JP4883602B2 - Plasma surface treatment method and plasma treatment apparatus - Google Patents

Description

  The present invention relates to a plasma surface treatment method, a plasma treatment apparatus, and a plasma treatment using the plasma generated by performing vacuum arc discharge (cathode arc discharge) in an arc discharge section set in a vacuum atmosphere at least as plasma for treatment. The present invention relates to an object subjected to surface treatment using an apparatus.

  In general, surface treatment is a technique for improving the aesthetics, performance, and durability of a solid surface. Among surface treatments, surface coating improves the appearance / decoration (color and gloss) of products, improves / provides corrosion resistance, improves / provides wear resistance, improves / provides fatigue resistance, and improves optical properties. Improvement and provision (antireflection film, reflection film, optical filter film, etc.), conductivity control (insulating film, semiconductive film, conductive film, transparent conductive film), thermal conductivity control (thermal conductive film, It is useful as a thermal insulating film), imparting magnetism, imparting catalytic properties, imparting slidability, and the like. In general, surface coatings are classified into wet methods and dry methods. Intermetallic compounds (nitrides, oxides, carbides, sulfides, silicides, borides, hydrides, etc.) in combination of metals (including Si) and non-metals useful as surface coatings are artificial In most cases, it is called fine ceramic or new ceramic. These ceramic thin films are difficult to form by a dry method having a low reactivity such as a dry method or vacuum deposition, and are exclusively formed using plasma that can utilize a high reactivity. For example, in the field of tools, various ceramic thin film coatings are applied to the surface of a tool base material in order to extend the life of the tool. Main examples are titanium nitride (TiN), chromium nitride (CrN), titanium carbide (TiC) films, and the like. In addition, since TiN has a gold color, it is being used as a material that can be used in place of gold, such as ornaments such as wristwatch housing bands, bracelets, and spectacle frames, kitchen utensils such as knives, knives, and scissors, and stationery.

The TiN film has good adhesion to steel and cemented carbide and exhibits characteristics such as being hard to seize with the workpiece material, but is slightly inferior in oxidation resistance. Therefore, Ti _X Al _Y N _Z (which may be described as (Ti, Al) N) in which aluminum is mixed with TiN may be used. The composition ratios (X, Y, Z,...) Of TiAlN and other intermetallic compounds are omitted unless otherwise specified. The TiAlN has the same hardness and friction coefficient as TiN, but has much higher high-temperature oxidation characteristics, and has the characteristic that the unchanged heat-resistant temperature in the atmosphere is about 800 ° C. TiAlN films have been applied to heavy cutting tools and various dies (press dies, plastic molding dies, die casting dies, glass lens molding dies, etc.). Also, TiCrN in which chromium is mixed with TiN (may be described as (Ti, Cr) N) has the same hardness and wear coefficient as TiN, but has much better high-temperature oxidation characteristics. High-temperature oxidation characteristics are slightly inferior to TiAlN, but they are excellent in corrosion resistance and are often used for plastic molding dies and die casting dies. CrAlN and CrVN are also used as a film of a tool for dry processing (high hardness material) as a high oxidation resistance and high hardness material. Thus, the demand for intermetallic compound ceramics of two kinds of different metals and nonmetals is also high. Furthermore, in order to further improve the functionality, development of intermetallic compound ceramics of three or more kinds of different metals and nonmetals is being carried out.

  By the way, as a method of generating plasma containing metal ions and non-metal solid ions (mainly carbon C), there is a vacuum arc (or also called a cathode arc) discharge method. The vacuum arc discharge method includes a cathodic arc discharge method for evaporating the cathode material and an anodic arc discharge method for evaporating the anode material. However, it is generally difficult to evaporate the anode material and is described in this specification. Unless otherwise specified, the vacuum arc discharge method is a cathode arc discharge method. Similarly, the term “vacuum arc” indicates a cathode arc unless otherwise specified. The vacuum arc plasma is a plasma formed by an arc discharge generated between the cathode and the anode in the arc discharge, the cathode material evaporates from the cathode spot existing on the cathode surface, and is formed by this cathode evaporation substance. In general, the anode is inert and does not evaporate. In addition, when a reactive gas and / or an inert gas (for example, a rare gas) is introduced as the atmospheric gas, the reactive gas or / and the inert gas are also ionized at the same time. Using such plasma, surface treatment can be performed by forming a thin film on a solid surface or implanting ions.

  However, the vacuum arc film forming apparatus has a problem inherent in surface treatment due to cathode material particles (hereinafter referred to as “droplets”) by-produced from the cathode when plasma is generated. In general, in vacuum arc discharge, vacuum arc plasma constituent particles such as cathode material ions, electrons, and cathode material neutral particles (atoms and molecules) are emitted from the cathode spot, and at the same time, sub-micron to several hundred microns (0.01). Droplets with a size of ˜500 μm are also emitted. However, the problem in the surface treatment is the generation of the droplets. If the droplets adhere to the substrate surface, the uniformity of the thin film formed on the substrate surface is lost, resulting in a defective product of the thin film. . For this reason, a method must be developed in which the droplets do not adhere to the substrate.

One method for solving the droplet problem is a magnetic filter method described in PJ Martin, RPNetterfield and TJKinder, Thin Solid Films 193/194 (1990) 77 (Non-patent Document 1). In this magnetic filter method, vacuum arc plasma is transported to a processing section through a curved droplet collecting duct. According to this method, the generated droplets are attached and captured (collected) on the inner wall of the duct, and a plasma flow containing almost no droplets is obtained at the duct outlet. In addition, a curved magnetic field is formed by an electromagnet arranged along the duct, and the plasma flow is bent by the curved magnetic field, so that the plasma is efficiently moved to the plasma processing portion.
PJMartin, RPNetterfield and TJKinder, Thin Solid Films 193/194 (1990) 77

  In most cases, a TiAlN film, which is an intermetallic compound of a dissimilar metal element and a nonmetal element, is formed by a vacuum arc deposition method. At present, a TiAl alloy formed by a melting method or a powder method is used as a cathode evaporant material (also called a target) which is a vacuum arc evaporation source. However, in this case, in order to synthesize a film in which the mixing ratio of Ti and Al is changed, it is necessary to prepare a cathode material having the composition each time, and since the material itself is expensive, the manufacturing cost increases. There was a problem. In addition, a Ti cathode and an Al cathode, which are arc evaporation sources, can be arranged close to the inner wall of a plasma processing chamber (deposition chamber) of a vacuum arc vapor deposition apparatus, but plasma generated from the Ti cathode and the Al cathode is generated. Since the workpieces (workpieces, workpieces) are surface-treated with the plasma generated from different positions, even if film deposition is performed while changing the position of the workpieces, an alternating laminated film of TiN film and AlN film is formed. As a result, it was difficult to form a TiAlN mixed film mixed at the atomic / molecular level and nano level. Moreover, the ideal removal of the droplets was difficult due to the direct arrangement of plasma from the Ti cathode and the Al cathode. In order to remove droplets, it is possible to use a magnetic filter type vacuum arc source to which the magnetic filter method is applied. In this case, too, a Ti magnetic filter type vacuum arc source and an Al magnetic filter type are used. When two vacuum arc evaporation sources are used, there is a problem that the film formed on the workpiece becomes a laminated film as described above.

  The present invention has been made in view of the above problems, and an intermetallic compound film (alloy film, mixed film, ceramic film) / multilayer film made of a plurality of substances, or a metal film made of a single substance, It is an object of the present invention to provide a plasma surface treatment method and a plasma treatment apparatus which can be smoothly formed without being affected by droplets, with a composition appropriately controlled in high purity. Further, for example, a vacuum arc film forming apparatus for a metal film that imparts desired surface characteristics and functions to an object to be processed and / or for an intermetallic compound containing two or more metals is compact with respect to a film forming chamber. It is an object of the present invention to provide a plasma surface treatment method and a plasma treatment apparatus capable of smoothly forming a high-purity metal film and / or an intermetallic compound film as a single film, a mixed film, or a multilayer film. And Further, for example, a metal film, an alloy film, or a ceramic film (nitride, oxide, carbide, sulfide, silicide, boride, hydride, etc.) that has been surface-treated using the plasma processing apparatus is provided. The purpose is to provide the object. By this surface treatment, the object is improved and imparted with aesthetic / decorative properties (color and gloss), improved and imparted corrosion resistance, improved and imparted wear resistance, improved and imparted fatigue resistance, optical Improve and impart properties (antireflection film, reflection (mirror) film, optical filter film, etc.), conductivity control (insulating film, semiconducting film, conductive film, transparent conductive film), thermal conductivity control ( Heat conductive film, heat insulating film), magnetism, catalytic property, slidability, etc. are performed.

  The present invention has been made to solve the above-mentioned problems. The first aspect of the present invention is to perform vacuum arc discharge (cathode arc discharge) in an arc discharge section set in a vacuum atmosphere. 1 plasma is generated, a second plasma is generated using a solid / liquid as a plasma source or a gas as a plasma working gas, and the first plasma and the second plasma are merged at an acute angle with respect to the transport direction of the common transport duct. After the electromagnetic introduction, the first plasma and the second plasma are electromagnetically induced to the plasma processing unit through the common transport duct, and the first plasma and the second plasma are shared by the common transport. A plasma surface that controls the timing of introduction into the duct and surface-treats the workpiece in the plasma processing section by the first plasma and the second plasma. It is a management method.

  In the second aspect of the present invention, the first plasma, the second plasma, and the third plasma are generated in a plasma generation unit that generates plasma using solid / liquid as a plasma source or gas as a plasma working gas, and these At least one of the first to third plasmas is generated based on vacuum arc discharge (cathode arc discharge) in an arc discharge section set in a vacuum atmosphere, and the first plasma and the second plasma And electromagnetically introducing the third plasma so as to merge at an acute angle with respect to the transport direction of the common transport duct, and then passing the first plasma, the second plasma, and the third plasma through the common transport duct. Electromagnetically inducting into the plasma processing unit, and supplying the first plasma, the second plasma, and the third plasma to the common transport duct By controlling the timing of entering the first plasma, a second plasma and the third plasma surface treatment method for surface treatment of the object to be treated in the by plasma plasma processing unit.

  According to a third aspect of the present invention, a first plasma, a second plasma, a third plasma, and a fourth plasma are generated in a plasma generation unit that generates plasma using solid / liquid as a plasma source or gas as a plasma working gas. And at least one of these first to fourth plasmas is generated based on vacuum arc discharge in an arc discharge part (cathode arc discharge) set in a vacuum atmosphere, and the first plasma and The first plasma and the second plasma are introduced electromagnetically so as to merge at an acute angle with respect to the transport direction of the common transport duct via the first plasma introduction path for joining the second plasma, The third plasma and the fourth plasma are common to each other via a second plasma introduction path that joins the three plasmas and the fourth plasma. After electromagnetically introducing so as to merge at an acute angle with respect to the transport direction of the feed duct, the first plasma, the second plasma, the third plasma, and the fourth plasma are passed through the common transport duct. The first plasma, the second plasma, the second plasma, the second plasma, the third plasma, and the fourth plasma are introduced into the common transport duct by electromagnetic induction in the processing unit. In the plasma surface treatment method, the object to be processed in the plasma processing unit is surface-treated by plasma, the third plasma, and the fourth plasma.

  According to a fourth aspect of the present invention, there is provided a first plasma generating means for generating a first plasma by performing a vacuum arc discharge (cathode arc discharge) in an arc discharge section set in a vacuum atmosphere, and a solid / liquid as a plasma source. Or a second plasma generating means for generating a second plasma using a gas as a plasma working gas, a common transport duct for electromagnetically introducing the first plasma and the second plasma, and an electromagnetic via the common transport duct The first plasma is introduced into the common transport duct electromagnetically from the first plasma generating means and the plasma processing section for subjecting the workpiece to the surface treatment with the first plasma and the second plasma introduced to the surface. Second plasma for electromagnetically introducing the second plasma from the first plasma introduction path and the second plasma generating means into the common transport duct And a control means for controlling the timing of introducing the first plasma and the second plasma into the common transport duct, the common of the first plasma introduction path and the second plasma introduction path This is a plasma processing apparatus in which the introduction angle of the transport duct with respect to the transport direction is set to an acute angle.

