JP2961790B2 - Method for producing boron nitride-containing thin film-coated substrate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a machine tool such as a cutting tool, a mold, a magnetic head, etc.
The present invention relates to a method for producing a boron nitride-containing thin film-coated substrate that improves wear resistance, prevents seizure, and improves slidability by coating a hard boron nitride thin film on the surface of a mechanical component.

[Conventional technology]

Boron nitride (hereinafter abbreviated as BN) is cubic zinc-blende-type boron nitride (hereinafter abbreviated as c-BN) or hexagonal graphite-type boron nitride (h-
BN), hexagonal wurtzite boron nitride (hereinafter referred to as w
-BN).

Since c-BN has the second highest hardness next to diamond and has excellent thermal and chemical stability, it is applied to fields requiring wear resistance such as cutting tools. In addition, it is also expected to be used for materials such as heat sink materials that make use of insulating properties and high thermal conductivity. Further, w-BN, like c-BN, has been applied to fields requiring abrasion resistance by taking advantage of its characteristics of excellent chemical stability, thermal shock resistance and high hardness.

However, c-BN and w-BN are both artificially synthesized under high temperature and high pressure, and the production cost becomes extremely high, and the synthesized c-BN and w-BN are synthesized. Can only obtain a granular or powdery solid, and its application range is also limited. Therefore, c-BN
Research on a method for forming a thin film of w-BN under low temperature and low pressure has been actively conducted by a physical vapor deposition method (PVD method) or a chemical vapor deposition method (CVD method).

For example, in a chemical vapor deposition method (CVD method), a substrate on which a thin film is deposited is placed in a reaction chamber and heated to a temperature close to 1000 ° C., and then diborane (B) containing elemental boron (B) is used.
Ammonia containing gas or nitrogen elements _{2 H 6) (N) (} Ammon
A source gas such as ia: NH ₃ ) gas is introduced into a reaction chamber and subjected to a thermal decomposition reaction to form a BN thin film on the surface of the substrate. However, even if a high-speed tool steel is used as a substrate in this method and an attempt is made to form a BN thin film on the surface, the high-speed tool steel is thermally degraded at a temperature of about 600 ° C. It is not possible, and the substrate on which the BN thin film is formed is limited. Further, the BN thin film formed by this method tends to be a thin film mainly composed of soft h-BN, and the above-mentioned properties of c-BN and w-BN cannot be fully utilized.

In addition, in the physical vapor deposition (PVD method), a reactive sputtering method in which boron is sputtered in a nitrogen gas atmosphere and a BN thin film is formed on the surface of the substrate has been attempted. As in the case of the method (2), only a thin film mainly composed of h-BN can be obtained.

Therefore, in recent years, attempts have been actively made to form a thin film of c-BN or w-BN under conditions of low temperature and low pressure using ions or plasma. For example, Japanese Patent Publication No. 58-2022 proposes to form a BN thin film on the surface of a substrate by irradiating nitrogen ions simultaneously with vacuum deposition of boron. According to this method, it is possible to form a thin film of c-BN or w-BN without particularly heating the substrate. There is an advantage that a new mixed layer is injected between the substrate and the BN thin film by being injected into the surface layer, and the adhesion of the BN thin film is greatly improved.

[Problems to be solved by the invention]

However, c-BN and w obtained by the above method
-Since BN thin films have particularly poor affinity for metals (wetting properties), when metal is used for the substrate, the adhesion of the thin films is weak, and it tends to be difficult to obtain a practically sufficiently durable one. .
Further, when the substrate coated with the BN thin film is exposed to a high temperature, the BN thin film is easily peeled off due to the difference in the coefficient of thermal expansion between the BN thin film and the substrate and the internal stress in the thin film. Further, there are problems such as peeling of the thin film due to an increase in internal stress inside the BN thin film caused by a difference in lattice constant between the substrate and the BN thin film, and crystal growth and hindrance of c-BN and w-BN.

The object of the present invention is not only that the formed thin film has high hardness, but also has high adhesion to the substrate and does not peel off under high temperature conditions, and contains a large amount of boron nitride having a c-BN structure. Obtain BN-containing thin film, c-BN and w-BN
To provide a method for producing a boron nitride-containing thin film-coated substrate that does not hinder the crystal growth of the thin film.

