KR930011165B1 - Apparatus for adhering diamond film on the plate and processing method thereof - Google Patents

Abstract

No content.

Description

Vapor deposition method of diamond film and its apparatus

1 is an explanatory view of the principle of a conventional apparatus used to form a diamond film on a substrate.

Figure 2a is a perspective view of a prior art cooler.

2b is a cross-sectional view of a prior art heat sink.

3 is an explanatory view of the principle of the apparatus of the present invention used to form a diamond film on an object or substrate.

4 is a cross-sectional view for explaining the present invention.

5 is a cross-sectional view of the heat sink employing the present invention.

6 is an X-ray diffraction pattern diagram of a second intermediate layer.

7 is a Raman spectrum diagram of the fourth embodiment.

8 is an X-ray diffraction pattern diagram in the case of having the protective film of the present invention.

9 is an X-ray diffraction pattern diagram when no protective film is provided.

10 is a view showing a diamond film coating apparatus according to the present invention,

11 is a cross-sectional view of an end of a substrate applied by the prior art.

12 is a cross sectional view of an end of a substrate applied in accordance with the present invention.

The present invention relates to a method and apparatus for vapor deposition of diamond films. More specifically, the present invention relates to an efficient method and apparatus for uniformly vapor-depositing a diamond film having excellent adhesion, hardness, and smoothness to an object or a substrate, and a method and apparatus for depositing the diamond film on a carburized material.

Diamond is an allotrope of carbon (C), has a diamond structure, has a high Moh's hardness of 10, and has a high thermal conductivity of 1000 or 2000 / mk over other materials. Therefore, various uses have been developed using these properties.

For example, its high hardness is used for drill bits or bites. Attempts have been made to apply a diamond film to tools made of high hardness small alloy alloys of the same tungsten carbide (WC). Also, diamond is used as a heat sink for LSI, VLSI or laser diodes or other semiconductor devices by utilizing its high thermal conductivity.

When applying a diamond film to a tool made of tungsten carbide (WC) or molybdenum carbide (MoC), chemical vapor deposition (CCVD) is used using a chemical vapor deposition apparatus (abbreviated CVD apparatus) similar to that shown in FIG. The film is grown directly, but the film is easily peeled off due to the difference in coefficient of thermal expansion.

⁴K

¹인반면, CVD의 선팽창계수는 임), 반응이 행해지는 800℃이상의 고온에서 상온으로 온도가 떨어지므로, 상기 다이아몬드막(13)이 처리대상물(1)로 부터 쉽게 박리된다.The operation of the conventional apparatus will be described below. The object (eg tool) or substrate to be treated is placed in a substrate holder 3 which is cooled by the coolant 2. The reaction chamber 4 is connected to the anode 6 and the cathode 7 for forming the plasma jet 5, and the starting gas 8 is supplied between the anode and the cathode. A DC power supply 10 is connected to the positive electrode 6 and the negative electrode 7, and a discharge port 11 is provided at the bottom of the reaction chamber 4. In order to CVD grow the diamond, a mixed gas of hydrogen (H ₂ ) and a hydrocarbon such as methane (CH ₄ ) is supplied into the reaction chamber 4 through the anode 6 and the cathode 7. The inside of the reaction chamber 4 is maintained at a low pressure by operating the discharge system for discharging from the discharge port 11, and in this state, an arc discharge 12 between the positive electrode 6 and the negative electrode 7 is carried out. ), The starting gas 8 is decomposed and plasmated by the heat, and the plasma jet 5 containing the carbon plasma strikes the metal plate 1, so that the diamond film 13 made of fine crystals is made of the metal plate 1 Is grown on). In this way, it is possible to grow the diamond film 13 on the object to be treated 1, but the coefficient of thermal expansion is different (for example, the coefficient of linear expansion of diamond is 0.0132 × 10).

⁴ K

^1, whereas the linear expansion coefficient of CVD is Im), the reaction was therefore dropped the temperature to room temperature at a high temperature is carried out over 800 ℃, the diamond film 13 is easily peeled off from the treated object 1.

Therefore, in the prior art as described above, when a diamond film is applied to a tool made of WC, for example, the diamond is removed by CVD after chemically removing an element (for example, Co) that lowers the adhesive force contained in the WC as a plastic strengthening agent. The film is grown or mechanically scratched and then grown on it. However, the thicker the film, the weaker the adhesion, so the growth thickness of the film was limited to only a few micrometers, and the adhesion was insufficient practically. As a method for solving such a problem, the present inventors have provided a coating layer 15 close to diamond with a thermal expansion coefficient on the object to be treated 1, as shown in FIG. A method of growing (13) has been proposed (Japanese Patent Laid-Open No. 1-145313 (issued September 9, 1987). However, the adhesive strength is still insufficient in practical use for tools. Has been used to make a drill bit and bite, however, for example, when a WC tool is applied with diamond, the coefficient of thermal expansion is different so that the coating is easily peeled off and cannot be used industrially. .