  According to a fifth aspect of the present invention, in the first to third plasma generating means for generating plasma using solid / liquid as a plasma source or gas as a plasma working gas, the first plasma, the second plasma, and the third plasma, respectively. And the plasma generating means based on the vacuum arc discharge (cathode arc discharge) in the arc discharge section in which at least the first plasma generating means is set in a vacuum atmosphere among the first to third plasma generating means. First to third plasma generating means, a common transport duct for electromagnetically introducing the first plasma, the second plasma, and the third plasma, and electromagnetically introduced via the common transport duct A plasma processing unit for surface-treating a workpiece by the first plasma, the second plasma, and the third plasma, A first plasma introducing path for electromagnetically introducing the first plasma from the first plasma generating means to the common transport duct; and an electromagnetically introducing the second plasma from the second plasma generating means to the common transport duct. A second plasma introduction path to be introduced; a third plasma introduction path for electromagnetically introducing the third plasma from the third plasma generating means to the common transport duct; the first plasma; the second plasma; Control means for controlling the timing of introducing three plasmas into the common transport duct, and transporting the common transport duct in the first plasma introduction path, the second plasma introduction path, and the third plasma introduction path This is a plasma processing apparatus in which the introduction angle with respect to the direction is set to an acute angle.

  According to a sixth aspect of the present invention, in the first to fourth plasma generating means for generating plasma using solid / liquid as a plasma source or gas as a plasma working gas, the first plasma, the second plasma, the third plasma, And from the plasma generating means based on the vacuum arc discharge in the arc discharge section in which at least the first plasma generating means is set in a vacuum atmosphere among the first to fourth plasma generating means. First to fourth plasma generating means, a first plasma introduction path for merging the first plasma and the second plasma, and a second plasma introduction path for merging the third plasma and the fourth plasma. A common transport duct for introducing the first plasma, the second plasma, the third plasma, and the fourth plasma; A plasma processing unit for surface-treating an object to be processed by the first plasma, the second plasma, the third plasma, and the fourth plasma introduced via a transport duct; the first plasma; the second plasma; Control means for controlling timing for introducing plasma, the third plasma, and the fourth plasma into the common transport duct, and the common transport of the first plasma introduction path and the second plasma introduction path. This is a plasma processing apparatus in which the introduction angle with respect to the transport direction of the duct is set to an acute angle.

  A seventh aspect of the present invention is the plasma processing apparatus according to the fourth aspect, wherein the first plasma introduction path, the second plasma introduction path, and the common transport duct are substantially Y-shaped when projected onto a plane. is there.

  According to an eighth aspect of the present invention, in any of the fourth to seventh aspects, the control means simultaneously introduces plasma from the respective plasma introduction paths into the common transport duct or separately in time. Or a plasma processing apparatus that is controlled at a timing that is partially performed at the same time.

  According to a ninth aspect of the present invention, in any of the fourth to eighth aspects, cathode material particles (hereinafter referred to as droplets) generated from the cathode of the arc discharge portion contained in the first plasma. Is a plasma processing apparatus in which a blocking member that prevents the first plasma from traveling in the traveling direction of the first plasma is provided on or near the inner surface of the first plasma introduction path and / or the common transport duct.

  According to a tenth aspect of the present invention, in any of the fourth to ninth aspects, a rotating magnetic field that generates a rotating magnetic field for mixing the plasma introduced from the plasma introduction paths into the common transport duct is provided. In the plasma processing apparatus, the generating means is provided in the common transport duct.

  An eleventh aspect of the present invention is the plasma processing apparatus according to any one of the fourth to tenth aspects, wherein the second plasma is generated by a plasma generation method for obtaining plasma directly from a solid.

  A twelfth aspect of the present invention is the plasma processing apparatus according to any one of the fourth to tenth aspects, wherein the second plasma is generated by a plasma generation method for obtaining a plasma by evaporating a solid.

  According to a thirteenth aspect of the present invention, in any one of the fourth to tenth aspects, a plasma processing apparatus that generates the second plasma by a plasma generation method that obtains plasma by gas or vaporized or misted liquid. It is.

  In a fourteenth aspect of the present invention, in any of the fourth to thirteenth aspects, at least one plasma generating means and / or a part or all or part of the common transport duct has the same or different waveform. And / or a plasma processing apparatus having bias voltage applying means for applying a bias voltage of a value.

  A fifteenth aspect of the present invention is a plasma processing apparatus according to any one of the fourth to fourteenth aspects, further comprising bias means for electrically biasing an anode of at least one plasma generation means.

  According to a sixteenth aspect of the present invention, in any one of the fourth to fifteenth aspects, a plasma traveling direction of a final part of the common transport duct is a z-axis direction, and a vertical plane is an xy plane, and the common transport is performed. This is a plasma processing apparatus in which a deflection coil for scanning plasma in the x direction and / or the y direction is disposed in a duct.

  According to a seventeenth aspect of the present invention, in the plasma processing unit, the plasma generated by the plasma processing apparatus according to any one of the fourth to sixteenth aspects according to any one of the fourth to sixteenth aspects is used. It is an object that has been surface treated.

According to the first aspect of the present invention, the first plasma and the second plasma are introduced so as to merge at an acute angle with respect to the transport direction of the common transport duct, and the first plasma and the second plasma are introduced. Is controlled to the surface of the workpiece in the plasma processing section by the first plasma and the second plasma. Since there are two plasma sources, it is possible to smoothly form a single metal film or an intermetallic compound film containing one kind of metal more smoothly than when only one plasma source is used. Also, when vaporizing different substances in the first plasma and the second plasma, by controlling the respective evaporation rates, it is possible to smoothly form a mixed film (alloy, intermetallic compound film) whose composition is controlled as desired. Can be done. Furthermore, since the timing at which each plasma is introduced into the duct can be controlled, it is possible to smoothly form a multilayer film or a super multilayer film as a laminated film of metal, alloy, or intermetallic compound. Here, the multilayer film is a film in which layers of several hundred nm to several μm are stacked, and the super multilayer film is a film in which layers of several tens of nm to several hundred nm are stacked. Since the first plasma and the second plasma from which droplets have been removed are introduced into the deposition chamber from the same direction while controlling the timing, atomic / molecular level / nano level control is provided, and a conventional vacuum arc deposition apparatus ( It is also possible to form an ultra-multilayer film in which layers of 1 nm or less to several tens of nm, which was difficult with an arc ion plating apparatus), are laminated.
In addition, since the first plasma and the second plasma are introduced into the plasma processing section by the common transport duct, the plasma processing apparatus having film forming functions using the first plasma and the second plasma can be made compact. Can be realized.
Further, since the first plasma and the second plasma are merged at an acute angle with respect to the transport direction of the common transport duct, the droplet generated in the arc discharge portion goes straight and near the confluence inlet inner wall of the common transport duct Collide with. Therefore, it is possible to prevent the droplets from passing through the common transport duct and enter the plasma processing unit, thereby improving the droplet removal efficiency and performing a higher-purity film forming process. Speaking only of droplet removal, it is conceivable that the plasma flows intersect at a right angle or more and merge, but the plasma transport efficiency is lowered. On the other hand, in this embodiment, since the merge is made at an acute angle with respect to the transport direction of the common transport duct, it is possible to perform a high-purity film formation process using plasma from which droplets have been removed without reducing transport efficiency. it can.

According to a second aspect of the present invention, the first plasma, the second plasma, and the third plasma are introduced so as to merge at an acute angle with respect to a transport direction of the common transport duct, and the first plasma and By controlling the timing at which the second plasma is introduced into the common transport duct, a surface treatment process can be performed on the workpiece in the plasma processing unit by the first plasma, the second plasma, and the third plasma. . Since there are three plasma sources, high-speed film formation of a single metal film or an intermetallic compound film containing one kind of metal can be smoothly performed by using at least two plasma sources. Further, in the plasma generation unit, when two or three kinds of substances are evaporated, and at least one plasma generates first to third plasmas formed of an evaporation substance different from other plasmas, the respective evaporation rates are generated. By controlling the above, it is possible to smoothly form a mixed film (alloy, intermetallic compound film) having a desired composition. Furthermore, since the timing at which each plasma is introduced into the duct can be controlled, the above-described laminated film (multilayer film, supermultilayer film, ultrasupermultilayer film) can be formed smoothly. The timing of the first plasma, the second plasma, and the third plasma from which the droplets have been removed is controlled and introduced into the deposition chamber from the same direction, so that the deposition of the multilayer film is controlled at the atomic / molecular level / nano level. In addition, it is possible to form an ultra-multilayer film, which is difficult with a conventional vacuum arc deposition apparatus (arc ion plating apparatus).
Furthermore, since the first plasma is merged at an acute angle with respect to the transport direction of the common transport duct, the droplet generated in the arc discharge section goes straight and collides with the vicinity of the inner wall of the common transport duct. Therefore, it is possible to prevent the droplets from passing through the common transport duct and enter the plasma processing unit, thereby improving the droplet removal efficiency and performing a higher-purity film forming process.

According to the third aspect of the present invention, the first plasma and the second plasma are moved in the transport direction of the common transport duct via the first plasma introduction path that joins the first plasma and the second plasma. The third plasma and the fourth plasma are introduced in such a manner as to join at an acute angle, and the third plasma and the fourth plasma are transported in the transport direction of the common transport duct via the second plasma introduction path that joins the third plasma and the fourth plasma. The first plasma, the second plasma, the third plasma, and the fourth plasma are introduced into the common transport duct by controlling the timing of introducing the first plasma, the second plasma, the third plasma, and the fourth plasma into the common transport duct. Surface treatment processing is performed on an object to be processed in the plasma processing unit by the second plasma, the third plasma, and the fourth plasma. Since there are four plasma sources, it is possible to smoothly form a single metal film or an intermetallic compound film containing one kind of metal more smoothly than when only one plasma source is used. In addition, when different materials are evaporated in each plasma source, by controlling the respective evaporation rates, it is possible to smoothly form a mixed film (alloy, intermetallic compound film) whose composition is controlled as desired. it can. Furthermore, since the timing at which each plasma is introduced into the duct can be controlled, it is possible to smoothly form a multilayer film, super multilayer film, or ultra super multilayer film of a metal, an alloy, or an intermetallic compound.
In addition, since the first plasma, the second plasma, the third plasma, and the fourth plasma are introduced into the plasma processing unit by the common transport duct, a plasma processing apparatus having a film forming function using these plasmas. Can be made compact.
Further, since the first plasma and the second plasma, or the third plasma and the fourth plasma are merged at an acute angle with respect to the transport direction of the common transport duct, a drop generated when any one of the plasmas is generated. The let goes straight and collides with the vicinity of the inner wall of the junction of the common transport duct. Accordingly, it is possible to prevent the droplets from passing through the common transport duct and enter the plasma processing unit, thereby improving the droplet removal efficiency and performing a higher purity film forming process. Also in the present embodiment, as in the first embodiment, the plasma flows are merged at an acute angle with respect to the transport direction of the common transport duct, so that the plasma from which the droplets have been removed is obtained without reducing transport efficiency. Can be used to perform high-purity film formation.

  According to the plasma processing apparatus of the fourth aspect of the present invention, the plurality of plasma generation sources of the first plasma and the second plasma, the first plasma introduction path and the second plasma introduction path, The introduction angle of the common transport duct with respect to the transport direction is set to an acute angle, the first plasma and the second plasma are introduced into the plasma processing unit via the common transport duct, and the introduction timing can be controlled. With this structure, the structure of the plasma processing apparatus can be simplified by arranging a plurality of plasma generation sources in a compact manner without restricting the space around the plasma processing unit such as a film forming chamber. Moreover, the droplet generated in the arc discharge part goes straight and collides with the vicinity of the inner wall of the common transport duct. Accordingly, the first plasma made of vacuum arc plasma, which improves the droplet removal efficiency by preventing the droplets from passing through the common transport duct and entering the plasma processing unit, is used as the common transport duct. Introducing via, smooth formation of high-purity single film, formation of high-purity mixed film / compound film, or laminated film (multilayer film / super multi-layer film / super-multi-layer film) Can do.

