JPS605882A - Formation of hard carbonaceous film on surface of substrate - Google Patents

Abstract

PURPOSE:To form an electrically insulating carbonaceous film with high hardness and transparency on the surface of a substrate by introducing gaseous hydrocarbon and gaseous Ar into a duoplasmatron in a specified volume ratio and irradiating generated ion beams on the substrate in vacuum. CONSTITUTION:A gaseous mixture having 2-5 volume ratio of gaseous hydrocarbon/gaseous Ar is introduced into a duoplasmatron 1 from the inlet 2 for introducing gases for electric discharge, and ion beams are generated in a state in which the hydrocarbon is partially decomposed by 30-90%. The beams 3 are irradiated on the surface of a substrate 6 placed on a substrate holder 6A in the deposition chamber 4 evacuated to 10<-3>-19<-6> Torr degree of vacuum. Voltage of -200--1,000V is impressed to the substrate 6 beforehand. By this method a hard and transparent carbonaceous film is formed on the surface of a lens or a decoration as well as a wear resistant tool.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a hard carbonaceous film on the surface of a substrate using a Duo Plasmatron, which is commonly known as an ion beam generator.

In general, the Duo Plasmatron is a well-known ion beam generator.

This Duo Plasmatron has a discharge gas introduction hole.
This device introduces Ar gas and generates the Ar gas as an A1-ion beam, and is used as a sputtering source for metal sputtering, for example, as shown in FIG. That is, in the sputtering apparatus using an ion beam shown in FIG.
r gas is introduced, and thereby an Ar ion beam 3 is generated and an Ar ion beam 3 is introduced into the vapor deposition chamber (l Q to
For example, an MO target 5 in a vacuum (vacuum of rr or higher) is irradiated, and the ζMog air is sputtered from the solid target 5 and is deposited on the surface of a substrate 60.

As described above, the Duo Plasmatron is known as an ion beam generator, and the inventors of the present invention conducted research to form a carbonaceous film using such a Duo Plasmatron, and as a result, Ar gas, which is known as a discharge gas, is introduced separately or in a mixed state through the discharge gas inlet of the hydrocarbon gastra or Duo Plasmatron, and as a result, Ri is released from the Duo Plasmatron.
When the ion beam containing the partially decomposed hydrocarbons ([)11] is irradiated onto the surface of a substrate placed in a deposition chamber and to which a negative voltage is applied, the surface of the substrate has a Vickers hardness. at 2500-5000 Kg/mA'
It was discovered when a hard carbonaceous film having z began to be formed.

Therefore, this invention was made based on the above knowledge, and it is possible to introduce hydrocarbon gas and Ar gas separately or in a mixed state through the discharge sludge introduction hole of the Duo Plasmatron, and to An ion beam is generated in which the hydrocarbons are partially decomposed at a ratio of 30 to 90 by introducing Ar gas at a ratio of hydrocarbon/A rf in a volume ratio of 2 to 5. This ion beam is heated in a vacuum of 10-3 to 10tOrr,
This method is characterized by the method of irradiating the surface of a substrate to which a voltage of 200 to 1000 V is applied to form a hard carbonaceous film on the entire surface of the substrate.

Next, in the method of this invention, explain the reason why the conditions for forming the carbonaceous film are limited as described below.

fa) Hydrocarbon/Ar ratio Hydrocarbons are partially decomposed in the Duo Plasmatron, carbon ions generated by this partial decomposition form a carbonaceous film, and the remaining 9 ions and active particles that are further decomposed form the carbonaceous film. It acts effectively on the formation of a film by vapor deposition, but if the ratio is less than 2, l\r becomes relatively too large compared to the hydrocarbon, and the formation rate of the carbonaceous film sharply decreases. On the other hand, if the ratio exceeds 5, there will be too much hydrocarbon compared to Ar, and the discharge in the duo-plasmatron will become inactive, resulting in the desired partial decomposition of the hydrocarbon. Since this makes it impossible to do so, the ratio was set at 2 to 5.

(1)) Vacuum degree of vapor deposition atmosphere Part 31. , H2 sky 141. ) is less than l Q torr, the distance between the duo-plasmatron and the substrate 6
This is also related to 1+, but ion beats collide with residual gas in the deposition atmosphere [-1] They lose charge and energy, which becomes an obstacle to carbon film formation;
If the degree of vacuum exceeds J'℃, the concentration of the ion beam in the deposition atmosphere will become relatively too low, and the deposition rate of carbon IP (film) will decrease significantly. ~l Otorr.

