JPS60116780A - Manufacture of high hardness boron nitride film - Google Patents

Abstract

PURPOSE:To form efficiently a high hardness boron nitride film of high quality on a substrate in a reaction chamber by introducing a gas contg. N and a gas contg. B into the chamber and by generating plasma by electron cyclotron resonance. CONSTITUTION:A coil 2 for an electromagnet is placed around the reaction chamber 1 of an electron cyclotron resonance type discharge apparatus. A magnetic field is applied to the inside of the chamber 1, and microwaves are introduced into the chamber 1 through a waveguide 3. A gas contg. N such as N2 or NH3 and a gas contg. B such as B2H6 or BCl3 are then introduced into the chamber 1 through an introducing pipe 4. Electron cyclotron resonance takes place, electrons collide with the introduced gases to generate plasma by discharge, and a high hardness boron nitride film is formed on a substrate 5 by vapor phase growth.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing a high hardness boron nitride film (hereinafter, boron nitride is abbreviated as BN) by utilizing electron cyclotron resonance plasma.

Cubic boron nitride (hereinafter abbreviated as CBN) and hexagonal close-packed boron nitride (hereinafter abbreviated as WBN) have excellent thermal shock resistance, thermal conductivity, hardness and wear resistance, and resistance to iron group metals at high temperatures. Because of its excellent properties, it is attracting attention for a wide variety of applications such as cutting members, wear-resistant members, and heat-resistant members, and along with this, research is being conducted into methods for producing high-quality CBN and WBN.

As a known manufacturing technology, ultra-high pressure is used using expensive equipment.
There is a method for synthesizing cBN films at high temperatures, but research is also being conducted on efficient synthesis of cBN films and wJ-films using vapor phase growth methods. That is, the plasma CVD method, the reactive ion blating method, etc. are still using CBN and W.
There have been no reports on the synthesis of BN, and recently there have been reports that CBN of relatively high quality could be synthesized by ionization synthesis. Incidentally, according to this ionization synthesis method, boron is evaporated onto a substrate by electron bombardment, and CBN is deposited on this substrate by simultaneously irradiating nitrogen ions.
This means that a film can be formed.

In addition to the previously proposed ionization synthesis method, the present inventor
In developing a new vapor phase growth method suitable for the synthesis of N and WBN, as a result of intensive research, we discovered that high quality CBN and WBN can be formed using electron cyclotron resonance plasma.

The present invention has been completed based on the above findings, and it is an object of the present invention to provide a novel method for producing high-hardness BNWA that efficiently synthesizes high-quality CBN and WBN films.

The method for producing a highly hard BN film according to the present invention involves introducing a nitrogen atom-containing gas and a boron atom-containing gas into a reaction chamber, and generating an electron cyclotron co-plasma inside the reaction chamber to vaporize BN onto a substrate. It is characterized by phase growth.

Hereinafter, one aspect of the present invention will be explained in detail.

The figure shows an electron cyclotron resonance discharge apparatus for forming CBN films and WBN films. and microwaves (2.45 GHz) are introduced into this reaction chamber (1) via a waveguide (3).

Nitrogen atom-containing gases such as Ng and NHs (hereinafter abbreviated as N-containing gas), as well as B2H6 and (C
11H6) At the same time that a boron atom-containing gas (hereinafter abbreviated as B-containing gas) such as aB, BCIs, BBra, etc. is introduced into the reaction chamber (1) through the introduction tube (4), electron cyclotron resonance occurs, and electrons are Contained gas and B
It collides with the contained gas to generate a discharge and generate plasma, which is vapor-phase grown as a CBN film and a WBN film on the substrate (5). In other words, the cyclotron frequency f of electrons is equal to the charge, B
: Magnetic flux density) causes cyclotron motion, and when this frequency f matches the frequency of microwaves (2,45GH2), it resonates, and as a result, electrons are released into each molecule of N-containing gas and B-containing gas. , collisions with ions and radicals significantly increase the highly excited state discharge phenomenon, and the generation of plasma becomes even larger. In order to generate this plasma, it is best to set the gas pressure within the reaction chamber (1) to 1O-3 to 1O-6jO], and the pressure can be significantly reduced compared to the known vapor phase growth method. Therefore, in addition to generating high-purity 1-raz →, the plasma generation rate is high and its lifetime is long, so high-quality CBN films and WBN films can be efficiently grown in vapor phase. Further, (6) is a gas outlet for exhaust gas that is no longer needed for the generation of this CBN@WBN.

In the present invention, in order to form a CBN film and a WBN film, N contained in each of the N-containing gas and the B-containing gas is
It is preferable to set the atomic ratio of the atoms and B atoms so that the atomic ratio of N atoms to B atoms is in the range of 1/10 to 10, and if it deviates from this set range, precipitation will occur.
The content of CBN and WBN is considerably reduced. It has been experimentally confirmed that this optimum condition is in five ranges from 1/2 to 3.

