JPH07278800A - Device for forming coated film and method therefor - Google Patents

Abstract

PURPOSE:To provide a device for forming a coated film and a method therefor for forming a metal coated film having good adhesion property by executing resistance heating on a ceramic coated film formed by executing ion-plating on a base material. CONSTITUTION:In a vacuum tank 51, a base material 14 connected to a bias power source 15 is subjected to Ti ion-plating in the presence of gaseous N2 as reaction gas by a HCD gun 21 to form a TiN coated film thereon, and then Au alloy vapor prepared by resistance heating is ionized by Ar ions from the output-controlled HCD gun 21 to form an Au alloy coating film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film forming apparatus and a film forming method for forming a metal film on a ceramic film.

[0002]

2. Description of the Related Art Titanium Nitride (TiN)
Is hard and chemically stable,
It is applied in many fields. For example, in the decorative field, TiN
Has a golden color and has good adhesion, so it is used as a base material for stainless steel in watch cases and bands.
Many products having an N coating film are manufactured. Then, for the formation of this TiN film, an ion plating technique, in particular, an ion plating technique by hollow cathode discharge (HCD), which has an ionization rate of about 40%, which is one digit or more larger than the others, is adopted. The film is dense and has good adhesion.

However, since the color tone of TiN is slightly different from that of gold (Au), and the reflectance is a little low,
There have been attempts to form further Au alloy coatings on top of the TiN coating. However, not only when the Au alloy coating is formed by resistance heating, but also when it is formed by RF ion plating, the adhesion of the Au alloy coating to the TiN coating is not sufficient, and so far it has not been practically used. I can't get anything to withstand.

That is, even if a metal such as Au or an Au alloy is evaporated on the TiN film by resistance heating to form a film, the vaporized metal vapor is in the atomic or molecular state and is ionized. Absent. Therefore, TiN
A large value cannot be expected because the adhesion force when deposited on the film and formed into a film depends only on the Van der Waals force.

Further, another device or power source is required to ionize the metal vapor. For example, 2-38
No. 926, in the embodiment using the film forming apparatus shown in FIG. 3, metal titanium 5 is evaporated by an electron beam evaporation device 4 as a direct current ion plating device while introducing nitrogen gas from the gas introduction system 2. , A titanium nitride film is formed on the substrate 3 by active reaction vaporization in which ionization is performed by a direct current ionization power source 6, and then gold 7 is evaporated by resistance heating while continuing the titanium nitride film formation to form a titanium nitride-gold alloy. A film is formed, and further, the evaporation of titanium and the introduction of nitrogen gas are stopped, and argon gas is introduced from the gas introduction system 2 to continue the evaporation of gold and apply high-frequency power to the high-frequency electrode coil 8 to remove only gold. A technique for forming a gold coating by high-frequency ion plating is disclosed (the same publication, column 3, line 12 to line 4).
Column line 11). The direct current ion plating mechanism includes a hollow cathode ion plating and a hot cathode ion plating in addition to the active reaction vapor deposition (the second column, line 19 to line 22 of the same publication). . However, the adhesion of the Au film obtained by this method is not yet satisfactory.

Further, as a means for forming a laminated film, Japanese Patent Publication No.
No. 147968 discloses a hollow cathode electron gun (1
In 1), Al and oxide cannot be evaporated, but
This is possible with the transverse electron gun (12), so this type of material is evaporated by the second evaporation source (8) and other materials are evaporated by the first evaporation source (7) to form a composite film, a laminated film. A film can be formed (page 3, lower right column, line 19 to page 4, upper left column, line 4), and the evaporation material (6) in the first evaporation source (7) by the hollow cathode electron gun (11). Evaporate
At the same time, the second evaporation source (8) is generated by the electron gun (12).
The evaporation material (6) therein is evaporated (the same publication, page 3, lower left column, lines 10 to 20).

During the ion plating, Ti is evaporated from the first evaporation source (7) and Si is evaporated from the second evaporation source (8), while O _{2 is used} as a reaction gas.
Is introduced, a composite film of TiO + SiO can be formed on the substrate (4) (the same publication, page 3, lower right column, lines 12 to 16).
Line), a laminated film can be formed by one step of ion plating by sequentially evaporating each evaporation material (the same publication, page 3, upper left column, lines 3 to 5).

