JPS5841351B2 - Katsuseikahannoujiyouchiyakuuchi - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention mainly uses metal carbides or nitrides on a substrate, especially Cr, AI, Si, Ti, ■, and Fe.

The present invention relates to an activated reactive vapor deposition method suitable for forming coatings of Co, Ni carbide, or Cr nitride.

As a conventional method of this kind, for example, Bun-sh
ah) method is known, but in this case the electron gun consists of a high-voltage electron gun that operates with high voltage and low current.
Since the electron beam current is relatively small, in order to obtain a film with a predetermined thickness, for example, 1 μm, on the substrate, the amount of metal evaporation is slowed down to correspond to the electron beam current.
In addition, the temperature of the substrate is increased to activate molecules on the surface of the substrate, or a probe serving as an auxiliary electrode is installed separately in the space between the substrate and the evaporation source to ionize and carbonize the metal vapor particles. It is necessary to effectively ionize hydrogen gas and other reactive gases, and in both cases, the film formed on the substrate is 700%
It has a relatively low hardness of less than 100 kg/m", and has the major drawback of poor wear resistance and corrosion resistance. Furthermore, in the case of the former, it takes a long time of 60 minutes to obtain a film of a specified thickness. ,
It also has the disadvantage of poor working efficiency, and in the latter case, the structure is complicated and the operation is relatively inefficient.

The object of the present invention is to obtain a method that eliminates such inconveniences, and the purpose of the present invention is to provide a method in which a crucible is placed in a processing chamber whose interior is kept in a relatively high vacuum atmosphere of hydrocarbon gas, nitrogen gas, or other reactive gas. An evaporation source made of a metal and a corresponding substrate are connected to the positive and negative sides of an operating power source, and the evaporation source is irradiated with an electron beam from an electron gun to evaporate the metal; The metal vapor particles generated by the evaporation are ionized, and the reaction gas is ionized, and the vapor particles are chemically reacted with the carbon component or nitrogen component of the ionized reaction gas while being deposited on the substrate. In the vacuum deposition type, a hollow hot cathode type electron gun is used as the electron gun,
Further, the temperature of the substrate is set to 20°C to 315°C, and the pressure of the reaction gas is set to 3×10=To
It is characterized by being set at rr to 5×10 −5 Torr.

Examples of the method of the present invention will be explained with reference to the attached drawings.

In the drawing, 1 indicates a processing chamber, and the inside of the processing chamber 1 is communicated with an external vacuum pump 3 through an exhaust port 2, and acetylene gas (C2H2) and other hydrocarbon gases from the outside are communicated through an air supply port 4. A relatively high vacuum of the gas, e.g.
It was kept in a high vacuum atmosphere of about r ~ 5 x 10-5 Torr.

In the drawing, 6 is an evaporation source placed on the lower side of the chamber 1, 7 is a substrate on the upper side of the chamber 1, and 8 is an external source to which a predetermined negative voltage, e.g., -50V, is to be applied to the substrate 7. A DC power source is shown, and the evaporation source 6 is configured to irradiate a metal 6b, such as metal Cr, in a crucible 6a with an electron beam from an electron gun 6c facing it.

In the drawing, 6d indicates an operating power source for the electron gun 6c.

The above is approximately equivalent to the conventionally proposed Pansha method in which the above-mentioned probe is omitted, but according to the present invention, the electron gun 6c is configured as a hollow hot cathode type that operates at low voltage and large current, In this way, a significantly larger amount of electron beam can be obtained at the front surface than in the conventional high-voltage type.

Furthermore, the drawing specifically shows the temperature of the substrate 7 between 20°C and 3°C.
In order to be able to adjust the temperature to 15° C., an electric heater 10 was placed at one end of the holder 7a on the back side of the substrate 7, and a refrigerant cooler 11 was placed at the other end.