As mentioned above, since diamond has high thermal conductivity, diamond has attracted attention as a heat sink for semiconductor devices and is currently used for utilization. 2 is a perspective view of the cooler, in which a heat sink 15 made of diamond is brazed with gold on a subcarrier 14 made of copper Cu. A semiconductor laser or other semiconductor chip 16 is attached to the upper end of the eat sink 15 by, for example, gold-tin solder.

FIG. 2B shows a cross-sectional structure of the heat sink 15, each having a thickness of about 2000 mm in the order in which the titanium (Ti) film 18, the platinum (Pt) film 19, and the gold (Au) film 20 are listed. It is formed. The reason why the Ti film 18 is used is that this film forms titanium carbide (Tic) together with the diamond film 17 and has excellent adhesion. The reason for interposing the Pt film 19 is to correct poor wettability of the Ti film 18 and the Au film 20. However, this heat sink 15 is considerably affected by the thermal conductivity of the metal film that seals the structure in view of the complexity of the structure. In addition, since the adhesion requires a high temperature, the semiconductor chip is easily made. Can be damaged, and also because the adhesion requires special techniques, the cost is high

According to the above apparatus, it is possible to form a diamond film 13 after placing a plate 1 on a substrate holder cooled by the cooling water 2.

As described above, diamond has a very good thermal conductivity of 2000 W / mK and is commercially available as a heat sink constituent material. However, as shown in FIG. 3, Ti / Pt / Au and a metal film are layered on the diamond film. Formed. Therefore, there is a problem that the thermal conductivity of the diamond is damaged and the manufacturing atoms are high.

²로서, 다른 물질(10¹³)에 비해 현저히 작으므로,특정 결정입자들만이 선택적으로 성장하여 그 표면이 매우 거칠어진다. 특히, 이러한 경향은 다이아몬드막이 두꺼울수록 두드러진다(막두께 2mm일 때 약 0.2mm).In addition, as described above, diamond is used in a high performance tool by using its hardness, and since its thermal conductivity is several times higher than that of copper, it is used as a heat sink of a device having a large amount of heat generation such as a laser diode. However, the surface of conventional thick diamond films is very rough so that the use of these films requires grinding of the surface with diamond disks. This polishing takes considerable time and effort. Diamond nucleation density is 10 ⁷ ~ 10 ⁹ Cm

² , which is significantly smaller than other materials 10 ¹³ , only certain crystal grains selectively grow and the surface becomes very rough. In particular, this tendency is more pronounced as the diamond film is thicker (about 0.2 mm when the film thickness is 2 mm).

In addition, as described above, attempts have been made to apply tools to diamond using the high hardness of the diamond film. As the method for synthesizing diamond, high pressure synthesis and low pressure synthesis are known. Although the high pressure synthesis method is suitable for forming a relatively large single crystal, there is a problem in that the operation of the device is cumbersome, the growth rate is very slow, and the cost is high. On the other hand, low pressure synthesis methods include microwave plasma chemical vapor deposition and electron assisted chemical vapor deposition. The growth rate is much faster than that of high pressure synthesis, and diamonds can be formed into microcrystals on the treated substrate.

In contrast, the present inventors have developed a chemical vapor deposition method (CVD) of a diamond film using a plasma jet chemical vapor deposition apparatus as shown in FIG. 1 described above. However, since the diamond film is grown by plasma jet CVD, CH ₄ and other hydrocarbons are rapidly decomposed to a high temperature in the arc discharge region, released as a plasma jet, and hit the metal plate 1 to lose energy, and then as diamond. Crystallize. At this time, not all the carbons (C) constituting the hydrocarbon are diamonds. A substantial amount of precipitate precipitates on the metal plate 1 in the form of amorphous carbon or graphite, but when a mixed gas of hydrogen gas (H ₂ ) and the hydrocarbon is used as the starting gas (8), the amorphous carbon or graphite Non-diamond components such as and reduced to other hydrocarbons and removed in gas phase

However, substantially the removal of the gas is incomplete, and the non-diamond component is detected in almost all the diamond films formed by the plasma jet CVD method. This was a factor of lowering hardness.

As mentioned above, diamond has a high hardness of 10,000Kg / mm ² and has attracted attention as a coating material for various tools, but the diamond film obtained by the plasma jet CVD method contains amorphous carbon or graphite, and the hardness is insufficient. It was.

In addition, conventionally, high hardness of diamond was used in a high performance tool, and its thermal conductivity was about several times synonymous, and was used as a heat sink of a high heat generation apparatus such as a semiconductor laser.

However, when the diamond film is formed by the CVD method, since the material of the substrate is a material capable of permeating carbon (carburizing materials such as Ni, Co and Fe), the carbon component is dispersed in the substrate and the diamond film Make synthesis impossible. Therefore, in the past, when a diamond film is used for a tool or a heat sink, the substrate (the arm in the case of the tool, the subcarrier in the case of the heat sink) is limited to not being a carburizing material. However, it would be very convenient if it is possible to form a hard film such as diamond on a soft material such as carburizing material.

Accordingly, it is an object of the present invention to solve the problems of the prior art as described above, and to provide a method and apparatus for vapor depositing a diamond film having excellent adhesion to the object on the object to be treated.

It is another object of the present invention to provide a diamond film suitable for a heat sink having excellent adhesion with a bonding metal without damaging the thermal conductivity of the diamond.