That is, what is disclosed here is a combination of the hollow cathode electron gun (11) and the electron gun (12), and TiO and SiO as the vapor deposition film. In addition to O ₂ as the reaction gas, Since N _{2 is} also disclosed (the same publication, page 3, lower right column, line 10), TiN may be included. However, it does not suggest any improvement in the adhesion of the metal coating to the ceramic coating.

In addition, Japanese Patent Laid-Open No. 1-96372 discloses a technique of using an EB gun and a plasma gun together. According to the embodiment, the EB gun is used as an evaporation means and the plasma gun is used as a plasma generation mechanism (the same publication, page 2, upper right column, line 13 to lower left column, line 5), which is a film forming material. Is separately performed (page 20, upper left column, line 20) in the same publication, and a plurality of film forming materials are not evaporated.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and a film forming apparatus for forming a metal film having good adhesion on a ceramic film on a substrate by a resistance heating method. It is an object to provide a method for forming the film. It should be noted that the ceramics here mean metal nitrides, oxides, carbides and borides, which are hard and dense.

[0011]

[Means for Solving the Problems] The above object is to evaporate a substrate connected to a bias power source and a hollow cathode discharge electron gun for forming a ceramic coating on the substrate in a vacuum chamber. A first evaporation source for evaporating a raw material, an inlet for a reaction gas, and an evaporation source by resistance heating for forming a metal coating on the ceramic coating assisted by the hollow cathode discharge electron gun. And a film forming apparatus comprising two evaporation sources.

Further, the above-mentioned object is to evaporate the evaporation raw material of the first evaporation source by a hollow cathode discharge electron gun in the presence of a reaction gas with respect to a base material connected to a bias power source in a vacuum chamber to form a ceramic coating. And then vaporize the evaporation raw material of the second evaporation source by resistance heating, ionize the vapor of the evaporation raw material of the second evaporation source by the plasma from the hollow cathode discharge electron gun, and A method for forming a coating film, which comprises forming a metal coating film.

Further, the above object is to evaporate the evaporation raw material of the first evaporation source by the hollow cathode discharge electron gun in the presence of the reaction gas with respect to the base material connected to the bias power source in the vacuum chamber to form the ceramic coating. Then, while continuing the evaporation from the first evaporation source, the evaporation raw material of the second evaporation source is evaporated by resistance heating, and the vapor of the second evaporation source is evaporated by the plasma from the hollow cathode discharge electron gun. It is ionized to form a mixed film of the evaporation material of the first evaporation source and the evaporation material of the second evaporation source on the ceramic film, and further evaporation of the evaporation material from the second evaporation source and the A film forming method characterized by forming a metal film on the mixed film by continuing only ionization.

[0014]

Function: A ceramic coating is formed on a substrate to which a bias voltage is applied by ion-plating a metal with a hollow cathode discharge electron gun in the presence of a reaction gas. Then, the metal vapor evaporated by resistance heating is charge-exchanged with the plasma from the hollow cathode discharge electron gun and ionized to form a metal film on the ceramic film under bias voltage. That is, since the energy applied to the metal vapor is used to improve the adhesion to the ceramic coating, the metal coating having excellent adhesion is formed on the ceramic coating.

Furthermore, by interposing a mixed coating of ceramic and metal between the ceramic coating and the metal coating, a metal coating with even better adhesion is formed.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A film forming apparatus and a film forming method therefor according to embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic sectional view of a film forming apparatus according to an embodiment of the present invention. That is, generally, it is an apparatus capable of performing ion plating by hollow cathode discharge (HCD) and vapor deposition by resistance heating. To describe this in detail, the vacuum chamber 51 is connected to a vacuum pump (not shown) above it. It has a vacuum exhaust port 52 and is provided with a heat transfer vacuum gauge 53. The entire vacuum chamber 51 is at ground potential by the ground electrode 54.