To explain its operation, the inside of the processing chamber 1 is evacuated by the vacuum pump 3 and air is supplied from the gas source 5 to create a relatively high vacuum of hydrocarbon gas such as acetylene gas 02H2, such as 1 x 1 O-3 Torr~. The substrate 7 is held in an atmosphere of 5 x 1 O-5 Torr, and a predetermined potential, for example OV, -50V is applied to the substrate 7 to operate the electron gun 6c. As a result, a significantly large amount of output electron beam is generated in front of the metal 6b, and the beam not only irradiates the metal 6b, that is, the metal Cr, and heats and evaporates it, but also collides with the vapor particles of the metal to ionize them. Furthermore, it collides with the acetylene gas in the outer space to ionize it, and the thus ionized Cr metal vapor particles chemically react with the ionized carbon component of the gas to become CryCx, which is deposited on the substrate 7 by the action of an electric field. is attracted to the metal carbide joint Cr3
Create a stoichiometrically stable coating of C2.

The film obtained in this way has extremely high surface hardness, has a fast film formation rate, and is highly corrosion resistant. Change.

Figure 2 shows the measurement results. In the figure, A, B, and C indicate temperatures of the substrate 7 of 20°G, 160'C, and 31°C.
5° C. In these cases, the potential of the substrate 7 is maintained at Ov by short-circuiting both terminals of the DC power supply 8 by the switch 12.

From this result, in order to obtain a coating with a high hardness of 1300 kg/7 or more over a wide range of temperatures of the substrate 7,
The degree of vacuum in the processing facility 1 is 3 x 10' Torr ~ 5 x
It is judged that it is preferable to set it to about 10''-' Torr.

In the above case, the electron gun 6C is 45cm. It is assumed that it operates at 70A, the pressure of argon gas as a carrier gas in the hollow hot cathode is 7.5 × 10-')-L, and the hardness is 50
gr is expressed as negative load Vickers hardness.

Furthermore, in order to form a CrN or Cr2N film on the surface of the substrate 7, nitrogen gas may be used as the reaction gas instead of the acetylene gas in the above embodiment.

That is, the gas source 5 comprises, for example, a cylinder of nitrogen gas, so that in the chamber 1 this gas is bombarded by the electron beam, ionizes, and reacts with the Cr vapor.

The above explanation is for the case where the potential of the substrate 7 is set to OV, and if it is set to -50V, the potential of the substrate 7 is set to OV.
The inventors have confirmed through experiments that the temperature range of the substrate 7 in which the hardness of the upper coating is 1300 kg/cIIL or more is widened.

Note that the temperature of the substrate 7 and the degree of vacuum in the processing chamber 1 during film formation can be uniquely determined by taking these measurement results and other characteristics of the film into consideration.

In this way, according to the present invention, a hollow hot cathode type electron gun that operates at low voltage and high current is used as the electron gun under the optimum temperature of the substrate and under the optimum vacuum pressure in the processing chamber. A large amount of electron beam can be obtained, and as it is, metal vapor is generated and the vaporized hydrocarbon gas is activated effectively and quickly, eliminating the delay in film formation rate in the conventional example, and further It also eliminates the inconvenience caused by the installation of probes, and it can be
It has the effect that a stoichiometrically stable coating with high hardness of 0 kg/- or more can be obtained with high efficiency.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view of an example of the method of the present invention, and FIG. 2 is a line diagram of an example of measurement results. 1...Processing chamber, 3...Vacuum pump, 5
...Reactant gas source, 6... Evaporation source, 7.
...Substrate, 8...DC power supply,
6b...metal, 6c...hollow hot cathode type electron gun.

Claims (1)

[Claims] 1 In a processing chamber whose interior is kept in a relatively high vacuum atmosphere of hydrocarbon gas, nitrogen gas, or other gas, an evaporation source made of metal in a crucible and a substrate facing it are connected to the positive side of the operating power source. The evaporation source is connected to the negative side and irradiated with an electron beam from an electron gun to evaporate the metal and ionize the metal vapor particles generated by the evaporation, as well as ionize the reaction gas described above. The electron gun is a hollow hot cathode type electron gun, in which the vapor particles are chemically reacted with the carbon component or nitrogen component of the reaction gas to be ionized and are attracted and deposited on the substrate. Using a gun, the temperature of the substrate is between 20° C. and 315° C., and the pressure of the reaction gas is between 3×10=Torr and 5×10′.
An activation reaction deposition method characterized by using Torr.