[Means for solving the problem]

In the method for producing a boron nitride-containing thin film-coated substrate according to claim (1) of the present invention, after the first step of irradiating the surface of the substrate with ions containing a nitrogen element (N), the silicon element (S
a second step of irradiating ions containing a nitrogen element (N) simultaneously, alternately or after the deposition of the substance containing i), and a deposition of a substance containing boron (B) after the second step; A third step of irradiating ions containing a nitrogen element (N) simultaneously, alternately or after the vapor deposition, to form a boron nitride-containing thin film-coated substrate by forming a boron nitride-containing thin film. , The irradiation amount of the ion containing nitrogen element (N) is 1 × 10 ¹⁵ to 1 × in terms of the number of nitrogen ions.
10 ¹⁷ [Number of ions / cm ² ], and the acceleration energy of the ions is in a range of 1 KeV to 40 KeV. In the second step, the irradiation amount of the ions containing the nitrogen element (N) is set to nitrogen ions. 1 × 10 ¹⁵ 〜1 ×
10 ¹⁷ [number of ions / cm ² ] and the acceleration energy of the ions is in the range of 1 KeV to 40 KeV, the silicon element (S
A thin film containing i) is laminated to a thickness of 100 to 5000 mm, and in the third step, the acceleration energy of the ions containing the nitrogen element (N) is set to 40 KeV or less, and the boron element (B) is contained. A thin film is laminated, and the ratio of the number of particles between boron atoms and nitrogen atoms contained in the thin film is set to 1 to 60.

In the method for producing a boron nitride-containing thin film-coated substrate according to claim (2), in the third step of forming the boron nitride-containing thin film according to claim (1), the material containing boron element (B) and the nitrogen element ( By intermittently or continuously reducing the transport ratio with the substance containing N), the ratio of the number of particles of boron atoms and nitrogen atoms in the thin film containing boron element (B) can be reduced. It increases intermittently or continuously as it moves from the surface to the inside.

An example of a thin film forming apparatus according to the present invention will be described with reference to FIG.

In a vacuum device (not shown), a base 2 that has been subjected to cleaning such as degreasing as necessary is fixed to a holder 1. Below the base 2, an evaporation source 3, which can be heated to a high temperature by an electron beam, a laser beam, a high frequency, or the like,
4 are provided. In the evaporation source 3, an evaporation substance 6 containing a boron element (B) made of elemental boron, boron oxide, boron nitride or the like, and in the evaporation source 4 elemental silicon, silicon oxide, or An evaporating substance 7 containing a silicon element (Si) made of silicon nitride or the like is contained therein. An ion source 5 of a Cuffman type or a bucket type using a cusp magnetic field for confining plasma is provided in a direction directly facing the base 2.

The ion source 5 is a device that ionizes a gas such as a nitrogen atom, a nitrogen molecule or a mixture of a nitrogen gas and an inert gas, and irradiates the surface of the substrate 2 as ions 8 containing a nitrogen element (N). Further, a film thickness meter 9 is provided in the vacuum device.
And a current measuring device 10 are arranged.

This film thickness meter 9 is a vibration-type film thickness meter using a quartz oscillator for measuring the film thickness of the deposition materials 6 and 7 deposited on the surface of the substrate 2 and the number of particles of boron atoms and silicon atoms. is there. The current measuring device 10 has a cup-shaped ion beam current having a secondary electron suppressing electrode such as a Faraday cup for measuring the amount of nitrogen ions of the ions 8 irradiated on the substrate 2, that is, the number of particles of nitrogen atoms. It is a measuring instrument or the like.

In the above configuration, as a first step, a gas containing a nitrogen element (N) is introduced into the ion source 5 and the surface of the substrate 2 is irradiated with ions 8 containing nitrogen ions. Irradiation of the ions 8 onto the substrate 2 has an effect of hardening the surface of the substrate 2, improving the wear resistance of the substrate 2 itself, and affecting the hardness of the BN-containing thin film.
The affinity between the substrate 2 and the thin film containing the silicon element (Si) laminated in the next second step is increased. At this time, the ion dose 8, 1 × 1 ¹⁵ ~1 × 1 with nitrogen ions number conversion
0 ¹⁷ [Number of ions / cm ² ], and the acceleration energy of irradiation ions is 1 KeV to 40 KeV.

