JPS60114571A - Formation of very hard coating layer - Google Patents

Abstract

PURPOSE:To form uniformly nuclei of diamond particles on a substrate in a very short time by leading a gaseous mixture having a specified composition consisting of H2, CxHy and TiCl4 in an activated state under a specified pressure to the surface of the substrate heated to a specified temp. CONSTITUTION:A substrate such as an Si-W-WC-6%Co alloy chip is heated to 300-1,100 deg.C, and a gaseous mixture consisting of H2, CxHy and TiCl4 is led in an activated state to the surface of the substrate to form a diamond film contg. Ti on the substrate. In the gaseous mixture, the amount of Ti is 0.005-0.1 atom% of the amount of C under 0.1-100Torr pressure. A CxHy CH4 may be used.

Description

[Detailed Description of the Invention] Methods for synthesizing diamond without using ultra-high pressure have been actively developed, and one of the methods is a low 11:CV synthesis method.
I) A law was invented. This method (soil 300℃~+10
Pressure 0.1 to + 0 on the substrate
Diamond 1 is deposited on the substrate by introducing a mixed gas of 01'Or r,, -Cxlly in an activated state.
It is a method for growing a thin carbon film that improves the structure. Furthermore, it is also possible to synthesize diamond particles of 10 μF or more using the same method.

To industrialize the above method, however, many difficulties must be overcome, the most important of which are:
The problem is that the conditions under which diamond-structured particles form nuclei on a substrate are extremely unstable and have poor reproducibility.

In other words, nucleation is extremely sensitive depending on the substance of the substrate, the surface roughness of the substrate, whether the substrate surface is clean, etc., and is not reproducible even if the same residue composition, pressure, and activation method are used each time. The current situation is that it is difficult.

The present invention solves the problems of the conventional method.
L<, diamond particles or films can be easily synthesized.

This has made it possible to manufacture various tools and parts that take advantage of diamond's wear resistance.

In the present invention, the conventional II, -Cxlly mixed if
, x into which a small amount of T1Cl is mixed. T1Cl4 in the mixed gas is calculated as the number of carbon atoms versus the number of Illi atoms, and is 0.005 to 0.1
range is suitable.

11□-Cxlly-T i C mixed in this range
I, the scum is introduced onto the substrate in an activated state (and 'II'
Compared to the case where CI4 is not mixed, the nuclei of diamonds are uniformly formed on the substrate in an extremely short time and the nuclei begin to grow. When the thin 11 convexes at this stage of nucleation were detected by fluorescent X-ray analysis, the '1゛i element, which was not detected when the substrate was rolled out, was detected.

This is because if it is L-, the warpage will not be sharp, and if it is 0.1 or more, it will actually inhibit the formation of the diamond layered substance.

Also, heating the substrate 111 □, once at 300"C~110
A temperature of 0° C. is good, and a temperature of 300″C or higher does not produce a diamond-forming substance, and a temperature of 1100″0 or higher does not produce a diamond-like substance.

The pressure is preferably 0.1 to +00 Torr, and like the temperature conditions, if the lower and upper limits of this range are exceeded, no diamond structure material will be formed.

There are various means for activating the mixed gas. All of the conventionally known thermoelectron emission methods, high frequency plasma methods, and microwave methods can be used in the present invention. In addition, the present inventors newly invented an arc method and found that this method can also form an extremely excellent diamond film.It promotes the formation of diamond nuclei and improves the synthesis of uniform films and the deposition rate. It can be obtained by growing a diamond film only in the summer of 2000.

Example-1 A tungsten coil was placed in a vertical quartz tube,
J top 7! Electricity was applied so that l'i'1 degree was 1800°C or higher.The metal or alloy pieces of each row were placed as a base at the bottom, about 50 mrn away from the coil.

A nichrome gland heater was heated from the outside of the quartz tube to bring the crystallinity of the substrate to 710°C. The bus composition is +12: 959'o, (-1j
A mixture of: 4.9%, T1Cl, and 0.1%) was flowed into the quartz tube from the top and the pressure was reduced to 10 Torr using a vacuum. By passing through a tungsten coil portion, the scum by thermionic radiation was reduced to 1% and introduced onto the substrate. Nonos θ11. The time between 11 and 1c was set to 10 minutes, and the ease of nucleation of the diamond-forming material was observed. For comparison, vapor deposition was performed under the same conditions except that the residue composition was 45%. The results are shown in Table-1.

Table-1 Example-2 11 famous metals or alloys in a 6-piece duplex
(Heat the substrate j!+?+ to 730℃ from the outside of the quartz cove with a nichrome wire heater, and place a high-frequency coil on the second part of the heater, and heat it to about 14M1b.
(mechahertz) high frequency is given. Crush composition is I+2:
92shi73, C114: 7.8%, i'1cI4:
The mixed scum of 0.2″3b is heated to 1 AI from the upper i'j3, and the pressure is reduced by 1'+ at the bottom of the tank. is internalized) t, , -1, -j, is expanded over the body.
L person time is 6 hours, diamond escape generation status is 81>M, r, 1. I guess so. Eye drop l” i C14
Compared with n:j without mixing, it is shown in A(, -2).

Table 2 Using a microwave-excited low-pressure diamond synthesis apparatus, the device has a part for introducing microwaves of approximately 2500 Mllz (mechahertz) through a waveguide, and a substrate is placed at the bottom of the introduction part. The synthesis reaction of Da E'mond was carried out for 30 minutes under known reaction conditions that do not involve using a substrate, and under conditions outside the scope of the present invention. Table 3 shows the conditions.

Table 3 Example 4 A W body substrate was placed inside a quartz tube, a tank stainless polarized pair was placed on the quartz tube, and a voltage of 2KV was applied between the electrodes.
O high school 1st 2. Pressure is applied with alternating current to create several arcs between the electrodes. The substrate was heated to 750° C. from 1+111 on the outside of the quartz tube. Reaction No. 7 11. ,: 96%
, (+++, : 3.cr・:., TiCIt a
C1l 9o wo use i, j5I from the quartz tube Dobe
The pressure was reduced to 4T (10°C) using a vacuum pump.

Reaction 11] 1 interval was 10 minutes, and for comparison 'J' i C
l, including moss (・Jr Susunawa l') II□: 96%,
Using the reaction residue of C11,: ln, diamond J'lI'lJ blue thing 7 no 1 is generated between the two.11
We compared the ease of 11. As a result, i' i C month. River ℃・2) "↓-"1 go of the present invention,'□4. Child line time t1
7 te yamo/1.4 niji notice'] of course'1'2-1 Ifll : ffg Vza/this is 112-(ko 11
U no no 1 Isuke, Diamond ti';

Procedural amendment oral format) %formula% 1. Display of incident Patent Application No. 1982-221806 2. Name of the invention Method of forming ultra-hard coating layer 3. Person who makes corrections Relationship to the incident: Patent applicant Otemachi-5-2, Chiyoda-ku, Tokyo (6261 Mitsubishi Metals Co., Ltd. Representative Ken Nagano 5. Date of amendment order Tables 1, 2, and 3 will be amended as shown in the attached sheet.

Claims (1)

[Claims] A method of coating a carbon-based thin film that cures a diamond structure containing a small amount of 1.