JP6832572B2 - Method of forming a decorative film by the magnetron sputtering method - Google Patents

Description

The present invention relates to a method for forming a decorative film by a magnetron sputtering method, and more particularly to a method for forming a titanium nitride (TiN) film and / or a titanium nitride (TiCN) film as the decorative film.

As a method for forming this kind of decorative film, particularly a titanium nitride film, there is a method conventionally disclosed in, for example, Patent Document 1. According to this prior art, it is said that the titanium nitride film having a golden color tone can be formed by an ion plating method or a sputtering method. For example, in the case of the ion plating method, the amount of evaporation of metallic titanium (Ti) as an evaporation material is constant. _{On the other hand, the flow rate of nitrogen (N 2} ) gas as a reactive gas is gradually or continuously reduced from the initial set amount. As a result, it is said that a golden titanium nitride film having a natural color tone is formed. It also discloses a case where the flow rate of nitrogen gas is not decreased but the flow rate of the nitrogen gas is gradually or continuously increased from the initial set amount. In this case, it is said that a slightly greenish titanium nitride film is formed. This means that the color tone of the titanium nitride film changes depending on the flow rate of the nitrogen gas, that is, the color tone of the titanium nitride can be controlled. On the other hand, in the case of the sputtering method, the sputtering amount of the target made of titanium is constant, and more specifically, the radio frequency (RF) power supplied to the target is constant, and the sputtering gas (sputtering gas) The flow rate of argon (Ar) gas as (sputter gas) is constant. Then, the flow rate of nitrogen gas as a reactive gas is gradually reduced. It is said that this also forms a golden titanium nitride film having a natural color tone.

Japanese Unexamined Patent Publication No. 7-243022

However, in the above-mentioned prior art, particularly in the case of the ion plating method, ionization means such as an electron gun and its surroundings are cleaned, and metallic titanium as an evaporation material is supplied and the like, in approximately one batch. There is a drawback that complicated work such as melting is required, which takes a considerable amount of time. Moreover, since nitrogen gas as a reactive gas is introduced in a place where metallic titanium as an evaporation material is in a molten state, nitrogen is solidified in the molten titanium as batches are stacked. As a result, the titanium is less likely to evaporate, and as a result, the reproducibility of the color tone of the titanium nitride film cannot be obtained.

On the other hand, in the case of the sputtering method, the temperature of the target is suppressed to a relatively low level by water cooling or the like, so that the target does not melt, and therefore nitrogen does not dissolve in the target. .. Therefore, a titanium nitride film having good color reproducibility can be obtained. In addition, the target has a life span that can be used over a plurality of batches (generally several tens to one hundred and several tens of times) instead of being replaced for each batch, and thus ion plating. Compared with the case by the law, the work in advance can be simplified, and the time required for the work can be shortened. That is, according to the sputtering method, all the above-mentioned drawbacks of the ion plating method are eliminated.

However, in the sputtering method in the prior art, the density of plasma is not so high. This is because the mode of the plasma is a high voltage and small current glow discharge. Therefore, the sputtered particles ejected from the surface to be sputtered of the target, that is, the titanium particles, have a low ionization rate, and the ionization rate is about several percent. Therefore, only a titanium nitride film having a relatively low hardness can be formed, that is, a titanium nitride film having a high hardness cannot be formed. Also, in terms of color tone, there is a problem that only a golden titanium nitride film lacking vividness (so to speak, dull) can be formed, that is, a bright golden titanium nitride film cannot be formed. ..

According to the ion plating method, since the plasma density is higher than that of the sputtering method, it is possible to form a bright golden titanium nitride film having high hardness. However, according to the ion plating method, it takes a considerable amount of time for the preliminary work, and the color tone reproducibility of the titanium nitride film cannot be obtained, as described above.

Therefore, an object of the present invention is to provide a method for forming the decorative film by a magnetron sputtering method, which can form a bright golden titanium nitride film having a higher hardness than the conventional one as a modified film. To do. In addition to the titanium nitride film, it is also an object of the present invention to form a titanium nitride film having high hardness and various color tones as the modified film.

In order to achieve this object, the present invention includes a gas introduction process, a sputtering power supply process, and a batch power supply process. In the gas introduction process, the sputter gas and the reactive gas are introduced into the vacuum chamber in which the object to be processed is accommodated and the magnetron cathode is provided. Then, in the sputtering power supply process, the vacuum chamber serves as an anode and the magnetron cathode serves as a cathode, and the sputtering power is supplied to both of them. As a result, the particles of the sputter gas are discharged to generate plasma inside the vacuum chamber, and more specifically, the plasma is generated by glow discharge. Further, in the bias power supply process, the vacuum chamber serves as an anode and the object to be processed serves as a cathode, and bias power is supplied to both of them. Here, the magnetron cathode has a target made of titanium and a magnetic field generating means for generating a magnetic field in the vicinity of the surface to be sputtered of the target. The magnetron cathode is provided so that the surface to be sputtered of the target faces the surface to be processed of the object to be processed. Therefore, the electrons (secondary electrons) in the plasma undergo spiral motion (cycloid motion and / or trochoidal motion) under the action of the magnetic field generated from the magnetic field generating means of the magnetron cathode. As a result, the density of plasma in the vicinity of the surface to be sputtered of the target on which the magnetic field acts is improved. Then, the ions in the plasma, particularly the ions of the particles of the sputter gas, collide with the surface to be sputtered of the target, so that the target particles, that is, the titanium particles, are knocked out from the surface to be sputtered. The titanium particles as so-called sputtered particles that have been knocked out fly toward the surface to be processed of the object to be processed. At the same time, the particles of the reactive gas are decomposed by the plasma. The reactive particles, which are the particles of the decomposed reactive gas, react with the titanium particles flying toward the surface to be treated of the object to be treated, and adhere to and deposit on the surface of the object to be treated. As a result, a reaction film containing titanium particles and reactive particles as components is formed as a decorative film on the surface to be treated of the object to be treated. Further, by supplying the bias power described above, ions of the titanium particles, that is, titanium ions are positively attracted to the surface to be treated of the object to be treated. Similarly, the ions of the reactive particles, so to speak, the reactive ions are also positively attracted to the surface to be treated of the object to be treated. As a result, the hardness of the decorative coating formed on the surface to be treated of the object to be treated can be increased.

On top of that, the present invention further comprises a thermionic emission process and an arc discharge induction process. In the thermionic emission process, electric power for thermionic emission is supplied to the filament provided between the surface to be sputtered of the target and the surface to be processed of the object to be processed. As a result, the filament is heated and thermoelectrons are emitted from the filament. Then, in the arc discharge induction process, the vacuum chamber serves as an anode and the filament serves as a cathode, and discharge power is supplied to both of them. As a result, the thermions emitted from the filament are accelerated, and the frequency of the accelerated thermions colliding with the particles of the sputter gas and the particles of the reactive gas increases, so that a low voltage and a large current are generated around the filament. An arc discharge is induced. In this state, in the above-mentioned gas introduction process, only nitrogen gas or the nitrogen gas and the hydrocarbon gas are introduced into the vacuum chamber as the reactive gas.

