge and efficient, controlled and uniform deposition of coatings in slender tubes through an external pre-ionized ion source, effectively solving the problem of excessive local heat input of hollow cathode discharge in the tube, which causes overheating, deformation and failure of the hollow cathode port. The principle is as follows: hollow cathode technology is a method for realizing efficient ionization discharge by utilizing the reciprocating oscillation of electrons between the cathode walls. The gas is pre-ionized by an external pre-ionized ion source. As the pre-ionized gas reaches the hollow cathode port through the hollow cathode tube, the unrecombined residual plasma (including electrons and ions) in the gas can be used for the hollow cathode discharge process at the port position, effectively reducing the difficulty of hollow cathode discharge, which is manifested as a lower excitation voltage under the same current, that is, the heat input to the hollow cathode port is reduced under the same plasma density, and local overheating deformation failure at the port position is avoided under non-water cooling conditions, while ensuring the high plasma density and high ionization rate of hollow cathode discharge; since the opening direction of the hollow cathode can be along the axis, and its anode can be coaxially placed in the tube, the plasma generated by the two can be controllably deposited on the inner wall of the slender tube under the action of the bias electric field between the anode and the slender tube member, effectively realizing the regulation of plasma energy. At the same time, by pulling and moving the slender tube member, effective contact between the discharge area and different positions of the inner wall of the slender tube member can be achieved, and uniform and effective deposition of the coating at all positions inside the slender tube member can be achieved.

[0029] 3. The inner diameter of the slender tube is small, and the structure of the traditional cylindrical magnetron or multi-arc target is complex, which is difficult to place in the slender tube. Therefore, it is very difficult to achieve sputtering coating of the slender tube by using a columnar target. Based on this situation, a hollow cathode target with a smaller size is innovatively placed inside the slender tube. The hollow cathode target is connected to the negative output end of the hollow cathode power supply, the positive output end of the hollow cathode power supply is connected to the anode rod and grounded, the slender tube is connected to the negative output end of the bias power supply, and the positive output end of the bias power supply is grounded. An insulating bracket is provided at the bottom of the slender tube, and the height of the insulating bracket can be adjusted up and down to adjust the slender tube, the hollow cathode target and the anode rod to be coaxial and at the same time keep them coaxial with the pre-ionization ion source, the anode ring and the opening.

[0030] 4. The present invention successfully realizes plasma discharge and efficient, controlled and uniform deposition of coatings in slender tubes through an external pre-ionized ion source, effectively solves the problem of excessive local heat input in hollow cathode discharge in the tube, which leads to overheating, deformation and failure of the hollow cathode port, and reduces the difficulty of hollow cathode discharge, which is manifested in lower excitation voltage at the same current, that is, lower heat input to the hollow cathode port at the same plasma density, and avoids local overheating, deformation and failure at the port position under non-water cooling conditions, while ensuring high plasma density and high ionization rate of hollow cathode discharge.

[0031] 5. The present invention reduces the discharge difficulty of the hollow cathode target, improves the discharge intensity of the hollow cathode target, reduces the heat input at the port of the hollow cathode target, and thus improves the deposition rate of the thin film by setting a pre-ionized ion source. The reciprocating mechanism drives the relative movement of the slender tube and the discharge area of ​​the hollow cathode target, thereby solving the problem of uniform and rapid deposition of thick films.

[0032] The invention is suitable for quickly and evenly depositing a thin film on the inner wall of a slender tube member by discharging in a pre-ionized hollow cathode tube. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The present invention is a schematic diagram of a device for quickly and uniformly depositing a thin film on the inner wall of a slender tube member by discharging in a pre-ionized hollow cathode tube, wherein 1 represents a pre-ionized ion source, 2 represents an anode ring, 3 represents a bottom plate, 4 represents a first insulating support, 5 represents a hollow cathode target, 6 represents a slender tube member, 7 represents a second insulating support, 8 represents an anode rod, 9 represents a pre-ionized power supply, 10 represents a hollow cathode power supply, 11 represents a bias power supply, 12 represents a reciprocating mechanism, 13 represents a pre-ionized box, and 14 represents an opening;