The irradiation amount of ion 8 is 1 × 10 ^{15 in} terms of the number of nitrogen ions.
If the number is smaller than [the number of ions / cm ² ], the effect of irradiation with ions 8 does not appear, and 1 × 10 ^{17 in} terms of the number of nitrogen ions.
If the number is larger than [the number of ions / cm ² ], many defects are formed inside the
The strength of the steel sheet deteriorates.

Further, when the acceleration energy of the ions 8 is smaller than 1 KeV, the irradiation effect of the ions 8 does not clearly appear because the depth of the ions 8 penetrating into the inside of the base 2 is small. Further, when the acceleration energy of the irradiation ions is greater than 40 KeV, many defects are formed inside the base 2 due to the influence of the irradiation of the ions 8 as in the case of the irradiation amount.

Next, after irradiating the surface of the substrate 2 with ions 8 containing nitrogen ions in a first step, a thin film containing a silicon element (Si) is laminated on the surface of the substrate 2 in a second step described below. I do.

In the second step, when the evaporation material 7 containing the silicon element (Si) is deposited on the surface of the base 2 from the evaporation source 4,
Alternately or after the deposition, ions 8 containing nitrogen element (N) are irradiated from an ion source 5. At this time, the irradiation amount of the ions 8 is in the range of 1 × 10 ¹⁵ to 1 × 10 ¹⁷ [number of ions / cm ² ] in terms of the number of nitrogen ions, and the acceleration energy of the ions 8 is 1 KeV to 40 KeV, and the silicon element ( A thin film containing Si) is laminated with a thickness in the range of 100 to 5000 mm.

The thin film containing the silicon element is made of the thin film containing the boron element (B) formed in the next third step and the substrate 2
Of the adhesion due to the difference in thermal expansion coefficient and lattice constant between the film and c, formed in the thin film containing the boron element (B).
By removing the effects such as hindering the crystal growth of -BN and W-BN structures, and irradiating the silicon thin film with ions containing a nitrogen element, the interface between the substrate and the silicon thin film causes the formation of both constituent atoms. Because a mixed layer consisting of
The adhesion between the silicon thin film and the substrate can be improved. However, when the irradiation amount of the ions 8 to be irradiated at this time is smaller than 1 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions, or when the acceleration energy of the irradiated ions is smaller than 1 KeV, the substrate 2 and silicon The formation of the mixed layer at the interface with the thin film containing the element (Si) becomes insufficient. When the irradiation amount is more than 1 × 10 ¹⁷ [number of ions / cm ² ] in terms of the number of nitrogen ions, or when the acceleration energy of the irradiation ions is more than 40 KeV, a defect generated in a thin film containing silicon element (Si) is generated. Is undesirably increased.

Further, when the thickness of the thin film to be laminated is less than 100 °, the effect of the above-mentioned thin film containing the silicon element (Si) is not clearly exhibited. Further, when the film thickness is more than 5000 °, when the substrate 2 is exposed to a high temperature, due to a difference in thermal conductivity from the thin film containing the boron element (B) laminated in the third step, A thermal gradient is generated in the boron nitride-containing thin film covering the surface of the base 2, and the thin film is easily peeled.

Subsequently, a thin film containing the boron element (B) is laminated on the surface of the silicon element (Si) -containing thin film laminated in the second step in a third step described below.

In the third step, the evaporation material 6 containing the elemental boron (B) is vapor-deposited on the surface of the substrate 2 from the evaporation source 3 simultaneously.
Alternating or after the deposition, the ion source 5 is irradiated with the nitrogen element (N). At this time, the acceleration energy of the ions 8 is set to 40 KeV or less, and the ratio of the number of particles of boron atoms and nitrogen atoms contained in the formed thin film containing the boron element (B) is controlled in the range of 1 to 60. Laminate.

If the acceleration energy of ion 8 is greater than 40 KeV,
Many defects are formed inside the thin film containing the boron element (B), and the characteristics of the thin film deteriorate. The lower limit of the acceleration energy of the irradiation ions is not particularly limited, but the lower limit of the acceleration energy is about 100 eV in consideration of the ion source 5 which can be practically created and used.