  According to the plasma processing apparatus of the fifth aspect of the present invention, since the first, second and third plasma generating means are provided, a single metal film or one kind of material can be obtained by two or three plasma generating means. High-speed film formation of an intermetallic compound film containing a metal can be performed smoothly. Furthermore, two or three types of plasma sources can be provided or supplied to the first to third plasma generating means, respectively, to generate the first to third plasmas formed from different substances. Therefore, a mixed film such as an alloy film or an intermetallic compound film having a desired composition can be smoothly formed by controlling the respective generation rates. Furthermore, since the timing of introducing each plasma into the common transport duct can be controlled, the above-described laminated film (multilayer film, super multilayer film, ultra super multilayer film) can be formed smoothly. In addition, since the first plasma is merged at an acute angle with respect to the transport direction of the common transport duct, droplets generated in the arc discharge portion are caused to travel straight and collide with the vicinity of the inner wall of the common transport duct. it can. Accordingly, since the droplets can be prevented from entering the plasma processing unit, it is possible to perform a film formation process with higher purity. Further, the timing of the first plasma, the second plasma, and the third plasma from which droplets have been removed is controlled, and these plasmas are introduced into the deposition chamber from the same direction through the common transport duct. The film formation of the laminated film can be controlled at the atomic / molecular level / nano level. Accordingly, it is possible to form an ultra-multilayer film, which has been difficult with a conventional vacuum arc deposition apparatus (arc ion plating apparatus).

  According to the plasma processing apparatus of the sixth aspect of the present invention, the first plasma and the second plasma generation source, or the third plasma and the fourth plasma generation source, The introduction angles of the first plasma introduction path and the second plasma introduction path with respect to the transport direction of the common transport duct are set to acute angles, and the first plasma, the second plasma, the third plasma, and the fourth plasma are set. Since the plasma is introduced into the plasma processing unit via the common transport duct and the introduction timing can be controlled, the space around the plasma processing unit such as a film forming chamber is not limited. The structure of the plasma processing apparatus can be simplified by arranging the plurality of plasma generation sources in a compact manner. In addition, the droplet generated in any of the plasma generation units travels straight and collides with the vicinity of the inner wall of the junction port of the common transport duct. Therefore, the droplets are prevented from passing through the common transport duct and entering the plasma processing unit to improve the droplet removal efficiency, and a plurality of plasma flows from which the droplets have been removed are passed through the common transport duct. Introduced via a high-speed film formation of single film, and more complex and high-purity mixed film / compound film, laminated film (multilayer film / supermultilayer film / ultra-multilayer film) Can be performed smoothly.

  According to a seventh aspect of the present invention, in the fourth aspect, when the first plasma introduction path, the second plasma introduction path, and the common transport duct are projected on a plane, they form a substantially Y shape. Since the introduction angle of the first plasma introduction path and the second plasma introduction path with respect to the transport direction of the common transport duct can be set to an acute angle, a plurality of plasma generation sources are arranged in a compact manner, A plasma processing apparatus having a simplified structure can be realized. In this embodiment, the first plasma introduction path and the second plasma introduction path are arranged in a substantially Y shape on one plane, and when the three-dimensional arrangement is projected on one plane, the approximate Y is obtained. Including the case of a letter shape.

  According to an eighth aspect of the present invention, in any one of the fourth to seventh aspects, the introduction of the first plasma and the second plasma from which the droplets have been removed into the common transport duct is simultaneously performed. Alternatively, since it has the control means for controlling at a timing that is performed separately or partially at the same time, the timing of introduction of the first plasma and the second plasma into the common transport duct is set as a film forming specification / condition. Accordingly, it is possible to smoothly form a single film, a mixed film, a multilayer film, a super multi-layer film, or a super-multi-layer film containing at least an evaporation material by vacuum arc plasma.

  According to a ninth aspect of the present invention, in any one of the fourth to eighth aspects, the droplet generated when the first plasma is generated is prevented from traveling in the traveling direction of the first plasma. Since the blocking member is provided on the first plasma introduction path and / or the inner surface of the common transport duct or in the vicinity of the inner surface, the droplets in the common transport duct are efficiently removed, and a single unit of high purity plasma is used. It is possible to smoothly form a single film, a mixed film, or a laminated film (multilayer film, supermultilayer film, and ultrasupermultilayer film).

  According to a tenth aspect of the present invention, in any one of the fourth to ninth aspects, a rotating magnetic field is generated for mixing the first plasma and the second plasma introduced into the common transport duct. The rotating magnetic field generating means is provided in the common transport duct, so that the rotation of the rotating magnetic field generated by the rotating magnetic field generating means causes the rotation of the plasma flow of the first plasma and the second plasma. A plasma flow diffused by rotation is introduced into the plasma processing unit, so that a more uniform film can be generated, and a high-quality film forming process can be performed.

  According to the eleventh aspect of the present invention, in any of the fourth to tenth aspects, the second plasma is generated by a plasma generation method for obtaining plasma directly from a solid. The second plasma using a method (cathode arc discharge method or anode arc discharge method), a shunting arc method, or various sputtering methods (for example, self-sputtering, unbalanced magnetron sputtering, V-shaped sputtering). Can be formed to form a single film, a mixed film, or a laminated film (multilayer film / supermultilayer film / ultra-multilayer film) according to various film formation specifications.

  According to the twelfth aspect of the present invention, in any one of the fourth to tenth aspects, the generation of the second plasma is performed by a plasma generation method for obtaining plasma by evaporating solids. Cathode arc, electron beam excited plasma, various types of sputtering (for example, high frequency sputtering, medium frequency sputtering, direct current sputtering, alternating current sputtering, magnetron sputtering), evaporate evaporated by resistance evaporation or electron beam evaporation, hollow cathode arc, Using a method of generating plasma with electron beam excitation plasma, direct current discharge, low frequency / medium frequency / high frequency plasma (inductive coupling type or capacitive coupling type), pulse plasma, microwave plasma, surface wave plasma, or electron shower plasma A single film, a mixed film, or a film according to various film formation specifications by generating the second plasma It is possible to perform the formation of the multilayer film (multilayer film, super multi-layer film, ultra-multi-layer film).

  According to a thirteenth aspect of the present invention, in any one of the fourth to tenth aspects, the second plasma is generated by a plasma generation method for obtaining plasma by gas or vaporized or misted liquid. The second plasma is generated using a method using DC discharge, low frequency / medium frequency / high frequency plasma, pulse plasma, microwave plasma, surface wave plasma, electron shower plasma, etc. according to various film forming specifications. A single film, a mixed film, or a laminated film (multilayer film / supermultilayer film / ultra-multilayer film) can be formed.

  According to a fourteenth aspect of the present invention, in any one of the fourth to thirteenth aspects, the first plasma generating unit and / or the second plasma generating unit, and / or the bias voltage applying unit. Since a bias voltage having the same potential or substantially the same potential as the plasma potential is preferably applied to a part or the whole of the common transport duct, the plasma flow to the plasma generation part side of the first plasma and / or the second plasma is performed. The generation efficiency can be suppressed or eliminated, the efficiency of transporting the generated plasma to the plasma processing section can be improved, and the film formation rate can be improved. In order to improve transport efficiency, a different waveform and / or the first plasma generation means and / or the second plasma generation means and / or a part or all or a part of the common transport duct may be used. A bias voltage of a value may be applied.

  According to a fifteenth aspect of the present invention, in any one of the fourth to fourteenth aspects, the bias for electrically biasing the anode of the first plasma generating means and / or the anode of the second plasma generating means. Thus, the apparent anode resistance is increased by the anode bias, and the transport efficiency of the generated plasma to the plasma processing section and the film forming speed can be improved.

  According to a sixteenth aspect of the present invention, in any one of the fourth to fifteenth aspects, the high purity plasma flow is scanned in the xy direction by the deflection coil, so that the plasma flow is spread over the entire surface of the workpiece. Irradiation can be performed uniformly, and a high-quality film can be formed on the workpiece.

  According to a seventeenth aspect of the present invention, the plasma processing is performed using the high-purity plasma of the first plasma and the second plasma generated by the plasma processing apparatus according to any one of the fourth to sixteenth aspects. It is possible to provide an object that is surface-treated in the part and coated with a high-performance mixed film such as AlTiN, TiCrN, CrAlN, CrVN, TiSiN, and CrSiN under composition ratio control. Moreover, the target object which coat | covered the AlTiN film | membrane in which the composition changed to the film thickness direction can be provided by changing the evaporation amount of Al and Ti with time.

Embodiments of a plasma processing apparatus to which a plasma surface processing method according to the present invention is applied will be described below in detail with reference to the accompanying drawings.
FIG. 1 is a sectional view of a plasma processing apparatus according to the present invention. The plasma processing apparatus according to the present invention is assembled as a plasma processing apparatus by being integrated with a plasma processing unit in which a workpiece (workpiece) is installed. In the plasma surface treatment method using this plasma processing apparatus, two types of first plasma 16 and second plasma 17 are used. Each plasma is vacuum arc plasma generated by performing a vacuum arc discharge in an arc discharge unit set in a vacuum atmosphere in the first plasma generation unit 2 and the second plasma generation unit 3. The first plasma 16 is introduced into the common transport duct 10 via the first plasma introduction path 22 connected to the first plasma generation unit 2. The second plasma 17 is introduced into the common transport duct 10 via the second plasma introduction path 23 connected to the second plasma generation unit 3.

  The plasma introduction angles of the first plasma introduction path 22 and the second plasma introduction path 23 are set at an acute angle with respect to the transport direction of the common transport duct 10. The first plasma 16 and the second plasma 17 join the common transport duct 10 via the first plasma introduction path 22 and the second plasma introduction path 23, respectively. At this time, since each plasma introduction angle is set at an acute angle with respect to the transport direction of the common transport duct 10, droplets generated with the generation of each plasma go straight and near the inner wall of the common transport duct 10. collide. Therefore, it is possible to prevent the droplets from passing through the common transport duct 10 and entering the plasma processing unit 1. The plasma flows of the first plasma 16 and the second plasma 17 from which droplets have been removed in this way are guided to the plasma processing unit 1 via the common transport duct 10. At this time, by controlling the timing of introducing the first plasma 16 and the second plasma 17 into the common transport duct 10, a single film, a mixed film, or a laminated film (with respect to the surface of the workpiece W in the plasma processing unit 1) Surface treatment processing such as formation of multilayer products, super multilayer films, and ultra super multilayer films is performed. A coil 25 for extracting the first plasma 16 and a coil 31 for extracting the second plasma 17 are disposed at the start ends of the first plasma introducing path 22 and the second plasma introducing path 23 on the plasma generation side. . In the plasma surface treatment in this embodiment, a reactive gas or a non-reactive gas (inert gas) can be introduced as necessary.

  The plasma processing unit 1 is a rectangular film forming chamber having a work arrangement table 7 having a self-revolving mechanism for placing a work W therein, and is constituted by a vacuum chamber 4. The vacuum chamber 4 is provided with a pressure gauge and a vacuum control device 5, a processing gas introduction control system switching device 6, and a vacuum exhaust port 8. A vacuum exhaust control device, an on-off valve, a vacuum pump, and the like to be connected to the vacuum exhaust port 8 are not shown. Note that the processing gas may be introduced from the plasma generation unit. On one side surface of the vacuum chamber 4, a plasma inlet 34 is opened. The plasma inlet 34 communicates with the plasma common transport duct 10 that guides the plasma generated from the two plasma generators 2 and 3. Between the vacuum chamber 4 and the last part of the common transport duct 10 is provided a scanner device 18 comprising an electromagnetic coil for scanning plasma in the chamber. The scanner device 18 includes a scanner coil 28 and a correction coil 29. The correction coil 29 corrects the direction of plasma deflection by the scanner coil 28. The correction coil 29 may be disposed between the scanner coil 28 and the plasma transport duct. Note that the film formation chamber does not necessarily have a square shape, and may have a cylindrical shape, a bell jar shape, or a modification thereof, as long as it has a container shape that can accommodate an object to be processed.