(C) Decomposition rate of hydrocarbons in the ion beam If the decomposition rate is less than 30%, the relative proportion of carbon ions that directly act on carbon film formation will be low, which will not only significantly slow down the film formation rate but also The film quality deteriorates due to a large proportion of undecomposed hydrocarbons, and on the other hand, when the decomposition ratio exceeds 90%, free Pil [carbon] is easily precipitated and the film quality becomes blackish. Because it becomes easier to graphitize, its decomposition rate is '53.
It has been set as 0 to 90 staff.

(d) Applied voltage to the substrate If the applied voltage is less than 1200V, not only the adhesion strength of the carbonaceous film to the substrate surface is weak, but also a film of good quality cannot be formed;
If it exceeds this, the deposition rate will slow down and the temperature of the formed film will rise, causing graphitization. Therefore, the applied voltage f is 1-200 to -too.

It was set as V.

Next, the method of the present invention will be specifically explained using examples.

An S1 wafer, a WCC cemented carbide chip, and a quartz glass plate were prepared as the example substrates, and hydrocarbon gas and Ar gas as a reaction gas were mixed in a state as shown in the schematic diagram in FIG. There is a device (hereinafter referred to as device A) that introduces hydrocarbon gas through the discharge gas introduction hole 2', and a device that introduces the hydrocarbon gas through the discharge gas introduction hole 2', and a device that introduces Ar gas through the discharge gas introduction hole 2, as shown in FIG. Equipment to be introduced (hereinafter referred to as B
The above-mentioned substrate was placed on a substrate holder 〇A''2 within ≦4 for evaporation using a device (referred to as a device), and was placed in contact with a Duo Plasmatron II under the conditions shown in Table 1, respectively. Methods 1 to 8 and 1 of the present invention, in which the entire reaction gas is introduced and a carbonaceous film is formed on the surface of the duo plasma.
Note that in Comparative Methods 1 to 5, any one of the carbonaceous film forming conditions (marked with * in Table 1) is outside the scope of this invention. The decomposition rate of hydrocarbons in the ion beam was measured using 4M phase mass spectrometry M-tK.

Next, the average film Jr7 of the carbonaceous film formed as a result,
Vickers hardness and electrical resistance were measured, and the color tone was observed.゛These results are also shown in Table 1.

From the results shown in Table 1, the carbonaceous films formed by methods 1 to 8 of the present invention all had high hardness, were perfect electrical insulators, and were transparent. On the other hand, as seen in Comparative Methods 1 to 5, if the formation conditions deviate from the scope of the invention, only a carbonaceous film is formed that is inferior in at least one of the above characteristics. It is clear that this cannot be done.

As mentioned above, according to the method of the present invention, it is possible to form a hard and transparent carbon film based on a hard and transparent carbon film. Cutting tools, dies, and nozzles.

If the tool is resistant to scratches, such as a guide member, the abrasion resistance will be significantly improved by the formation of the carbonaceous film, and if the substrate is a solar cell or the like, the carbonaceous・The formation of a carbonaceous film improves corrosion resistance and also acts as a protective film.Furthermore, if the substrate is a lens or ornament that requires full translucency, this carbonaceous film will protect it well. Industrial effects such as 1-1) are brought about.

[Brief explanation of drawings]

FIG. 1 is a schematic explanatory diagram of a conventional spasoaking apparatus using an ion beam, and FIGS. 2 and 3 are schematic explanatory diagrams showing an apparatus for implementing the method of the present invention. In the drawing, 1. Duo plasmatron, 2. 2'... Gas introduction hole at the bottom, 3. Ion beam,
4... Vapor deposition chamber, 5... Target, 6... Substrate. Applicant Mitsubishi Metals Co., Ltd. Agent Tomi 1) 1st Husband and 1 other person Figure 1 Figure 2 Figure 3

Claims (1)

[Claims] Hydrocarbon gas and Ar gas are introduced separately or in a mixed state through the discharge gas introduction hole of Duo Plasmatron, and the ratio of hydrocarbon gas and Ar gas is: hydrocarbon/A1''.
The ion beam is introduced at a volume ratio of 2 to 5 to generate an ion beam in which the hydrocarbon is partially decomposed at a rate of 30 to 90%.
A method for forming a hard carbonaceous film on the surface of a substrate, the method comprising irradiating the surface of the substrate to which a voltage of -200 to -1000V is applied in a vacuum of ~10 torr.