Further, the ratio of the number of particles of boron atoms to the number of nitrogen atoms in the BN-containing thin film laminated in the third step (hereinafter referred to as B / N
Speaking of the case where the composition is formed with a constant composition ratio), when the acceleration energy of the ions 8 is less than 2 KeV, B / N
When the composition ratio is 1 to 6, when the acceleration energy is less than 2 KeV to 5 KeV, the B / N composition ratio is 1 to 10, and when the acceleration energy is 5 KeV or more, the B to N composition ratio becomes 1 to 20. It is preferable to do so.

Furthermore, the value of the B / N composition ratio in the thickness direction of the BN-containing thin film may vary, but in this case, the B / N composition ratio of the BN-containing thin film varies from the surface of the thin film to the substrate. The layers are stacked so as to increase intermittently or continuously as they move toward the surface side of No. 2. In this case, the formation of the BN-containing thin film is started in a state where the B / N composition ratio reaching the surface of the substrate 2 is controlled so that the value of the B / N composition ratio becomes 4 to 60. ,
The value of the B / N composition ratio of the thin film to be laminated is controlled by changing the value of the B / N composition ratio intermittently or continuously, so that the value of the B / N composition ratio of the surface of the BN thin film finally becomes 1 to 10. Form a film.

Furthermore, the acceleration energy of the ions 8 may be changed as needed during the lamination of the BN-containing thin film in the third step. For example, at the start of the formation of a BN-containing thin film, the substrate 2
After irradiation with ions 8 at an acceleration energy of 2 to 40 KeV to form a BN thin film having a predetermined thickness,
In order to form a thin film having few defects or the like inside the thin film to be stacked, a forming method such as stacking a predetermined thickness by setting the acceleration energy of the ions 8 to 2 KeV or less may be used.

The BN-containing thin film formed in the third step is:
There is no particular limitation except that the B / N composition ratio in the thin film and the acceleration energy of the ions 8 are controlled within the range described above.
Even when the B / N composition ratio is changed intermittently or continuously in the thickness direction of the thin film, the thickness of the thin film layer having each B / N composition ratio in the thin film may be selected as appropriate without any limitation. However,
Also in this case, if the B / N composition ratio is out of the range of 1 to 60, the thermal expansion coefficient and lattice constant of the formed BN-containing thin film and the substrate 2 and the thin film containing silicon element (Si) are reduced. Becomes insufficient or c near the surface of the thin film
-BN or w-BN content is reduced,
It adversely affects properties such as chemical stability. In addition, even if the value of the B / N composition ratio is within the range, if the acceleration energy of the irradiation ions is out of the range, the content of c-BN and W-BN in the thin film laminated near the surface is reduced. Less, high hardness, heat
It adversely affects properties such as chemical stability.

Further, when irradiating the ions 8 containing nitrogen ions in the first, second and third steps, the inert gas is mixed with the nitrogen gas unless the irradiation amount and the acceleration energy of the ions 8 are out of the range. Alternatively, the ions of the inert gas may be simultaneously irradiated.

〔Example〕

Example 1 In the apparatus described with reference to FIG. 1, a base 2 made of degreased and washed high-hardness steel (high-speed steel) was fixed to a holder 1, and boron (purity: 99%) was used as an evaporation substance 6 as an evaporation source 3. Then, silicon (purity: 99.999%) was disposed as an evaporating substance 7 in the evaporating source 4, and the inside of the vacuum apparatus was maintained at a high vacuum of 2 × 10 ⁻⁶ Torr or less. The evaporation sources 3 and 4 can be heated by an electron beam to deposit evaporation substances 6 and 7 on the surface of the base 2. The ion source 5 has a bucket type structure, into which nitrogen gas (purity: 99.999%) is introduced, and ions 8 composed of a nitrogen element.
Then, the surface of the base 2 can be irradiated.

In such a configuration, as a first step, the surface of the substrate 2 was irradiated with ions 8 of nitrogen gas introduced into the ion source 5 and ionized. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions, and irradiation was performed at an acceleration energy of 10 KeV.