[0034] Figure 2 This is a surface electron microscope image of a thin film deposited on the inner wall of a slender tube with an inner diameter of 6 mm using a hollow cathode target in the embodiment;

[0035] Figure 3 This is a cross-sectional electron microscope image of a thin film deposited using a hollow cathode target in an embodiment;

[0036] Figure 4 This is an indentation morphology of a thin film deposited using a hollow cathode target in an embodiment;

[0037] Figure 5 4 is a discharge current and voltage waveform diagram of the hollow cathode target power supply in the embodiment. DETAILED DESCRIPTION

[0038] Specific implementation method 1: Figure 1 As shown, in this embodiment, a device for quickly and uniformly depositing a thin film on the inner wall of a slender tube member by discharge in a pre-ionized hollow cathode tube comprises a pre-ionized ion source 1, an anode ring 2, a hollow cathode target 5, a slender tube member 6, an anode rod 8, a pre-ionized power supply 9, a hollow cathode power supply 10, a bias power supply 11 and a pre-ionized box 13;

[0039] The other end of the pre-ionization ion source 1 is connected to the negative output end of the pre-ionization power supply 9, the positive output end of the pre-ionization power supply 9 is connected to the anode ring 2 and one end of the hollow cathode target 5, the other end of the hollow cathode target 5 is connected to the negative output end of the hollow cathode power supply 10, the positive output end of the hollow cathode power supply 10 is connected to one end of the anode rod 8 and grounded, the elongated tube 6 is connected to the negative output end of the bias power supply 11, and the positive output end of the bias power supply 11 is connected to the anode rod 8 and grounded;

[0040] An opening 14 is provided on one side of the pre-ionization box 13, one side of the opening 14 is connected to one end of the hollow cathode target 5, and the other side of the opening 14 is the anode ring 2; the pre-ionization ion source 1, the anode ring 2, the opening 14, the hollow cathode target 5, the elongated tube 6 and the anode rod 8 are coaxially arranged;

[0041] The other end of the hollow cathode target 5 is sleeved on one end of the slender tube 6, and the other end of the slender tube 6 is sleeved on the other end of the anode rod 8;

[0042] The pre-ionization ion source 1 and the anode ring 2 are arranged inside the pre-ionization box 13, and the working gas enters the pre-ionization box 13; the pre-ionization ion source 1, the anode ring 2 and the pre-ionization box 13 constitute a pre-ionization device.

[0043] In this embodiment, the inner diameter of the slender tube member 6 is 6-100 mm, the length is 10-1000 mm, and the material is carbon steel, stainless steel, titanium alloy, copper alloy or aluminum alloy.

[0044] Specific embodiment 2: This embodiment is different from the specific embodiment 1 in that it also includes a bottom plate 3, a first insulating bracket 4, a second insulating bracket 7 and a reciprocating mechanism 12; the pre-ionization device is fixed on the bottom plate 3; the hollow cathode target 5 is fixed on the bottom plate 3 through the first insulating bracket 4; the anode rod 8 is fixed on the bottom plate 3 through the first insulating bracket 4; the slender tube member 6 is fixed on the reciprocating mechanism 12 through the second insulating bracket 7; the reciprocating mechanism 12 is arranged on the bottom plate 3; the second insulating bracket 7 is pulled by the reciprocating mechanism 12 to drive the slender tube member 6 to reciprocate at a uniform speed along the axial direction. The rest is the same as the specific embodiment 1.

[0045] Specific embodiment 3: This embodiment is different from the specific embodiment 1 in that the hollow cathode target 5 is made of Cr, Ti, Ta, Cu, Ni, Zn, Nb, Sn, Al, Fe, Mg or Zr;

[0046] Or it can be nickel-chromium alloy, nickel-aluminum alloy, nickel-iron alloy, nickel-vanadium alloy, titanium-aluminum alloy, titanium-aluminum-silicon alloy, gold-tin alloy, gold-palladium alloy, molybdenum-niobium alloy, ruthenium-chromium alloy, boron-iron alloy or silicon-iron alloy. Others are the same as the first embodiment.