A base 14 is attached above the inside of the vacuum chamber 51 so as to be connected to an external bias power source 15 so as to be rotatable in the direction of arrow p. An HCD gun (hollow cathode discharge electron gun) 21 is provided below the inside through the side wall from the outside of the vacuum chamber 51 together with an HCD crucible 22 as an HCD evaporation source. The HCD gun 21 is externally provided. Connected to the HCD power supply 23, and further to the DC power supply 26.
The HCD gun 21 to a negative potential, and the HCD crucible 2
2 is a positive potential. HCD for crucible 22 for HCD
Evaporation raw material 25 is loaded. HCD gun 21
An argon (Ar) gas inlet 24 for plasma is provided in the. Similarly, a resistance heating boat 32 made of tantalum (Ta) as an evaporation source for resistance heating, which is connected to an external resistance heating power source 33, is arranged in the lower part of the inside.
An evaporation raw material 35 for resistance heating is loaded therein.

Further, an HCD shutter 28 opened / closed in the direction of arrow q is provided directly above the HCD crucible 22, and a resistance heating shutter opened / closed in the direction of arrow r is provided immediately above the resistance heating boat 32. 38 is provided, and in FIG. 1, both shutters 28 and 38 are closed. And
When the HCD shutter 28 is in the closed state and the resistance heating shutter 38 is in the open state, the base material 14 cannot be seen from the HCD crucible 22. There is provided an opening for allowing Ar ions in the plasma, which emerge from 21 and recoil on the HCD crucible 22, to irradiate and ionize the vapor of the vaporization raw material 35 from the resistance heating boat 32. FIG. 2 is a diagram conceptually showing the situation.

In addition, a reaction gas inlet 44 is provided at the bottom of the vacuum chamber 51, a heater 16 for residual heat is provided just above the base material 14, and a portion directly below the HCD crucible 22 and the resistance heating boat 32. A heater 17 for auxiliary heating is provided on one side. The illustration of the power supply and connection of the heaters is omitted.

The coating film forming apparatus according to this embodiment is constructed as described above. Next, its function is as follows: gold (Au) and palladium as metal coatings are deposited on a titanium nitride (TiN) coating as a ceramic coating. Example 1 in the case of forming an Au alloy coating composed of (Pd) will be described.

Example 1 A watch case made of stainless steel was prepared as the base material 14. Crucible 22 for HCD
Is charged in Ti and the resistance heating boat 32 is charged in Au alloy, the base material 14 is mounted in the vacuum chamber 51, and 1 × 10 ⁻³ P is attached.
The material is evacuated to below a and the preheater 16 is used for the base material 14
Was preheated and the energization of the auxiliary heater 17 was started. Next, Ar gas was introduced into the vacuum chamber 51 to a pressure of 1 Pa, and a negative voltage of (−) 3 KV was applied to the base material 14 to perform sputter cleaning with Ar ions.

Next, a TiN coating film was formed on the base material 14.
That is, with the HCD shutter 28 and the resistance heating shutter 38 both closed, Ar gas for plasma was introduced from the Ar gas inlet 24 at a flow rate of 20 cc / min.
At this time, the heat conduction vacuum gauge 53 indicates that the pressure in the vacuum chamber 51 is 0.
It was shown to be 1 Pa. When the HCD gun 21 is operated to increase the output to more than 30 V × 150 A, Ti in the HCD crucible 22 melts and starts evaporation. Output 30
The shutter 28 for HCD was opened to V × 200A.
At the same time, nitrogen (N ₂ ) gas is supplied from the reaction gas inlet 44 to 20
It is introduced at a flow rate of 0 cc / min, and (-) 3 is added to the substrate 14.
A negative voltage of 0V was applied. In this way, the TiN film was deposited on the base material 14 at a film forming rate of 0.3 μm / min, and the TiN film having a thickness of 3 μm was formed in 10 minutes. Here, the HCD shutter 28 is closed, and the HC
The output of the D gun 21 was set to 30V × 140A. Further, the inflow of N ₂ gas as a reaction gas was stopped.