That is, according to the present invention, in addition to the plasma generated by glow discharge, extremely high-density plasma generated by arc discharge is generated around the filament, that is, between the surface to be sputtered of the target and the surface to be processed of the object to be processed. Occurs in. Therefore, the titanium particles ejected from the surface to be sputtered of the target pass through the extremely high-density plasma space due to this arc discharge while flying toward the surface to be processed of the object to be processed. As a result, the titanium particles are activated and have at least higher energy than the ground state, and are ionized particularly efficiently. Similarly, reactive particles are also more activated and more efficiently ionized. By improving the ionization rate, the amount of ions positively attracted to the surface to be treated increases, so that the hardness of the decorative coating formed on the surface to be treated can be increased. At the same time, since the mutual bonding force between the titanium particles forming the decorative film and the reactive particles is increased, the decorative film can be densified.

Here, for example, when only nitrogen gas is introduced into the vacuum chamber as the reactive gas, a titanium nitride film is formed as a decorative film. And in particular, a bright golden titanium nitride film can be formed. Further, the color tone of the titanium nitride film changes depending on the flow rate of the nitrogen gas, and for example, a golden titanium nitride film lacking vividness can be formed.

On the other hand, when a nitrogen gas and a hydrocarbon-based gas are introduced into the vacuum chamber as the reactive gas, a titanium carbonitride film is formed as a decorative film. Then, the color tone of the titanium nitride film changes depending on the flow rate of the nitrogen gas and the hydrocarbon gas, especially the mutual flow rate ratio, and the titanium nitride film having various color tones can be formed.

The flow rate ratio of the hydrocarbon gas to the nitrogen gas is more than 0 and preferably 50 or less. When the flow rate ratio referred to here is other than 0, nitrogen gas and hydrocarbon-based gas are introduced into the vacuum chamber as reactive gases, and a titanium carbonitride film is formed as a decorative film.

Further, as the hydrocarbon gas, acetylene (C ₂ H ₂ ) gas is suitable. In addition to acetylene gas, the hydrocarbon gas includes methane (CH ₄ ) gas, ethylene (C ₂ H ₄ ) gas, ethane (C ₂ H ₆ ) gas, and the like, and carbon and hydrogen in these gases. From the relationship of the composition ratio with the above, acetylene gas is the most suitable, that is, the titanium carbide film can be formed most efficiently.

As described above, according to the present invention, despite the method of forming a modified film by the magnetron sputtering method, as the modified film, for example, a golden titanium nitride film having a higher hardness than the conventional one is formed. can do. It is also possible to form a titanium carbonitride film having high hardness and exhibiting various color tones. This greatly contributes to the use of the modified coating and the expansion of the target.

It is a schematic diagram which shows the schematic structure of the magnetron sputtering apparatus which concerns on one Embodiment of this invention. It is a schematic diagram which looked at the inside of the magnetron sputtering apparatus from above. It is a schematic diagram which shows the schematic structure of the magnetron cathode in the same embodiment. It is a schematic diagram which shows the mutual positional relationship between a magnetron cathode and a filament in the same embodiment. It is a list showing an example of the film formation condition and property of the titanium nitride film as a decorative film in the same embodiment in comparison with the one in the prior art. It is an external photograph of the object to be treated which formed the titanium nitride film. It is a list showing an example of the film formation condition and property of the titanium nitride film as a decorative film in the same embodiment in comparison with the one in the prior art. It is a list which shows the condition and result of the experiment in the same embodiment. It is an appearance photograph of each sample in the same experiment.

An embodiment of the present invention will be described in detail below.

The method for forming the decorative coating according to the present embodiment is formed by, for example, the magnetron sputtering apparatus 10 shown in FIGS. 1 and 2. The magnetron sputtering apparatus 10 includes a hollow, roughly rectangular parallelepiped vacuum chamber 12. The vacuum chamber 12 is installed in a state where a portion corresponding to one surface of the rectangular parallelepiped is an upper surface, a portion corresponding to another surface facing the upper surface is a lower surface, and a portion corresponding to the other four surfaces is a side surface. Has been done. In the horizontal direction of the inside of the vacuum chamber 12, the length dimension of one side surface is, for example, about 1100 mm. The height dimension inside the vacuum chamber 12 is, for example, about 800 mm. The shape and dimensions of the vacuum chamber 12 are examples, even if they get tired of it, and are appropriately determined according to various situations such as the size and number of objects 100 to be processed, which will be described later. Further, the vacuum chamber 12 itself is made of a metal having high corrosion resistance and heat resistance, for example, stainless steel such as SUS304, and its wall portion is connected to a ground potential as a reference potential.

An exhaust port 14 is provided at an appropriate position on the wall portion of the vacuum chamber 12, for example, at a position deviated from the center of the wall portion forming the lower surface (position on the left side in FIG. 1). A vacuum pump as an exhaust means (not shown) is coupled to the exhaust port 14 via an exhaust pipe (not shown) outside the vacuum tank 12. The vacuum pump also functions as a pressure control means for controlling the pressure P in the vacuum chamber 12. In addition, an automatic pressure control device (not shown) is provided in the middle of the exhaust pipe, and this automatic pressure control device also functions as a pressure control means.

Further, at an appropriate position inside the wall portion forming the side surface of the vacuum chamber 12 (appropriate position of the right side wall portion in FIGS. 1 and 2), the magnetron cathode is electrically insulated from the vacuum chamber 12. 16 are arranged. With reference to FIG. 3, the magnetron cathode 16 is a substantially rectangular flat plate-shaped target 162 made of high-purity titanium (for example, a purity of 99.99% or more) and one main surface of the target 162. It has a magnet unit 164 provided on the back side. The magnet unit 164 has a permanent magnet 166 as a magnetic field generating means and a housing 168 for accommodating the permanent magnet 166. Further, the permanent magnet 166 has, for example, an N pole 166a as one magnetic pole having a substantially rectangular frame shape provided along the peripheral edge of the target 162 while being in close contact with the back surface of the target 162, and a target inside the N pole 166a. It has an S pole 166b as a substantially square bar-shaped other magnetic pole provided so as to extend along the longitudinal direction of the target 162 while being in close contact with the back surface of the 162. The dimensions of the target 162 are, for example, 457 mm in the longitudinal direction (length dimension), 127 mm in the lateral direction (width dimension), and 8 mm in the thickness direction (thickness dimension). Further, a substantially rectangular groove-shaped gap 166c is provided between the N pole 166a and the S pole 166b of the permanent magnet 166. Further, the housing 168 is provided with, for example, a water cooling mechanism as a cooling means (not shown) for cooling the entire magnetron cathode 16 including the housing 168.

The magnetron cathode 16 is arranged so that the surface to be sputtered, which is the other main surface (front surface) of the target 162, is directed toward the center of the vacuum chamber 12, and the longitudinal direction of the target 162 extends along the vertical direction. Has been done. The magnetron cathode 16 is covered with the earth shield 18 except for the surface to be sputtered of the target 162, in other words, the magnetron cathode 16 is covered with the earth shield 18 with the surface to be sputtered exposed. The earth shield 18 is made of a metal having high corrosion resistance and heat resistance, for example, a stainless steel such as SUS304. The earth shield 18 is electrically insulated from the magnetron cathode 16 and is electrically connected to the vacuum chamber 12. Although not shown, the portion of the wall of the vacuum chamber 12 where the magnetron cathode 16 and the earth shield 18 are provided is used during maintenance of the magnetron cathode 16 and the earth shield 18 including replacement of the target 162. In consideration of workability, it is desirable that the door can be opened and closed like a sliding door or a hinged door.