Another object of the present invention is to provide a method of forming a flat diamond film on a substrate.

Another object of the present invention is to provide a method of forming a diamond film having a high hardness on a substrate.

It is another object of the present invention to provide a method of forming a diamond film on a carburized substrate.

According to the present invention, the diamond film is formed on the object to be treated by chemical vapor deposition in the same apparatus; Forming a first intermediate layer of a mixture of a main component element of the object and a component element of a diamond hardener; Forming a second intermediate layer of a mixture of the element and the diamond element of the diamond hardener on the first intermediate layer; A diamond film forming method is provided, wherein a diamond film is formed on the second intermediate layer.

According to the present invention, there is also provided a forming method of applying diamond onto a substrate, wherein the diamond film is synthesized on the substrate by a CVD method using a gas of a diamond forming material and a gas of a diamond nucleation promoting element. .

In addition, according to the present invention, the reaction chamber is vacuumed by the exhaust system, and a mixed gas of hydrocarbon gas and hydrogen gas is supplied between the anode and the cathode installed in the reaction chamber to generate a carbon plasma jet by arc discharge. A diamond film is formed on the substrate to be generated and processed, and at this time, hard carbide is formed by adding powder of at least one element selected from the group consisting of tungsten, molybdenum, silicon and titanium which can be combined with a non-diamond carbon component in the plasma jet. A diamond film synthesis method is provided.

Further, according to the present invention, (i) a protective film is formed on a substrate made of a carburized material by plasma injection using an element capable of easily forming a high melting point carbide, and (ii) a plasma on the protective film. A diamond film synthesizing method characterized by forming a diamond film by CVD.

Moreover, according to this invention, it is an apparatus which forms a diamond film on a process target or a substrate; An electrode forming member having a first polarity comprising an airtight body and a discharge gas supply pipe having a high temperature plasma spray nozzle open therein; An electrode forming member having an opposite polarity disposed opposite to the nozzle in the hermetic body; And a power supply system having a DC power supply supplying a DC voltage between the electrode having the first polarity and the counter polarity electrode, and supplying gas through the discharge gas supply pipe between the electrodes to which the DC power is supplied. A direct current plasma torch which forms the gas into a high temperature plasma by direct current arc discharge between electrodes and injects the high temperature plasma as a plasma jet through the nozzle; A starting gas supply system for supplying a gaseous starting compound for vapor deposition to the plasma jet; A powder supply tube for supplying metal powder to the arc discharge unit; and a diamond support substrate for supporting a substrate in the non-equilibrium plasma and for depositing a high temperature plasma chemical vapor deposition film on the substrate in a gas phase. A forming apparatus is provided.

Moreover, according to this invention, in the method of forming a diamond film by a chemical vapor deposition method on a to-be-processed object or a board | substrate; By supplying two or more component elements in powder form to the plasma jet of the gas generated by the direct current arc discharge, a mixture of the main component of the object and the component of the diamond plasticizer (i) and the component of the diamond plasticizer Forming at least two intermediate layers consisting of an element and diamond and a mixture (ii); Supplying a starting gas containing hydrogen and a carbon source between the anode and the cathode of the high temperature plasma chemical vapor deposition apparatus to generate a plasma jet containing a radicalized carbon compound to form a diamond film on the intermediate layer; The diamond film production method is characterized in that the diamond film is firmly deposited on the side surface of the object by rotating the object to be inclined 30 to 60 ° with respect to the flow direction of the plasma jet during the formation of the intermediate layer and the diamond film.

According to the first aspect of the present invention, two or more intermediate layers are formed on the object to be treated using a CVD apparatus for forming a diamond film as a method for enhancing the adhesion between the object and the diamond film. In other words, the first intermediate layer / second intermediate layer / diamond film (or the first intermediate layer / second intermediate layer / third intermediate layer / diamond film) is formed.

The operation of the apparatus of the present invention will be briefly described.

The object to be treated (eg a tool) or the substrate is placed on the substrate holder 3 cooled by the cooling water 2. Above the reaction chamber 4, an anode 6 and a cathode 7 for forming a plasma jet 5 are provided. The starting gas 8 is supplied between this anode and the cathode. In order to form the metal layer, the powder supply pipe 9 is opened at the end of the anode 6. The DC power supply 10 which connects the positive electrode 6 and the negative electrode 7 is provided. At the bottom of the reaction chamber 4, an outlet 11 is provided. In order to CVD grow diamond, a mixed gas of hydrogen (H ₂ ) and a hydrocarbon, for example methane (CH ₄ ), is supplied into the reaction chamber 4 through the anode 6 and the cathode 7. The discharge system for discharging through the discharge port 11 is operated to maintain the inside of the reaction chamber 4 at a low pressure. In this state, an arc discharge 12 is generated between the positive electrode 6 and the negative electrode 7, As the starting gas 8 is decomposed and converted into plasma, a plasma jet 5 containing carbon plasma strikes the metal plate 1, thereby growing a diamond film 13 made of microcrystal on the metal plate 1. . In the present invention, a metal powder is supplied to the arc discharge 12 through the powder supply 9 to grow a mixed film of metal and diamond, and H ₂ is used as the starting gas 8 to grow only the metal film. The metal powder or the inorganic material powder (ie, silicon) is supplied to the arc discharge 12 through the powder supply pipe 9.

