TWI595110B - Preparation of Multivariate Alloy Reactive Coating by Vacuum Ion Evaporation - Google Patents

Description

Preparation of multi-alloy reactive coating process by vacuum ion evaporation

The invention relates to a process for preparing a multi-alloy reactive coating by vacuum ion evaporation, which is a wet coating process, which is a processing method for forming a film of binary, ternary or multi-alloy materials on a workpiece surface.

The ceramic film is coated on the surface of the workpiece to effectively improve the strength or use efficiency of the workpiece. In the prior art, especially the vacuum ion evaporation method, most of them only use a single metal or a non-metal as a target to react with a reactive gas. Films are produced. However, in order to have different properties of various materials, it is also attempted to plate binary, ternary or multi-component targets, but the melting points between the multiple targets are different and cannot be placed simultaneously on the same crucible. For meta, ternary or multi-targets, different targets can be placed separately on multiple crucibles, and each target is plated on the surface of the workpiece in sequence, but the surface film coated in this way is There are different material properties in each layer, so the properties that each material can exert are limited, and the processing efficiency of performing vapor deposition is not good.

In view of the above-mentioned shortcomings, the inventor believes that it has the urgent need to make corrections, and that it has been engaged in the design and manufacture of related products for many years, and has always adhered to the excellent design concept, and researched and created the above disadvantages. After continuous efforts, the invention finally introduced a multi-alloy reactive coating process by vacuum ion evaporation, which improves the product's efficacy by correcting the excellent product structure.

The main object of the present invention is to provide a wet coating process for overcoming a multi-target on a single crucible and effectively performing the plating of the multi-target on the workpiece, so that the plated surface film can be layered. It also contains multiple materials, which in turn can provide the best material properties and improve the efficiency of the processing.

In order to achieve the above object, the present invention prepares a multi-alloy reactive coating process by vacuum ion evaporation, which is a process carried out in a vacuum evaporation furnace, which is prepared by a cylindrical crucible. At the center or the outside of the vacuum evaporation furnace, the crucible is internally provided with a desired solid alloy target, and the crucible is provided with a cooling water path surrounding the periphery of the alloy target, and the alloy target can be two a meta-, ternary, or multi-alloy target, followed by heating the material in the crucible to control the gradual melting of the material, thereby allowing the material in the crucible to evaporate uniformly, and the evaporated atoms are dissociated into ions by the electron beam. While the workpiece to be plated is biased (the bias voltage is 5~1000V with a negative bias power supply, the beam current is 20~300A), the electric field magnetic field is used to accelerate the ions, and the selectivity is biased. The reaction gas is introduced before or after the pressure source step, and the reaction gas is also dissociated into ions by the electron beam, and the dissociated positive ions are attracted by the negatively charged bias power source and collide with the workpiece to be plated around the crucible. Waiting The surface of the plated workpiece is arranged to form an alloy film, and a film layer of 0.1 to 10 μm is formed on the surface of the workpiece to be plated, cooled, and then cooled.

Thereby, the process realizes placing a multi-target on a single crucible and effectively performing the plating of the multi-target on the workpiece, thereby achieving the best material characteristics and improving the efficiency of the processing process.

Further, since the difference between the properties of the surface of the workpiece to be plated and the film layer of the coating is quite large, if the film layer is directly coated on the surface of the workpiece, a pole is generated. If the internal stress is too high, the film layer peeling phenomenon will occur. Therefore, a transition layer is pre-plated between the surface of the workpiece to be plated and the film, and the transition layer has a small difference in surface properties from the workpiece to be plated. In order to accomplish the operation, in the step of preparing the alloy target, the material of the transition layer is placed through the alloy target, or the material of the transition layer may be embedded in the alloy target. Or placed at the same time on the alloy target and embedded in the alloy target, so that the material of the transition layer can also be coated on the surface of the workpiece before or during the plating of the alloy target of the film layer or The alloy film layer can be strengthened by forming a transition layer between the film layers and a gradient film layer having a transition layer.

The process of the present invention can also be combined with the old technology to complete the process of more meta-forms, and a single or a plurality of conventional SPUTTER sputtering devices or ARC arc-discharge sputtering devices can be provided in the vacuum evaporation furnace, and the SPUTTER The sputtering device or the ARC arc discharge sputtering device is configured to dispose at least one target material, and the sputtering device is activated in the initial stage, the middle stage or the end stage to excite the target material, thereby cooperating with the alloy of the film layer of the crucible The target material can form a layered layer or a multi-stage film layer.

Therefore, the process of the present invention can effectively overcome the preparation of the multi-target on a single crucible and effectively plate the multi-target on the workpiece, and can be combined with the old technology, in addition to the preparation of the alloy target. More meta-forms and coated film structures.

