JPS60194067A - Formation of hard film - Google Patents

Abstract

PURPOSE:To form easily various kinds of hard films on a substrate by using a laser vapor deposition installation by using graphite, carbon, metal, alloy, metallic compd., ceramics, etc. for forming a rotating body on which convergent laser light is irradiated. CONSTITUTION:Convergent laser light is irradiated on a rotating body under rotation in a vessel and the particles evaporating from the rotating body are deposited on a substrate, thereby forming a hard film thereon. The rotating body is made of a mixture composed of >=2 different materials selected from graphite, carbon, metal, alloy, metallic compd. and ceramics. The construction thereof is columnar, cylindrical body, conical body, disk body, and ring body. If such rotating body is formed of a powder mixture composed of, for example, metallic titanium and carbon, the hard film of titanium carbide can be formed on the substrate. The dense, strong and hard film is formed on the substrate with good adhesion at a high deposition rate by the above-mentioned method.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a method for forming a hard film with excellent wear resistance, heat resistance, corrosion resistance, etc. on a substrate, and more specifically, relates to a method for forming a hard film having excellent wear resistance, heat resistance, corrosion resistance, etc. on a substrate. The present invention relates to a method of forming an alloy, a single compound, a composite compound, a solid solution, or a hard film formed by laminating these materials by irradiating a material with a high-power laser beam.

[Technical Background of the Invention and Problems Therewith] Plasma spray methods, chemical vapor deposition methods, and physical vapor deposition methods are conventionally known as methods for forming hard films on substrates.

Among these methods, the plasma spray method has the advantage of a high film formation rate, but has the disadvantage that it is difficult to form a dense and strong film.

In addition, in the chemical vapor deposition method, for example, when forming a laminated hard film on a substrate, the deposition temperature of each of the 11 layers to be laminated may be different, so the laminated film may be formed simultaneously in one container. This means that controlling the temperature during the manufacturing process becomes complicated, and when forming a composite hard film, the chemical reactions used to synthesize each material that makes up the layer are different from each other, so it is difficult for the chemical reactions to coexist. This chemical vapor deposition method has the drawback that the deposition rate of the film constituent materials on the substrate is slow. .

On the other hand, in the physical vapor deposition method, it is possible to form a dense and strong hard film by applying the representative methods, ion blating method and sputtering method. The disadvantage is that the speed is low.

Therefore, a method has recently been proposed in which a high-power laser beam is irradiated onto an irradiated sample of film constituent materials placed in a vacuum container to vaporize the sample, and the evaporated particles are deposited on a substrate. .

However, conventional laser evaporation equipment used in this method either irradiates the surface of the irradiated sample placed on a support plate with a laser beam from a vertical direction and scans the laser beam, or It has a structure in which the sample is rotated around the normal axis of the support plate to move the irradiation point position, and the applied irradiation energy is also CO
It was less than too-w with 2 lasers.

In methods using such conventional laser evaporation equipment, the deposition rate of evaporated particles onto the substrate is not necessarily high, and the strength of the formed film is not very high. Therefore, the application of this method is limited to film formation for optical components and electronic components.

Therefore, the present inventors constructed the irradiated sample in the laser vapor deposition apparatus as a rotary body, for example, in a cylindrical shape, which rotates on its axis in a vacuum container, and irradiated the outer circumferential surface of the rotary body with a convergent laser beam from a tangential direction. A device with this as its main feature was developed and filed as Japanese Patent Application No. 57-225587. When this device is used, the evaporated particles are supplied to the substrate in a high density and stably, increasing the deposition rate of the sample on the substrate.The formed film is also dense and strong, and the bond between the substrate and film increases. This improved adhesion has made it possible to produce a variety of useful functional materials.

Since then, efforts have been made to manufacture even more useful hard films by applying the above laser vapor deposition apparatus and method.

[Object of the Invention] An object of the present invention is to provide a method for easily forming various hard films on a substrate using a laser evaporation apparatus.

[Summary of the Invention] The method for forming a hard film of the present invention includes irradiating a rotating body that rotates on its axis within a container with a focused laser beam, and depositing particles evaporated from the rotating body on a substrate. The rotating body is characterized in that it is made of at least two substances selected from the group consisting of graphite, carbon, metals, alloys, metal compounds, and ceramics.

The method of the present invention will be explained in detail below with reference to the apparatus illustrated in the drawings.