Next, an Au alloy film was formed. That is, the HCD shutter 28 and the resistance heating shutter 38
With both closed, energize the resistance heating boat 32,
Heating by Joule heat was started. The Au alloy melted at a voltage of 30 V and a current magnitude of 100 A. Here, the output of the HCD gun 21 is 30 V × 140 A which does not melt Ti, and the resistance heating shutter 38 is opened while the HCD shutter 28 is closed. at this point,
The heat transfer vacuum gauge 53 showed a pressure of 0.1 Pa. The vapor of the Au alloy evaporated from the resistance heating boat 32 is TiN.
By the time it reaches the coated substrate 14, the HCD gun 21
Since they collide with Ar ions in the plasma from the above and are ionized by charge exchange, they reach the TiN-coated substrate 14 to which a bias voltage of (−) 30 V is applied and deposit with good adhesion. Thus, a 0.5 μm thick Au alloy film was formed on the 3 μm thick TiN film.

The adhesion of this Au alloy coating to the TiN coating was measured according to JIS H8504, 15 Peeling Test Method, 1
The test was carried out according to the 5.1 tape test method. However, nothing was peeled off and adhered to the adhesive surface of the cellophane adhesive tape, and no abnormality was observed in the Au alloy coating on the base material 14 side. For comparison, when the adhesion was also examined on the TiN film on which the Au alloy film was formed only by resistance heating without ionization, peeling adhered to the adhesive surface of the cellophane adhesive tape. Further, the method described in Japanese Utility Model Publication No. 2-38926, which is described as a conventional technique, that is, the Au alloy coating formed on the TiN coating by high frequency ion plating is partially peeled off by an adhesion test using cellophane adhesive tape. Admitted.

(Examples 2 to 10) A TiN film having a thickness of 3 μm was formed on the substrate 14 in the same procedure as in Example 1, and gold (Au) was used on the TiN film instead of the Au alloy of Example 1. , Silver (A
g), platinum (Pt), palladium (Pd), rhodium (Rh), nickel (Ni), chromium (Cr), aluminum (Al), and copper (Cu), each having a thickness of 0.
It was formed as a metal coating of 5 μm. In addition, those obtained by forming these metal coatings only by resistance heating and those formed by the method described in Japanese Utility Model Publication No. 2-38926 are also prepared, and as in Example 1, an adhesion test with a cellophane adhesive tape is performed. Was done. The results are shown in Table 1.

[0027]

[Table 1]

The codes in Table 1 display the following contents. × ・ ・ ・ Peeling △ ・ ・ ・ Partially peeling ○ ・ ・ ・ ・ ・ Not peeling Note that Au, Ag, Pt, Pd, and R were formed on the TiN film.
An alloy coating film made of 2 to 3 kinds of metals selected from h, Ni, Cr, Al and Cu was prepared by the same procedure as in Example 1, and all of them gave good adhesion test results.

(Embodiment 11) Instead of N ₂ gas as the reaction gas in Embodiment 1, oxygen (O ₂ ) gas, methane (CH ₄ ) gas, (N ₂ / O ₂ ) mixed gas, (CH ₄ /
N ₂ ) mixed gas and (CH ₄ / N ₂ / O ₂ ) mixed gas are introduced separately to replace the TiN film in Example 1 with a TiO ₂ film (blue), a TiC film (gray white),
Ceramic coatings of TiC _m N _n coating (gold, brown) and TiC _x N _y O _z coating (blue to yellow, black) were formed. In the above, m + n = 1 and x + y + z = 1, and the same applies to the following description.

Then, on these ceramic coatings, A
u, Ag, Pt, Pd, Rh, Ni, Cr, Al, Cu
One having a metal coating formed of one of the above or two or three alloys showed good adhesion.

(Example 12) In Example 1, Cr was charged in place of Ti charged in the HCD crucible 22, and the reaction gas was N ₂ , CH ₄ , (CH ₄ / N ₂ ), or (C).
H ₄ / N ₂ / O ₂ ) as a substitute for the TiN coating in Example 1 as CrN coating (gray white), CrC coating (gray white), CrC _m N _n coating (gray), or CrC _x N _y.
An O _z coating was formed.

Then, on these ceramic films, Au,
A metal coating made of one of Ag, Pt, Pd, Rh, Ni, Cr, Al, and Cu, or a metal alloy of two or three was formed, but all showed good adhesion.

