JPH01270596A - Deposition of diamond coating film - Google Patents

Abstract

PURPOSE:To increase the number of diamond crystal nuclei deposited at the initial stage of reaction, reduce the particle size of the deposited diamond film and improve the uniformity and adhesivity of the film by oscillating a substrate at high frequency in the formation of a diamond coating film on the surface of the substrate. CONSTITUTION:A diamond coating film is deposited on a surface of a substrate by using a carbon source gas such as methane, acetone or carbon monoxide preferably in combination with hydrogen gas and activating the gas by plasma discharge with a thermionic emission material or by high-frequency or microwave irradiation while oscillating the hot substrate usually at a frequency of 15kHz and an output of 1-500W.

Description

[Detailed Description of the Invention] [Industrial Application] The present invention is a method of depositing and forming a diamond film on the surface of a substrate such as a tool such as a cutting tool or an electronic component such as a heat sink by a vapor phase synthesis method. Concerning how to do so.

[Prior art] A raw material gas containing a carbon source is heated using a thermionic radiation material, plasma discharge by high frequency, plasma discharge by microwave, etc. to activate "C", and a substrate is placed in this atmosphere and diamond is coated on its surface. A method of depositing and forming a film is known. In this method, the surface of the substrate is pretreated to activate the surface to increase the number of diamond crystal nuclei that precipitate at the initial stage of the reaction, and also to remove the precipitated diamond. Attempts have been made to improve the adhesion between the coating layer and the substrate.
No. 04695, No. 61-52363, No. 62
-226889, etc.) [The invention attempts to solve the problem! However, in all of the above conventional methods, diamond crystal nuclei are precipitated on fine protrusions on the surface of the substrate at the initial stage of the reaction, and it is usually difficult to uniformly form these fine protrusions on the surface of the substrate. For this reason, the formation of diamond crystal nuclei that precipitate at the initial stage of the reaction becomes uneven on the surface of the substrate.
The deposited tire mont coating had the disadvantage of large variations between products. In addition, although the above pretreatment is improved over the untreated one, nucleation is still insufficient, and as a result, the crystal grain size of the Tiemon coating obtained is highly heterogeneous, ranging from 5μIη to 10μmn. Moreover, the adhesion of the nucleus was also inadequate.

From the above-mentioned viewpoint, the present inventor conducted research to form a homogeneous Tiresen l-11i film on various substrates, and as a result, formed a Tiremont film on the surface of the base material. When the base material is vibrated at a high frequency to form the coating, 4
The Thai A. Mont crystal nucleus that comes out of No. 1 increases significantly, and as a result, the Ti A. Mont. It has been discovered that the name has become a secret and has excellent secrecy.

[Object of the invention] The object of the invention is to reduce the amount of Tiemon 1 precipitated at the initial stage of the reaction.
To provide a method for depositing and forming a Tiemon 1 coating in which crystal nuclei are formed uniformly on the substrate surface m1, and the deposited coating has small variations between products.

[Means for Solving the Problems] -4-Layer In order to achieve the objective, the present invention includes carbon source scum and is activated by thermionic emission, plasma discharge by high frequency or microwave, etc. In a method of depositing and forming a coating on the surface of a heated substrate by placing a heated substrate in a heated raw material waste,
A configuration was adopted in which the film was formed on the substrate using high frequency C vibration waves.

As carbon source residue (for example, various hydrocarbons such as methane, ethane, and acetylene, carbons such as acetone, alcohols such as ethanol, carbonic acid residue, and carbon oxide can be used as a single source). Among them, methane, acetate, and carbon oxide are preferable, and the action of the carbon source residue and hydrogen is also preferable. Suppresses precipitation and reduces the amount of precipitation and precipitation. It should be noted that C may be used without any problem by mixing inert residue such as alcon into the raw material residue.

3. The conditions for vibrating the substrate vary depending on the shape and natural frequency of the substrate, but the usual frequency is from 15 kHz to 50 kHz, and the output is from 1 watt to 500 watts.

If the frequency is less than 15 kilohertz or the power is less than 1 watt, it may be ineffective in promoting nucleation.

Further, even if the frequency exceeds 50 kilohertz or the output exceeds 500 watts, no corresponding effect can be obtained with respect to the output increase.

[Operations and Effects of the Invention] According to the method of the present invention, by vibrating the substrate, blood can always be purified to a highly active state in the substrate.

Therefore, by depositing and forming a film on the tire film while vibrating it, the tire film becomes homogeneous and atomized, resulting in excellent adhesion. In addition, the number of diamond crystal nuclei that precipitate in the initial stage of the reaction increases significantly.
A film can be formed quickly. 5 [Example 1] The present invention (y)-j will be explained in detail by way of an example.

FIG. 1 shows a deposition forming apparatus 100 for depositing a Tiresen l-coat by plasma discharge using 11 microphone waves. This apparatus 100 includes a quartz reaction vessel 1 into which raw material scum including carbon source scum is introduced, and a substrate 10 installed inside the vessel)
an installation stand 2 for heating the loaf, and a glass discharge generator 3 for heating the raw material scraps near the loaf stand 2 with microwaves; It is equipped with an ultrasonic vibrator 4 that transmits vibrations.

The reaction vessel 1 has an upright cylindrical shape, and a raw material waste introduction 1''2 is provided in the center of the top plate 11, and a wall ttill
14 is provided at the bottom of 13 for discharging raw material waste, and a tire flam 16 is used for the bottom plate 15. The installation stand 2 consists of a white plate 21 placed in the middle of the front container 1, and a support rod 22 that supports the center of the first side and is installed (-) through the bottom plate 5. Become. In this embodiment, the installation base 2 is a board.
Activities T-4h) fiWi is changing.