Further, as shown in FIG. 1, the magnetron cathode 16 is connected to a sputtering power supply device 20 as a sputtering power supply means outside the vacuum chamber 12. Then, the magnetron cathode 16 is supplied with DC power having a negative potential based on the ground potential as the sputtering power Es from the sputtering power supply device 20. In other words, the vacuum chamber 12 is used as an anode and the magnetron cathode 16 is used as a cathode, and DC sputtering power Es is supplied to both of them. The sputter power supply device 20 that is a supply source of the sputter power Es has a constant power mode that operates so that the power value of the sputter power Es is constant, and a so-called sputter voltage that is a voltage component of the sputter power Es. Alternatively, it is also referred to as a target voltage.) It operates so that the constant voltage mode that operates so that Vs is constant and the sputtering current (also referred to as target current) Is, which is a current component of the sputtering power Es, is constant. It has three operation modes, a constant current mode, and here, it is set to operate in a constant power mode.

In addition, a filament 22 as a thermionic emission means is provided in front of the magnetron cathode 16, specifically, in front of the surface to be sputtered of the target 162. The filament 22 is, for example, a linear linear body having a diameter of about 1 mm, and its material is a refractory metal such as molybdenum (Mo), tungsten (W), tantalum (Ta), and carbon (C). It is used. Here, with reference to FIG. 4 as well, particularly with reference to FIG. 4 (a), the filament 22 is viewed from a direction opposite to the direction in which the magnetron cathode 16 is arranged in the horizontal direction. For example, when viewed from the center of the vacuum chamber 12, the center of the surface to be sputtered of the target 162 is along the vertical direction, that is, along the longitudinal direction of the target 162, in other words, the target 162 is sputtered. It is provided so as to extend parallel to the surface. Further, as shown in FIG. 4B in particular, the filament 22 has a predetermined distance D from the surface to be sputtered of the target 162. This distance D is extremely inconvenient, for example, if it is excessively small, the filament 22 may come into contact with the surface to be sputtered of the target 162 or the earth shield 18. On the other hand, if the distance D is excessively large, the action of the magnetic field by the magnet unit 164 (permanent magnet 166) around the filament 22 becomes weak, and it becomes difficult to induce an arc discharge described later. Therefore, the distance D is appropriately 5 mm to 50 mm, for example, 25 mm. The length dimension of the filament 22 is equal to or greater than the length dimension of the target 162, and strictly speaking, is equal to or greater than the length dimension of the erosion region 162a described later of the target 162, for example, 500 mm. Is. In addition, although not shown, tension is applied to both ends or either end of the filament 22 to apply an appropriate tension to the filament 22 in order to maintain the linear state of the filament 22. A tension applying mechanism is provided as a means.

With reference to FIG. 1 again, both ends of the filament 22 are connected to, for example, an AC cathode power supply device 24 as a thermionic emission power supply means outside the vacuum chamber 12. Then, the filament 22 is heated to 2000 ° C. or higher by receiving the cathode power Ec as the thermionic emission power from the cathode power supply device 24 to emit thermions. The cathode power supply device 24 is not limited to an alternating current device, and may be a direct current device.

Further, the filament 22 is connected to a discharge power supply device 26 as a discharge power supply means outside the vacuum chamber 12. Then, the filament 22 receives a negative potential DC power with reference to the ground potential as the discharge power Ed from the discharge power supply device 26. In other words, the vacuum chamber 12 is used as an anode and the filament 22 is used as a cathode, and DC discharge power Ed is supplied to both of them. The discharge power supply device 26, which is the supply source of the discharge power Ed, has a constant power mode that operates so that the power value of the discharge power Ed becomes constant, and the same as the sputter power supply device 20 described above. A constant voltage mode that operates so that the discharge voltage Vd, which is a voltage component of the discharge power Ed, is constant, and a constant current that operates so that the discharge current Id, which is a current component of the discharge power Ed, is constant. It has three operation modes, a mode and. However, the discharge power supply device 26 is set to operate in the constant voltage mode.

Then, paying attention to the inside of the vacuum chamber 12 where the filament 22 is provided, a plurality of objects 100, 100, ... Are arranged in the vacuum chamber 12. Specifically, a central axis Xa extending along the vertical direction is set at substantially the center of the vacuum chamber 12 in the horizontal direction, and the objects to be processed 100, 100, ... Have the central axis Xa. They are arranged at equal intervals along the circumferential direction of the central circle. Each object to be processed 100 is an elongated cylindrical object such as a decorative pipe described later, and extends in the vertical direction, that is, in the direction along the central axis Xa of the vacuum chamber 12. , It is held by a holder 28 as a holding means. Each holder 28 is coupled to the vicinity of the peripheral edge of the disk-shaped revolution table 32 via the gear mechanism 30. The center of the revolution table 32 is located on the central axis Xa of the vacuum chamber 12, and at the center of the revolution table 32, one end of the rotating shaft 34 extending along the central axis Xa of the vacuum tank 12 is located. It is fixed. The other end of the rotary shaft 34 is coupled to the shaft 36a of the motor 36 as a rotary drive means outside the vacuum chamber 12.

That is, when the motor 36 is driven and the shaft 36a of the motor 36 rotates in the direction indicated by the arrow 200 in FIG. 1, for example, the revolution table 32 rotates in the same direction, that is, in the direction indicated by the arrow 200 in FIG. Rotate. Along with this, each object to be processed 100 rotates about the central axis Xa of the vacuum chamber 12, and revolves, so to speak. At the same time, due to the rotational driving force transmission action of each gear mechanism 30, each holder 28 rotates about the vertical axis Xb passing through itself in the direction indicated by the arrow 202, for example, in FIGS. 1 and 2, respectively. Then, as the holder 28 itself rotates, the object to be processed 100 held by the holder 28 also rotates in the same direction, so to speak, rotates on its axis. The diameter of the revolution path (PCD; Pitch Circle Diameter) of the object to be processed 100 is, for example, about 600 mm. The revolution speed of the object 100 to be processed (rotation speed of the revolution table 32) is, for example, 0.5 rpm to 1 rpm. On the other hand, the rotation speed of the object 100 to be processed (the rotation speed of the holder 28 itself about the vertical axis Xb) is, for example, 30 rpm to 60 rpm, that is, 60 times the revolution speed. In addition, in FIGS. 1 and 2, 12 objects to be processed 100, 100, ... (Holders 28, 28, ... And gear mechanisms 30, 30, ...) are provided, but this number is an example. , Other numbers may be used.

At the same time, each object to be processed 100 is subjected to a substrate from a substrate bias power supply device 38 as a bias power supply means outside the vacuum chamber 12 via a holder 28, a gear mechanism 30, a revolution table 32 and a rotating shaft 34. Bias power Eb is supplied. In this substrate bias power Eb, the value of the substrate bias voltage Vb, which is a voltage component thereof, is a high level value of a positive potential based on the ground potential, a low level value of a negative potential based on the ground potential, and the like. It is a so-called bipolar pulse power that alternately transitions to. The high level value of the substrate bias voltage Vb is constant, for example, + 37V with respect to the ground potential. On the other hand, the low level value of the substrate bias voltage Vb can be arbitrarily adjusted, and the average value (DC conversion value) of the substrate bias voltage Vb can be arbitrarily set by this low level value. Further, the frequency of the substrate bias power Eb can also be arbitrarily set within the range of, for example, 50 kW to 250 kW. The duty ratio of the substrate bias power Eb (the ratio of the period during which the value of the substrate bias voltage Vb becomes a high level value in one cycle of the substrate bias voltage Vb) can also be arbitrarily set. Here, the frequency of the substrate bias power Ed is set to, for example, 100 kHz, and the duty ratio is set to, for example, 30%.