Next, as a second step, the surface of the substrate 2 irradiated with the ions 8 in the previous step is coated with a vaporized substance 7 made of silicon.
At the same time, a thin film containing elemental silicon (Si) was laminated to a thickness of 500 ° by irradiating ions 8 of nitrogen gas. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions, and irradiation was performed at an acceleration energy of 10 KeV.

Then, as a third step, at the same time as depositing an evaporating substance 6 made of boron on the surface of the silicon element (Si) -containing thin film laminated in the previous step, the ion source 5 is irradiated with nitrogen gas ions 8. To form a thin film containing BN.
At this time, first, the acceleration energy of the ion 8 is set to 10 KeV.
And the B / N composition ratio in the thin film becomes 15
After laminating to a film thickness of 10, the acceleration energy of ions 8 is 10 KeV
As it was, the evaporation amount of the evaporating substance 6 was controlled so that the B / N composition ratio in the thin film became 3, and the film was further laminated to a thickness of 3000 し た to finally form a 5500 薄膜 thin film.

Example 2 As a first step, the surface of the substrate 2 was irradiated with ions 8. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions as in Example 1, and irradiation was performed at an acceleration energy of 10 KeV.

Next, as a second step, the surface of the substrate 2 is irradiated with ions 8 at the same time as the deposition of the deposition material 7 to deposit silicon element (Si).
Was laminated to a thickness of 500 mm. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions as in Example 1, and irradiation was performed at an acceleration energy of 10 KeV.

Then, as a third step, the BN-containing thin film was laminated on the surface of the silicon element (Si) -containing thin film laminated in the previous step by irradiating ions 8 simultaneously with the evaporation of the evaporating substance 6. At this time, first, the acceleration energy of the ions 8 is set to 500 eV, the evaporation amount of the evaporating substance 6 is controlled so that the B / N composition in the thin film becomes 10, and the lamination of the thin film is started.
Each time the film was laminated to a thickness of 200 mm, the evaporation amount of the evaporating substance 6 was controlled so as to decrease the B / N composition ratio by one, and the film was laminated to a film thickness of 2000 mm to finally form a thin film of 2500 mm.

Example 3 As a first step, the surface of the substrate 2 was irradiated with ions 8. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions as in Example 1, and irradiation was performed at an acceleration energy of 10 KeV.

Next, as a second step, ions 8 are irradiated simultaneously with the evaporation of the evaporating substance 7 so that the surface of the base 2 has a silicon element (Si).
Was laminated to a thickness of 500 mm. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [the number of ions / cm ² ] in terms of the number of nitride ions as in Example 1, and irradiation was performed at an acceleration energy of 10 KeV.

Then, as a third step, the BN-containing thin film was laminated on the surface of the silicon element (Si) -containing thin film laminated in the previous step by irradiating ions 8 simultaneously with the evaporation of the evaporating substance 6. At this time, the acceleration energy of the ions 8 was set to 2 KeV, and the B / N composition ratio in the thin film was set to 3 so as to be laminated to a thickness of 5000 ° to finally form a 5500 ° thin film.

Comparative Example 1 As a first step, the surface of the substrate 2 was irradiated with ions 8. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions, and irradiation was performed at an acceleration energy of 50 KeV.

Next, as a second step, ions 8 are irradiated simultaneously with the evaporation of the evaporating substance 7 so that the surface of the base 2 has a silicon element (Si).
Was laminated to a thickness of 500 mm. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions as in Example 1, and irradiation was performed at an acceleration energy of 10 KeV.

Then, as the third step, the silicon element (S
A thin film containing BN was laminated on the surface of the thin film containing i). At this time, similarly to the first embodiment, first, the acceleration energy of the ions 8 is set to 10 KeV, and the B / N composition ratio in the thin film is set to 15
After stacking to a thickness of 2000 mm so that
While keeping the acceleration energy of 10 KeV, the B / N composition ratio in the thin film was set to 3, and the film was further laminated to a thickness of 3000 を to finally form a 5500 薄膜 thin film.

Comparative Example 2 As a first step, the surface of the substrate 2 was irradiated with ions 8. At this time, the irradiation amount of the ions 8 was set to 1 × 10 ¹⁸ [the number of ions / cm ² ] in terms of the number of nitrogen ions, and irradiation was performed at an acceleration energy of 10 KeV.