[0047] Specific embodiment 4: This embodiment is different from specific embodiment 1 in that the pre-ionization ion source 1 is divided into a hollow cathode pre-ionization ion source, a magnetron sputtering pre-ionization ion source or an arc pre-ionization ion source according to different discharge modes; the material of the pre-ionization ion source 1 is Cr, Ti, Ta, Cu, Ni, Zn, Nb, Sn, Al, Fe, Mg or Zr;

[0048] Or it can be nickel-chromium alloy, nickel-aluminum alloy, nickel-iron alloy, nickel-vanadium alloy, titanium-aluminum alloy, titanium-aluminum-silicon alloy, gold-tin alloy, gold-palladium alloy, molybdenum-niobium alloy, ruthenium-chromium alloy, boron-iron alloy or silicon-iron alloy. Others are the same as the first embodiment.

[0049] In this embodiment, the material of the pre-ionization ion source 1 and the material of the hollow cathode target 5 may be the same or different.

[0050] In this embodiment, the pre-ionization ion source 1 is a hollow cathode pre-ionization ion source, and the working gas enters the pre-ionization box (13) through one end of the hollow cathode pre-ionization ion source;

[0051] The pre-ionization ion source 1 is a magnetron sputtering pre-ionization ion source or an arc pre-ionization ion source, and the working gas enters the pre-ionization box (13) through the gas inlet of the magnetron sputtering pre-ionization ion source or the arc pre-ionization ion source.

[0052] Specific embodiment 5: This embodiment is different from specific embodiment 1 in that the pre-ionization power supply 9, hollow cathode power supply 10 and bias power supply 11 can all be a DC power supply, a pulse power supply, a high voltage power supply, a radio frequency power supply, an intermediate frequency power supply or a high power pulse power supply. The rest is the same as specific embodiment 1.

[0053] Specific implementation method 6: This implementation method is a method for using a device for quickly and uniformly depositing a thin film on the inner wall of a slender tube by discharging in a pre-ionized hollow cathode tube. It is implemented by the following steps:

[0054] 1. Self-glow cleaning of the inner wall of slender tubes:

[0055] The vacuum chamber is evacuated, and the working gas enters the pre-ionization box 13, and the vacuum chamber pressure is maintained at 0.1-50 Pa. The positive output end of the bias power supply 11 is connected to the anode rod 8 and grounded, and the negative output end is connected to the slender tube member 6. The voltage of the bias power supply 11 is controlled to be -50-2000V, and the duty cycle is 5%-100%. The plasma generated by the hollow cathode discharge effect is used to self-glow clean the inner surface of the slender tube member 6 to obtain the slender tube member after self-glow cleaning;

[0056] 2. Hollow cathode enhanced glow cleaning of the inner wall of slender tubes:

[0057] Maintain the vacuum chamber pressure at 0.1-50 Pa, connect the negative output end of the pre-ionization power supply 9 to the pre-ionization ion source 1, connect the positive output end to the anode ring 2 and one end of the hollow cathode target 5, connect the other end of the hollow cathode target 5 to the negative output end of the hollow cathode power supply 10, connect the positive output end of the hollow cathode power supply 10 to one end of the anode rod 8 and ground, connect the elongated tube after self-glow cleaning to the negative output end of the bias power supply 11, connect the positive output end of the bias power supply 11 to the anode rod 8 and ground, and control the voltage of the pre-ionization power supply 9 to 400-2000V , peak current 0.1~100A, duty cycle 0.1%~100%, working gas is ionized by pre-ionization ion source 1, and then moves to hollow cathode target 5, voltage of hollow cathode power supply 10 is 400~2000V, peak current 0.1~100A, duty cycle 0.1%~100%, bias power supply 11 voltage is -50~-2000V, duty cycle 5%~100%, working gas is further ionized by hollow cathode target 5, hollow cathode enhanced glow cleaning is performed, and slender tube after hollow cathode enhanced glow cleaning is obtained;