Further, an appropriate position inside the wall portion forming the side surface of the vacuum chamber 12 and outside the revolution path of the objects to be processed 100, 100, ..., For example, sandwiching the central axis Xa of the vacuum chamber 12. A carbon heater 40 as a temperature control means is provided at a position opposite to the position where the magnetron cathode 16 is provided (the position on the left side in FIGS. 1 and 2). The carbon heater 40 is connected to a heater heating power supply device (not shown) outside the vacuum chamber 12. Then, the carbon heater 40 receives heat from the heater heating power supply device to generate DC or AC heater heating power, and in particular, heats the objects to be processed 100, 100, ....

Further, as shown in FIG. 1, a gas introduction pipe 42 for introducing various gases such as a discharge gas into the vacuum chamber 12 is provided at an appropriate position in the vacuum chamber 12, preferably in the vicinity of the filament 22. It is provided. Then, a plurality of individual, for example, four branch pipes 44, 46, 48 and 50 are coupled to the gas introduction pipe 42 outside the vacuum chamber 12. One of these four branch pipes 44, 46, 48 and 50, for example, the branch pipe 44 is for introducing a rare gas as a sputtering gas, for example, argon gas into the vacuum chamber 12, that is, illustrated. Not coupled to the source of the argon gas. The branch pipe 44 for argon gas has, for example, an opening / closing valve 44a as an opening / closing means for opening / closing the flow of the argon gas, and a mass flow controller 44b as a flow rate controlling means for controlling the flow rate of the argon gas. And are provided. Then, one of the other branch pipes 46, 48 and 50, for example, the branch pipe 46 is for _{introducing, for example, hydrogen (H 2} ) gas as a cleaning gas into the vacuum chamber 12, that is, not shown. It is coupled to the hydrogen gas source. The branch pipe 46 for hydrogen gas is also provided with an on-off valve 46a for opening and closing the flow of the hydrogen gas and a mass flow controller 46b for controlling the flow rate of the hydrogen gas. Further, one of the other branch pipes 48 and 50, for example the branch pipe 48, is for introducing, for example, nitrogen as a first reactive gas into the vacuum chamber 12, that is, of the nitrogen gas (not shown). It is bound to the source. The branch pipe 48 for nitrogen gas is also provided with an on-off valve 48a for opening and closing the flow of the nitrogen gas and a mass flow controller 48b for controlling the flow rate of the nitrogen gas. The remaining branch pipe 50 is for introducing a hydrocarbon-based gas as a second reactive gas, for example, acetylene gas, into the vacuum chamber 12, that is, it is coupled to a supply source of the acetylene gas (not shown). Has been done. The branch pipe 48 for acetylene gas is also provided with an on-off valve 50a for opening and closing the flow of the acetylene gas and a mass flow controller 50b for controlling the flow rate of the acetylene gas. The on-off valves 44a, 46a, 48a and 50a are manually operated, but the mass flow controllers 44b, 46b, 48b and 50b are controlled by the main controller 52 as a control means described later. These gas introduction pipes 42, branch pipes 44, 46, 48 and 50, on-off valves 44a, 46a, 48a and 50a, and mass flow controllers 44b, 46b, 48b and 50b (strictly speaking, the main controller). It functions as a gas introduction means (including 52).

In addition, between the magnetron cathode 16 and the revolution path of the object 100 to be processed, in detail, the surface to be sputtered (strictly speaking, the outer surface of the earth shield 18) of the target 162 and the object 100 to be processed closest to the surface to be sputtered. A shutter 54 as a shutter means is provided at a position closer to the object to be processed 100 than the filament 22. The shutter 54 has a substantially rectangular flat plate shape, and both main surfaces thereof are in a state of being aligned with the surface to be sputtered of the target 162. Then, the shutter 54 moves (slides) in the horizontal direction as shown by an arrow 204 in FIG. 2 by a driving force of a motor as a shutter driving means (not shown). In other words, the shutter 54 is in an open state in which the surface to be sputtered of the target 162 is exposed toward the space where the objects to be processed 100, 100, ... Are placed, and the surface to be sputtered of the target 162 is exposed to the objects to be processed 100, 100, 100. It is possible to transition to a closed state that shields from the space where ，… is placed. The motor as a shutter driving means for driving the shutter 54 is also controlled by the main controller 52.

As described above, the main controller 52 controls the mass flow controllers 44b, 46b, 48b and 50b, and the motor as a shutter driving means. The main controller 52 also controls the sputter power supply device 20, the cathode power supply device 24, and the discharge power supply device 26 described above. Further, the main controller 52 also controls the motor 36 as a rotation driving means. Such a main controller 52 is realized by, for example, a personal computer. The lines connecting the main controller 52 and each control target by the main controller 52 are not shown in consideration of the legibility of the drawings.

According to the present embodiment, the magnetron sputtering apparatus 10 can be used to form, for example, a titanium nitride film as a decorative film on the surface of the objects to be processed 100, 100, ..., So to speak, the surface to be processed. Further, a titanium nitride film can be formed as the decorative film. Strictly speaking, a titanium layer as an intermediate layer is formed prior to the formation of these decorative coatings. On top of that, the decorative coating as a main layer is formed. By providing the titanium layer as the intermediate layer in this way, the adhesion of the decorative coating film to the surface to be processed of the objects to be processed 100, 100, ..., Which is the object of film formation, can be improved.

Specifically, first, the objects to be processed 100, 100, ... Are installed in the vacuum chamber 12, that is, the objects to be processed 100, 100, ... Are attached to the holders 28, 28, ... Then, the inside of the vacuum chamber 12 is exhausted by the vacuum pump until the pressure P reaches ^{, for example, about 2 × 10 -3 Pa.} After this so-called evacuation, or in parallel with this evacuation, the motor 36 is driven and the self-revolution of the objects to be processed 100, 100, ... Is started. Then, the carbon heater 40 heats the objects to be processed 100, 100, ... To, for example, about 150 ° C. As a result, the impurity gas contained in the objects to be treated 100, 100, ... Is discharged, and the so-called degassing treatment is performed. In this degassing treatment, the shutter 54 is conventionally closed (to prevent contamination of the sputtered surface of the target 162), but the target 162 is covered by the pre-sputtering treatment described later. It may be in the open state (because the sputtered surface is cleaned).

After this degassing treatment is performed for a predetermined time (about 30 minutes to 1 hour), the heating by the carbon heater is stopped, and then the discharge cleaning treatment is performed. In this discharge cleaning process, the shutter 54 is opened. Then, the cathode power Ec is supplied to the filament 22. As a result, the filament 22 is heated to 2000 ° C. or higher, and thermions are emitted from the filament 22. At the same time, the electric power Ed for discharge is supplied to the filament 22. That is, the vacuum chamber 12 is used as an anode and the filament 22 is used as a cathode, and the discharge power Ed is supplied to both of them. As a result, the thermions emitted from the filament 22 as the cathode are directed toward the wall of the vacuum chamber 12 which is the anode, and are particularly close to the filament 22 and have the same potential as the vacuum chamber 12. Accelerate towards. In this state, argon gas is introduced into the vacuum chamber 12. Then, the accelerated thermions collide with the argon gas particles, and the impact causes the argon gas particles to be ionized to generate plasma 300. Here, since the magnetic field generated by the permanent magnet 166 described above is generated in the vicinity of the surface to be sputtered of the target 162 including the periphery of the filament 22, the thermions emitted from the filament 22 exert the action of this magnetic field. Receive and spiral. As a result, the frequency of thermions colliding with the argon gas particles increases, and the plasma 300 becomes denser. Such an aspect of the plasma 300 is an arc discharge with a low voltage and a large current. Further, hydrogen gas is introduced into the vacuum chamber 12. Then, the hydrogen gas particles are also ionized to form the plasma 300. The introduction of the argon gas into the vacuum chamber 12 and the introduction of the hydrogen gas into the vacuum chamber 12 may be started at the same time.