1‧‧‧Ion cleaning

2‧‧‧Preparation of alloy targets

3‧‧‧heating until the material melts

4‧‧‧guided bias power supply

5‧‧‧Introduction of reaction gases

6‧‧‧ Film formation

7‧‧‧Cooling out of the furnace

The first figure is a block diagram of the process of the present invention.

The second figure is a schematic cross-sectional view of the structure of the crucible and the alloy target described in the process of the present invention.

The third figure is a transition layer material structure placed above the alloy target described in the process of the present invention. Schematic diagram of the section.

The fourth figure is a schematic cross-sectional view of the material structure of the embedded transition layer inside the alloy target described in the process of the present invention.

The fifth figure is a schematic cross-sectional view of the internal structure of the alloy target embedded in the process of the present invention and the transition layer material disposed above.

The sixth drawing is another block diagram of the process of the present invention.

The invention relates to a process for preparing a multi-alloy reactive coating process by vacuum ion evaporation, and [refer to the first figure] is a process carried out in a vacuum evaporation furnace, and the steps of the process mainly include: ion cleaning (1) The process of cleaning the surface of the workpiece to be plated by dissociating the inert gas into positively charged ions to the workpiece to be plated is a conventionally used step, so it will not be discussed in detail; the alloy target is prepared. (2), [please refer to the second figure] to prepare a cylindrical crucible, which is located in the center of the vacuum evaporation furnace, which is provided with a solid solid alloy target in which the desired crucible is placed. And a cooling water circuit surrounding the periphery of the alloy target, and the alloy target may be a binary, ternary, or multi-alloy target; heating to melt the material (3), heating the material in the crucible, The heating method may be resistance heating, electron beam heating or high frequency induction evaporation source or pulsed laser spraying to control the stage of material melting, thereby uniformly evaporating the raw materials in the crucible, and evaporating the atoms again. Electron beam dissociation into ions; While the bias power supply (4), to be plated of the workpiece to bias the guide bias (the sum of 5 ~ 1000V bias power of negatively charged, the electron beam current 20 to 3, 00A), the ion is accelerated by the electric field magnetic field, wherein the beam current 200A is optimal at a bias voltage of 100 V; and the introduction of the reaction gas (5) is selectively performed before or after the step of biasing the power source (4) Performing, introducing a reaction gas while the atom is dissociated into ions by the electron beam, and the reaction gas is also dissociated into ions by the electron beam, and the reaction gas system is selected according to a film formed by the target; film formation (6) The dissociated positive ions are attracted by the negatively charged bias power source and collide with the workpiece to be plated around the crucible, and the alloy film is arranged on the surface of the workpiece to be plated; the furnace (7) is cooled, and the surface of the workpiece is formed. After the thickness of the film layer, vacuum cooling is performed, and it can be selectively cooled with nitrogen gas, and then cooled to be discharged.

The invention adopts a vacuum ion evaporation method to prepare a multi-alloy reactive coating process, (refer to the first figure). The following is illustrated by using a titanium (Ti) or aluminum (Al) alloy target on a tungsten steel workpiece as an implementation case. This embodiment can complete a tungsten steel tool or mold coated with TiAlN alloy: the cavity pressure of the vacuum evaporation furnace for processing the process is set to 10 ^-3 torr~10 ^-4 torr, the temperature is set to 450 ° C, and the titanium and aluminum are used. The alloy target is fabricated at a ratio of 50% titanium and 50% aluminum and placed in the special crucible, followed by heating. In this embodiment, a hollow cathode type high-power electron beam is used to heat the material in the crucible. Control the melting speed of the material by controlling the convergence or divergence of the electron beam, so that the raw material in the crucible is uniformly evaporated, and the evaporated atoms are dissociated into ions by the electron beam, and the reaction gas nitrogen (N2) is introduced, and the reaction gas is also introduced. The electron beam is dissociated into ions, and then the workpiece to be plated is biased by 100V, the beam current is 200A, and the electric field magnetic field is used to accelerate the ions, and the dissociated positive ions are attracted by the negatively charged bias power source. The workpiece to be plated is arranged on the surface of the workpiece to be plated to form an alloy film, and an alloy film layer of 0.1 to 10 μm is formed to be cooled and discharged to complete the process.