  The common transport duct 10 and the scanner device 18 are arranged linearly with respect to the plasma inlet 34, in other words, toward the center of the chamber. A first plasma introduction path 22 and a second plasma introduction path 23 are connected to the starting end side of the common transport duct 10 in a substantially Y shape in plan view. In the present embodiment, the introduction angle of the first plasma introduction path 22 and the second plasma introduction path 23 is set to approximately 45 ° with respect to the common transport duct. In other words, the angle formed by the first plasma introduction path 22 and the common transport duct 10 and the angle formed by the second plasma introduction path 23 and the common transport duct 10 are set to approximately 135 °.

  FIG. 2 shows a configuration example of a Y-shaped plasma transport duct around the common transport duct 10. The diameter of the common transport duct 10 is enlarged, and a later-described mixer coil (electromagnetic coil) 21 is disposed in the enlarged diameter portion 19.

  FIG. 3 is a diagram for comparing the case (3B) in which the enlarged diameter portion 19 is provided with the Y-shaped transport path 35 (3A) having a constant duct cross-sectional diameter without providing the enlarged diameter portion 19. 3, the same members as those in FIG. 2 are denoted by the same reference numerals. The droplets by-produced from the cathode of the vacuum arc are emitted from all directions from the cathode spot formed on the cathode surface, and move straight after the emission. Most of the droplets adhere to and are absorbed by the solid surface when they collide with the solid, but some of the droplets reflect on the solid surface. This reflection droplet repeats reflection while losing kinetic energy at the time of reflection, and eventually adheres to the solid surface and is absorbed. When the reflection droplet reaches the object to be processed, the flatness of the surface of the target object subjected to the surface treatment is lowered, the composition uniformity is lost, and the film quality is lowered. The droplets emitted in the direction of the first plasma introduction path 22 or the second plasma introduction path 23 go straight toward the inner wall of the common transport duct 10 as indicated by an arrow 33. When the common transport duct 10 is not expanded in diameter, as indicated by an arrow 36, the ratio of the droplets reflected on the inner wall entering the scanner device 18 side, that is, toward the plasma processing unit 1 increases. When the enlarged diameter portion 19 shown in (3B) of FIG. 3 is provided, the direction of reflection of the droplets in the enlarged diameter portion 19 can be changed in the reverse direction as indicated by the arrow 37, and enters the scanner device 18 side. Therefore, the droplet removal efficiency can be improved. In the present embodiment, as shown in FIG. 2, the enlarged diameter portion 19 is provided in the middle of the common transport duct 10.

  Furthermore, it is preferable to provide a blocking member for preventing the droplet from traveling in the traveling direction of the first plasma 16 or the second plasma 17 in order to increase the droplet removal efficiency. FIG. 2 shows an orifice 32 as a blocking member. The orifice 32 is formed of a perforated disk whose hollow portion has an inner diameter smaller than the inner diameter of the duct. By attaching the orifice 32 to the inner surface side of the common transport duct 10, the first plasma introduction path 22 and the second plasma introduction path 23, a local diameter reduction of the transport duct occurs and the droplets proceed toward the plasma processing unit 1. Can be further reduced.

  In the present embodiment, the orifice 32 is attached to the inner surface side of the first plasma introduction path 22 and the second plasma introduction path 23 and the inner surface of the common transport duct 10. Further, a perforated disk-like baffle 38 is attached in a pleated manner as another blocking member on the inner surface side of the first plasma introduction passage 22 and the second plasma introduction passage 23 and the inner surface of the common transport duct 10. The baffle 38 is usually composed of a plurality of plate-like pieces, and has a function of capturing or reflecting the droplet and preventing the droplet from traveling toward the plasma processing unit 1. The difference in inner and outer diameters of one piece of baffle 38 is about 3 to 15 mm. The baffles 38 on the inner surfaces of the first plasma introduction path 22 and the second plasma introduction path 23 are vertically attached to the duct wall. On the other hand, the baffle 38 on the inner surface of the enlarged diameter portion 9 of the common transport duct 10 is mounted in the duct at an inclination angle that is inclined forward in a direction opposite to the progress of the droplet. The inclination angle of the baffle 38 with respect to the duct wall is set to 30 to 150 °, and it is preferable to set the angle so that the droplets can be efficiently removed according to the location and position of the duct. The baffle 38 may be attached so as to be separated from the inner wall surface by about 0.5 to 5 mm without contacting the inner wall. The orifice 32 has an inner diameter smaller than that of the baffle 38, the inner diameter is about 30 to 80 mm, and the plate thickness is 0.5 to 3 mm. Further, the baffle 38 is attached to a removable deposition tube (which is disposed so as to cover the inner wall of the plasma transport duct: also referred to as a deposition tube or a deposition plate) for preventing dirt on the inner wall of the duct. It is preferable in terms of maintenance.

  The first plasma generation unit 2 is disposed on the start end side of the first plasma introduction path 22, and the second plasma generation unit 3 is disposed on the start end side of the second plasma introduction path 23. The first plasma generation unit 2 has a vacuum arc discharge unit composed of an anode (anode) 12 and a cathode (cathode) 13. Similarly, the second plasma generating unit 3 also has a vacuum arc discharge unit composed of an anode 14 and a cathode 15. Each arc discharge unit includes a trigger electrode (not shown), arc stabilizing magnetic field generators (electromagnetic coils or permanent magnets) 24 and 30 in addition to the cathode and anode electrodes. The trigger electrode is an electrode for inducing a vacuum arc between the cathode and the anode. The arc stabilizing magnetic field generators 24 and 30 are arranged at the outer periphery of the vacuum chamber or behind the cathode (inside or outside the arc source part) in the arc discharge part, and stabilize the cathode generated by the vacuum arc and the plasma generated by the arc discharge. Is for. A DC power source, a pulse power source, a pulse superimposed DC power source, or the like can be used as a power source for each arc discharge unit.

The cathodes 13 and 15 are sources for supplying a main constituent material of plasma, and the forming material is not particularly limited as long as it is a solid having conductivity. Regardless of whether it is a simple metal, an alloy, an inorganic simple substance, an inorganic compound (metal oxide / nitride) or the like, they can be used alone or in combination of two or more. The constituent particles of the plasma are not only the plasma-charged particles (ions, electrons) originating from the vaporized substances from the cathodes 13 and 15 in the arc discharge section, or the vaporized substances and the introduced gas (source), Includes neutral particles of molecules and atoms. The deposition conditions in the plasma processing method (vacuum arc deposition method) are: current: 1 to 600 A (desirably 5 to 500 A, more desirably 10 to 150 A). Further, voltage: 5 to 100 V (desirably ¹⁰ to 80 V, more desirably ¹⁰ to 50 V), pressure: 10 ⁻¹⁰ to 10 ² Pa (desirably 10 ⁻⁶ to 10 ² Pa, more desirably 10 ⁻⁵ to 10 ¹ Pa). As the simple metal, all of typical metals and transition metals can be used. Among them, Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Ag, In, Sn, Sb, Hf, Ta, Pt, Au, Hg, Pb, Nd, etc. are used. It's easy to do. Examples of the alloy or intermetallic compound include TiAl, TiCr, TiSi, AlSi, AlCr, and NdFe. Examples of inorganic simple substance include C. In addition, examples of the inorganic compound (ceramics) include oxides such as TiO ₂ , ZnO, SnO ₂ , ITO (Indium-Tin-0xide: indium oxide mixed with tin), In ₂ O ₃ , Cd ₂ SnO ₄ , and CuO. Furthermore, carbides / nitrides such as TiN, TiAlC, TiC, CrN, TiCN, etc. can also be mentioned. In order to synthesize metal and alloy films or to form a film having a cathode material composition, no gas is introduced or various inert gases described later are used. Further, by introducing the reactive gas described above, a nitride (eg, AlN, TiN, CrN, CuN, ZnN, HfN, TaN) is formed as a film in which the composition of the cathode material and the composition of the reactive gas are mixed. , TiAlN, TiCrN, CrAlN, CrVN, etc.), oxides (eg, Al ₂ O ₃ , TiO ₂ , CrO, CuO, ZnO, ZrO ₂ , InZnO, TiAlO, ZrAlO, etc.), nitride oxides (eg, AlNO, TiNO, CrNO, etc.), carbides (eg, AlC, TiC, CrC, HfC, TaC, WCoC, WNiCrC, TiMoC, WTiTaC, WTiC / TiMo, etc.), carbonitrides (eg, AlCN, TiCN, CrCN, WTiCN, WTiTaCN) , MoCN, etc.), carbonate (TiAlCO, Zr) bCO etc.), hydrocarbons product (e.g., ALCH, etc.), oxide hydrides (e.g., TiOH, etc.), silicides (silicide; _{eg, FeSi, FeSi 2, NiSi,} TiSi 2, MoSi 2, CoSi 2, TaSi ₂ , WSi, etc.), silicide nitride (eg, AlSiN, TiSiN, CrSiN, etc.), boride (eg, TiBN, etc.), sulfide (eg, MoS ₂ , etc.), fluoride, chloride, etc. A film can be obtained. In addition, when graphite (C) is used for the cathode, it is possible to synthesize diamond-like carbon film, hydrogen-containing diamond-like carbon film, metal-containing diamond-like carbon film, Si-containing diamond-like carbon film, or fluorinated diamond-like carbon film. It is.

ITO, ATO, AZO, ZnO, etc. formed by the plasma processing apparatus according to the present invention are used as a transparent conductive film, and FeTbCo, FeGdCo, NdDyCo alloy, etc. are used as magneto-optical recording films, such as CoCr, CoNi, FeNi alloy, etc. Is a perpendicular magnetic recording film, Si ₃ N ₄ , SiC, AlN, Al ₂ O ₃ , SiO _2, etc. are insulating protective films, and Cr, SiO ₂ , Al, MgF _2, etc. are optically utilized (reflection film, antireflection) MoSi ₂ , TaSi ₂ , WSi ₂ , TiSi ₂ etc. as slidable films, TiC, TiN, TiB ₂ , ZrB ₂ , LaB ₆ etc. as functional films, ZnS: Mn, ZnS: RE has suitable characteristics as a light-emitting element for electroluminescence.

  The material for forming the anodes 12 and 14 is not particularly limited as long as it does not evaporate even at the plasma temperature and is a non-magnetic material having conductivity. Regardless of whether it is a simple metal, an alloy, an inorganic simple substance, an inorganic compound (metal oxide / nitride) or the like, they can be used alone or in combination of two or more. The material used for the above-mentioned cathode can be appropriately selected and used. In the present embodiment, the anode is formed of stainless steel, copper, carbon material (graphite: graphite) or the like, and it is desirable to attach a cooling mechanism such as a water cooling type or an air cooling type to the anode. Also, the shape of the anode is not particularly limited as long as it does not block the entire progress of the arc plasma, and it is cylindrical (regardless of cylinder or square tube), coiled, U-shaped, and vertically and horizontally You may form by arrange | positioning in parallel one pair, arrange | positioning in one place somewhere on the upper and lower sides, right and left, or several places.