Next, as a second step, ions 8 are irradiated simultaneously with the evaporation of the evaporating substance 7 so that the surface of the base 2 has a silicon element (Si).
Was laminated to a thickness of 500 mm. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions as in Example 1, and irradiation was performed at an acceleration energy of 10 KeV.

Then, as a third step, the BN-containing thin film was laminated on the surface of the silicon element (Si) -containing thin film laminated in the previous step by irradiating ions 8 simultaneously with the evaporation of the evaporating substance 6. At this time, as in the first embodiment, first, the acceleration energy of the ions 8 is set to 10 KeV, and the B / N composition ratio in the thin film is increased.
After laminating the film to a thickness of 2000 ° so as to have a thickness of 15, and keeping the acceleration energy of the ions 8 at 10 KeV, the B / N composition ratio in the thin film becomes 3 and further laminating the film to a thickness of 3000 °. Finally, a thin film of 5500Å was formed.

Comparative Example 3 As a first step, the surface of the substrate 2 was irradiated with ions 8. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions, and irradiation was performed at an acceleration energy of 10 KeV.

Next, as a second step, ions 8 are irradiated simultaneously with the evaporation of the evaporating substance 7 so that the surface of the base 2 has a silicon element (Si).
Was laminated to a film thickness of 8000 mm. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions as in Example 1, and irradiation was performed at an acceleration energy of 10 KeV.

Then, as a third step, the BN-containing thin film was laminated on the surface of the silicon element (Si) -containing thin film laminated in the previous step by irradiating ions 8 simultaneously with the evaporation of the evaporating substance 6. At this time, as in the first embodiment, first, the acceleration energy of the ions 8 is set to 10 KeV, and the B / N composition ratio in the thin film is increased.
After laminating the film to a thickness of 2000 ° so as to have a thickness of 15, and keeping the acceleration energy of the ions 8 at 10 KeV, the B / N composition ratio in the thin film becomes 3 and further laminating the film to a thickness of 3000 °. Finally, a thin film of 13000Å was formed.

Comparative Example 4 As a first step, the surface of the substrate 2 was irradiated with ions 8. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions, and irradiation was performed at an acceleration energy of 10 KeV.

Next, without laminating the thin film containing the silicon element (Si) in the second step, the third step is to irradiate the ions 8 simultaneously with the vapor deposition of the evaporating substance 6 to irradiate the surface of the base 2 with the thin film.
Thin films containing BN were laminated. At this time, as in the case of the second embodiment, first, the acceleration energy of the ions 8 is set to 500 eV, the lamination of the thin films is started so that the B / N composition ratio in the thin films becomes 10, and the thickness of the thin films becomes 200 °. Each time the layers were stacked, the B / N composition ratio was reduced by one, and the layers were stacked to a thickness of 2000 ° to finally form a thin film containing BN of 2000 °.

Comparative Example 5 The surface of the base 2 was irradiated with the ions 8 simultaneously with the evaporation of the evaporating substance 7 as the second step, without irradiating the surface of the base 2 with the ions 8 in the first step. Thin films containing silicon element (Si) were laminated to a thickness of 500 mm. At this time, the irradiation amount of the ions 8 was set to 5 × 10 ¹⁵ [number of ions / cm ² ] in terms of the number of nitrogen ions as in Example 1, and irradiation was performed at an acceleration energy of 10 KeV.

Next, as a third step, a thin film containing BN was laminated on the surface of the thin film containing silicon element (Si) laminated in the previous step by irradiating ions 8 simultaneously with the vapor deposition of the evaporating substance 6. At this time, as in the second embodiment, first, the acceleration energy of the ions 8 is set to 500 eV, and the B / N composition ratio in the thin film is increased.
Start lamination of thin films so that the thickness becomes 10
The B / N composition ratio is reduced by 1 each time
The film was laminated to a thickness of 000 mm to finally form a thin film of 2500 mm.

As a result of measuring the X-ray diffraction peak of each thin film in order to confirm the crystal structure of the thin film formed under the above conditions, the X-ray diffraction peak of 2θ = 43.34 ° indicating the existence of the c-BN structure was found in any of the thin films. It was confirmed to contain the c-BN structure.