When the substrate bias power Eb is supplied to the objects to be processed 100, 100, ... In the state where the plasma 300 is generated by the arc discharge in this way, the argon ions and hydrogen ions in the plasma 300 are respectively processed. It is positively incident on the surface to be treated of the object 100, particularly the surface to be processed of the object 100 to be treated which is exposed to the plasma 300. As a result, the sputtering action caused by the argon ions colliding with the surface to be treated of each object 100 to be treated and the hydrogen ion chemically react with the impurities adhering to the surface to be treated of each object 100 to be treated. By the chemical reaction action, impurities are removed from the surface to be treated of each of the objects to be treated 100, that is, a discharge cleaning treatment is performed. The argon gas in this discharge cleaning process functions as a discharge gas for generating the plasma 300, and also functions as a cleaning gas for realizing the discharge cleaning process by the sputtering action as described above. On the other hand, the hydrogen gas functions as a cleaning gas that realizes a discharge cleaning process by a chemical reaction as described above, and also functions as a discharge gas.

In this discharge cleaning process, the flow rate of argon gas is set to, for example, 50 mL / min, and the flow rate of hydrogen gas is set to, for example, 150 mL / min. The pressure P in the vacuum chamber 12 is, for example, 0.2 Pa. Further, the discharge power Ed is set to, for example, 500 W. Specifically, the discharge power supply device 26, which is the supply source of the discharge power Ed, operates in the constant voltage mode as described above so that the discharge voltage Vd, which is a voltage component of the discharge power Ed, becomes 50 V. .. In this state, the heating temperature of the filament 22 is controlled by the cathode power Ec so that the discharge current Id, which is a current component of the discharge power Ed, becomes 10 A, that is, the amount of thermions emitted from the filament 22 is controlled. To. As a result, the discharge power Ed is set to 500 W (= 50 V × 10 A). In addition, for the substrate bias power Eb, the average value of the substrate bias voltage Vb, which is a voltage component thereof, is −600 V. Incidentally, when the average value of the substrate bias voltage Vb is -600V, the low level value of the substrate bias voltage Vb is about -873V (= [-600V- {37V x 0.3}] /0.7). Is. Further, the substrate bias current Ib, which is a current component of the substrate bias power Eb at this time, is about 4A. This means that the relatively large substrate bias current Ib of about 4 A is flowing through the objects to be processed 100, 100, ... That is, so many ions are flowing to the objects 100, 100, ... It is shown that the light is incident on the surface to be treated, and that a larger discharge cleaning treatment effect (particularly, a bombardment effect due to the sputtering action of argon ions) can be obtained.

After this discharge cleaning process is performed for a predetermined time (about 30 minutes), a pre-sputtering process for cleaning the surface to be sputtered of the target 162 is performed. Therefore, the introduction of hydrogen gas into the vacuum chamber 12 is stopped. At the same time, the shutter 54 is closed. Then, the sputtering power Es is supplied to the magnetron cathode 16. That is, the vacuum chamber 12 is used as an anode and the magnetron cathode 16 is used as a cathode, and the sputtering power Es is supplied to both of them. Then, the argon ions in the plasma 300 are accelerated toward the magnetron cathode 16 which is a cathode, and particularly collide with the surface to be sputtered of the target 162, that is, sputter. By the sputtering action by the argon ion, dirt such as oxides and organic impurities adhering to the surface to be sputtered of the target 162 is removed, and the surface to be sputtered is cleaned. In this pre-sputtering process, the argon gas particles are also discharged by supplying the sputtering power Es, and a high voltage and small current glow discharge is induced. That is, the plasma 300 is in a state that includes (combines) the glow discharge in addition to the above-mentioned arc discharge. Then, the surface to be sputtered of the target 162 is efficiently cleaned by the action of the extremely high-density plasma 300 including the arc discharge. Further, as described above, since the magnetic field is generated in the vicinity of the sputtered surface of the target 162, the density of the plasma 300 in the vicinity of the sputtered surface of the target 162 becomes particularly high. As a result, the surface to be sputtered of the target 162 can be cleaned more efficiently. In particular, since the density of the plasma 300 in the region following the gap 166c of the permanent magnet 166 described above is high, this region is sputtered more efficiently (intensively).

The flow rate of argon gas in this pre-sputtering treatment is, for example, 150 mL / min. The pressure P in the vacuum chamber 12 is, for example, 0.5 Pa. Further, the discharge power Ed is set to, for example, 500 W (= 50 V × 10 A). In addition, the sputtering power Es is set to, for example, 8 kW. The sputtering power supply device 20, which is a supply source of the sputtering power Es, operates in a constant power mode so that the sputtering power Es becomes constant as described above. Further, regarding the substrate bias power Eb, the average value of the substrate bias voltage Vb, which is a voltage component thereof, is set to −100 V. Incidentally, when the average value of the substrate bias voltage Vb is -100V, the low level value of the substrate bias voltage Vb is about -159V (= [-100V- {37V × 0.3}] /0.7). Is. In this pre-sputtering process, the shutter 54 is closed, so that the dirt removed from the surface to be sputtered of the target 162 adheres to the surface to be processed of the objects to be processed 100, 100, ... The surface to be processed of the processed objects 100, 100, ... Will not be soiled.

After this pre-sputtering treatment is performed for a predetermined time (about 3 to 5 minutes), a film forming treatment for forming a titanium layer as an intermediate layer is performed. Therefore, the shutter 54 is opened. Then, the argon ions in the plasma 300 collide with the surface to be sputtered of the target 162 after the pre-sputtering treatment, and the particles of the target 162, that is, the titanium particles are knocked out from the surface to be sputtered. Then, the titanium particles as so-called sputtered particles that have been knocked out are subjected to the treatment of the object 100 to be processed, which is particularly exposed to the plasma 300 toward the surface to be processed of the objects 100, 100, .... It flies toward the surface, adheres to the surface to be treated, and accumulates. As a result, a titanium layer is formed on the surface to be treated of the objects to be treated 100, 100, .... Here, the titanium particles ejected from the surface to be sputtered of the target 162 pass through the extremely high-density plasma 300 including an arc discharge while flying toward the surface to be processed of the objects to be processed 100, 100, ... pass. This activates the sputtered particles and further ionizes them so that they have at least higher energy than in the neutral state. By doing so, the hardness and densification of the titanium layer can be achieved.