(Example 13) HCD crucible 2 of Example 1
Zirconium (Zr) was charged in place of Ti charged in No. ₂ , and the reaction gas was changed to N ₂ to form a ZrN coating (thin gold color) on the base material 14. Then, the same procedure as in Example 1 was used to form A.
u, Ag, Pt, Pd, Rh, Ni, Cr, Al, Cu
Among these, a metal coating consisting of one type of alloy alone or an alloy of 2 to 3 types was formed, and all of these metal coatings showed good adhesion.

Example 14 In place of Ti in Example 1, hafnium (Hf) was charged, the reaction gas was N ₂ , and Hf was used.
An N coating (thin gold color) is formed, and Au, Ag, Pt, Pd, Rh, Ni, Cr, and the like are formed thereon by the same procedure as in Example 1.
A metal coating made of one kind of Al or Cu or a alloy of two or three kinds was formed, and all of these metal coatings showed good adhesion.

Among the combinations of the various ceramic coatings and the various metal coatings described above, the following combinations are preferable as those exhibiting the same type of color tone. TiN (gold) + Au (gold) CrN (gray white) + Pt (platinum) CrC _m N _n (gray) + Rh (rhodium) ZrN (light gold) + Au / Pd alloy (light gold)

(Example 15) In the process for forming the Au alloy film in Example 1, the same operation was performed until the resistance heating boat 32 was supplied with a current of 100 A at a voltage of 30 V to melt the Au alloy. . After the Au alloy has melted, set the output of the HCD gun to 30 V x 160 A
Both the CD shutter 28 and the resistance heating shutter 38 are opened. At this time, the pressure in the vacuum chamber 51 was 0.1 Pa.

Ar ion and HCD from HCD gun 21
Ti ions from the crucible 22 sufficiently circulate in the vacuum chamber 51, and the vapor of the Au alloy from the resistance heating boat 32 reaches the TiN-coated substrate 14 by the time Ar is reached.
Ions and Ti ions collide with each other and are charge-exchanged to be ionized. The ionized vapor of the Au alloy and Ti ions collide with the base material 14 to which a bias voltage of (−) 30 V is applied and adhere with good adhesion. A mixed layer was formed. The thickness of this mixed layer may be about 0.1 μm, and the time required for layer formation was about 1 minute.

After that, the HCD shutter 28 is closed again in the same manner as in the first embodiment, that is, the HCD gun 2 is closed.
The output of 1 was set to 30 V × 140 A, and the vapor of the Au alloy was ionized and deposited on the substrate 14.

Thus, a mixed layer having a thickness of 0.1 μm was formed on the TiN coating having a thickness of 3 μm, and an Au alloy coating having a thickness of 0.5 μm was further formed thereon. This A
The adhesion of the u alloy coating was equal to or higher than that in the case of Example 1. However, this method has a drawback that a mixed layer having different color tones appears when the Au alloy coating film is scraped off. It is the color tone of Ti in the mixed layer.

Example 16 In the case of forming an Au film on a TiN film by the same procedure as in Example 1,
When ionizing Au vapor generated by resistance heating,
When the magnitude of the output of the HCD gun 21 and the abrasion resistance of the Au coating formed are examined, the optimum value of the output is 30V.
It was found to be in the range of x110A to 30V x 150A. The results are shown in Table 2. The abrasion resistance is Au
The surface of the coating was rubbed with a cotton swab 500 times or more to see if the TiN coating was exposed.

[0041]

[Table 2]

Although the respective embodiments of the present invention have been described above, the present invention is not limited to these, and various modifications can be made based on the technical idea of the present invention.

For example, in the film forming apparatus of the embodiment, the tip of the plasma from the HCD gun 21 is directed toward the HCD crucible 22, and the HCD is used for ionizing the vapor of the Au alloy generated by resistance heating. Although the output of the gun 21 is lowered to a value at which Ti in the HCD crucible 22 does not evaporate, if the direction of the tip of plasma from the HCD gun 21 can be changed, Ti ion plating and Au alloy vapor The film can be formed without adjusting the output in the optimum direction according to the ionization.

Further, in each of the examples of film formation, metal nitrides, carbides, oxides, or mixed systems of these are exemplified as the ceramic film, but borane (B ₂ H ₆ ) gas is used as the reaction gas. It is also possible for the ceramic coating to be a metal boride.