Then, c of the BN thin film obtained in each of the examples and comparative examples
Example 1 to determine the relative content ratio of -BN structure crystals
The peak intensity per unit film thickness in the X-ray diffraction peak at 2θ = 43.34 ° is set to 1, and the values obtained from the peak intensity per unit film thickness of each thin film are compared and shown in the following table. Also,
The following table compares the values of the hardness of each thin film measured with a micro Vickers hardness tester (load: 10 g) and the values of the adhesion measured with an automatic scratch tester equipped with an AE sensor. In addition, the test condition of the adhesion by the automatic scratch tester equipped with an AE sensor is such that a continuous load of 1 to 60 [N] (1N = 0.10197 kg) is applied at a constant speed while the thin film is scratched, and a load at which the AE signal rapidly rises ( Lc) was measured.

As described above, in Examples 1, 2 and 3, the ion 8 was used in the first step and the acceleration energy was adjusted so that the irradiation amount was 1 × 10 ¹⁵ [the number of ions / cm ² ] in terms of the number of nitrogen ions. Was irradiated at 10 KeV.

Then, as a second step, ions 8 are emitted at the same time as the evaporation of the evaporating substance 7 and the irradiation amount is 1 in terms of the number of nitrogen ions.
After irradiating the substrate 2 with a thin film containing silicon (Si) to a thickness of 500 mm by irradiating the substrate 2 with an acceleration energy of 10 KeV so as to obtain 10 ¹⁵ [number of ions / cm ² ], the third step In the first embodiment, the acceleration energy of the ions 8 is set to 10 KeV, the value of the B / N composition ratio is set to 15, and the film thickness is set to 2000 mm.
After stacking, the acceleration energy is kept at 10 KeV and B
The film was further laminated at 3000 ° so that the / N composition ratio became 3, to finally form a thin film of 5500 °.

In the second embodiment, in the third step, the lamination of thin films is started with the acceleration energy of the ions 8 set to 500 eV and the value of the B / N composition ratio set to 10. N composition ratio is 1
It is laminated to a thickness of 2000 Å and finally 2500 膜厚
Was formed.

In Example 3, in the third step, the acceleration energy of the ions 8 was set to 2 KeV, the B / N composition ratio was set to 3, and a thin film of 5000 ° was laminated to finally form a thin film of 5500 °.

In this case, the thin films obtained in any of the examples contain a large amount of boron nitride having a c-BN structure, have a high hardness of 5300 (Kg / m ² ) or more, and have an adhesion to the substrate 2 of 32 [N] ( 1N = 0.
10197kg) or higher.

In contrast to the results of Examples 3 and 4, Comparative Example 1 was performed under the condition that the value of the acceleration energy of the ions 8 in the first step deviated from 50 KeV, and then the thin film was irradiated in the second and third steps. Was formed.

In Comparative Example 2, the irradiation was performed under the condition that the value of the irradiation amount of the ions 8 in the first step deviated from 1 × 10 ¹⁸ [the number of ions / cm ² ] in terms of the number of nitrogen ions. A thin film was formed in the step.

In Comparative Example 3, a thin film containing silicon element (Si) was laminated in the second step to a thickness deviating from the condition of 8000 °, and then the third step was performed to form a thin film.

In Comparative Example 4, the thin film containing the silicon element (Si) was not laminated in the second step, and the thin film was formed on the surface of the base 2 in the third step.
Only a thin film containing BN was laminated to form a thin film.

Further, in Comparative Example 5, a thin film was formed in the second and third steps without irradiating the surface of the base 2 with the ions 8 in the first step.

Therefore, the thin film obtained in each of the comparative examples was c
-The content of boron nitride in the BN structure is the same or 10% to 40% less than that of the example, and the altitude is 4500 (Kg / m
² ) and low. Further, the adhesion to the substrate 2 is 12 to 18
[N] (1N = 0.10197 kg), which is about half as low as that of each embodiment.