The flow rate of argon gas in the film forming process for forming the titanium layer is, for example, 150 mL / min. The pressure P in the vacuum chamber 12 is, for example, 0.5 Pa. Further, the discharge power Ed is set to, for example, 1000 W. Specifically, the filament 22 is heated by the cathode power Ec so that the discharge voltage Vd, which is a voltage component of the discharge power Ed, is 50 V, and the discharge current Id, which is a current component of the discharge power Ed, is 20 A. The temperature is controlled. As a result, the discharge power Ed is set to 1000 W (= 50 V × 20 A). In addition, the sputtering power Es is set to, for example, 8 kW. As for the substrate bias power Eb, the average value of the substrate bias voltage Vb, which is a voltage component thereof, is set to −100 V. By performing the film forming process under such conditions for, for example, 5 to 10 minutes, a titanium layer having a film thickness of about 0.1 μm to 0.3 μm is formed. In the film forming process for forming the titanium layer, the region following the gap 166c of the permanent magnet 166 is sputtered more efficiently, as in the case of the above-mentioned pre-sputtering process.

After the film forming process for forming the titanium layer is performed, the film forming process for forming the titanium nitride film is performed. Therefore, nitrogen gas is introduced into the vacuum chamber 12. Then, the particles of the nitrogen gas are decomposed by the plasma 300. Then, the decomposed nitrogen gas particles, particularly nitrogen ions, react with sputtered particles flying toward the surface to be treated, particularly titanium ions, of the object to be treated 100, 100, ..., And the object to be treated 100. , 100, ... Adheres to the surface to be treated, and particularly adheres to and deposits on the surface to be treated of the object 100 to be treated, which is exposed to the plasma 300. As a result, a titanium nitride film, which is a reaction film of nitrogen and titanium, is formed on the surface to be treated of the objects to be treated 100, 100, ....

In the film forming process for forming the titanium nitride film, the flow rate of argon gas is, for example, 150 mL / min. The flow rate of nitrogen gas is, for example, 40 mL / min. However, immediately after the start of introduction of this nitrogen gas, the flow rate of the nitrogen gas is not immediately set to the expected flow rate of 40 mL / min, but is stepwise or continuous over a predetermined time (several minutes). Is gradually increased to the desired flow rate of 40 mL / min. As a result, a so-called inclined layer is formed in the vicinity of the boundary between the titanium nitride film and the titanium layer, in which the composition ratio of nitrogen and titanium changes stepwise or continuously along the film thickness direction of the titanium nitride film. By forming such an inclined layer, the adhesion of the titanium nitride film can be further improved. Further, in the film forming process for forming the titanium nitride film, the pressure P in the vacuum chamber 12 is set to, for example, 0.5 Pa. Further, the discharge power Ed is set to, for example, 1000 W (= 50 V × 20 A). In addition, the sputtering power Es is set to, for example, 8 kW. As for the substrate bias power Eb, the average value of the substrate bias voltage Vb, which is a voltage component thereof, is set to −100 V.

In the film forming process for forming the titanium nitride film, the titanium particles knocked out from the surface to be sputtered of the target 162 are in the process of flying toward the surface to be processed of the objects to be processed 100, 100, ... It is activated by passing through an extremely dense plasma 300 containing an arc discharge, which has at least a higher energy than the neutral state, and is particularly efficiently ionized. Similarly, the nitrogen gas particles are also activated by the high density plasma 300 and ionized more efficiently. By improving the ionization rate, the amount of ions incident on the surface to be treated of the objects to be treated 100, 100, ... Is increased, so that the hardness of the titanium nitride film formed on the surface to be treated can be further increased. At the same time, since the mutual bonding force between the titanium particles and the nitrogen particles forming the titanium nitride film is increased, the titanium nitride film can be densified. In the film forming process for forming the titanium nitride film, the region following the gap 166c of the permanent magnet 166 is larger than that in the above-mentioned pre-sputtering process and the film forming process for forming the titanium layer. It is sputtered efficiently. As a result, as shown in FIG. 4, sputter marks having a substantially rectangular loop shape (or oval loop shape), so-called erosion John region 162a, appear so as to follow the gap 166c.

When the titanium nitride film having a predetermined film thickness is formed (assumed to be) by the film forming process for forming the titanium nitride film, the introduction of argon gas and nitrogen gas into the vacuum chamber 12 is stopped. .. At the same time, the supply of the sputtering power Es to the magnetron cathode 16 is stopped, and the supply of the cathode power Ec and the discharge power Ed to the filament 22 is stopped. As a result, the plasma 300 disappears. Further, the supply of the substrate bias power Eb to the objects to be processed 100, 100, ... Is stopped. Then, a certain cooling period is set while the pressure in the vacuum chamber 12 is gradually returned to the vicinity of the atmospheric pressure. After that, the drive of the motor 36 is stopped, so that the rotation of the objects to be processed 100, 100, ... Is stopped. Then, the inside of the vacuum chamber 12 is opened to the outside, and the objects to be processed 100, 100, ... Are taken out from the inside of the vacuum chamber 12. This completes a series of processes including the film forming process for forming the titanium nitride film.

FIG. 5 shows the properties of the titanium nitride film formed by a series of treatments in this manner, in particular, a film forming process for forming the titanium nitride film is performed over 6 hours. The object to be processed 100 here is a cylindrical decorative pipe made of SUS304, which has a diameter of 50 mm and a length of 300 mm and is mirror-finished. Further, as a comparison target, by stopping the supply of the cathode power Ec and the discharge power Ed to the filament 22, the mode of the plasma 300 is intentionally made solely by glow discharge, that is, the same as the sputtering method in the prior art described above. The state of the above was simulated, and the film-forming process for forming titanium nitride was also performed for 6 hours by this pseudo-configured conventional technique. The properties of the titanium nitride film formed by this pseudo-conventional technique are also shown in FIG.

As shown in FIG. 5, according to the titanium nitride film according to the present embodiment, the value of Knoop hardness is particularly large as compared with the titanium nitride film according to the prior art. That is, according to the present embodiment, it can be seen that a titanium nitride film having a higher hardness than that of the prior art is formed. This is mainly due to the fact that, according to the present embodiment, the ionization rate by the plasma 30 is higher than that of the prior art, that is, the amount of ions incident on the surface to be treated of the object 100 to be treated is large. This can be seen from the fact that the value of the substrate bias current Ib is much larger than that of the prior art according to the present embodiment. Further, the titanium nitride film according to the present embodiment has a smaller film thickness than the titanium nitride film according to the prior art. From this, it can be seen that according to the present embodiment, a denser titanium nitride film is formed as compared with the prior art. Further, paying attention to the color tone, the titanium nitride film according to the present embodiment has a larger L value, a value, and b value than the titanium nitride film according to the prior art. This means that the titanium nitride film according to the present embodiment exhibits a bright golden color tone as compared with the titanium nitride film according to the prior art.

FIG. 6 shows an external photograph of the decorative pipe on which the titanium nitride film according to the present embodiment shown in FIG. 5 is formed and the decorative pipe on which the titanium nitride film formed by the prior art shown in FIG. 5 is formed. .. As can be seen from FIG. 6, the titanium nitride film according to the present embodiment exhibits a bright golden color tone. On the other hand, the titanium nitride film produced by the prior art exhibits a dull golden color tone. From this as well, it is clear that according to the present embodiment, a titanium nitride film having a bright golden color tone is formed as compared with the prior art.

Next, a case where a titanium carbonitride film is formed as a decorative film will be described. In this case, instead of the film forming process for forming the titanium nitride film in the series of processes described above, the process for forming the titanium nitride film is performed. That is, after the film forming process for forming the titanium layer as the intermediate layer is performed, the film forming process for forming the titanium nitride film is performed.

