JPH06287741A - Wear resistant electroconductive thin film and wear resistant member - Google Patents

Abstract

PURPOSE:To coat the surface of nonmetallic base material such as oxides of glass and ceramics with an electroconductive thin film excellent in wear resistance with excellent adhesion by coating the surface of the base material with the thin film of Cr and the thin film of CrN having specified crystal orientation properties. CONSTITUTION:On the surface of the oxide-based ceramics base material such as silica glass and alumina, silica, the thin film of Cr is formed in 3000Angstrom thickness by a vacuum deposition method such as an ion plating method. On the Cr thin film as a substrate, the hard film of CrN having crystal orientation properties that the ratio of the peak intensity of (111) to the peak intensity of (200) in X-ray diffraction is regulated to 0.5 to 4.0 is formed in 2 to 5mum thickness by a vacuum deposition method. Since the Cr thin film forms the oxidized film of Cr with oxygen in the oxide-based base material to improve its adhesion to the surface of the base material, the hard CrN film good in electroconductivity can be formed with excellent adhesion to the base material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wear resistant member used as a magnetic disk, a magnetic head slider, a home electric appliance such as AV or OA equipment, or an electric component, and in particular, it is coated on the surface of a base material of the member. And a wear-resistant conductive thin film.

[0002]

2. Description of the Related Art CrN and Cr are used for chromium nitride.
There are a ₂ N, since with a greater hardness both chemically stable, corrosion resistant than conventional, as a coating material capable of providing a wear resistance or lubricity, automotive Ya used under severe sliding conditions It is used for surface coating of bearing members of machine tools.

For example, in Japanese Unexamined Patent Publication No. 1-290785, in order to obtain a bearing member excellent in wear resistance while ensuring high lubricity, a Cr-N-based alloy coated on the surface of a base material made of stainless steel is used. It is described that the hardness film is effective.

Further, Japanese Patent Application Laid-Open No. 61-257466 proposes a corrosion-resistant coating formed by laminating a composite coating of Cr and CrN on a base material by vacuum vapor deposition in order to prevent erosion of a steam turbine blade. There is.

[0005]

Conventionally, almost all metals such as SUS have been generally used as the base material or base material modified by the coating of chromium nitride.

On the other hand, recently, a flatter surface which is smoother than that of a metal base material can be obtained. Therefore, in particular, magnetic disks, magnetic head sliders, home electric appliances such as AV or OA equipment, and base materials made of glass, ceramics or the like for electrical parts. Is being considered.

Therefore, a Cr-N-based coating is applied to the base material made of such glass or ceramics as is the case with the conventional metal base material, and the conductive material is excellent in wear resistance and lubricity. Attempts have been made to obtain parts.

However, even if a Cr-N-based coating is applied to a substrate made of glass or ceramics by using the conventional technique for coating a metal substrate, Cr has sufficient adhesion to the substrate. No N-based coating could be obtained. The coating obtained by the conventional method has a problem that it is easily peeled off from the base material when a slight external pressure is applied, and the abrasion resistance is significantly deteriorated.

The present invention has been made in view of the above-mentioned situation, and is a conductive material which is provided on a base material made of a material other than metal such as glass and ceramics with good adhesiveness and is excellent in wear resistance. The purpose is to provide a thin film. A further object of the present invention is to provide a wear resistant member obtained by coating the surface of a base material with a conductive thin film having wear resistance.

[0010]

A wear resistant conductive thin film according to the present invention is a conductive thin film for imparting wear resistance by coating the surface of a substrate made of at least one of ceramics and glass. , The ratio of the peak intensity of (111) to the peak intensity of (200) I (111) / I (200) in X-ray diffraction is 0.5 or more.
A layer made of CrN having a crystal orientation of 0 or less is provided.

The wear-resistant conductive thin film according to the present invention comprises a layer made of Cr to be provided on a substrate, and a ratio of the peak intensity of (111) to the peak intensity of (200) I (111) in X-ray diffraction. / I (200) is 0.5 or more and 4.0
You may laminate | stack with the layer which consists of CrN which shows the following crystal orientations.