The plasma discharge generating device 3 consists of a waveguide 31 provided at the center outer periphery of a reaction vessel and an oscillator 32 set aside at one end of the waveguide 31.
A plunger 33 for plasma adjustment is attached opposite to C.

Next, the operation of the precipitation forming apparatus 100 will be explained.

A base body (10 x 10 x 5 mm) 10 made of cemented carbide is placed on the base plate 21 of the installation base 2 in the reaction vessel 1 . The raw material gas meteor into the reaction vessel 1 is a methane gas of 0.5 sec.
The hydrogen gas was set to 99.5 sec, and the raw material gas was introduced through the raw material gas inlet 12 provided on the top plate 1, and on the other hand, the raw material gas was exhausted from the raw material gas outlet 114 located in the first part of the wall pipe 13. The pressure inside the reaction vessel 1 is maintained at 50 Tor+-.

In this state, the oscillator 32 provided at the center outer periphery of the reaction vessel 1
Microwaves emitted through the waveguide 31, for example, with a frequency of 2°450 MHz and an output of 500 Watts, are adjusted by the plasma adjustment plunger 33, and a plasma discharge by the microwave is generated around the base 10. let Then, the substrate 10 is vibrated by the ultrasonic vibrator 4 at a frequency of 20 kilohertz and an output of 50 watts via the installation table 2, and the raw material gas is heated and activated by plasma discharge, and the substrate surface temperature is raised by 1. This plasma discharge promotes activation of the raw material gas near the substrate surface 11, and a diamond film is formed on the substrate surface. In this state, the substrate temperature was set at 900° C., and film formation was performed for 6 hours to form a diamond film on the substrate 10.

FIG. 2 shows a state in which the tire material 1 to the film are formed while the substrate 10 is vibrated by the ultrasonic vibrator 4.

By vertically vibrating the installation table 2 as shown by the solid line A, particles 10a made of microcrystals are uniformly formed on the base 10, as shown in FIG. A less uniform film was formed.

In order to compare with the example, FIG.
A tire mon I layer is shown in which a diamond film is formed in the same manner as in the example described above. Nonuniform particles consisting of large and small particles 10a were formed on the substrate 10, and a film with many gaps was formed.

As a result, when the coating layer of the substrate 10, which was vibrated by the ultrasonic vibrator 4, was observed with an electron microscope, a uniform film with a thickness of 5 μm and excellent occlusion properties was found on the substrate 1, consisting of microcrystals with an average grain size of 1 μm.
Formed on 0. However, when the coating layer of the substrate 10, which is not vibrated by the ultrasonic vibrator 4, is observed under an electron microscope, a film composed of non-uniform particles having a particle size of 3/1 m to 10 μm is formed.

As described above, according to the present invention, the surface of the substrate 10 is compressed and stretched by the vibration action from the ultrasonic vibrator 4 and is activated, so diamond crystal nuclei are significantly increased at the initial stage of the reaction. As a result, highly uniform particles made of microcrystals are formed, so that a highly precise diamond coating can be formed.

Other examples include the thermionic emissive material method shown in FIG.
There is a plasma discharge method using high frequency as shown in FIG.

The thermionic emitting material method shown in FIG. Thermionic emitting material 52 is heated while maintaining it at a predetermined pressure.

This heating activates the raw material gas and increases the temperature of the substrate surface, causing Tiase 1 to film to be deposited and formed on the surface of the substrate 10. , In the high-frequency plasma discharge method shown in FIG. 6, the base 10 is placed on the installation stand 2 in the container 61, the raw material gas is introduced from 1'' 12, and is discharged from one side, and the pressure is maintained at a predetermined pressure. A plasma discharge is generated around the base 110 at a predetermined frequency and a predetermined output using a high frequency coil 62 provided at the central outer circumference of the container.

This plasma discharge activates the raw material gas by heating and increases the temperature of the substrate surface, causing a diamond coating to be deposited and formed on the surface of the substrate 10.

These other embodiments also provide the same effects as the first embodiment.

In addition, in the above embodiment, whether a substrate is used as the base material or
It may be a tool such as a chip, or a diaphragm for a speaker.

[Brief explanation of the drawing]

FIG. 1 is a schematic front view of a deposition forming apparatus for depositing a Gouy-\-Mont film by plasma discharge using microwaves, showing an embodiment of the present invention, and FIG. 2 is an enlarged view of the main parts thereof.
FIG. 3 is an enlarged view of the substrate surface according to the present example, FIG. 4 is an enlarged view of the substrate surface according to the comparative example, and FIG. 5 is a schematic front view of a tire bond film deposition forming apparatus according to another example of the present invention. , FIG. 6 shows a tire monitor according to still another embodiment.
FIG. 3 is a schematic diagram of the end surface of the film deposition forming apparatus. In the figure: 4... Super wave oscillator 10... Substrate 32... Oscillator 52 - Thermionic electron emitting material 62... High frequency coil

Claims (1)

[Claims] 1) By placing a heated substrate in a raw material gas containing carbon source gas and activated by a thermionic radiation material or plasma discharge by high frequency or microwave, diamonds are formed on the surface of the substrate. A method for depositing and forming a diamond film, characterized in that the film is formed while vibrating the substrate at a high frequency.