4 is a cross-sectional view for explaining the present invention. In FIG. 4, the object to be treated 21 is a fired body made of WC or Mo ₂ C, in which a fire hardening agent 23 such as cobalt (Co) is dispersed. In the present invention, the main component material (99.9 to 90% by weight) of the object to be treated (1), that is, WC or MoC and the component elements (0.1 to 10% by weight) of the diamond calcining agent, that is, cobalt (Co), iron (Fe), nickel A first intermediate layer 24 made of a mixture with (Ni) and other transition metals is formed. The second intermediate layer 25 is a component element (0.1 to 10% by weight) of the diamond plastic strengthening agent, that is, cobalt (Co), iron (Fe), nickel (Ni) and other transition metals, and diamond (99.9 to 90% by weight) Consists of a mixture of

In addition, according to a preferred embodiment of the present invention, an agent comprising three intermediate layers, i.e., component element (a) (99.9 to 90% by weight) of the object and component element (b) (0.1 to 10% by weight) of the diamond hardener 1 intermediate layer (i), the mixture of the material of this 1st intermediate layer and diamond (c) (b): 0.1-10 weight%, (a) + (c): 99.9-90 weight%, (a) / (c) = 10/90 to 90/10) to form a third intermediate layer (iii).

In the present invention, by forming two or more intermediate layers in the above manner and gradually changing the composition of the object to be treated 21 and the diamond film 22, it is possible to form a diamond film which does not occur even when formed to a thickness of about 100 μm. .

There is no particular restriction on the thickness of the intermediate layer and the diamond film, but the preferred thickness of each intermediate layer is 2 to 10 μm, preferably 4 to 8 μm, and the preferred thickness of the diamond film is 10 to 100 μm, more preferably 20 to 40 μm. . In addition, the size of the powder is preferably 0,1 to 8 µm, more preferably 0.4 to 1 µm.

According to the second aspect of the present invention, the surface, bottom or whole of the diamond film formed by the plasma jet chemical vapor deposition method can be formed in the state of a mixed phase of component elements of a metal bonded to the diamond film.

In the present invention, the CVD apparatus can be used to form a mixture of diamond and the surface of the diamond film, the bottom or the whole diamond and the metal element.

5 is a cross-sectional structure diagram of a diamond film when used for the heat sink of a semiconductor device, and a mixed layer of diamond and Cu 929 is formed on the bottom surface 27 of the diamond film 26, and this bottom surface is The upper surface 28 is in contact with the semiconductor chip 16 of FIG. 2, for example.

In addition, in mechanical applications using the hardness of diamond, a mixed layer can be formed only on the bottom surface to be bonded to an object, or the entire film can be formed as a mixed layer.

The reason is that the diamond film formed by the CVD method is polycrystalline so that shear phenomenon occurs easily at the crystal interface. The crystal is relatively weak, but the mechanical layer is excellent because the metal is interposed in the mixed layer.

That is, when using a diamond film as a thermal conductor, the mixed layer may be a bonding portion. In the case of using the hardness, the whole film can be formed as a mixed layer to remove the shear phenomenon.

According to the third aspect of the present invention, a diamond-forming starting gas (e.g., H ₂ methane) and reducing metals (i.e., Pt), carburized metals (Ni, Co, Fe, etc.) or metals which easily form carbides or A flat diamond film can be formed on a substrate by the CVD method using a gas of an element that promotes nucleation of diamond such as a semiconductor (W, Si, Mo, Ti, etc.).

In the present invention, the diamond forming starting gas and the diamond nucleating element gas can be simultaneously or alternately sprayed by the CVD method, or the starting gas is continuously sprayed and the nuclear promoting element gas is intermittently sprayed to form a diamond coating film. have. In other words, when synthesizing diamond by vapor phase synthesis, the method of the present invention simultaneously forms a diamond film and sprays a diamond nucleation promoting element to generate a large amount of high-density nuclei to suppress specific crystal grain growth and to smooth or flat diamond. Can provide the membrane. Therefore, this invention intends to form a diamond coating film by the CVD method using said source gas.

According to the fourth aspect of the present invention, a carbon plasma jet by arc discharge is supplied by supplying a mixed gas of hydrocarbon gas and hydrogen gas between an anode and a cathode installed in the reaction chamber while evacuating the reaction chamber in a vacuum by the discharge system. To form a diamond film on the substrate, wherein the plasma of any one element of tungsten (W), molybdenum (Mo), silicon (Si), or titanium (Ti) that can be bonded to a carbon component other than diamond is By adding a hard carbide to the jet, a diamond film having a desired high hardness can be formed on the substrate.

In the present invention, a diamond film can be formed by using the plasma CVD CVD equivalent shown in FIG. At this time, for example, powders such as W, Mo, Si, T, and i, which may form hard carbide, are added through a powder supply tube to react with amorphous carbon, graphite, and other non-diamond components, thereby making tungsten carbide (WC, Hardness 2200kg / mm ² ), molybdenum carbide (Mo ₂ C, hardness 1800k g / mm ² ), silicon carbide (SiC, hardness 2300kg / mm ² ), titanium carbide (TiC, hardness 3000kg / mm ² ) and the like.