[0058] 3. Deposition on the inner wall of tube and barrel:

[0059] The negative output end of the pre-ionization power supply 9 is connected to the pre-ionization ion source 1, the positive output end is connected to the anode ring 2 and one end of the hollow cathode target 5, the other end of the hollow cathode target 5 is connected to the negative output end of the hollow cathode power supply 10, the positive output end of the hollow cathode power supply 10 is connected to the anode rod 8, and the negative output end of the bias power supply 11 is connected to the slender tube after the hollow cathode enhanced glow cleaning, the positive output end of the bias power supply 11 is grounded, the vacuum chamber pressure is maintained at 0.1-50Pa, and the voltage of the pre-ionization power supply 9 is controlled to be 400-2000. V, peak current 0.1~100A, duty cycle 0.1%~100%, the voltage of the hollow cathode power supply 10 is 400~2000V, the peak current 0.1~100A, the duty cycle 0.1%~100%, the voltage of the bias power supply 11 is -0.1~-500V, the duty cycle 5%~100%, the working gas is ionized by the pre-ionization ion source 1, and then further ionized by the hollow cathode target 5, and hollow cathode coating is performed to complete the uniform deposition of a thin film on the inner wall of the slender tube, that is, the method for using the device is completed.

[0060] Specific embodiment 7: This embodiment is different from specific embodiment 6 in that the working gas in step 1 is argon, helium, neon, krypton, xenon, radon, oxygen, nitrogen, hydrogen, methane, hydrogen sulfide, ammonia, Ar+O 2 、Ar+N 2 、Ar+H 2 , O 2 +N 2 , O 2+CH 4 , Ar+He or Ar+Xe; when the working gas is a mixed gas, the two are mixed in any ratio. Other steps and parameters are the same as those in the sixth embodiment.

[0061] Specific embodiment eight: This embodiment differs from specific embodiment six in that the time of the self-glow cleaning in step one is 15 minutes to 600 minutes. The other steps and parameters are the same as those in specific embodiment six.

[0062] Specific embodiment 9: This embodiment is different from specific embodiment 6 in that the time of hollow cathode enhanced glow cleaning in step 2 is 15 minutes to 600 minutes. Other steps and parameters are the same as those in specific embodiment 6.

[0063] Specific embodiment 10: This embodiment is different from specific embodiment 6 in that the time of hollow cathode coating in step 3 is 10 minutes to 600 minutes. Other steps and parameters are the same as those in specific embodiment 6.

[0064] The beneficial effects of the present invention are verified by the following examples:

[0065] Example:

[0066] A method for using a device for quickly and uniformly depositing a thin film on the inner wall of a slender tube by discharging in a pre-ionized hollow cathode tube, which is implemented by the following steps:

[0067] 1. Self-glow cleaning of the inner wall of slender tubes:

[0068] The vacuum chamber is evacuated, and the working gas enters the pre-ionization box 13, and the vacuum chamber pressure is maintained at 10Pa. The positive output end of the bias power supply 11 is connected to the anode rod 8 and grounded, and the negative output end is connected to the slender tube member 6. The voltage of the bias power supply 11 is controlled to be -900V, and the duty cycle is 30%. The plasma generated by the hollow cathode discharge effect is used to self-glow clean the inner surface of the slender tube member 6 to obtain the slender tube member after self-glow cleaning;

[0069] 2. Hollow cathode enhanced glow cleaning of the inner wall of slender tubes:

[0070] The pressure of the vacuum chamber is maintained at 10Pa, the negative output end of the pre-ionization power supply 9 is connected to the pre-ionization ion source 1, the positive output end is connected to the anode ring 2 and one end of the hollow cathode target 5, the other end of the hollow cathode target 5 is connected to the negative output end of the hollow cathode power supply 10, the positive output end of the hollow cathode power supply 10 is connected to one end of the anode rod 8 and grounded, the slender tube after self-glow cleaning is connected to the negative output end of the bias power supply 11, the positive output end of the bias power supply 11 is connected to the anode rod 8 and grounded, and the pre-ionization ion source 1 is controlled. The voltage of the ionization power supply 9 is 600V, the peak current is 40A, and the duty cycle is 30%. The working gas is ionized by the pre-ionization ion source 1 and then moves to the hollow cathode target 5. The voltage of the hollow cathode power supply 10 is 650V, the peak current is 50A, and the duty cycle is 40%. The voltage of the bias power supply 11 is -1000V and the duty cycle is 30%. The working gas is further ionized by the hollow cathode target 5, and hollow cathode enhanced glow cleaning is performed to obtain a slender tube after hollow cathode enhanced glow cleaning;

[0071] 3. Deposition on the inner wall of tube and barrel:

[0072] The negative output end of the pre-ionization power supply 9 is connected to the pre-ionization ion source 1, the positive output end is connected to the anode ring 2 and one end of the hollow cathode target 5, the other end of the hollow cathode target 5 is connected to the negative output end of the hollow cathode power supply 10, the positive output end of the hollow cathode power supply 10 is connected to the anode rod 8, and the negative output end of the bias power supply 11 is connected to the slender tube after the hollow cathode enhanced glow cleaning, and the positive output end of the bias power supply 11 is grounded. The vacuum chamber pressure is maintained at 10Pa to control the pre-ionization. The voltage of the ionization power supply 9 is 1000V, the peak current is 36A, and the duty cycle is 1.5%. The voltage of the hollow cathode power supply 10 is 1000V, the peak current is 36A, and the duty cycle is 1.5%. The voltage of the bias power supply 11 is -400V, and the duty cycle is 30%. The working gas is ionized by the pre-ionization ion source 1, and then further ionized by the hollow cathode target 5 to perform hollow cathode coating, thereby completing the uniform deposition of a thin film on the inner wall of the slender tube, thereby completing the method of using the device.

[0073] In this embodiment, the pre-ionization power supply 9 is a pulse power supply; the hollow cathode power supply 10 is a pulse power supply; and the bias power supply 11 is a DC power supply.

[0074] The slender tube member 6 in step 1 of this embodiment is made of maraging steel with an inner diameter of 6 mm and a length of 120 mm.

[0075] In step 2 of this embodiment, the hollow cathode target 5 is made of Cu. The pre-ionization ion source is a hollow cathode pre-ionization ion source with an inner diameter of 4 mm, made of Cu. The anode rod 8 is a high temperature resistant metal Mo rod.

[0076] Figure 2This is a surface electron microscope image of a thin film deposited on the inner wall of a slender tube with an inner diameter of 6 mm using a hollow cathode target in the embodiment. It can be seen that the surface of the film layer is relatively smooth, without accumulation and enrichment of larger particles, indicating that the film layer deposited in the experimental device for quickly and uniformly depositing a thin film on the inner wall of a slender tube by discharging in a pre-ionized hollow cathode tube has good uniformity.

[0077] Figure 3 This is a cross-sectional electron microscope image of the thin film deposited on the hollow cathode target in the embodiment. It can be seen that the film thickness is 279nm and is relatively dense, indicating that the experimental device for quickly and evenly depositing a thin film on the inner wall of a slender tube by discharging in a pre-ionized hollow cathode tube is feasible and stable.