In the present invention, the base material is preferably made of oxide ceramics. The oxide ceramics may be a metal oxide such as alumina (Al ₂ O ₃ ) or a non-metal oxide such as silica (SiO ₂ ). The base material is preferably made of silica glass.

In the present specification, the ratio of the peak intensity of (200) to the peak intensity of (111) I (111) / I (200) in X-ray diffraction of CrN is CrN.
It is used as an index for evaluating the crystal orientation of the, and can be obtained as follows.

In the present invention, the crystal orientation of CrN is determined by simply comparing the magnitudes of the peak intensities of (111) and (200) among the peaks of CrN obtained by the θ-2θ method of X-ray diffraction. Looking for.

That is, in general, to measure the crystal orientation, a rocking curve is drawn for a corresponding peak from several peak waveforms obtained by the θ-2θ method of the X-ray diffraction method, and a half thereof is drawn. A method of determining in which direction the orientation is based on the size comparison of the value widths is adopted. Further, it is known that simply comparing the peak intensities of the respective peaks appearing in the θ-2θ method may be simply performed. In the case of the present invention, the latter simple method is used. Generally CrN
Is measured by the X-ray diffraction θ-2θ method, 2θ = 38 °
Strong peaks appear in the vicinity, around 44 ° and around 64 °. In hk1 display, (111) and (20
The crystal directions of 0) and (220) are shown. Normally thin film CrN
Has extremely strong peaks at either 38 ° or 44 °. That is, since the crystal orientation is often (111) or (200), it is possible to compare the magnitude of the orientation by comparing these two peaks.

In the present invention, in X-ray diffraction (20
The ratio of the peak intensity of (111) to the peak intensity of (0) I (111) / I (200) is not less than 0.5 and not more than 4.0. A vacuum evaporation method such as arc ion plating or sputtering can be used to form a desired film thickness on the substrate. The film thickness of the layer made of CrN can be in the range of 1 to 10 μm, and more preferably in the range of 2 to 5 μm.

When ion plating utilizing PF excitation is used, for example, N ₂ gas atmosphere, pressure 2
0-100 mm Torr, RF power 300-1000
By adjusting the bias voltage applied to the substrate under the film forming conditions of W and the substrate temperature of 250 to 500 ° C., the CrN film can be formed while arbitrarily controlling the crystal orientation of CrN.

When the arc ion plating is used, for example, an N ₂ gas atmosphere and a pressure of 30 to 1 are used.
Under the film forming conditions of 00 mmTorr and an arc current of 80 to 160 A, by changing the distance between the vapor deposition source of the film forming material and the substrate, the crystal orientation of CrN can be arbitrarily controlled to form the film of CrN. You can

However, since the ionization rate of arc ion plating is several times higher than that of ion plating, it is possible to efficiently form a layer of CrN having higher adhesion.

In the X-ray diffraction, the ratio of the peak intensity of (111) to the peak intensity of (200) I (11
1) / I (200) is 0.5 or more and 4.0 or less, but the specific resistance of the layer made of CrN exhibiting crystal orientation can be selected at a desired value, but in general, it is about 10 ⁻³ to The range is preferably 10 ⁰ Ωcm.

Since Cr is an element that is very easily oxidized, a layer made of Cr is formed on a base material made of a material containing a large number of oxygen atoms, such as a base material made of oxide ceramics or silica glass. When provided, the Cr layer forms a thin oxide layer at the interface with the substrate and adheres well to the substrate surface. Further, such a layer made of Cr exhibits strong adhesion to a layer made of CrN provided on the outside thereof.

It is preferable that the Cr layer is continuously formed with the CrN layer provided on the outer side thereof by using a vacuum deposition method such as ion plating, arc ion plating, or sputtering.

The thickness of the layer made of Cr is more preferably about 1/10 of the thickness of the layer made of CrN provided outside thereof, as will be shown in the following examples. For example, when the thickness of the layer made of CrN is about 3 μm, the thickness of the layer made of Cr is 1000Å
It is preferably in the range of 3000Å.

Further, the adhesion of the CrN layer to the substrate can be expected to be improved by providing a Cr layer exhibiting a polycrystalline state as a base layer and providing a CrN layer on the surface thereof. In order to further increase the adhesiveness and the adhesiveness of the second layer made of, it is desirable to pretreat the surface of the base material. For example, it is preferable to perform a pretreatment such as cleaning by bombarding on the surface of the base material before providing the layer made of Cr or the layer made of CrN.