That is, for example, amorphous carbon and carbon of graphite are more active than diamond and thus selectively bind with metal element radicals in the plasma state to form hard carbide.

That is, in the present invention, a diamond film is grown by a plasma jet CVD method using a mixed gas of a hydrocarbon such as CH ₄ and H ₂ gas as a raw material gas, and at this time, the diamond polycrystal due to insufficient reduction and removal of H ₂ gas. A small amount of non-diamond diamond components present in the layer are converted to hard carbide to increase the hardness.

According to the fifth aspect of the present invention, a protective film is formed by plasma injection using an element that can easily form a solid solution carbide on a carburized substrate, and then a diamond film is deposited on the protective film by plasma CVD. By forming, a diamond film can be formed on the board | substrate made from a carburizing material.

That is, according to the present invention, it is possible to coat the diamond film on the carburized substrate by providing a coating film for diamond synthesis on the surface of the substrate when synthesizing the diamond by vapor phase synthesis.

Examples of carburized materials used in the present invention include Fe, Ni, Co and other metals. In addition, WC, Si, Mo, M, etc. are preferable as an element which can easily form a solid solution carbide. As will be evident in the examples which follow, it is possible to implement the method of the invention using the above materials and using the same apparatus.

In forming the protective film in the method of the present invention, hydrogen, argon, helium or other inert gas is introduced into the apparatus and then converted into plasma by DC arc discharge. By the high heat generated at this time, the element which easily forms the solid solution carbide introduced through the other supply pipe is melted to form a protective film on the substrate. According to the sixth aspect of the present invention, the diamond film is uniformly and firmly deposited on the side surface of the object or substrate as shown in FIGS. 10 to 12 degrees.

That is, when the above-described intermediate layer and the diamond film are formed on the object (or substrate) 1, the plasma jet 5 does not sufficiently hit the side surface 30 of the object 1, so that the side surface 30 of the object The desired layered stones and diamond film are not deposited. However, according to this aspect, the object 1 is rotated by inclining the object 1 during formation of the intermediate layer and the diamond film and inclining 30 to 60 degrees with respect to the flow direction of the plasma jet 5 (see? In FIG. 10). The intermediate layer and the diamond film are deposited uniformly and firmly on the side 30 of the.

For example, according to the first aspect of the present invention, when the intermediate layer 39 and the diamond film 40 are deposited on the side surface 30 of the object 1, the plasma jet 5 reaches the side 30. And the side surface 30 is not well covered by the intermediate layer 39. Therefore, as shown in FIG. 11, the diamond film 40 is sometimes deposited directly on the side surface 39. FIG. Therefore, the diamond film 40 on the side surface 30 may be easily peeled off or uniformity may occur between the intermediate layer 30 and the diamond film 40, especially at the end of the object 1.

On the contrary, according to this aspect, since the object 1 is rotated at an angle of θ with respect to the flow direction of the plasma jet 5, as shown in FIG. 12, the side surface 30 of the object 1 has an intermediate layer 44. 39 and the diamond film 40 can be uniformly and firmly coated. As shown in FIG. 12, for example, by introducing powder into the plasma jet 5 formed from hydrogen gas or inert gas through the supply pipe 9, for example, WC (the same material as the object), for example, 2 to 5 탆 thick. By forming the first intermediate layer 41 and introducing a powder of Fe, Co, Nb and / or Ta through the supply pipe 9 to the plasma jet 5 generated from the hydrogen gas and the carbon source, for example. For example, the second intermediate layer 42 having a thickness of 10 to 20 µm is formed, and for example, Fe, Co, Ni, Nb and / or the plasma jet 5 formed from a hydrogen gas and a carbon source (hydrocarbon gas such as methane). Alternatively, Ta (the same metals used for forming the second intermediate layer 42) may be introduced through a supply pipe to form, for example, a third intermediate layer 43 of two types. Thereafter, a diamond film 40 having a thickness of, for example, 30 to 50 µm is formed by the same method as described above.

The object (or substrate) 1 can be rotated and inclined by any conventional method. For example, as shown in FIG. 10, the support (31) of the object (or substrate) 1 comprises a cooled support 32 for supporting the object 1, which rotates the support 32. It consists of a motor 34 provided with a rotating shaft 33 for the purpose, a movable part 35 holding the motor 34 and an arc-shaped guide member 36 which makes it easy to move the movable part 35. The surface to be coated in 1) is inclined at an angle of θ. In this aspect, the object 1 is moved to be inclined with respect to the plasma jet flow direction, but the plasma torch may similarly move.

Example

The present invention is described in detail by the following examples, but the present invention is not limited by these examples.