Gas introduction may not be performed in the chamber of the plasma processing unit 1, but a gas introduction system (not shown) and a gas exhaust system (not shown) may be connected. A general-purpose system can be used as these systems. The gas introduction flow rate is controlled to be constant, and the degree of vacuum (pressure) of the entire container is controlled to be constant by controlling the exhaust flow rate. The introduced gas may be introduced from the arc discharge part or may be introduced from both the plasma processing part 1 and the arc discharge part. When introducing from both the plasma processing unit 1 and the plasma generating unit, the type of gas may be different. As the introduction gas, when no reactive gas is used, a rare gas (usually for maintaining a constant pressure) is used. , Ar, and He) are appropriately used. When a reactive gas is used, it reacts with evaporated particles (plasma particles) using a cathode material or the like as a source to easily form a multi-compound film. Examples of reactive gases include N ₂ , O ₂ , air, water vapor, H ₂ , carbon dioxide (CO, CO ₂ ), aliphatic hydrocarbon gas (CH ₄ , C ₂ H ₂ , C ₂ H ₄ , C ₂ H ₆ , C ₃ H ₄ , C ₃ H ₆ , C ₃ H ₈ , C ₄ H ₆ , C ₄ H ₈ , C ₄ H _10, etc.), aromatic hydrocarbon vapor (C ₆ H ₆ , C ₇ H ₈ , C ₈ H ₁₀ , C ₁₀ H ₈ etc.), fluorine gas (CF ₄ , CHF ₃ , C ₂ F ₆ , C ₄ F ₈ , C ₅ F ₈ , etc.), fluorine element-containing liquid vapor (C ₆ F ₆ , C, such as _{6 F 14, C 7 F 14} , C 7 F 16, C 8 F 16, C 10 F 18, C 7 H 5 F 3, C 17 H 28 F 3), silane gas (SiH _4, etc.) , Nitriding gas (amine gas, imine gas, amide gas, etc.), chloride gas, sulfide gas, Near, boron-containing gas (boron trifluoride, Shiboran, etc. pentaborane), halogen gas, such as, and available mixture of these gases is not limited in particular. Non-reactive gases include He, Ne, Ar, Kr, and Xe. Here, in order to control the reactivity, a rare gas may be mixed to adjust the concentration of the reactive gas. Further, alcohol vapor, organometallic gas, or vapor of organometallic liquid (such as various metal alkoxides) can be used as the reactive gas.

As described above, the common transport duct 10, the first plasma introduction path 22, and the second plasma introduction path 23 are connected in a Y shape on one plane, and the first plasma 16 and the second plasma 17 are connected to the common transport duct 10. And merge at an acute angle. (4A) in FIG. 4 schematically shows the merging direction of each plasma flow. The plasma flow 16a of the first plasma 16 indicated by the arrow a and the plasma flow 17a of the second plasma 17 indicated by the arrow b merge and are transported in the transport direction of the common transport duct 10 indicated by the arrow A2.
The common transport duct 10 may be bent and connected within a range A1 of −90 to 90 ° from the plane formed by the first plasma introduction path 22 and the second plasma introduction path 23. In the case of such a three-dimensional Y-shaped duct, the total bending angle from the plasma generating portion to the film forming position increases, and thus the droplet removal efficiency is further increased.

  In addition, by applying such a three-dimensional Y-shaped duct, four plasma generation sources are connected by two three-dimensional Y-shaped ducts, which are also connected by Y-shaped ducts. Is also possible. An example is shown in FIG. 4 (4B). In first to fourth plasma generation units (not shown) for generating plasma using solid / liquid as a plasma source or gas as a plasma working gas, a first plasma 40, a second plasma 41, a third plasma 44, respectively. And the fourth plasma 45 is generated. Among these first to fourth plasma generation units, at least one generates plasma based on vacuum arc discharge in an arc discharge unit set in a vacuum atmosphere. The first transport duct portion B1 is composed of plasma transport paths C1 and C2 and the start end portions of the first plasma introduction path C3, and the first plasma 40 and the second plasma 41 are first through the plasma transport paths C1 and C2, respectively. The plasma is combined at the start end of the plasma introduction path C <b> 3 to become a combined plasma 42. The second transport duct portion B2 includes plasma transport paths D1 and D2 and a start end portion of the second plasma introduction path D3, and the third plasma 44 and the fourth plasma 45 pass through the plasma transport paths D1 and D2, respectively. The plasma is merged at the start end of the plasma introduction path D <b> 3 to become a merged plasma 43.

  The plasma introduction angles of the plasma transport paths C1 and C2 are set to a three-dimensional arrangement that forms an acute angle when projected onto one plane with respect to the transport direction of the first plasma introduction path C3. In addition, the plasma introduction angles of the plasma transport paths D1 and D2 are set to a three-dimensional arrangement that forms an acute angle when projected onto one plane with respect to the transport direction of the second plasma introduction path D3. Droplets are removed at the stage of introduction of the first plasma 40, the second plasma 41, the third plasma 44, and the fourth plasma 45 into the plasma introduction paths.

  The combined plasma 42 and the combined plasma 43 are introduced into a common transport duct portion B3 including a terminal portion of the first plasma introducing path C3, a terminal portion of the second plasma introducing path D3, and a common transport duct E, The combined plasma 42 and the combined plasma 43 are further combined to form a combined plasma 46. That is, the combined plasma 42 of the first plasma 40 and the second plasma 41 is introduced into the common transport duct E communicating with the plasma processing unit (not shown) through the first plasma introduction path C3. Similarly, the combined plasma 43 of the third plasma 44 and the fourth plasma 45 is introduced into the common transport duct E through the second plasma introduction path D3, and the first plasma 40, the second plasma 41, the third plasma 44, and the The four plasmas 45 finally become the merged plasma 46. The plasma introduction angles of the first plasma introduction path C3 and the second plasma introduction path D3 are set to a three-dimensional arrangement that forms an acute angle when projected onto one plane with respect to the transport direction of the common transport duct E. In addition, since the droplets are removed even at the stage of introducing the combined plasmas 42 and 43, the droplets can be removed more efficiently in the entire plasma processing apparatus using the four plasma generation sources, and the film formation speed can be improved. It becomes feasible.

  The number of plasma generators and plasma introduction paths depends on the structure of the generated film (multilayer film, super multilayer film, ultra super multilayer film, etc.), composition ratio (single film, mixed film, compound film, etc.), and the deposition rate Designed. Even in the case of a plasma processing apparatus having three plasma generation units, a plasma introduction path is connected to each of the plasma generation units for generating the first to third plasmas, and the common transport duct of each plasma introduction path is in the transport direction. The introduction angle is set to an acute angle. Here, at least the plasma generating unit that generates the first plasma includes plasma generating means including a vacuum arc discharge unit. One embodiment of the plasma processing apparatus having three plasma generation units extends the length of the common transport duct 10 in the plasma processing apparatus of FIG. 1 and introduces plasma into the middle stage of the extended common transport duct 10. The third plasma introduction path is configured to be connected. In this case, the plasma generation unit connected to the middle stage of the common transport duct 10 can be replaced with the first plasma generation unit of FIG. 1 that generates vacuum arc plasma, and the first and third or all plasma generation units. It is also possible to arrange a plasma generating means comprising a vacuum arc discharge part.

  As another example of the plasma processing apparatus having three plasma generation units, in (4B) of FIG. 4, when the plasma generation means for generating the first plasma is composed of a vacuum arc discharge unit, There is a form in which any one plasma generation means of the fourth plasma is removed. In addition, the first to third plasma introduction paths can be connected to different positions of the common transport duct, and plasma can be sequentially introduced into the common transport duct from the plasma introduction path connected to the starting end position of the common transport duct. That is, the first to third plasmas may be introduced at an acute angle with respect to the transport direction of the common transport duct, and it is not necessary to arrange all the first to third plasma introduction paths on the same plane. The first to third plasma introduction paths can be connected to any position and direction of the common transport duct that satisfies the above condition (the introduction angle is an acute angle).

  FIG. 5 shows a rotating magnetic field applying portion 19 </ b> A by a mixer coil 21 provided on the outer periphery of the enlarged diameter portion 19 of the common transport duct 10. As shown in FIG. 5 (5A), a guide consisting of a guide coil 26 that attracts the confluent plasma 50 of the first plasma 16 and the second plasma 17 to the common transport duct 10 side on the plasma inlet side of the enlarged diameter portion 19. On the outlet side of the coil portion 20, a converging coil portion 27A including a converging coil 27 for converging the plasma flow is disposed. The merged plasma 50 is introduced into the guide coil portion 20 with a plasma flow diameter 51 corresponding to the inner diameter of the duct, passes through the enlarged diameter portion 19, and is then discharged from the converging coil portion 27A with a plasma flow diameter 53 corresponding to the inner diameter of the duct.

  As shown in FIG. 5 (5B), the mixer coil 21 includes two pairs of coils. One is composed of first rotating magnetic field coils 54, 55 arranged opposite to each other and connected in series or in parallel, and the other is arranged orthogonal to the first rotating magnetic field coils 54, 55 and arranged opposed to each other, in series. Or it consists of the 2nd rotating field coils 56 and 57 connected in parallel. These magnetic field coils generate a magnetic field B in the common transport duct 10 in a direction perpendicular to the transport direction. As shown in FIG. 6, when the alternating currents R <b> 1 and R <b> 2 shifted by a half cycle are passed through the first rotating field coils 54 and 55 and the second rotating field coils 56 and 57, as shown in FIG. 5 (5 </ b> B). In addition, a rotating magnetic field Br that rotates two-dimensionally is generated. The plasma 58 induced in the enlarged diameter portion 19 receives the rotating action of the rotating magnetic field Br, rotates inside the duct, is once diffused / expanded in the enlarged diameter portion 19, and then reduced in diameter by the converging coil portion 27A. As a result, the mixed plasma 59 is uniformly mixed. By discharging the mixed plasma 59 by the converging coil unit 27A and introducing it into the chamber of the plasma processing unit 1, a film forming process using a high-purity plasma mixed more uniformly can be performed.

  FIG. 7 shows another example of the mixer coil 21. In this example, a three-phase mixer coil 21 is used. FIG. 8 shows a comparative example in which the mixer coil 21 is not used. 7 and 8, the same members as those in FIG. 5 are denoted by the same reference numerals. A coaxial translation coil 19B is provided on the outer periphery of the enlarged diameter portion 19 in FIGS. The coaxial translation coil 19 </ b> B generates a magnetic field Bz along the straight traveling direction (transport direction) of the common transport duct 10. In the case of FIG. 7, as shown in FIG. 7B, a mixer coil 21 composed of three pairs of coils is used. Each set includes first rotating magnetic field coils 21A and 21D, second rotating magnetic field coils 21B and 21E, and third rotating magnetic field coils 21C and 21F that are arranged opposite to each other and connected in series. These magnetic field coils are separated from each other by 60 °.

As shown in FIG. 9, when the alternating currents R ₁ , R ₂ , and R ₃ shifted by 120 ° are passed through the _first to third rotating magnetic field coils, they are combined with the magnetic field Bz by the coaxial translation coil 19B. 7 (7A), a rotating magnetic field Br that rotates three-dimensionally is generated. The first plasma 16 and the second plasma 17 introduced into the duct are rotated by the rotating magnetic field Br, rotate inside the duct, and become a mixed plasma 53A that is diffused and mixed inside the enlarged diameter portion 19. The mixed plasma 53A becomes a plasma flow with a high degree of mixing that is evenly diffused by the action of the rotating magnetic field Br that rotates three-dimensionally. The energization control to the first to third rotating magnetic field coils and the first and second rotating magnetic field coils of FIG. 5 generates a single-phase, three-phase or polyphase alternating current from a commercial power source, On the other hand, the voltage is adjusted using a variable voltage regulator. A method of supplying power from a commercial three-phase power supply via a voltage variable regulator is most effective from the viewpoint of ease of power supply and the rotational diffusion efficiency of plasma.

As shown in FIG. 8, when the mixer mechanism is not provided, the plasma 16 and the plasma 17 do not mix and are transported as separated plasma 53B.
In the mixer section, since the plasma diffuses more than the plasma diameter in the duct before and after the mixer section, the diameter of the mixer section needs to be larger than the diameter of the common transport duct before and after the mixer section. That is, the enlarged diameter portion 19 of the common transport duct 10 has two functions and meanings of droplet removal and mixer space securing.