FIG. 1 is a schematic diagram showing an example of a laser evaporation apparatus used in the method of the present invention, where l represents a parallel laser beam emitted from a laser oscillator (not shown).

The optical path of the laser beam 1 is changed in the horizontal direction by a plane mirror 2, and after passing through a condensing lens 3 and being converged, the laser beam 1 is introduced into a container 5 through a transmission window 4.

A rotating body 7 is arranged in the container 5 so as to rotate in the direction of arrow P in response to the rotation of the central axis 6. This is the sample to be irradiated.

The convergent laser beam introduced into the container 5 is again converted in its optical path by the plane mirror 8, and is irradiated onto the outer peripheral surface of the rotating body 7 from the tangential direction of the rotating body as shown in the figure.

Regarding the condenser lens 3, its focal length and arrangement position are appropriately selected so that the convergent laser beam is focused near the irradiation point Q of the rotating body 7.

While the convergent laser beam is irradiated, the rotating body 7 is rotated about the shaft 6 at an appropriate speed. Furthermore, if this rotating body has a cylindrical body, a cylindrical conical body, or a curved convex body structure, if the structure is such that it can swing by a distance corresponding to the length in the direction of the central axis of the rotating body, rotation can be achieved. The entire outer circumferential surface of the body 7 is uniformly heated to prevent thermal cracking, and the entire irradiated sample on the outer circumferential surface of the rotating body 7 can be uniformly evaporated. In addition, if the rotating body is a plate body such as a ring body or a disc body, the same effect can be obtained if the convergent laser beam irradiated to the plate surface can be scanned over a distance corresponding to the radius of the plate surface. can get.

By being irradiated with the focused laser beam, the outer peripheral surface sample near the irradiation point Q is evaporated, and the evaporated particles are emitted in the direction of arrow R and deposited on the substrate 9 . Reference numeral 10 denotes a movable shutter disposed in front of the substrate 9 for arbitrarily adjusting the deposition time of the evaporated particles onto the substrate 9.

Note that if the irradiated sample constituting the rotating body 7 is made of a material that is extremely prone to thermal cracking, a preheater 11 as shown in the figure is placed near the outer peripheral surface of the rotating body 7 to preheat the rotating body 7. By doing so, it is possible to prevent damage to the rotating body 7 during irradiation with the focused laser beam.

Now, the present invention provides one or more exemplified devices in which the rotating body 7
is characterized in that it is made of at least two or more of the following substances: graphite, carbon, metals, alloys, metal compounds, and ceramics. That is, the rotating body according to the present invention is a structure in which two or more types of different materials coexist with each other having independent characteristics.

Specifically, the following embodiments can be cited as preferred examples.

First, the structure of a zero-rotating body, which is a rotating body made of a mixture of two or more different types of substances, is a cylindrical body as shown in FIG. 2, and a cylindrical body as shown in FIG.

Various forms can be mentioned, such as a conical body as shown in Figure 4, a curved convex body as shown in Figure 5, a disc body as shown in Figure 6, and a ring body as shown in Figure 7. . For example, when forming a hard film of titanium carbide from a rotating body made of a mixed powder of titanium metal and carbon, a rotating body with such a structure may be used to form a hard film of titanium carbonitride from a rotating body made of a mixed powder of titanium carbide and titanium nitride. It is effective when forming a hard film of a substance mainly composed of silicon nitride or a solid solution called sialon from a rotating body made of a mixed powder of silicon nitride, aluminum oxide, and yttrium oxide. .

Note that when a cylindrical body as shown in Fig. 3 is used as a rotating body, if a convergent laser beam is irradiated to the outer peripheral surface of the cylindrical body from a tangential direction, the cylindrical body (Fig. 2), It is possible to obtain the same effect as when using a conical body (Fig. 4) or a curved convex body (Fig. 5), but in particular, convergence from the tangential direction (direction of the rotational axis) to the inner wall surface of the cylindrical body can be obtained. By irradiating the wall surface with laser light, the evaporation direction of the particles is aligned, making it easier to deposit the evaporated particles on the substrate, and also prevents the evaporated particles from scattering into the container and contaminating the entire inner wall of the container. It is also possible to obtain further effects such as suppression.