Example 1

A fired body having a fire strengthening agent of Co and a composition of WC-10% Co was used as the object to be treated (1). WC and Co were used as component materials of the first intermediate layer 24. Further, the by component material of the second intermediate layer 25 is made using a diamond bonded with Co, the second intermediate layer and diamond film growth conditions are the use of the CVD apparatus shown in FIG. 3 and 10 ~ 50ℓ minutes, the H ₂ gas / Gas CH ₄ was supplied in an amount of 0.05 to 1 l / min. In addition, the arc current was set to 10 to 70 A, and the arc voltage change range was set to 50 to 150 V. The pressure reduction degree of the reaction chamber was kept in the range of 1-10 kPa.

When the intermediate layer is grown on the treatment object, H ₂ gas is supplied as a starting gas to generate a plasma jet. In this state, WC and Co powder having a particle size of 1 to 5 μm through the powder supply pipe 9 are 0.01 to 0.1. The mixture was fed at a rate of cc / hour to plasma to grow a mixture having a thickness of 20 μm.

The source gas was changed to a mixed gas of H ₂ and CH ₄ , and a plasma jet was generated by supplying a co-powder having a particle size of 1 to 5 μm through the powder supply pipe 9 to generate a plasma jet. Two intermediate layers were formed.

FIG. 6 shows the X-ray diffraction pattern of the second intermediate layer, and the diffraction lines of diamond (abbreviated as D) and the diffraction lines of Co are well represented, indicating that they are mixed layers. Next, a plasma jet was generated using a mixed gas of H ₂ and CH ₄ as a raw material gas to form a diamond film having a thickness of about 100 μm on the top. The adhesion of the diamond film formed by this method to the object to be treated was strong. Tensile test results showed a value of 600kg / mm ² or more.

Example 2

The CDV apparatus shown in FIG. 3 was used, and the flow rate was changed to supply starting gas 8 of 10-50 L / min of hydrogen (H ₂ ) gas and methane gas (CH ₄ ) of 0.05-1 L / min. . Moreover, the metal powder which consists of Cu powder whose particle size is 1-5 micrometers was supplied through the supply pipe 9 at the rate of 0.01-0.1 / cc time.

When a mixed gas of CH ₄ gas and H ₂ gas was used as the starting gas 8, the diamond film 13 was formed, and when the metal powder was mixed, a mixed layer of diamond metal was formed. In addition, when gas and metal powder were used, a metal film was formed. Next, the conditions for CVD growth were that the reduced pressure of the reaction chamber 4 was 1 kPa to 10 kPa, the arc current was 10 to 70A, and the arc voltage was 50 to 150V. Therefore, a 50-micrometer-thick diamond film having a mixed layer of Cu having a thickness ratio of about 5: 1 between the upper surface and the bottom surface was formed. Next, using this diamond film as a heat sink and using a solder having a melting point of 250 ° C. to join the subcarrier or to couple a laser diode to the top of the film, it was possible to solder sufficient bonding strength.

Example 3

In the apparatus shown in FIG. 3, hydrogen gas, methane gas or other starting gas 8 was introduced from the upper end of the plasma torch in the reaction chamber and formed into plasma by DC arc discharge. This plasma 5 was hit on the substrate 1 to form a diamond film 13. During this synthesis process, metal powder may be introduced together with the source gas to spray metal vapor on the diamond surface. In carrying out this example, a WC substrate having a hydrogen gas of 10 to 50 L / min, methane gas of 0.05 to 1 L / min and a thickness of 0.5 mm and a surface area of 10 x 10 mm ² was used. As the spraying powder material, 0.001 to 0.0001 cc of powder having a particle size of 1 to 5 µm were supplied whenever the diamond film thickness increased by 0.1 mm. Arc current was 10-70A and arc voltage was 50-150V. In addition, the pressure-reduction degree of the reaction chamber was 1 kPa-10 kPa. As a result, even in the case of the diamond film having a thickness of 2 mm or more, the surface roughness was 0.05 mm or less.

A diamond film was synthesized under the same synthesis conditions except for the use of other metal powders, and the surface roughness was measured. The results are shown in Table 1.

TABLE 1

Example 4

The CVD apparatus shown in FIG. 3 was used, and a cemented carbide of W containing 8% was used as the metal plate 1. The starting conditions of the starting gas (8) were to change the flow rate of hydrogen (H2) gas within the range of 10-50 l / min, and to change the flow rate of methane (CH ₄ ) gas within the range of 0.05-1 l / min. W powder having a silver particle size of 1 to 5 µm was supplied at a rate of 0.01 to 0.1 cc / hour. Next, the conditions for CVD were 1 kPa-10 kPa, and the arc current was 10-70 arc voltages 50-150, respectively.

¹부근에 비정질 탄소의 넓은 피이크가 관찰됐다.7 shows the Raman spectrum 30 of the film obtained by supplying W as an additive and the Raman spectrum 31 of the film obtained without adding an additive. As can be seen from Figure 7, 1500 Cm in the spectrum of the film without the additive

A broad peak of amorphous carbon was observed around ¹ .

¹의 뾰쪽한 다이아몬드 피크를 관찰하는 것이 가능했고, 1500Cm

¹부근의 비정질 탄소 피이크는 극히 낮았다.On the other hand, 1333Cm of the spectrum 30 of the film obtained by supplying W

It was possible to observe the pointed diamond peak of ¹ , 1500cm

The amorphous carbon peak near ¹ was extremely low.