  FIG. 10 shows the film formation experiment results using the common transport duct having the mixer function of FIG. This is a case where a vacuum arc is used for the first plasma 16 and the second plasma 17. Cu (oxygen-free copper) was used for the cathodes of the first plasma generation unit 2 and the second plasma generation unit 3. The arc current of the vacuum arc in each plasma generator was 100A DC. The pressure in the apparatus (the whole from the vacuum arc part to the film formation chamber) was 0.005 to 0.01 Pa, and no atmospheric gas was introduced. Further, the scanner device 18 is not operated to confirm only the mixer effect by the mixer coil 21. In the comparative example of FIG. 10, the mixer coil 21 is not used, that is, the first to third rotating magnetic field coils are not operated, and the film formation result is shown in (10A) of FIG. When the mixer is not activated, the plasma beam (first plasma 16) transported from the first plasma generator 2 of the first vacuum arc and the plasma transported from the second plasma generator 3 of the second vacuum arc. The beam (first plasma 17) is merely a plasma flow 53B subjected to the action of the translational magnetic field Bz by the coaxial translation coil 19B, and is separated without being diffused. As a result, the center of the generated film is two places. On the other hand, when the mixer is activated, as shown in FIG. 10 (10B), the first plasma 16 and the second plasma 17 introduced into the duct are subjected to the rotating action of the three-dimensional rotating magnetic field Br, Since the plasma beam discharged from the common transport duct 10 is a plasma flow 53A in which the first plasma 16 and the second plasma 17 are combined together, the center of the generated film is at one place. From the comparative experiments described above, it has been clarified that the mixing effect of the plasma flow by the rotating magnetic field of the mixer coil 21 leads to a good film formation result.

  The plasma processing apparatus having the above configuration adjusts the generation timing of the first plasma and / or the second plasma, or the introduction timing to the common transport duct 10, for example, to introduce into the common transport duct 10 simultaneously or temporally. And a single film containing a film formed by vacuum arc plasma according to the film forming specifications and usage conditions of the workpiece (the first arc cathode and the second arc cathode are the same type). Film), mixed film (film generated when the first arc cathode and the second arc cathode are different), or laminated film (multilayer film, super multilayer film, ultra super multilayer film). It can be done smoothly. In addition, the plasma processing apparatus according to the present embodiment supplies the two types of first and second plasmas 16 and 17 to the plasma processing unit 1 through the common transport duct 10 according to the film formation specifications and use conditions. Therefore, it is possible to realize a compact structure of the plasma processing apparatus.

  In order to clarify the structural features of the present invention, an apparatus structure example of a plasma processing apparatus studied at the stage leading to the present invention is compared with the above embodiment. 11 and 12 show a comparative example, but the same members as those in the embodiment of the present invention are denoted by the same reference numerals and description thereof is omitted.

  FIG. 11 is a cross-sectional configuration diagram of a plasma processing apparatus shown as a comparative example. This is a case where the first plasma generation unit 101 and the second plasma generation unit 102 using a vacuum arc (cathode arc) as an evaporation source / plasma source are directly attached to the side surface of the vacuum film formation chamber 100. Each of the first plasma generation unit 101 and the second plasma generation unit 102 includes an arc discharge unit including a cathode 103, an anode 104, and a stabilizing electromagnetic coil 105, and generates a first plasma 106 and a second plasma 107, respectively. In this case, since the cathode of the vacuum arc as an evaporation source faces the workpiece W in the chamber, the droplets 108 and 109 emitted from each cathode easily adhere to the workpiece W. In addition, since the first plasma generation unit 101 and the second plasma generation unit 102 are directly attached to the film forming chamber 100, the ratio of the first plasma generation unit 101 and the second plasma generation unit 102 to the side surfaces of the chamber increases and the apparatus structure is complicated.

  FIG. 12 is a cross-sectional configuration diagram of another plasma processing apparatus shown as a comparative example. This is an example in which a torus-type plasma magnetic transport duct 209 having a plasma transport coil 205 disposed in the second plasma generation unit 201 is provided and a filtered arc is disposed as an evaporation source. The second plasma 203 uses a vacuum arc evaporation source to which a torus (part of a donut-shaped duct) type magnetic filter is connected. This torus type filtered arc is effective in the case of a cathode that discharges molten droplets such as Cr and Al. Since the molten droplet 206 is fixed when it comes into contact with the solid, it can be collected mainly on the inner wall of the outer periphery of the torus duct. The first plasma generation unit 202 is connected to a T-shaped plasma transport duct 208 that also serves as a droplet collection unit that collects the droplets 207. However, in this case, the droplets can be separated and collected. However, since there are individual connection ports of the plasma flow of the first plasma 204 and the second plasma 203 to the film forming chamber 200, a plurality of them are provided. If it is to be arranged, the wall area of the film forming chamber is further restricted, and practically difficult to implement.

  In particular, in the case of FIGS. 11 and 12, when the workpiece W is disposed and processed in one place in the film forming chambers 100 and 200, the processing by the first plasma and the processing by the second plasma are simultaneously performed in a complex manner. There is a defect that it cannot be performed by a process from the same direction. On the other hand, in the present embodiment, since each plasma is introduced via the common transport duct 10, a plurality of plasma generation sources are arranged in a compact manner without restricting the space in the film forming chamber. Simplification can be realized. Further, since the common transport duct 10, the first plasma introduction path 22 and the second plasma introduction path 23 are connected in a substantially Y shape on one plane, the plasma introduced via the common transport duct 10 is droplets. The high-purity film is removed, and a single film, a mixed film, or a laminated film (multilayer film, super multilayer film, ultra super multilayer film) can be formed smoothly and with high accuracy. Therefore, as shown in FIGS. 11 and 12, removal of droplets, limitation of the wall area of the film forming chamber, precise formation of a single film / mixed film / laminated film (multilayer film, super multilayer film, ultra super multilayer film), etc. To solve the problem at once, and to realize a compact plasma processing device and smooth and precise formation of single film / mixed film / laminated film (multilayer film, super multilayer film, ultra super multilayer film). Yes.

The controllability of the film forming process using the plasma processing apparatus according to the present invention will be described below. FIG. 13 is a schematic cross-sectional view of an object formed using the plasma processing apparatus according to the present invention. In the example of (13A), a single film or a mixed film L9 is formed on the surface of the workpiece W. The single film or mixed film L9 generates the first plasma and the second plasma simultaneously and introduces them into the film forming chamber through the common transport duct, thereby forming a uniform single film or mixed film. Be filmed. For example, when the first plasma uses Ti as the plasma source, the second plasma uses Al as the plasma source, and nitrogen gas is introduced as a reactive gas into the film forming chamber, the mixed film L9 is an intermetallic compound Ti _X Al _Y. An _NZ film is formed on the surface of the workpiece W. As for the composition ratios X, Y, and Z, for example, if the first plasma is generated under a certain condition and the generation method of the second plasma is controlled, a mixed film having the desired composition ratios X and Y can be obtained. When the second plasma is a vacuum arc, a Ti _X Al _Y N _Z film having desired composition ratios X and Y can be formed by adjusting the arc current.

  (13B) is a schematic cross-sectional view of an object on which formed films L10 and L11 having different film thicknesses are formed. (14A) of FIG. 14 shows a timing chart of the film forming process for the generated films L10 and L11 shown in (13B). The lower part of (14A) shows a timing chart of the generation film L11. According to this timing chart, the plasma for forming the generation film L11 is generated and introduced into the plasma processing unit, whereby the generation film L11 is formed on the surface of the workpiece W. Is deposited. Further, in the upper part of (14A), a timing chart of a film forming process for the generated film L10 is shown. According to this timing chart, plasma for forming the generated film L10 is generated, and this plasma is introduced into the film forming chamber. As a result, the generation film L10 is further formed on the surface of the generation film L11, and a laminated film (multilayer film, super multilayer film, ultra super multilayer film) is formed on the surface of the workpiece W. Further, by introducing a reactive gas or the like into the film formation chamber, the generated films L10 and L11 are formed from a metal film, a carbon film, a silicon film, or an intermetallic compound. For example, nitrogen is introduced into the film formation chamber. By using two plasma sources in which one plasma source is made of Ti and another plasma source is made of Al, a TiN film and an AlN film can be laminated on the surface of the workpiece W as generation films L10 and L11. . By alternately laminating such two types of generated films, the laminated film shown in FIG. 13C can be formed, and the timing chart of the film formation process in the laminated film formation is shown in FIG. 14B). Further, two types of generated films having different composition ratios can be alternately stacked as the generated films L10 and L11 to form a stacked film.

  FIG. 15 is a schematic cross-sectional view of an object on which a laminated film having transition mixed films L3 and L6 or a boundary layer L8 is formed. In (15A), the transition mixed film L3 is formed, and (16A) in FIG. 16 shows a timing chart in the film forming process. First, a product film L2 is formed on the surface of the work W, and a transition mixed film L3 is formed thereon to form a desired product film L1. For example, a TiN film is formed as the generation film L2, a TiAlN film is formed as the transition mixed film L3, and an AlN film is formed as the generation film L1 thereon, whereby the TiN film and the AlN film are formed. It is possible to relax the difference in stress and form a laminated film made of an intermetallic compound with good adhesion. As shown in the lower part of FIG. 16 (16A), the formation of the generation film L2 is performed in a state where the second plasma is constantly introduced. When forming a TiN film, an AlN film, or a TiAlN film, nitrogen gas is always introduced into the film forming chamber. Next, the first plasma and the second plasma are alternately sent to the common transport duct. Thereby, the transition mixed film L3 is formed. After the formation, the supply of the second plasma is stopped to bring the first plasma into a steady introduction state. At this time, since the transition mixed film L3 is formed in advance as an intermediate underlayer, the generated film L1 can be stably laminated.

  (15B) of FIG. 15 shows a multilayer film in which the generated films of (15A) are alternately laminated. (16B) of FIG. 16 shows a timing chart of the multilayer film forming process. By repeating the same process as (16A), it is possible to form a multilayer stacked structure in which the generation film L4 is formed on the generation film L5 with the transition mixed film L6 interposed therebetween. FIG. 15 (15C) shows a case where the transition mixed film L7 is formed thickly on the generated film L8 by using the above transition mixed film forming process. As shown in the timing chart of (16C) of FIG. 16, in this case, only the transition mixed film L7 is formed without bringing the first plasma into the steady introduction state. Note that, when executing the multilayer stacked film formation process, the drive control of the plasma generation unit necessary for plasma introduction timing control is managed by a sequence control device or a computer control device (not shown). In addition, when adjusting the composition ratio of a generated film made of an intermetallic compound such as a TiAlN film, the current value and its waveform in the plasma generating part are varied, and the evaporation rate and the evaporation time per unit time are changed. Further, if the plasma is generated at the same time at the boundary time for switching the film formation between the first plasma and the second plasma, it is possible to form an inclined film having a composition gradient between the generated films.

  FIG. 17 is a schematic diagram for explaining the plasma generation method used in the present invention. The generation method of the second plasma may be appropriately selected according to the film formation specifications and conditions. As an applicable plasma generation method, for example, there is a plasma generation method for obtaining plasma directly from a solid. A vacuum arc discharge shown in (17A) (cathode arc discharge (or anodic arc discharge is also acceptable) employed in the present embodiment), a high voltage pulse current source 90 as shown in (17B) is connected, and a high voltage high current pulse current is used. There is a shunting arc that induces plasma from the target material 91. Various types of sputtering (self-sputtering, magnetron sputtering, V-shaped sputtering) may be used.

  FIG. 18 is a schematic diagram for explaining another plasma generation method used in the present invention. As shown in (18A), the magnetron sputter includes unbalanced magnetron sputter. The sputter target 94 disposed in the vicinity of the permanent magnet 92 is used as a sputter evaporation source 96 to evaporate the solid, and the solid evaporate is unbalanced. The plasma flow is induced by plasmaizing by the plasma function of the domagnetron itself or by the inductively coupled RF plasma source coil 93. Further, as shown in (18B), the V-shaped sputtering includes a sputtering evaporation source 97 in which one set or a plurality of sets of permanent magnets 95 are arranged in a V-shape. In the case of V-shaped sputtering, as in the case of an unbalanced magnetron, the evaporated substance is turned into plasma by electrons leaking from the sputtering region due to an unbalanced magnetic field.