〔The invention's effect〕

In the method for producing a boron nitride-containing thin film-coated substrate according to claim (1) of the present invention, as a first step, ions containing a nitrogen element (N) are converted to nitrogen ions on the surface of the substrate in terms of the number of nitrogen ions.
Irradiation at an acceleration energy of 1 KeV to 40 KeV so that an irradiation amount of × 10 ¹⁵ to 1 × 10 ¹⁷ [number of ions / cm ² ] is obtained. Then, as a second step, a substance containing a silicon element (Si) is used. At the same time, alternately, or after the deposition of, the ions containing nitrogen element (N) are converted into 1 × 10
Irradiation is performed at an acceleration energy of 1 KeV to 40 KeV so that the irradiation amount becomes ¹⁵ to 1 × 10 ¹⁷ [number of ions / cm ² ], and a silicon-containing thin film is laminated to a thickness of 100 to 5000 mm. As a process, at the same time, alternately, or after the deposition of the substance containing the boron element (B), the ions containing the nitrogen element (N) are irradiated with an acceleration energy of 40 KeV or less to laminate the boron (B) -containing thin film. And B / N in this thin film
By forming a thin film with a composition ratio of 1 to 60, c-
A boron nitride-containing thin film containing a large amount of boron nitride having a BN structure, having high hardness, and having good adhesion to a substrate can be obtained.

The method for producing a boron nitride-containing thin film-coated substrate according to claim (2) is the method for producing a boron nitride-containing thin film-coated substrate according to claim (1). By controlling the transport ratio between the deposition and the irradiation ions containing nitrogen element (N) intermittently or continuously, the B / N composition ratio in the laminated thin film shifts from the surface to the inside. A thin film that increases intermittently or continuously can be obtained, and a boron nitride-containing thin film that contains a large amount of boron nitride having a c-BN structure, has high hardness, and has good adhesion to a substrate can be obtained.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a production apparatus of a method for producing a boron nitride-containing thin film-coated substrate according to the present invention. 2 ... substrate, 3,4 ... evaporation source, 5 ... ion source, 6,7 ...
Evaporated substance, 8… Ion, 9… Film thickness gauge, 10… Current measuring instrument

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C23C 14/22 C23C 14/22 F (72) Inventor Hajime Kuwahara 47, Takanecho Umezu, Ukyo-ku, Kyoto-shi, Kyoto Nichiden Electric Co., Ltd. (56) References JP-A-3-97848 (JP, A) JP-A-60-204687 (JP, A) JP-A-61-159301 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name ) C22C 14/00-14/58 B23B 27/14 B23B 15/28

Claims (2)

(57) [Claims] 1. The method according to claim 1, wherein after the first step of irradiating the surface of the substrate with ions containing nitrogen element (N), the nitrogen element (N) is deposited simultaneously, alternately or after the deposition of the substance containing silicon element (Si). ) And irradiating with ions containing nitrogen element (N) simultaneously, alternately or after the deposition of the material containing boron (B) after the second step. A boron nitride-containing thin film-coated substrate for forming a boron nitride-containing thin film in a third step, wherein in the first step, the irradiation amount of the ion containing nitrogen element (N) is changed to nitrogen ion 1 × 10 ¹⁵ to 1 × 10 in terms of number
¹⁷ [Ion number / cm ² ] and the acceleration energy of the ions is in a range of 1 KeV to 40 KeV. In the second step, the irradiation amount of the ions containing the nitrogen element (N) is set to the number of nitrogen ions. 1 × 10 ¹⁵ to 1 × 10 in conversion
¹⁷ [ion number / cm ² ], and the acceleration energy of the ions is in a range of 1 KeV to 40 KeV, the silicon element (Si)
Is deposited in a thickness of 100 to 5000 mm. In the third step, the acceleration energy of the ions containing nitrogen element (N) is reduced to 40 KeV or less, and the boron element (B)
A method for producing a boron nitride-containing thin film-coated substrate, comprising: laminating a thin film containing the same; 2. In a third step, the transport ratio between the substance containing the boron element (B) and the substance containing the nitrogen element (N) is reduced intermittently or continuously, so that the boron element (B) is reduced. 3. The method according to claim 1, wherein the ratio of the number of particles of boron atoms to the number of nitrogen atoms in the thin film containing (i) increases intermittently or continuously as the film moves from the surface to the inside of the thin film. A method for producing a boron nitride-containing thin film-coated substrate according to (1).