It should be noted that the gas used in the production method of the present invention does not necessarily have to be divided into N-containing gas and B-containing gas;
A single type of gas containing N atoms and B atoms such as Ha and AJIBIIN4 and having a content ratio of these atoms in the range of 1/10 to 10 may be introduced.
The substrate (5) on which the CBN film and WBN film are formed needs to be maintained at a temperature within a predetermined range during the deposition, so that the 90BN@WBN structure is formed by vapor phase growth. It can be adhered to the substrate (5) and developed into a film while maintaining the . Its board temperature.

The temperature is preferably -100 to 500°C, and if it is outside this range, amorphous and hexagonal EN will increase, making it impossible to obtain high-quality CBN and WBN films.
Jvt? 1. s Thus, according to the method for manufacturing a high hardness BN film according to the present invention, the atomic ratios of N atoms and B atoms contained in each of the N-containing gas and the B-containing gas introduced into the reaction chamber can be specified to a predetermined quantitative ratio. At the same time, when the gas pressure in the reaction chamber is set within a predetermined range and electrons are collided with these gases to cause a discharge due to electron cyclotron resonance, highly excited □ state radicals and ions with SP8 hybrid orbitals are generated. etc. are generated with high efficiency and long life, and as a result, very high quality CBN and WBN films are formed on the temperature-set substrate.

Next, examples of the present invention will be described.

〔Example〕

Using the above-mentioned 'fcWL child cyclotron resonance discharge device, first, Nl! While increasing the flow rate of B'9 He gas to 2.5 times that of the gas, N9 gas and B+'Ha gas! The total flow rate was set to 106 *J/- and was introduced into the reaction chamber (1). In this case, the atomic ratio of N atoms to B atoms is 2.5. From this point, reaction chamber (1)
The internal pressure was set at 10°C.

Next, the electromagnet coil /l/ (the second coil is placed in the reaction chamber (
1) Apply a magnetic field inside and microwave (2.45GH2
) was introduced into the reaction chamber (1) via the waveguide (3) to generate electron cyclotron resonance plasma.

After continuing these conditions for 3 hours, a 5 μm thick layer of B was deposited on the substrate (5).
The N film was grown by chemical vapor deposition.

When the BN film thus obtained was analyzed by X-ray diffraction, peaks identified as CBN (111) and WBN (002) were confirmed, and their existence was confirmed.

As is clear from the above-mentioned examples, according to the method for producing a high-hardness BN film according to the present invention, electron cyclotron resonance glasma with high ion density is efficiently generated from the N-containing gas and the B-containing gas. -WBH
The synthesis of was significantly promoted, and a highly hard BN film with very low impurities and high EC quality could be formed on the substrate.

Since heat sources for plasma generation such as carbon fibers and filaments are not used, defects in the heat sources may cause damage to the CBN film and W.
It also has the advantage that the formation of the BH film is not inhibited and stable production can be maintained, and as a result, a highly reliable method for producing a high hardness BN film suitable for mass production type f can be provided.

[Brief explanation of the drawing]

The figure is a schematic diagram of an electron cyclotron resonance type discharge device for forming cubic boron nitride and hexagonal close-packed boron nitride. (11...Reaction chamber, (21--Electromagnetic coil, (3
)...Waveguide tube, +41, Gas introduction tube, <51-
··substrate. Patent Applicant: Kyocera Corporation February 10, 1980 Director General of the Patent Office Mr. Waka Seisoo 1, Indication of Case: 1982 Patent Application No. 224985 2
, Title of the invention: Method for manufacturing high-hardness boron nitride film 3, Person making the amendment 4, Date of amendment order Voluntary amendment 5, ``Claims column'' of the specification to be amended, ``Detailed description of the invention'' 6. Contents of amendment (1) The scope of the claims of the Toyonaka Patent Specification is amended as follows. "High hardness nitriding characterized by introducing a nitrogen atom-containing gas and a boron atom-containing gas into a reaction chamber and generating electron cyclotron resonance plasma inside the reaction chamber to grow boron nitride on a substrate in a vapor phase. ``Method for manufacturing a boron film.'' (2) Specification Toyonaka, page 2, line 10, page 2, line 11,
Page 3, line 5, page 3, line 19, page 5, line 12, page 5, line 15, page 5, line 16, page 6, line 10
line, page 6, line 20, page 7, line 6, page 7, line 1
Line 6, page 8 fJ9 line says “substrate”, replace it with “substrate”
and correct it. that's all

Claims (1)

[Claims] High hardness boron nitride characterized by introducing a nitrogen atom-containing gas and a boron atom-containing gas into a reaction chamber and generating electron cyclotron resonance plasma inside the reaction chamber to grow boron nitride on a substrate in a vapor phase. Membrane manufacturing method.