  FIG. 19 is a schematic diagram for explaining another plasma generation method used in the present invention. Furthermore, as another applicable plasma generation method, there is a plasma generation method in which a solid is evaporated and then converted into plasma. In this case, resistance evaporation, electron beam evaporation, etc. can be used in addition to hollow cathode arc, electron beam excited plasma, and various types of sputtering (high frequency sputtering, medium frequency sputtering, DC sputtering, AC sputtering, magnetron sputtering). In the resistance evaporation method, as shown in (19A), the evaporation material 82 accommodated in the evaporation boat 81 is used as the resistance evaporation source 80, and the plasma is induced with the assistance of the capacitively coupled plasma source electrode 83. In the electron beam evaporation method, as shown in (19B) of FIG. 19, an electron beam 85 is irradiated to an evaporation target 86 as an electron beam evaporation source 84, and plasma is induced by assisting with an inductively coupled plasma source coil 87. . As a plasma for converting the evaporated material evaporated by these methods into a plasma, a hollow cathode arc, an electron beam excitation plasma, a direct current discharge, a low frequency / medium frequency / high frequency plasma (see FIG. 18 for an example of inductive coupling type. Capacitive coupling) Examples of the molds can be obtained by using pulse plasma, microwave plasma, surface wave plasma, electron shower plasma, or the like (see FIG. 19A).

  Furthermore, as another applicable plasma generation method, a method of converting a gas or a vaporized or misted liquid into plasma can be used. DC discharge, low frequency / medium frequency / high frequency plasma, hollow cathode arc, pulse plasma, microwave plasma, surface wave plasma, or electron shower plasma can be used. FIG. 20 shows a method of transporting a gas or vaporized or misted liquid through the introduction pipe portion 303 and converting it into plasma by the plasma generating unit 300 ((20A) in FIG. 20), and a gas or vaporized or misted liquid. Is converted into plasma by the plasma generator 301 disposed in the chamber 302 ((20B) in FIG. 20). When plasma is generated by the plasma generation unit 300 through which the introduction pipe unit 303 penetrates, high-frequency plasma (inductive coupling type and capacitive coupling type) and microwave plasma can be used. When the plasma is formed in the chamber 302, the above-described methods such as DC discharge, low frequency / medium frequency / high frequency plasma, hollow cathode arc, pulse plasma, microwave plasma, surface wave plasma, or electron shower plasma can be used. When forming a film containing a material that cannot be used in a vacuum arc, such as Si, for example, a method other than a vacuum arc may be used.

  FIG. 21 is a schematic configuration diagram of the scanner device 18 used in the present embodiment. The diameter of the plasma flow to be transported is 30 mm to 70 mm. This is equal to the film formation area. Therefore, when a film is to be formed in a region beyond that, or when a plurality of objects to be processed are arranged in a region beyond that, a desired film can be obtained by scanning plasma. As shown in (21A), a scanner device 18 is disposed near the exit of the common transport duct 10. As shown in the sectional view of (21B), the scanner coil 28 of (21A) includes an X-direction electromagnet 63 and a Y-direction electromagnet 64, and is attached to the outer periphery of the scanner section duct. If scanning in only one direction is sufficient, only one of the X-direction electromagnet 63 and the Y-direction electromagnet 64 may be provided.

FIG. 22 is a waveform diagram showing the drive current used in the scanner device 18. As shown in FIG. 22A, the plasma flow is periodically deflected and oscillated by the co-spinning magnetic field 65 oscillating in one direction by passing the co-sintering current 72 through the electromagnet of the scanner coil 28, and the film forming position is set to 1. It can be scanned dimensionally. On the other hand, when the X-direction electromagnet 63 and the Y-direction electromagnet 64 are attached as shown in FIG. 21 (21B), the X-direction electromagnet 63 and the Y-direction electromagnet 64 are respectively attached as shown in FIG. 22 (22B). , B ₃ , which is a combined magnetic field of magnetic field B ₁ generated by X-direction electromagnet 63 and B ₂ generated by Y-direction electromagnet 64 by flowing currents 70 and 71 having a phase difference and periodically changing. The film formation position can be scanned two-dimensionally by controlling the direction and angle of the plasma flow by changing the direction and strength with time. As for the crossing current (periodic current), a sine wave or a triangular wave can be used relatively easily, but more practically, an arbitrary waveform generator, computer control / It is desirable to freely control the waveform by sequence control. It is also possible to change the period of the periodic current flowing through the X direction coil and the Y direction coil. In order to suppress the diffusion of the plasma flow, an electromagnetic coil for applying a translation (Z direction, plasma flow traveling direction) magnetic field 66 may be provided in the scanner unit.

  FIG. 23 is a schematic wiring diagram for explaining a bias voltage application method according to the present invention. When a bias voltage is applied to the anode by the power source 504, the plasma transport efficiency is improved by 1 to 25%, and the film formation rate can be increased. Further, in order to efficiently transport the plasma to the plasma processing unit 1 through the plasma transport path such as the common transport duct 10, the scanner device 18, the common transport duct 10, and the second plasma introduction as shown in FIG. A bias voltage from the bias power sources 503, 502, and 501 may be applied to the path 23 (or the first plasma introduction path 22), respectively. The bias voltage is preferably −30 V to +30 V, and in particular, the same voltage as the plasma potential, that is, +10 V to +20 V, particularly +15 V ± 3 V is often suitable. When a suitable bias voltage is applied to the plasma transport duct system, the plasma transport efficiency and the deposition rate are improved several times. In order to apply a bias to the plasma transport duct, the film forming chamber and the plasma transport duct (including the scanner section) must be individually insulated. The present invention can also be applied to the case where the vacuum chamber itself of the first plasma generation unit 2 is used as an anode.

  When the anode is biased, the resistance of the anode is apparently improved, so that the current maintaining the plasma tends to flow to another region where it easily flows. In this case, since the place where it easily flows is the film forming chamber of the plasma processing unit 1 at the ground potential, the efficiency of transporting the plasma to the film forming chamber is improved. The anode bias voltage is suitably 0V to 10V, more preferably 0.5V to 5V.

  FIG. 24 is a schematic wiring diagram for explaining another method of bias voltage application according to the present invention. Hereinafter, description of the members described in FIG. 23 is omitted. As shown in the figure, a bias device 500 comprising a resistor or a power source is connected in series with the anode 12. When a bias voltage is applied to the anode 12 of the first plasma generation unit 2 (or the second plasma generation unit 3) by the bias device 500, the plasma transport efficiency can be further improved. When the bias device 500 is a resistor, the resistance value is appropriately about 0Ω to 0.2Ω, and more preferably 0.005Ω to 0.1Ω. Since deposits accumulate on the anode surface of the vacuum arc, the surface resistance changes every moment. Therefore, an electronic load that can externally control the resistance value may be used.

  FIG. 25 is a schematic wiring diagram for explaining still another method of bias voltage application according to the present invention. This figure shows a wiring diagram of an example of a system in which the vacuum chamber 600 itself of the first plasma generation unit 2 is used as an anode, and a plasma transport duct bias and an anode bias are applied by a bias voltage from a power source 504. The plasma transport duct and the scanner unit may be insulated and different bias voltages may be applied. That is, the bias voltage at the corresponding position may be changed according to the plasma state at each position. It is preferable to apply a voltage substantially equal to the plasma potential at each position as the bias voltage to be applied. A cascade bias in which a further subdivided bias is applied in accordance with the plasma transport direction may be performed.

  The present invention is not limited to the above-described embodiments and modifications, and includes various modifications and design changes within the technical scope without departing from the technical idea of the present invention. Needless to say.

  The plasma surface treatment method and the plasma treatment apparatus according to the present invention can be applied to a plasma processing apparatus mainly used for industrial purposes, and can form a film on the surface of a metal or non-metal workpiece. Therefore, a single processing apparatus for forming a single film or laminated film such as a metal, a semiconductor, an insulator, a DLC film, or a mixed film / alloy film, a ceramic film or a compound semiconductor film formed from a plurality of substances. A plasma surface treatment method and a plasma treatment apparatus can be realized. Furthermore, a simplified plasma processing apparatus can be provided by arranging a plurality of plasma generation sources in a compact manner. In addition, it is possible to smoothly form a multilayer multilayer film / mixed film including a film by at least vacuum arc plasma, and to use a high-purity plasma to perform a high-performance, high-purity coating film on an object to be processed. Can be formed. In addition, it is possible to realize a plasma processing apparatus that forms a high-performance, high-purity coating film on an object to be processed using high-purity plasma from which droplets have been removed.

  Further, by means of a plasma generation means for obtaining plasma directly from a solid, a plasma generation means for obtaining plasma by evaporating a solid, a plasma generation means for obtaining plasma with a gas or a vaporized or misted liquid, and a vacuum arc plasma. In addition, it is possible to provide a plasma processing apparatus for forming a high-purity single film, mixed film, or laminated film according to various film formation specifications. In addition, it is possible to provide a plasma processing apparatus for multilayer film formation that easily performs film formation control in accordance with various film specifications and conditions such as film thickness and layer configuration. Furthermore, it is possible to provide a plasma processing apparatus for forming a multilayer film, which has high droplet removal efficiency and plasma transport efficiency and can form a film at high speed using high-purity plasma.

  The object according to the present invention is a high-performance film formed from a metal film, an alloy film, a semiconductor film, an insulator film, a non-metal film such as a DLC film, or the like, or a high-performance laminated film composed of various films And can be used as various industrial products to which suitable wear resistance, heat resistance, corrosion resistance, oxidation resistance, conductivity, durability, and the like are imparted. More specifically, various cutting tools such as semiconductor wiring films, hard metal cutting tools, soft metal cutting tools, dry cutting tools, high-speed cutting tools, resin molding dies, semiconductor molding dies, sintered bodies・ Various manufacturing equipment, products, and their components, such as ceramic molds, molds requiring releasability, press molds, mechanical parts, sliding parts, water-repellent parts, corrosion-resistant parts, etc. Can be used.