The invention adopts a vacuum ion evaporation method to prepare a multi-alloy reactive coating process, and the alloy target in the crucible can be a non-alloy pure metal material or a non-metal material, and the ratio between the alloy targets is determined according to the The characteristics of the plated workpiece are set. The following are the alloy elements currently available for combination and their suitable combination ratios: the alloy elements of the selectable combination are titanium (Ti), chromium (Cr), aluminum (Al), tantalum. (Si), tungsten (W), tantalum (Ta), carbon (C), vanadium (V); common alloys are combined with Ti-Al, Ti-Cr, Ti-Si, Ti-Al-Cr, Ti-Al -Cr-Si, Ti-Ta, Ti-W, Ti-V; at present, the suitable combination ratio of each alloy is Ti (30~70%)-Al (70~30%), Ti(40~80%)-Cr (60~20%), Ti(90~80%)-Si(10~20%), Ti(30~45%)-Al(30~45%)-Cr(10~40%), Ti(30 ~40%)-Al(30~40%)-Cr(15~30%)-Si(5~10%), Ti(60~80%)-Ta(20~40%), Ti(60~80 %) -W (20~40%), Ti (90~80%)-V (10~20%).

The invention prepares a multi-alloy reactive coating process by vacuum ion evaporation method, and the currently applicable reaction gas is nitrogen (N2), methane (CH4), acetylene (C2H2) or formane (SiH4), which is usually nitrogen (N2) and Methane CH4): TiAlN film and TiCrN can be prepared by using nitrogen (N2) as the reaction gas in combination with Ti-Al, Ti-Cr, Ti-Si, Ti-Al-Cr, Ti-V or Ti-Al-Cr-Si materials. Thin film, TiSiN film, TiAlCrN film, TiVN or TiAlCrSiN film; TiCN film or TiCrCN film can be prepared by using methane (CH4) as reaction gas with Ti or Ti-Cr material; in addition, Ti-Ta, Ti-W, Ti- Gases such as nitrogen (N2), methane (CH4), acetylene (C2H2) or formane (SiH4) can be used for materials such as V.

The invention prepares a multi-alloy reactive coating process by vacuum ion evaporation, and can additionally add a transition layer, [refer to the first figure and the third figure], in the step of preparing the alloy target (2), through the alloy A material of the transition layer is placed over the target, and the material of the transition layer may be pre-coated on the surface of the workpiece before the alloy target of the film layer, thereby forming the transition layer, that is, [please together Referring to the fourth and fifth figures, the material of the transition layer may also be embedded in the alloy target or placed on the alloy target and embedded in the alloy target, so that the material of the transition layer may also be Forming the transition layer or the gradient layer with a transition layer before or after coating the alloy target of the film layer on the surface of the workpiece or between the film layers, Alloy film layer.

The invention adopts the vacuum ion evaporation method to prepare a multi-alloy reactive coating process, (refer to the sixth figure), which can be combined with the old technology to complete the process of more meta-forms, except that the alloy to be vapor-deposited in the crucible is changed in the above manner. In addition to the target, a single or a plurality of conventional SPUTTER sputtering devices or ARC arc discharge sputtering devices are provided in the vacuum evaporation furnace, and the SPUTTER sputtering device or ARC arc type The discharge sputtering device is configured to dispose at least one target material, and the sputtering device is activated in the initial stage, the middle stage or the end stage to excite the target material, thereby forming a gradient layer in combination with the alloy target of the film layer of the crucible. a thin film layer of a multi-stage or multi-stage type, in which it is assumed that the target material is chromium (Cr) in the SPUTTER sputtering device or the ARC arc discharge sputtering device, and the SPUTTER sputtering device or the ARC arc discharge sputtering device It is started in the middle of vapor deposition, and until the film is completed, it can control 0% of the chromium (Cr) element in the innermost layer of the film layer, and the chromium (Cr) element in the middle layer of the film layer is gradually stretched to 20%~ 40%, the outer layer of chromium (Cr) element in the film layer averages 40%, so that if a plurality of different target materials are combined, and the film layer is opened or closed at different stages of the coating, a multi-stage film layer can be produced. .

In summary, it is understood that the present invention is novel, and the present invention is not found in any publication, and is in compliance with the provisions of Articles 21 and 22 of the Patent Law.

There are many known materials, and the possibility of combination can not be mentioned one by one, and the materials that have not been found are also rare. Only the combination of elements of the alloy target selected above, the ratio of element combinations, and the reaction The alternatives to gases, etc., are merely preferred and preferred embodiments of the invention, and are not intended to limit the scope of the invention. That is, the equivalent changes and modifications made by the invention in accordance with the scope of the invention are still within the scope of the invention.