In each of the examples for forming the coating, a stainless steel watch case was used as the base material 14.
Various metals and ceramics other than stainless steel 14
Can be used as.

Further, in each of the examples of film formation, a two-layer structure in which a metal film is formed on a ceramic film is illustrated, but it is also possible to form a film having a multilayer structure in which these are alternately laminated. is there.

Furthermore, for example, in Example 1 for forming a film, a TiN film, that is, a ceramic film is formed by ion plating of Ti in the coexistence of N ₂ gas, and Au alloy vapor by resistance heating is formed thereon. The Au alloy film was ionized to form an Au alloy film, but Ti ion plating was carried out without introducing N ₂ gas to form a Ti metal film, which was vaporized by resistance heating and ionized Au alloy. The film forming apparatus of the present invention can also be applied to the case where an Au alloy film is formed by steam.

[0048]

As described above, according to the film forming apparatus and the film forming method of the present invention, the resistance is formed on the ceramic film formed by ion plating by the hollow cathode discharge method in the presence of the reaction gas. Since various metal coatings and alloy coatings with good adhesion can be formed by heating, they are expected to be applied in various fields in the field of decoration. Also,
Since ion plating by the hollow cathode discharge method and vapor deposition by the resistance heating method are performed in the same vacuum chamber, it is possible to form a film with high production efficiency.

[Brief description of drawings]

FIG. 1 is a schematic vertical sectional view of a film forming apparatus according to an embodiment of the present invention.

FIG. 2 is a schematic vertical cross-sectional view of the same apparatus, showing a situation where a resistance heating shutter is opened.

FIG. 3 is a schematic vertical sectional view of a film forming apparatus as a first conventional example.

FIG. 4 is a schematic vertical sectional view of a composite ion plating apparatus as a second conventional example.

[Explanation of symbols]

 14 Base Material 15 Bias Power Source 21 HCD Gun 22 Crucible for HCD 24 Ar Gas Inlet Port 28 Shutter for HCD 32 Resistive Heating Boat 38 Resistive Heating Shutter 44 Reaction Gas Inlet Port 51 Vacuum Chamber

Claims (5)

[Claims] 1. A base material connected to a bias power supply in a vacuum chamber, and a first evaporation source for evaporating an evaporation source by a hollow cathode discharge electron gun for forming a ceramic coating on the base material. And a second evaporation source for evaporating an evaporation raw material by resistance heating for forming a metal film on the ceramic film by being assisted by the hollow cathode discharge electron gun. Film forming device. 2. A ceramic coating is formed on a base material connected to a bias power source in a vacuum chamber by evaporating an evaporation source of a first evaporation source with a hollow cathode discharge electron gun in the presence of a reaction gas. Then, while vaporizing the vaporization raw material of the second vaporization source by resistance heating, the vapor of the vaporization raw material of the second vaporization source is ionized by the plasma from the hollow cathode discharge electron gun to form a metal coating on the ceramic coating. A method for forming a film, which comprises forming the film. 3. The output of the hollow cathode discharge electron gun when ionizing the vapor of the vaporization raw material of the second evaporation source is set to an output at a level at which the vaporization raw material of the first evaporation source is not vaporized. Film forming method. 4. A ceramic coating is formed on a base material connected to a bias power source in a vacuum chamber by evaporating an evaporation source of a first evaporation source with a hollow cathode discharge electron gun in the presence of a reaction gas. Next, while continuing the evaporation from the first evaporation source, the evaporation raw material of the second evaporation source is evaporated by resistance heating, and the vapor of the second evaporation source is ionized by the plasma from the hollow cathode discharge electron gun, A mixed coating of the evaporation material of the first evaporation source and the evaporation material of the second evaporation source is formed on the ceramic coating, and further only evaporation of the evaporation raw material from the second evaporation source and the ionization are continued. And forming a metal coating on the mixed coating. 5. The film forming method according to claim 4, wherein the output of the hollow cathode discharge electron gun in the ionization at the time of forming the metal film is set to a level at which the evaporation source of the first evaporation source is not evaporated. .