Specifically, nitrogen gas is introduced into the vacuum chamber 12, and acetylene gas is introduced into the vacuum chamber 12. Then, the nitrogen gas particles are decomposed by the plasma 300, and the acetylene gas particles are also decomposed by the plasma 300. Then, these decomposed nitrogen gas particles, particularly nitrogen ions, and the decomposed acetylene gas particles, particularly carbon ions, fly toward the surface to be treated of the objects to be treated 100, 100, ... In particular, it reacts with titanium ions and adheres to the surface to be treated of the objects to be processed 100, 100, ..., And in particular, to the surface to be processed of the object to be processed 100 exposed to the plasma 300. accumulate. As a result, a titanium carbonitride film, which is a reaction film of nitrogen, carbon, and titanium, is formed on the surface to be treated of the objects to be treated 100, 100, ....

In the film forming process for forming the titanium nitride film, the flow rate of argon gas is, for example, 150 mL / min. The flow rate of nitrogen gas is set to, for example, 20 mL / min, and the flow rate of acetylene gas is also set to, for example, 20 mL / min. However, immediately after the start of introduction of these nitrogen gas and acetylene gas, the flow rate of each of the nitrogen gas and acetylene gas is not immediately set to the expected flow rate of 20 mL / min, but a predetermined time (several minutes) is set. It is multiplied and gradually or continuously gradually increased, and finally the desired flow rate of 20 mL / min is obtained. As a result, in the vicinity of the boundary between the titanium carbonitide film and the titanium layer, the composition ratio of nitrogen and carbon and titanium changes stepwise or continuously along the film thickness direction of the titanium carbonitride film. Is formed. By forming such an inclined layer, the adhesion of the titanium carbonitride film can be further improved. The other conditions are the same as in the film forming process for forming the titanium nitride film. That is, the pressure P in the vacuum chamber 12 is 0.5 Pa. The discharge power Ed is 1000 W (= 50 V × 20 A). Further, the sputtering power Es is set to 8 kW. As for the substrate bias power Eb, the average value of the substrate bias voltage Vb, which is a voltage component thereof, is set to −100 V. In the film forming process for forming the titanium nitride film, the region following the gap 166c of the permanent magnet 166 is sputtered more efficiently as in the film forming process for forming the titanium nitride film. As shown in FIG. 4, a substantially rectangular loop-shaped erosion John region 162a appears so as to follow the gap 166c.

FIG. 7 shows the properties of the titanium nitride film formed by performing the film forming process for forming the titanium nitride film over 6 hours. The object to be processed 100 here is a square plate made of SUS304 that has been mirror-finished with a side length of 50 mm and a thickness of 1 mm. Further, as a comparison target, a pseudo-conventional technique similar to that in FIGS. 5 and 6 described above is configured, and the film-forming process for forming titanium nitride is also performed for 6 hours by this pseudo-conventional technique. Went over. The properties of the titanium nitride film formed by this pseudo-conventional technique are also shown in FIG.

As shown in FIG. 7, according to the titanium nitride film according to the present embodiment, the value of Knoop hardness is particularly large as compared with the titanium nitride film according to the prior art. That is, it can be seen that, as with the titanium nitride film, the titanium nitride film has a higher hardness than the prior art according to the present embodiment. As described above, according to the present embodiment, the main reason for this is that the ionization rate of the plasma 30 is higher than that of the prior art, that is, the amount of ions incident on the surface of the object 100 to be processed is large. It is a factor. This can be seen from the fact that the value of the substrate bias current Ib is much larger than that of the prior art according to the present embodiment. In both the present embodiment and the prior art, the Knoop hardness value of the titanium nitride film shown in FIG. 7 is larger than the Knoop hardness value of the titanium nitride film shown in FIG. This is probably because the titanium nitride film contains carbon, so that the titanium nitride film has a higher hardness than the titanium nitride film. Focusing on the film thickness, the titanium nitride film according to the present embodiment has a smaller film thickness than the titanium nitride film according to the prior art. From this, it can be seen that, as with the titanium nitride film, according to the present embodiment, a denser titanium nitride film is formed as compared with the prior art. Incidentally, in both the present embodiment and the prior art, the film thickness of the titanium nitride film shown in FIG. 7 is larger than the film thickness of the titanium nitride film shown in FIG. This is probably because the titanium nitride film contains carbon, and in particular, titanium carbide (TiC) is formed, so that the titanium nitride film is thicker than the titanium nitride film. Probably due to. The color tone cannot be judged from FIG. 7 at all.

In addition, the following experiments were conducted.

That is, with respect to the titanium nitride film, the titanium nitride film was formed by keeping the flow rate of argon gas as a sputter gas constant and changing the flow rate of nitrogen gas as a reactive gas. Then, it was confirmed how the color tone of the titanium nitride film changes due to the difference in the flow rate of the nitrogen gas. Further, regarding the titanium nitride film, the titanium nitride film was formed by keeping the flow rate of argon gas as a sputter gas constant and changing the mutual flow rate ratio of nitrogen gas and acetylene gas as reactive gases. The flow rate of the entire reactive gas including both nitrogen gas and acetylene gas was kept constant. Then, it was confirmed how the color tone of the titanium nitride film changes due to the difference in the flow rate ratios of the nitrogen gas and the acetylene gas. Further, for reference, a titanium carbide film was formed by using only acetylene gas as the reactive gas. Then, the color tone of this titanium carbide film was also confirmed. These results are shown in FIG. The object to be processed 100 here is the same as that in FIG. 7 described above, that is, it is a square plate made of SUS304 that has been subjected to mirror surface processing having a side length dimension of 50 mm and a thickness dimension of 1 mm.

As shown in FIG. 8, the color tones of each of the seven samples 1 to 7 were confirmed. The sample 1 is the material itself of the object to be treated 100 that has not been subjected to any treatment. Further, the samples 2 and 3 have a titanium nitride film formed therein, and the flow rates of nitrogen gas during the film forming process for forming the titanium nitride film are different from each other. Further, the samples 4 to 6 have a titanium nitride film formed therein, and the flow rate ratios of the nitrogen gas and the acetylene gas at the time of the film forming process for forming the titanium nitride film are different from each other. is there. Then, in the sample 7, a titanium carbide film for reference is formed.

As can be seen from FIG. 8, for example, the samples 2 and 3 on which the titanium nitride film is formed show a golden color tone, but the color tone differs depending on the difference in the flow rate of nitrogen gas. Specifically, it is presumed that the smaller the flow rate of the nitrogen gas, the lighter the gold color, and the larger the flow rate of the nitrogen gas, the darker the gold color. Further, the colors of the samples 4 to 6 on which the titanium carbonitride film is formed differ depending on the difference in the flow rate ratio between the nitrogen gas and the acetylene gas. Generally speaking, it is presumed that the smaller the flow rate ratio of acetylene gas to nitrogen gas, the more brownish the color tone is exhibited, and ultimately, the closer to the properties of the titanium nitride film, the golden color tone is exhibited. On the other hand, it is presumed that the larger the flow rate ratio of acetylene gas to nitrogen gas, the more grayish the color tone is exhibited, and finally, the property of the titanium carbide film of Sample 7 is approached and the light gray color tone is exhibited. Will be done. That is, by appropriately setting the flow rate ratio of acetylene gas to nitrogen gas, for example, by appropriately setting it in the range of 0 to 50, a titanium nitride film and / or a titanium carbonitride film exhibiting various color tones can be obtained. Can be formed. The titanium carbide film of sample 7 exhibits the light gray color tone, and this color tone seems to be substantially the same as the material itself of the object 100 to be processed of sample 1, that is, SUS304 itself. Be done.