[0078] Figure 4 This is the indentation morphology of the thin film deposited by the hollow cathode target in the embodiment. The HRC test method is one of the commonly used methods to evaluate the bonding strength between the film layer and the substrate material. When measuring the bonding strength, the Rockwell hardness tester indenter is a 120° conical diamond indenter, the loading load is set to 1470N (150kgf), and the load is maintained for 10s. The indentation morphology was analyzed using an ultra-depth of field optical microscope VHX-1000E (KEYENCE, Japan). Compared with the VDI3198 standard atlas, the bonding strength is divided into 6 levels (HF1-HF6). The research results show that the bonding strength between the film layer and the substrate has reached the level of HF1-HF2. The HRC indentation morphology is complete, the indentation is a complete circular indentation, there are no radial cracks and large areas of demolding area.

[0079] Figure 5 3 is a discharge current and voltage waveform of the hollow cathode target power supply in the embodiment. The figure shows that during the film deposition process in this embodiment, the actual sputtering power supply pulse voltage is 1000V, the pulse peak current is 36A, the corresponding frequency is 1000Hz, and the pulse width is 15μs.

[0080] This embodiment realizes the pre-ionization of gas through an external pre-ionization ion source. As the pre-ionized gas reaches the hollow cathode port through the hollow cathode tube, the uncompounded residual plasma (including electrons and ions) in the gas can be used for the hollow cathode discharge process at the port position, effectively reducing the difficulty of hollow cathode discharge, which is manifested as a lower excitation voltage under the same current, that is, the heat input to the hollow cathode port is reduced under the same plasma density, and the local overheating deformation failure at the port position is avoided under non-water cooling conditions, while ensuring the high plasma density and high ionization rate of hollow cathode discharge; since the opening direction of the hollow cathode can be along the axis, and its anode can be coaxially placed in the tube, the plasma generated by the two can be controllably deposited on the inner wall of the slender tube member under the action of the bias electric field between the anode and the slender tube member, and this method effectively reduces the temperature rise on the surface of the slender tube member material. Under the premise of ensuring the mechanical properties of the material, the requirements of film thickness and uniformity are met.

[0081] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A device for quickly and uniformly depositing a thin film on the inner wall of a slender tube by discharging in a pre-ionized hollow cathode tube, characterized in that It comprises a pre-ionization ion source (1), an anode ring (2), a hollow cathode target (5), a slender tube (6), an anode rod (8), a pre-ionization power supply (9), a hollow cathode power supply (10), a bias power supply (11) and a pre-ionization box (13); One end of the pre-ionization ion source (1) is connected to the negative output end of the pre-ionization power supply (9), the positive output end of the pre-ionization power supply (9) is connected to the anode ring (2) and one end of the hollow cathode target (5), the other end of the hollow cathode target (5) is connected to the negative output end of the hollow cathode power supply (10), the positive output end of the hollow cathode power supply (10) is connected to one end of the anode rod (8) and is grounded, the slender tube member (6) is connected to the negative output end of the bias power supply (11), and the positive output end of the bias power supply (11) is connected to the anode rod (8) and is grounded; An opening (14) is provided on one side of the pre-ionization box (13), one side of the opening (14) is connected to one end of the hollow cathode target (5), and the other side of the opening (14) is an anode ring (2); the pre-ionization ion source (1), the anode ring (2), the opening (14), the hollow cathode target (5), the slender tube (6) and the anode rod (8) are coaxially arranged; The other end of the hollow cathode target (5) is sleeved on one end of the slender tube member (6), and the other end of the slender tube member (6) is sleeved on the other end of the anode rod (8); The preionization ion source (1) and the anode ring (2) are arranged inside a preionization box (13), and the working gas enters the preionization box (13); the preionization ion source (1), the anode ring (2) and the preionization box (13) constitute a preionization device.

2. A device for rapidly and uniformly depositing a thin film on the inner wall of a slender tube by discharge in a pre-ionized hollow cathode tube according to claim 1, characterized in that It also comprises a bottom plate (3), a first insulating support (4), a second insulating support (7) and a reciprocating mechanism (12); the pre-ionization device is fixed on the bottom plate (3); the hollow cathode target (5) is fixed on the bottom plate (3) through the first insulating support (4); the anode rod (8) is fixed on the bottom plate (3) through the first insulating support (4); the slender tube member (6) is fixed on the reciprocating mechanism (12) through the second insulating support (7); the reciprocating mechanism (12) is arranged on the bottom plate (3); the second insulating support (7) is pulled by the reciprocating mechanism (12) to drive the slender tube member (6) to reciprocate at a uniform speed along the axial direction.