From this Raman scattering, it was confirmed that the amount of the non-diamond component of the diamond film synthesized by the above method was extremely small.

In addition, the hardness of the diamond film formed by the above method is about 10,000kg / mm ² , and is close to the hardness of natural diamond.

It should be noted that even when Mo, Si or Ti metal powder is supplied through the powder supply plate 9 to form carbide, the diamond film forming conditions are the same, and a diamond film having a hardness similar to that of forming WC can be obtained. .

In the apparatus shown in FIG. 3, a 0.5 mm thick Ni substrate 1 was used, and an inert gas (or hydrogen) was introduced at a rate of 10 to 50 liters / minute into the plasma torch in the reaction chamber 4. Next, with an arc current of 10 to 70 A and an arc voltage of 50 to 150 V, the inert gas was arc discharged to convert into plasma. It should be noted that the reduced pressure of the reaction chamber was 1 kPa to 10 kPa.

Simultaneously with plasma formation of the inert gas, a WC powder having a thickness of 1 to 5 µm was supplied at a rate of 0.01 to 0.1 / hour through a powder supply device. The powder was melted by the high temperature plasma and deposited on the substrate 1 together with the plasma jet 5 to form a protective film.

Next, the powder supply from the powder supply pipe 9 was stopped, and a starting gas for forming diamond (methane or hydrogen) was introduced into the reaction chamber 4. The supply amounts of methane gas and hydrogen gas were 0.05-1 L / min and 10-100 L / min, respectively. This starting gas was converted into a plasma by the DC arc discharge 12, and at the same time, this plasma jet 5 was deposited on the protective film to form a diamond film 13. The diamond film obtained by the method of the present invention was analyzed by X-ray to reveal the pattern. This pattern is shown in FIG. As can be clearly seen from this pattern, both the protective film pattern and the diamond pattern are shown, and the diamond film is clearly synthesized.

On the other hand, X-ray analysis was performed on the substrate without a protective film. The pattern is shown in FIG. As apparent from Fig. 9, only the pattern of (Ni) of the substrate was shown, and the pattern of diamond did not appear, thus confirming that no diamond film was formed.

According to the present invention, it is possible to coat a diamond film having excellent adhesion on the object to be treated, thus providing a highly reliable diamond tool.

According to the present invention, the surface, bottom or whole of the diamond film is formed on the mixed layer by using a CVD apparatus capable of forming a mixed layer of a diamond film and a metal by the CVD growth method while changing the combination of the starting gas and the metal powder. By forming it, a diamond film excellent in adhesive force can be obtained at low cost.

In addition, as described above, in the method of the present invention, since the diamond film is formed by the CVD method using a predetermined source gas, the smoothness of the thick diamond film surface can be significantly improved, the manufacturing cost can be reduced, and the working efficiency can be increased.

According to the present invention, a diamond film having a low content of amorphous carbon, graphite or other non-diamond component can be easily synthesized, thereby providing a diamond tool at low cost.

As described above, in the present invention, after further forming a protective film made of a predetermined material on the substrate, by synthesizing the diamond film, it is possible to obtain the effect of allowing the diamond film to be coated on the carburized substrate which was not possible before.

Claims (24)