FIG. 9 shows an external photograph of each sample 1 to 7. Each of these samples 1 to 7 is blasted on one half surface (the left half surface in FIG. 9) in order to make it easy to understand the difference in color tone. As can be seen from FIG. 9, for example, with respect to the samples 2 and 3 on which the titanium nitride film is formed, it is clear that the golden color tone differs depending on the difference in the flow rate of the nitrogen gas. Then, it is clear that the colors of the samples 4 to 6 on which the titanium carbonitride film is formed are different due to the difference in the mutual flow rate ratio of the nitrogen gas and the acetylene gas.

In order to obtain these results, for example, it is desirable that the discharge current Id, which is a current component of the discharge power Ed, is 5 A or more. This is because when the discharge current Id is smaller than 5A, the density of the plasma 300 becomes insufficient, and a sufficient reaction cannot be obtained to form a high-hardness decorative film, that is, the high-hardness decorative film is formed. Because you can't do it. Therefore, it is desirable that the discharge current Id is 5 A or more.

Further, it is desirable that the average value of the substrate bias voltage Vb, which is a voltage component of the substrate bias power Eb, is in the range of −50 V to −300 V. If the absolute value of the average value of the substrate bias voltage Vb is excessively small, the impact effect of the ions incident on the surface to be processed of each object to be processed 100 becomes insufficient, and the adhesion and denseness of the decorative film are sufficiently sufficient. It cannot be obtained, and the decorative film having high hardness is not formed. On the other hand, if the absolute value of the substrate bias voltage Vb is excessively large, the so-called edge effect, in which the discharge is concentrated at the corners (edges) of the respective objects to be processed 100, becomes remarkable, which is inconvenient. From these facts, the average value of the substrate bias voltage Vb is preferably −50V to −300V, and more preferably −75V to −150V.

As described above, according to the present embodiment, although the film formation treatment is performed by the magnetron sputtering method, the modified film can be formed by using the arc discharge type magnetron sputtering method using arc discharge, for example. It is possible to form a bright golden titanium nitride film having a higher hardness than before. It is also possible to form titanium nitride films having high hardness and various color tones. This is expected to greatly contribute to the use of the modified coating and the expansion of the target.

The present embodiment is a specific example of the present invention, and does not limit the scope of the present invention.

For example, acetylene gas has been adopted as the hydrocarbon gas, but the acetylene gas is not limited to this, and other hydrocarbon gases such as methane gas, ethylene gas, and ethane gas may be adopted. However, from the relationship of the composition ratio of carbon and hydrogen in these hydrocarbon-based gases, acetylene gas is the most suitable, that is, the titanium carbonitride film can be formed most efficiently.

Further, as the magnetron cathode 16, a magnet-fixed type in which the permanent magnet 166 is fixed, that is, the position of the permanent magnet 166 does not move is adopted, but the present invention is not limited to this. For example, even if a so-called wide area erosion type magnet is adopted in which the permanent magnet 166 moves along the back surface of the target 162 to sputter the surface to be sputtered of the target 166 over a wide area and thus reduce the non-erosion region. Good.

Further, in the present embodiment, a titanium film as an intermediate layer is provided, but this titanium film may not be provided. However, as described above, when the titanium film is provided, the adhesion of the decorative film as the main layer can be improved.

In addition, the target 162 of the magnetron cathode 16 is not limited to a substantially rectangular flat plate shape, but may be, for example, a substantially disc shape, and in the extreme, the surface to be sputtered is a curved surface. May be good. Further, the shape of the filament 22 is appropriately determined according to the shape of the target 16 (surface to be sputtered).

The magnetron cathode 16 is not limited to one, and a plurality of magnetron cathodes 16 may be provided. In this case, it is desirable that a plurality of the magnetron cathodes 16 are provided along the circumferential direction of the central axis Xa of the vacuum chamber 12. At the same time, it is desirable that the filament 22 is attached to each magnetron cathode 16. According to this configuration, the film formation speed can be improved, and thus the productivity can be improved.

Further, bipolar pulse power is adopted as the substrate bias power Eb, but the present invention is not limited to this. For example, when the objects to be processed 100, 100, ... Are conductive substances, DC electric power may be adopted. However, since abnormal discharge may occur due to gas or the like contained in the objects to be processed 100, 100, ..., It is desirable to adopt bipolar pulse power from the viewpoint of preventing such abnormal discharge. Further, pulse power or high frequency power other than this bipolar pulse power may be adopted.

10 Magnetron Sputtering Device 12 Vacuum Tank 16 Magnetron Cathode 20 Sputtering Power Supply Device 22 Filament 24 Cathode Power Supply Device 26 Discharging Power Supply Device 38 Board Bias Power Supply Device 42 Gas Introductory Pipe 44, 46, 48, 50 Branch Pipes 44a, 46a, 48a, 50a Opening and Closing Valves 44b, 46b, 48b, 50b Mass flow controller 50 Main controller 100 Processed object 162 Target 164 Magnet unit 300 Plasma

Claims (3)

A gas introduction process in which a sputter gas and a reactive gas are introduced into a vacuum chamber in which a workpiece is housed and a magnetron cathode is provided.
A sputtering power supply process in which the particles of the sputtering gas are discharged and plasma is generated inside the vacuum chamber by supplying sputtering power to both of them using the vacuum chamber as an anode and the magnetron cathode as a cathode.
A bias power supply process in which the vacuum chamber is used as an anode and the object to be processed is used as a cathode to supply bias power to both of them.
Equipped with
The magnetron cathode has a titanium target and a magnetic field generating means for generating a magnetic field in the vicinity of the surface to be sputtered of the target, and the surface to be sputtered is provided so as to face the surface to be processed of the object to be processed. Has been
A reaction containing titanium particles ejected from the surface to be sputtered by collision of ions in the plasma with the surface to be sputtered and reactive particles which are particles of the reactive gas decomposed by the plasma. A film is formed on the surface to be treated as a decorative film.
In the method of forming a decorative film by the magnetron sputtering method,
A thermoelectron emission process in which the filament is heated by supplying electric power for thermionic emission to a filament provided between the surface to be sputtered and the surface to be processed to emit thermions.
An arc discharge inducing process in which the thermoelectrons are accelerated and an arc discharge is induced around the filament by supplying electric power for discharge to both of them with the vacuum chamber as an anode and the filament as a cathode.
Further equipped,
In the gas introduction process, introducing only nitrogen gas or the nitrogen gas and a hydrocarbon gas as the reactive gas into the inside of the vacuum chamber.
A method for forming a decorative film by a magnetron sputtering method, which comprises. A nitrogen gas and a hydrocarbon-based gas are introduced into the vacuum chamber as the reactive gas, and the flow rate ratio of the hydrocarbon-based gas to the nitrogen gas is greater than 0 and 50 or less .
The method for forming a decorative film by the magnetron sputtering method according to claim 1. Nitrogen gas and hydrocarbon gas are introduced into the vacuum chamber as the reactive gas, and the hydrocarbon gas is acetylene gas.
The method for forming a decorative film by the magnetron sputtering method according to claim 1.