The second type is a rotating body formed by forming two or more types of different materials separately as one structure and combining them.
Two or more pieces can be centripetally combined to form a cylinder, a cylindrical body, a cone, or a curved convex body (Fig. 8: In the case of a cylinder), or two or more plate bodies with a fan-shaped cross section made of different materials. , two or more cylindrical bodies, cylindrical bodies, conical bodies, or curved convex bodies made of different materials, which are combined centripetally to form a ring body or a disc body (Fig. 9: In the case of a disc body), Two rings or disks made of different materials and having different diameters may be connected integrally in the axial direction of the rotating body (Fig. 10: In the case of a continuous columnar body).
Two or more concentric rings can be combined into a ring body or a disc body (in the case of two concentric ring bodies in Figure 11), and other
These are various types of rotating bodies, such as a rotating body made of one material and at least one other different substance in an appropriate shape and combined (FIGS. 12 and 13).

These rotating bodies can be used in various ways depending on the purpose of forming a hard film and its use. For example, in the case of a rotating body made of a mixture of two or more different substances shown in the first section, it is possible to mix and mold them in a powder state. It can be used as a rotating body or by pre-sintering the rotating body to give it appropriate hardness and strength. Such a mixed rotating body can be used, for example, to form a hard film made of an alloy by a rotating body made of two or more metals, or to form a composite compound, solid solution, or mixture by a rotating body made of two or more single compounds. It is also possible to form a hard film. A rotating body formed by combining two or more types of different materials shown in the second part as one structure, and combining these structures, has the same rigidity as the mixed rotating body shown in the first part. Not only is it possible to form a film, but also a laminated hard film can be formed by combining, for example, a rotating body consisting of a structure as shown in Fig. 1θ or Fig. 11.

In the method of the present invention, the direction of deposition of the irradiated sample on the substrate is approximately one direction, so by rotating or rocking the substrate, the desired hard film can be formed on the entire surface of the substrate even if it has a complex shape. be able to. Furthermore, by introducing a plurality of convergent laser beams, it becomes possible to perform simultaneous vapor deposition or laminated vapor deposition of various irradiated samples, giving rise to the possibility of developing new functional materials.

In addition, the substrate can be cooled with water, liquid nitrogen, etc., or heated with heater heating, laser heating, etc., and the hard film on the substrate can be made amorphous or crystalline depending on the intended use. can do. In particular, when the substrate is heated, the adhesion between the formed hard film and the substrate can be improved. The substrate may be cooled or heated by any conventional method as long as it is cooled or heated in vacuum or in an atmosphere.

Furthermore, in the method of the present invention, while depositing the evaporated particles of the sample to be irradiated on the substrate, ions are irradiated thereon,
The deposited material can be ionized by high frequency or microwave radiation, or the evaporated particles can be accelerated by a bias voltage. By performing such treatment, the evaporated particles are activated and a hard film with excellent adhesion to the substrate can be formed.

Furthermore, the method of the present invention can be carried out not only in vacuum but also in various inert gases, reactive gases, or mixed gases thereof. For example, by using various metals as the sample to be irradiated,
This is vaporized using a focused laser beam in a nitrogen atmosphere.
At the same time, for example, by irradiating with nitrogen gas ions, a hard film of nitrides of these metals can be formed on the substrate.

As the substrate used here, a variety of materials can be used depending on the purpose, such as metal, alloy, tool steel, cemented carbide, cermet, or ceramic.

[Examples of the Invention] Example 1 A mixed powder of 80 wt% of titanium metal powder and 20 wt% of carbon powder was formed into a cylindrical body, and then presintered at 1200° C. in vacuum to form a rotating body. This rotating body and 10-10%C
A substrate made of O alloy was set in a container. Inside the vessel IX
After exhausting to 10'Tart, the rotating body is set to 3Orpm.
Preheat to 1000℃ while rotating, and heat the substrate to 700℃.
preheated to. Next, from the laser oscillator, C1 of 7001i1
A 11C02 convergent laser beam was irradiated onto the outer peripheral surface of the rotating body from a tangential direction to evaporate it, and the evaporated particles were deposited on the substrate surface. The hardness of the obtained hard membrane was 2 on the micro Vickers scale.
It was 800-3000 kg/rats2. The thickness of the hard membrane was 107 mm, and the deposition rate was about 1 km/1 inch. When this hard film was analyzed by X-ray diffraction, it was confirmed that it was TiC.