1‧‧‧Ion cleaning

2‧‧‧Preparation of alloy targets

3‧‧‧heating until the material melts

4‧‧‧guided bias power supply

5‧‧‧Introduction of reaction gases

6‧‧‧ Film formation

7‧‧‧Cooling out of the furnace

Claims (10)

A process for preparing a multi-alloy reactive coating process by vacuum ion evaporation is carried out in a vacuum evaporation furnace, and the steps of the process mainly include: preparing an alloy target, and preparing a cylindrical crucible, the crucible The pot is located at the center of the vacuum evaporation furnace, and the crucible is internally provided with a desired solid alloy target, and the crucible is provided with a cooling water path surrounding the periphery of the alloy target, and the alloy target can be two a meta-, ternary, or multi-alloy target; heating until the material melts, heating the material in the crucible to control the stage of melting of the material, thereby allowing the material in the crucible to evaporate uniformly, and evaporating the atom and then being electronized The beam is dissociated into ions; the bias voltage source is used to accelerate the ions when the workpiece to be plated is biased, and the bias voltage is 5~1000V with a negative bias voltage source, and the beam current is 20~300A. The introduction of the reaction gas is selectively performed before or after the step of biasing the power source, and the reaction gas is introduced while the atom is dissociated into ions by the electron beam, and the reaction gas is also dissociated by the electron beam. The reaction gas system is selected according to the film formed by the target; the film is formed, and the dissociated positive ions are attracted by the negatively charged bias power source and collide with the workpiece to be plated around the crucible, and are to be plated. The surface of the workpiece is arranged to form an alloy film; after cooling, the film is formed on the surface of the workpiece to be plated to form a film layer of 0.1 to 10 μm, and then cooled, and then cooled. The multi-alloy reactive coating process is prepared by vacuum ion evaporation according to the first aspect of the patent application, wherein in the step of preparing the alloy target, a transition layer is placed above the alloy target previously placed in the crucible The material of the transition layer may be pre-coated on the surface of the workpiece to be plated before the alloy target of the film layer to form the transition layer. The multi-alloy reactive coating process is prepared by vacuum ion evaporation according to the first aspect of the patent application, wherein in the step of preparing the alloy target, a transition layer is embedded in the alloy target previously located in the crucible The material is such that the material of the transition layer is coated on the surface of the workpiece to be plated or between the film layers during the plating of the film layer, thereby forming a layered film layer having a transition layer. The multi-alloy reactive coating process is prepared by vacuum ion evaporation according to the first aspect of the patent application, wherein in the step of preparing the alloy target, a transition layer is placed above the alloy target previously placed in the crucible The material and the material of the transition layer are embedded in the alloy target at the same time, so that the material of the transition layer is coated on the surface of the workpiece to be plated and the film layer during the plating of the film layer, thereby forming a transition layer Gradient film layer. The multi-alloy reactive coating process is prepared by vacuum ion evaporation according to the first aspect of the patent application, wherein a single or a plurality of conventional SPUTTER sputtering devices or ARC arc discharge sputtering devices are disposed in the vacuum evaporation furnace. And the SPUTTER sputtering device or the ARC arc discharge sputtering device is configured to dispose at least one target material, and the sputtering device is activated in the initial stage, the middle stage or the end stage of the evaporation to excite the target material, thereby cooperating with the crucible The alloy target of the film layer can form a gradient layer or a multi-stage film layer. According to the first application of the patent scope, the multi-alloy reactive coating process is prepared by vacuum ion evaporation, wherein the vacuum pressure of the vacuum evaporation furnace is set to 10 ^-3 torr to 10 ^-4 torr in the coating stage, and the temperature is set. Below 450 °C. The multi-alloy reactive coating process is prepared by vacuum ion evaporation according to the first aspect of the patent application, wherein in the step of preparing the alloy target, the alloy elements selected from the group are titanium, chromium, aluminum, tantalum, tungsten. , bismuth, carbon or vanadium. According to the seventh application of the patent scope, a multi-alloy reactive coating process is prepared by vacuum ion evaporation, wherein the alloy has a combination ratio of titanium (30-70%)-aluminum (70-30%) and titanium (40~). 80%)-Chromium (60~20%), Titanium (90~80%)-釸(10~20%), Titanium (30~45%)-Aluminum (30~45%)-Chromium (10~40% ), titanium (30~40%)-aluminum (30~40%)-chromium (15~30%)-釸(5~10%), titanium (60~80%)-钽(20~40%), Titanium (60~80%)-tungsten (20~40%), titanium (90~80%)-vanadium (10~20%). The multi-alloy reactive coating process is prepared by vacuum ion evaporation according to the first aspect of the patent application, wherein in the step of introducing the reaction gas, the reaction gas may be any of nitrogen, methane, acetylene or formane. The multi-alloy reactive coating process is prepared by vacuum ion evaporation according to the first aspect of the patent application, wherein the step of biasing the power supply is a negatively biased bias power supply with a bias voltage of 100 V and a beam current of 200 A. For the best.