Producing by chemical vapor deposition on a substrate or an object to be treated; Forming a first intermediate layer of a mixture of a main component element of the object and a component element of a diamond calcining agent on the object to be treated; Forming a second intermediate layer of a mixture of diamond and a component element of a diamond plasticizer on the first intermediate layer; Forming a diamond film on the second intermediate layer, all of which are formed in the same apparatus. 2. The diamond film forming method according to claim 1, wherein another intermediate layer composed of a main component element of the object, a component element of the plastic strengthening agent, and diamond is formed between the first and second intermediate layers. The method of claim 1, wherein the diamond film is arc discharged while supplying a starting gas containing hydrogen and a carbon source between the anode and the cathode of the high temperature plasma chemical vapor deposition apparatus; Supplying a gaseous carbon compound to the generated plasma jet to radicalize the gaseous carbon compound so that hydrogen molecules are substantially decomposed into hydrogen atoms; Diamond film forming method comprising the step of striking the radicalized plasma jet on the object to be treated. The method of claim 1, wherein the powder is melted and melted by supplying a powder jet of a main component element of the object and a component powder of a plasticizer to the plasma jet while forming a plasma jet of fluorinated gas or hydrogen gas in the first intermediate layer. A diamond film forming method, characterized in that formed by a method comprising the step of depositing the elements on the object. 2. The diamond film forming method according to claim 1, wherein a plasma jet of hydrogen gas and a carbon source is formed, and a second intermediate layer is formed by supplying the calcining agent powder to the plasma jet. The method of claim 1, wherein the second intermediate layer comprises forming a plasma jet of hydrogen gas and a carbon source, and supplying the plasma jet with the component powder of the main component element of the object and the powder of the plasticizer powder. Diamond film forming method characterized by forming. The method of claim 1, wherein the calcining agent is at least one metal selected from the group consisting of cobalt, iron, and nickel. A diamond film characterized by comprising a diamond film (i) formed on a metal plate by chemical vapor deposition and a mixed layer (ii) made of a metal component element bondable with the diamond film contained on the surface, bottom or whole of the film. 9. The diamond film according to claim 8, wherein the metal element is at least one metal selected from the group consisting of Cu and Ag. Arc discharge while supplying a discharge gas containing hydrogen and a carbon source between the anode and the cathode of the high temperature plasma chemical vapor deposition apparatus; Supplying a gaseous carbon compound to the generated plasma jet to radicalize the gaseous carbon compound so that hydrogen molecules are substantially decomposed into hydrogen atoms; And forming a diamond film on the object by striking the radicalized plasma jet on the object to be treated. A method of forming a diamond film according to claim 8, wherein a plasma jet of hydrogen gas and a carbon source is formed while the main component element powder of the metal plate is supplied to the plasma jet to form the mixed layer. A diamond film forming method characterized by synthesizing a diamond film on a substrate by a CVD method using a source gas for diamond formation and a diamond nucleation promoting element gas. 13. The method of claim 12, wherein the diamond nucleation promoting element is at least one element selected from the group consisting of a reducing metal, a carburizing metal, a metal which can easily form carbides, and semiconductors that can easily form carbides. Phosphorus diamond film formation method. The diamond film forming method according to claim 13, wherein the reducing metal is platinum. The method of claim 13, wherein the carburized metal is nickel, cobalt, and iron. The method for forming a diamond film according to claim 13, wherein the metals and semiconductors capable of easily producing carbide are tungsten, silicon, titanium, and molybdenum. 13. The method of claim 12, wherein the diamond film is arc discharged while supplying a discharge gas containing hydrogen and a carbon source between the anode and the cathode of the high temperature plasma chemical vapor deposition apparatus; Supplying a gaseous carbon compound to the generated plasma jet to radicalize the gaseous carbon compound to supply diamond nucleation promoting element powders while the hydrogen molecules are substantially decomposed; And hitting the radicalized plasma jet onto the object to be treated. The reaction chamber is decompressed to a vacuum state by the exhaust system, and a carbon plasma jet is generated by arc discharge while supplying a mixed gas of hydrocarbon gas and hydrogen gas between the anode and the cathode installed in the reaction chamber. To form a diamond film, wherein a diamond film is formed by adding a powder of at least one element selected from the group consisting of tungsten, molybdenum, silicon and titanium, which can be combined with a non-diamond carbon component in the plasma jet. Way, (i) forming a protective film on the carburizing substrate by a plasma injection method using an element capable of easily forming a high melting point carbide, and (ii) forming a diamond film on the protective film by plasma CVD. Phosphorus diamond film synthesis method, 20. The method of claim 19, wherein the element capable of easily forming carbide is at least one element selected from the group consisting of tungsten carbide silicon, molybdenum, titanium and tungsten. 20. The method of claim 19, wherein the diamond film is arc discharged while supplying a discharge gas containing hydrogen and a carbon source between the anode and the cathode of the high temperature plasma chemical vapor deposition apparatus; Supplying a gaseous carbon compound to the generated plasma jet to radicalize the gaseous carbon compound so that hydrogen molecules are substantially decomposed into hydrogen atoms; And bombarding the radicalized plasma jet onto the object to be treated. 20. The method of claim 19, wherein the protective film is formed by supplying the elemental powder to the plasma jet while forming a plasma jet of inert gas or hydrogen. An apparatus for forming a diamond film on an object to be treated; An electrode forming member having a first polarity including an airtight body and a discharge gas supply pipe having a high temperature plasma spray nozzle open therein; An electrode forming member having an opposite polarity disposed opposite to the nozzle in the sealed body; And a power supply system having a DC power supply for supplying a DC voltage between the electrode having the first polarity and the counter polarity electrode, and supplying a gas through the discharge gas supply pipe between the electrodes to which the DC power is supplied. A direct current plasma torch which forms the gas into a high temperature plasma by direct current arc discharge between electrodes and injects the high temperature plasma as a plasma jet through the nozzle; A starting gas supply system for supplying a gaseous starting compound for vapor deposition to the plasma jet; A powder supply pipe for supplying metal powder to the arc discharge part; And a substrate support mechanism for supporting a substrate in the non-equilibrium plasma and allowing a high temperature plasma chemical vapor deposition film to be deposited in the gas phase on the substrate. By supplying two or more component elements in powder form, respectively, to the plasma jet of the gas generated by the direct current arc discharge, a mixture of the main component element of the object and the component element of the diamond calcining agent (i) and the component of the diamond calcining agent Forming at least two intermediate layers consisting of a mixture of elements with diamond (ii); A chemical vapor deposition method comprising forming a diamond film on the intermediate layer by supplying a starting gas containing hydrogen and a carbon source between an anode and a cathode of a high temperature plasma chemical vapor deposition apparatus to generate a plasma jet containing a radicalized carbon compound. To form a diamond film on the object or substrate, wherein the diamond film is firmly formed on the side surface of the object by rotating the object to incline 30 to 60 ° with respect to the flow direction of the plasma jet during formation of the intermediate layers and the diamond film. Diamond film production method characterized in that the deposition.

Images