Example 2 It was made of S r a Na powder containing a small amount of S + 02, and had four pillars with a fan-shaped cross section and a central angle of 60 degrees.
It consists of a mixed powder of 03-2o mao1% Y2O3, and has two pillars with a fan-shaped cross section with a central angle of 30 degrees and AffiN-20.
Two pillars made of a mixture of MaO1% Y2O3 and having a fan-shaped cross section with a central angle of 30 degrees were prepared. These eight different types of cylindrical materials were mentally combined so that they were adjacent to each other to form a rotating body. All 203-Si02 ceramic ceramic was used as the substrate. These rotating bodies and the substrate were set in a container, and evaporated particles were deposited on the surface of the substrate in the same manner as in Example 1.

The hardness of the obtained hard film was 1800 on the micro Vickers scale.
kg/am2 and the film thickness was 5 layers. The deposition rate at this time was approximately 0.5 #L m/win. When this hard film was subjected to X-ray diffraction, it was found to be a substance mainly composed of Si3N4 containing a solid solution considered to be sialon.

Example 3 A cylindrical body made of hexagonal boron nitride (outer diameter 50 tw, inner diameter 10 m, length 30 mm) and a cylindrical body made of titanium nitride (outer diameter 50 m1, inner diameter 10 m, length a0) were used. Combined in the axial direction to form a continuous cylindrical body (outer diameter 50 cm, inner diameter l)
A rotating body was formed by forming an intestine (length: 80 mm). The substrate used was Si3N ceramics. Set the rotating body and the substrate in the container, and set the inside of the container to IX 10” orr.
After exhausting the air to
First, the titanium nitride rotating body was evaporated by irradiating the outer peripheral surface of the rotating body with a focused laser beam of 100 OW from a zero-order laser beam oscillator that had been preheated to 00°C and the substrate was preheated to 1000°C. After that, the hexagonal boron nitride rotating body was evaporated to deposit evaporated particles on the substrate surface.

The hardness of the obtained hard film was 4000 Knoop. The hard membrane was a laminated film in which the first layer was 5IL and the second layer was also 5IL. X-ray diffraction of this hard film showed that the first layer, which is the inner layer,
Although the layer was titanium nitride, the outer second layer was amorphous.

[Effects of the Invention] As is clear from the above description, the method of the present invention can form a dense and strong hard film on a substrate with good adhesion to the substrate and at a high deposition rate. Therefore, by appropriately selecting the sample to be irradiated and selecting the combination with the substrate, new functional materials can be manufactured, which has great industrial value.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an example of a laser vapor deposition apparatus used when carrying out the method of the present invention, and FIGS. 2 to 13 are conceptual perspective views showing specific examples of the rotating body according to the present invention. It is. 1-Laser light 2.8 Single plane mirror 3-Condensing lens 4-Transmission window 5-Vacuum container 6-Central axis 7-Rotating body (irradiated sample) 9-Substrate 1O-Shutter 11-Child thermal heater designated representative Todoroki Tatsukuni Hajime Hajime Tsukuni Figure 1 Figure 4 If Figure 7 Figure 1o Figure 13 Continued from page 1 [Phase] Inventor Nobuo Yasunaga Ibaraki 1 Kyusho-0 Inventor Noboru Tarumi Ibaraki Kei 1 Inventor within the laboratory Akira Kohara Ibaraki-based 1 laboratory @ inventor Ike 1) Masayuki Ibaratomo 1 0 within the laboratory Inventor Jun Sato - Yokohama city @ inventor Authenticity Old history Uko, Yozaki city 1-1-4 Baien, Sakuramura, Osamu District, Agency of Industrial Science and Technology

Claims (1)

[Claims] (1) A method for forming a film by irradiating a rotating body that rotates on its axis within a container with a focused laser beam and depositing particles evaporated from the rotating body on a substrate, wherein the rotating body is made of graphite. , carbon, metal, alloy, metal compound, or ceramics. (2) The method for forming a hard film according to claim 1, wherein the rotating body has a structure of a cylinder, a cylinder, a cone, or a curved convex body. (3) The method for forming a hard film according to claim 1, wherein the rotating body has a ring or disk structure. (4) The method of forming a hard membrane according to claim 1, 2 or 3, wherein the rotating body is formed by mentally uniting two or more pillars or plates having a fan-shaped cross section. (5) The rigid body according to claim 1 or 2, wherein the rotating body is formed by integrally connecting two or more cylindrical bodies, cylindrical bodies, or conical bodies in the axial direction of the rotating body. How to form a film. (8) The rotating body is a ring body or a disc body with different diameters.
(The method for forming a hard membrane according to claim 1 or 3, which comprises combining l1 or more in a concentric circle.