It is a section lineblock diagram of a plasma treatment apparatus concerning the present invention. It is a Y-shaped plasma transport duct block diagram around a common transport duct. It is a figure for comparing the case where an enlarged diameter part is provided, and the case where an enlarged diameter part is not provided. It is a figure which shows the direction of the plasma flow in the substantially Y-shaped connection state of a common transport duct, a 1st plasma introduction path, and a 2nd plasma introduction path, and a 3-dimensional duct Y-shaped connection example. It is a figure which shows the rotating magnetic field provision part by a mixer coil. It is a wave form diagram of cross seeding current supplied to the 1st rotating field coil and the 2nd rotating field coil. It is a coil arrangement | positioning figure of a mixer apparatus part. It is a figure which shows the comparative example (when not having a mixer coil) with FIG. FIG. 8 is a waveform diagram of a crossing current used in the case of FIG. 7. It is a figure which shows the film-forming experiment result using the common transport duct which has a mixer function of FIG. It is a cross-sectional block diagram of the plasma processing apparatus shown as a comparative example. It is a cross-sectional block diagram of the other plasma processing apparatus shown as a comparative example. It is a schematic sectional drawing which shows the film-forming example given to the workpiece | work using the plasma processing apparatus which concerns on this invention. It is a timing chart of the film-forming process of FIG. It is a schematic sectional drawing which shows the film-forming example which forms a transition mixed film and a boundary layer. It is a timing chart of the film-forming process of FIG. It is a schematic diagram for demonstrating the plasma generation method used for this invention. It is a schematic diagram for demonstrating the other plasma generation method used for this invention. It is a schematic diagram for demonstrating the further another plasma generation method used for this invention. It is a schematic diagram for demonstrating another plasma generation method used for this invention. 1 is a schematic configuration diagram of a scanner device according to the present invention. It is an example of the waveform of the drive current used for the scanner apparatus which concerns on this invention. It is a schematic wiring diagram for demonstrating the method of bias voltage application which concerns on this invention. It is a schematic wiring diagram for demonstrating another method of the bias voltage application which concerns on this invention. It is a schematic wiring diagram for demonstrating another method of the bias voltage application which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Plasma processing part 2 1st plasma generation part 3 2nd plasma generation part 4 Vacuum chamber (deposition chamber)
5 Pressure gauge and vacuum control system switchgear 6 Processing gas introduction control system switchgear 7 Work arrangement table 8 Vacuum exhaust port 9 Plasma transport path 10 Common transport duct 12 Anode 13 Cathode 14 Anode 15 Cathode 16 First plasma 16 a Plasma Stream 17 Second plasma 17a Plasma stream 17a
18 Scanner device 19 Expanded diameter portion 19A Rotating magnetic field applying portion 19B Coaxial translation coil 20 Guide coil portion (electromagnetic coil)
21 Mixer coil (electromagnetic coil)
22 First plasma introduction path 23 Second plasma introduction path 24 Arc stabilizing magnetic field generator (electromagnetic coil or permanent magnet)
25 First plasma extraction coil (electromagnetic coil)
26 Guide coil (electromagnetic coil)
27 Convergence coil (electromagnetic coil)
27A Convergence coil (electromagnetic coil)
28 Scanner coil (electromagnetic coil)
29 Correction coil (electromagnetic coil)
30 Arc stabilizing magnetic field generator (electromagnetic coil or permanent magnet)
31 Drawer coil (electromagnetic coil)
32 Orifice 33 Arrow 34 Plasma inlet 35 Y-shaped transport path 36 Arrow 37 Arrow 38 Baffle 40 First plasma 41 Second plasma 42 Merged plasma 43 Merged plasma 44 Third plasma 45 Fourth plasma 46 Merged plasma 50 Merged plasma 51 Plasma flow Diameter 53 Plasma flow diameter 53A Mixed plasma 53B Plasma 54 First rotating magnetic field coil (electromagnetic coil)
55 First rotating field coil (electromagnetic coil)
56 Second rotating field coil (electromagnetic coil)
57 Second rotating field coil (electromagnetic coil)
58 Plasma 59 Mixed plasma 63 X direction electromagnet (electromagnetic coil)
64 Y-direction electromagnet (electromagnetic coil)
65 Cross-spreading magnetic field 66 Translation (Z-direction) magnetic field 67 Deflection plasma flow 70 Current 71 Current 72 Current 80 Resistance evaporation source 81 Evaporation boat 82 Evaporation material 83 Capacitive coupling plasma source electrode 84 Electron beam evaporation source 85 Electron beam 86 Evaporation Target 87 Inductively coupled plasma source coil 90 High-voltage pulse current source 91 Target material 92 Permanent magnet 93 Inductively coupled plasma source coil 94 Sputter target 95 Permanent magnet 96 Sputter evaporation source 97 Sputter evaporation source 100 Deposition chamber 101 First plasma generator 102 First 2 Plasma generator 103 Cathode 104 Anode 105 Stabilized electromagnetic coil (or permanent magnet)
108 droplet 109 droplet 200 deposition chamber 201 second plasma generator 202 first plasma generator 203 second plasma 204 first plasma 205 plasma transport coil (electromagnetic coil)
206 Droplet 207 Droplet 208 T-shaped plasma transport duct 209 Torus type plasma magnetic transport duct 300 Plasma generation section 301 Plasma generation section 302 Chamber 303 Introduction pipe section 500 Bias device (resistance or power supply)
501 Bias power source 502 Bias power source 503 Bias power source 504 Power source a Arrow b Arrow A1 Range A2 Arrow B Magnetic field Br Rotating magnetic field Bz Magnetic field B ₁ Magnetic field B ₂ Magnetic field B ₃ Magnetic field B1 First transport duct part B2 Second transport duct part B3 Common transport Duct section C1 Plasma transport path C2 Plasma transport path C3 First plasma introduction path D1 Plasma transport path D2 Plasma transport path D3 Second plasma introduction path E Common transport duct L1 Generation film L2 Generation film L3 Transition mixed film L4 Generation film L5 Generated film L6 Transition mixed film L7 Transition mixed film L8 Generated film L9 Generated film L10 Generated film L11 Generated film R1 Cross seeding current R2 Cross seeding current R3 Alternating current W Work

Claims (15)

A first plasma is generated by performing a vacuum arc discharge in an arc discharge section set in a vacuum atmosphere, a second plasma is generated using a solid / liquid as a plasma source or a gas as a plasma working gas, and the first plasma and After the second plasma is electromagnetically introduced so as to merge at an acute angle with respect to the transport direction of the common transport duct, the first plasma and the second plasma are electromagnetically transmitted to the plasma processing unit via the common transport duct. The timing of introducing the first plasma and the second plasma into the common transport duct and controlling the timing of introducing the first plasma and the second plasma into the common transport duct. Mixing by a rotating magnetic field generated in a duct, and processing in the plasma processing unit by the first plasma and the second plasma Plasma surface treatment method, which comprises surface treatment of. A first plasma, a second plasma, and a third plasma are generated in a plasma generation unit that generates plasma using solid / liquid as a plasma source or gas as a plasma working gas, and of these first to third plasmas At least one is generated based on a vacuum arc discharge in an arc discharge section set in a vacuum atmosphere, and the first plasma, the second plasma, and the third plasma are generated in a transport direction of a common transport duct. And electromagnetically introducing the first plasma, the second plasma, and the third plasma to the plasma processing unit via the common transport duct, and introducing the first plasma, the second plasma, and the third plasma to the plasma processing unit. The timing of introducing the plasma, the second plasma, and the third plasma into the common transport duct is controlled, and the common plasma Two or more of the first plasma, the second plasma, and the third plasma introduced into the transport duct are mixed by a rotating magnetic field generated in the common transport duct, and the first plasma and the second plasma are mixed. A plasma surface treatment method characterized in that surface treatment is performed on an object to be treated in the plasma treatment unit with plasma and the third plasma. A first plasma, a second plasma, a third plasma, and a fourth plasma are generated in a plasma generation unit that generates plasma using solid / liquid as a plasma source or gas as a plasma working gas, and the first to second plasmas are generated. At least one of the four plasmas is generated based on vacuum arc discharge in an arc discharge section set in a vacuum atmosphere, and a first plasma introduction path for joining the first plasma and the second plasma is provided. And the second plasma that electromagnetically introduces the first plasma and the second plasma so as to merge at an acute angle with respect to the transport direction of the common transport duct, and joins the third plasma and the fourth plasma. Via the introduction path, the third plasma and the fourth plasma join at an acute angle with respect to the transport direction of the common transport duct. After the electromagnetic introduction, the first plasma, the second plasma, the third plasma, and the fourth plasma are electromagnetically induced to the plasma processing unit via the common transport duct, Controlling the timing of introducing the plasma, the second plasma, the third plasma, and the fourth plasma into the common transport duct, and the first plasma, the second plasma, Two or more kinds of the third plasma and the fourth plasma are mixed by a rotating magnetic field generated in the common transport duct, and the first plasma, the second plasma, the third plasma, and the fourth plasma are mixed. A plasma surface treatment method, comprising subjecting an object to be treated in the plasma treatment section to surface treatment. A first plasma generating means for generating a first plasma by performing a vacuum arc discharge in an arc discharge section set in a vacuum atmosphere; and generating a second plasma using a solid / liquid as a plasma source or a gas as a plasma working gas. A second plasma generating means; a common transport duct for electromagnetically introducing the first plasma and the second plasma; and the first plasma and the second plasma electromagnetically introduced via the common transport duct. A plasma processing unit for surface-treating an object to be processed, a first plasma introduction path for electromagnetically introducing the first plasma from the first plasma generation unit to the common transport duct, and a second plasma generation unit A second plasma introduction path for electromagnetically introducing the second plasma into the common transport duct; the first plasma; and the second plasma. Control means for controlling the timing of introducing zuma into the common transport duct, and setting the introduction angle of the first plasma introduction path and the second plasma introduction path with respect to the transport direction of the common transport duct to an acute angle A rotating magnetic field generating means for generating a rotating magnetic field for mixing the plasma introduced into the common transport duct from each plasma introduction path is provided in the common transport duct. In the first to third plasma generation means for generating plasma using solid / liquid as a plasma source or gas as a plasma working gas, the first plasma, the second plasma, and the third plasma are generated, respectively. Of the first to third plasma generation means, at least the first plasma generation means comprises first to third plasma generation means comprising plasma generation means based on vacuum arc discharge in an arc discharge section set in a vacuum atmosphere; A common transport duct for electromagnetically introducing one plasma, the second plasma, and the third plasma; the first plasma, the second plasma, and the electromagnetically introduced via the common transport duct; A plasma processing unit for surface-treating the object to be processed with a third plasma; A first plasma introduction path for electromagnetically introducing a zuma into the common transport duct; a second plasma introduction path for electromagnetically introducing the second plasma from the second plasma generating means into the common transport duct; A third plasma introduction path for electromagnetically introducing the third plasma from the third plasma generating means into the common transport duct; and introducing the first plasma, the second plasma, and the third plasma into the common transport duct. Control means for controlling timing, and setting the introduction angle of the first plasma introduction path, the second plasma introduction path, and the third plasma introduction path with respect to the transport direction of the common transport duct to an acute angle, Two or more of the first plasma, the second plasma, and the third plasma introduced into the common transport duct from each plasma introduction path Providing the rotating magnetic field generating means for generating a rotating magnetic field to focus on the common transport duct plasma processing apparatus according to claim. In the first to fourth plasma generating means for generating plasma using solid / liquid as a plasma source or gas as a plasma working gas, respectively, a first plasma, a second plasma, a third plasma, and a fourth plasma are generated, and Of these first to fourth plasma generating means, first to fourth plasma generating means comprising plasma generating means based on vacuum arc discharge in an arc discharge section in which at least the first plasma generating means is set in a vacuum atmosphere. A first plasma introduction path for joining the first plasma and the second plasma, a second plasma introduction path for joining the third plasma and the fourth plasma, the first plasma, and the second plasma A common transport duct for introducing plasma, the third plasma and the fourth plasma, and the common transport duct A plasma processing unit for surface-treating an object to be processed by the first plasma, the second plasma, the third plasma, and the fourth plasma, and the first plasma, the second plasma, and the third plasma. And control means for controlling the timing of introducing the fourth plasma into the common transport duct, and introducing the first plasma introduction path and the second plasma introduction path in the transport direction of the common transport duct. An angle is set to an acute angle, and two or more of the first plasma, the second plasma, the third plasma, and the fourth plasma introduced from the plasma introduction paths to the common transport duct are mixed. A plasma processing apparatus, wherein a rotating magnetic field generating means for generating a rotating magnetic field is provided in the common transport duct. The plasma processing apparatus according to claim 4, wherein the first plasma introduction path, the second plasma introduction path, and the common transport duct form a substantially Y shape when projected onto a plane. 8. The control unit according to claim 4, wherein the control unit controls the introduction of plasma from the respective plasma introduction paths to the common transport duct at the same time, separately in time, or partially simultaneously. Plasma processing equipment. Introducing the first plasma includes a blocking member that prevents cathode material particles (hereinafter referred to as droplets) generated from the cathode of the arc discharge portion contained in the first plasma from traveling in the traveling direction of the first plasma. The plasma processing apparatus according to any one of claims 4 to 8, provided on a road and / or an inner surface of the common transport duct or in the vicinity thereof. The plasma processing apparatus according to any one of claims 4 to 9, wherein the second plasma is generated by a plasma generation method for obtaining plasma directly from a solid. The plasma processing apparatus according to claim 4, wherein the second plasma is generated by a plasma generation method for obtaining plasma by evaporating solids. The plasma processing apparatus according to any one of claims 4 to 9, wherein the second plasma is generated by a plasma generation method for obtaining plasma by gas or vaporized or misted liquid. The plasma processing apparatus according to any one of claims 4 to 12, further comprising bias voltage applying means for applying a bias voltage to at least one plasma generating means and / or the common transport duct. The plasma processing apparatus according to claim 4, further comprising bias means for electrically biasing an anode of at least one plasma generation means. The plasma traveling direction of the last part of the common transport duct is a z-axis direction, a vertical plane is an xy plane, and a deflection coil for scanning the plasma in the x direction and / or the y direction is disposed in the common transport duct. The plasma processing apparatus in any one of 4-14.