3. The device for rapidly and uniformly depositing a thin film on the inner wall of a slender tube by discharge in a pre-ionized hollow cathode tube according to claim 1, characterized in that The hollow cathode target (5) is made of Cr, Ti, Ta, Cu, Ni, Zn, Nb, Sn, Al, Fe, Mg or Zr; Alternatively, it may be a nickel-chromium alloy, a nickel-aluminum alloy, a nickel-iron alloy, a nickel-vanadium alloy, a titanium-aluminum alloy, a titanium-aluminum-silicon alloy, a gold-tin alloy, a gold-palladium alloy, a molybdenum-niobium alloy, a ruthenium-chromium alloy, a boron-iron alloy or a silicon-iron alloy.

4. The device for rapidly and uniformly depositing a thin film on the inner wall of a slender tube by discharge in a pre-ionized hollow cathode tube according to claim 1, characterized in that The pre-ionization ion source (1) is divided into a hollow cathode pre-ionization ion source, a magnetron sputtering pre-ionization ion source or an arc pre-ionization ion source according to different discharge modes; the material of the pre-ionization ion source (1) is Cr, Ti, Ta, Cu, Ni, Zn, Nb, Sn, Al, Fe, Mg or Zr; Alternatively, it may be a nickel-chromium alloy, a nickel-aluminum alloy, a nickel-iron alloy, a nickel-vanadium alloy, a titanium-aluminum alloy, a titanium-aluminum-silicon alloy, a gold-tin alloy, a gold-palladium alloy, a molybdenum-niobium alloy, a ruthenium-chromium alloy, a boron-iron alloy or a silicon-iron alloy.

5. The device for rapidly and uniformly depositing a thin film on the inner wall of a slender tube by discharge in a pre-ionized hollow cathode tube according to claim 1, characterized in that The pre-ionization power supply (9), hollow cathode power supply (10) and bias power supply (11) can all be direct current power supplies, pulse power supplies, high voltage power supplies, radio frequency power supplies, medium frequency power supplies or high power pulse power supplies.

6. A method for using the device for rapidly and uniformly depositing a thin film on the inner wall of a slender tube by discharge in a pre-ionized hollow cathode tube as claimed in claim 1, characterized in that: It is implemented as follows:

1. Self-glow cleaning of the inner wall of slender tubes: The vacuum chamber is evacuated, and the working gas enters the pre-ionization box (13), and the vacuum chamber pressure is maintained at 0.1-50 Pa. The positive output end of the bias power supply (11) is connected to the anode rod (8) and grounded, and the negative output end is connected to the slender tube member (6). The voltage of the bias power supply (11) is controlled to be -50-2000V, and the duty cycle is 5%-100%. The plasma generated by the hollow cathode discharge effect is used to self-glow clean the inner surface of the slender tube member (6), and the slender tube member after self-glow cleaning is obtained; 2. Hollow cathode enhanced glow cleaning of the inner wall of slender tubes: The vacuum chamber pressure is maintained at 0.1-50 Pa, the negative output end of the pre-ionization power supply (9) is connected to the pre-ionization ion source (1), the positive output end is connected to the anode ring (2) and one end of the hollow cathode target (5), the other end of the hollow cathode target (5) is connected to the negative output end of the hollow cathode power supply (10), the positive output end of the hollow cathode power supply (10) is connected to one end of the anode rod (8) and grounded, the elongated tube after self-glow cleaning is connected to the negative output end of the bias power supply (11), the positive output end of the bias power supply (11) is connected to the anode rod (8) and grounded, and the voltage of the pre-ionization power supply (9) is controlled to 40 The invention relates to a method for preparing a hollow cathode target material (5) comprising: a first ionization source (1) and a second ionization source (2) of a hollow cathode target material (5); a first ionization source (1) and a second ionization source (3) of a hollow cathode target material (5); a first ionization source (14) and a second ionization source (4) of a hollow cathode target material (5); a first ionization source (15) and a second ionization source (5) of a hollow cathode target material (5); a first ionization source (16) and a second ionization source (27) of a hollow cathode target material (5); a first ionization source (17) and a second ionization source (28) of a hollow cathode target material (5); a first ionization source (18) and a second ionization source (29) of a hollow cathode target material (5); a first ionization source (19) and a second ionization source (20) of a hollow cathode target material (5); a first ionization source (19) and a second ionization source (21) of a hollow cathode target material (5); a first ionization source (11) and a second ionization source (22) of a hollow cathode target material (5); a first ionization source (11) and a second ionization source (23) of a hollow cathode target material (5); a first ionization source (11) and a second ionization source (24) of a hollow cathode target material (5); a first ionization source (12) and a second ionization source (25) of a hollow cathode target material (5); a first ionization source (13) and a second ionization source (26) of a hollow cathode target material (5); a first ionization source (14) and a second ionization source (27) of a hollow cathode target material (5); a first ionization source (15) and a second ionization source (28) of a hollow cathode target material (5); a first ionization source (16) and a second ionization source (2 3. Deposition on the inner wall of tube and barrel: The negative output end of the pre-ionization power supply (9) is connected to the pre-ionization ion source (1), the positive output end is connected to the anode ring (2) and one end of the hollow cathode target (5), the other end of the hollow cathode target (5) is connected to the negative output end of the hollow cathode power supply (10), the positive output end of the hollow cathode power supply (10) is connected to the anode rod (8), and the negative output end of the bias power supply (11) is connected to the slender tube member after the hollow cathode enhanced glow cleaning, the positive output end of the bias power supply (11) is grounded, the vacuum chamber pressure is maintained at 0.1-50 Pa, and the voltage of the pre-ionization power supply (9) is controlled to 4 The hollow cathode power supply (10) has a voltage of 400 to 2000 V, a peak current of 0.1 to 100 A, a duty cycle of 0.1% to 100%, a bias power supply (11) has a voltage of -0.1 to -500 V, and a duty cycle of 5% to 100%, the working gas is ionized by a pre-ionization ion source (1), and then further ionized by a hollow cathode target (5), and hollow cathode coating is performed to complete the uniform deposition of a thin film on the inner wall of a slender tube, thus completing the use method of the device.

7. A method for using the device for rapidly and uniformly depositing a thin film on the inner wall of a slender tube by discharge in a pre-ionized hollow cathode tube according to claim 6, characterized in that The working gas described in step 1 is argon, helium, neon, krypton, xenon, radon, oxygen, nitrogen, hydrogen, methane, hydrogen sulfide, ammonia, Ar+O2, Ar+N2, Ar+H2, O2+N2, O2+CH4, Ar+He or Ar+Xe; when the working gas is a mixed gas, the two are mixed in any ratio.

8. The method for using the device for rapidly and uniformly depositing a thin film on the inner wall of a slender tube by discharge in a pre-ionized hollow cathode tube according to claim 6, characterized in that The time of the self-glow cleaning in step 1 is 15 minutes to 600 minutes.

9. The method for using the device for rapidly and uniformly depositing a thin film on the inner wall of a slender tube by discharge in a pre-ionized hollow cathode tube according to claim 6, characterized in that The time for the hollow cathode enhanced glow cleaning in step 2 is 15 minutes to 600 minutes.

10. The method for using the device for rapidly and uniformly depositing a thin film on the inner wall of a slender tube by discharge in a pre-ionized hollow cathode tube according to claim 6, characterized in that The time for hollow cathode coating in step 3 is 10 min to 600 min.

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