According to the present invention, it is possible to provide a wear resistant member formed by coating a thin film having the above-mentioned properties.

The wear resistant member according to the present invention is provided on a base material made of at least one of ceramics and glass, and has a peak intensity of (111) with respect to a peak intensity of (200) in X-ray diffraction. Ratio I (11
1) / I (200) is a thin film of CrN having a crystallographic orientation of 0.5 or more and 4.0 or less, and the thin film is provided in a portion in contact with another member. To do.

The wear resistant member according to the present invention is provided so as to cover a base material made of at least one of ceramics and glass, a layer provided on the base material and made of Cr, and a layer made of Cr. And the ratio of the peak intensity of (111) to the peak intensity of (200) I (111) / I (200) in X-ray diffraction is 0.5 or more.
A layer made of CrN having a crystal orientation of 0 or less, and a thin film formed by stacking a layer made of Cr and a layer made of CrN is provided at a portion in contact with another member. To do.

Further, the thin film having the above-mentioned properties according to the present invention may be brought into contact with another member by sliding.

In the present invention, a wear resistant member that can be used as a magnetic disk, a magnetic head slider, a home electric appliance such as AV or OA equipment, or an electrical component is mentioned as a typical object. The application range of the wear-resistant member is not limited to the above-mentioned members, but includes application to all other members that require similar characteristics.

[0030]

Although CrN is conventionally formed as a polycrystalline thin film by using a vapor deposition method such as sputtering and ion plating, it is often crystallized in either (111) or (200).

As a result of a detailed study, the present inventors have found that when a metal substrate such as SUS is used, even if CrN is crystallographically oriented to either (111) or (200), The adhesion of the thin film to the base material does not deteriorate, but if a base material made of a material other than metal such as ceramics or glass is used, the crystal orientation of CrN must be controlled within a specific range. Cr with satisfactory adhesion
It was revealed that a thin film made of N could not be obtained.

In X-ray diffraction, the ratio of the peak intensity of (111) to the peak intensity of (200) I (111) /
Cr so that I (200) is 0.5 or more and 4.0 or less
By controlling the crystal orientation of N, the internal stress in the thin film is relaxed, so that the conductive thin film has sufficient adhesiveness and excellent wear resistance on the substrate made of at least one of ceramics and glass. Can be obtained.

Further, between the substrate and the layer made of CrN,
By providing a layer made of Cr as an underlayer with a thickness of about 1/10 of the thickness of the layer made of CrN, for example, C
The layer made of r and the layer made of CrN exhibit strong adhesion to each other, and the adhesion of the layer made of CrN to the base material can be further enhanced.

As described above, since Cr is an element that is very easily oxidized, if a material containing a large number of oxygen atoms, for example, a base material made of oxide ceramics or silica glass is selectively used, it is made of Cr. The layer forms a thin oxide layer at the interface with the substrate and adheres well to the substrate surface. Therefore, it is possible to obtain a wear-resistant conductive thin film with improved adhesion to the substrate.

A member having improved sliding characteristics can be obtained by coating the wear resistant conductive thin film as described above on the base material of a member which comes into contact with another member by known ion plating, arc ion plating or the like. Can be provided.

[0036]

【Example】

Example 1 Using an ion plating (IP), an arc ion plating (AIP), and a sputtering (SP), a Cr film having a thickness of 3 μm was formed on a silica glass substrate.
An N layer was formed and the relationship between the X-ray diffraction peak intensity ratio of CrN and the adhesion was examined.

In the IP method, N ₂ gas is used and the pressure is 20
mmtorr, RF power 300W, substrate temperature 250 ° C
The CrN layer was formed while changing the crystal orientation of CrN by changing the bias voltage applied to the substrate under the above film forming conditions.

On the other hand, in the AIP method, N ₂ gas is used,
The CrN layer was formed while changing the crystal orientation of CrN by changing the distance between the evaporation source and the substrate under the film forming conditions that the pressure was 30 mmtorr, the arc current was 80 A, and the substrate temperature was not intentionally heated.

In the SP method, N ₂ gas is used, pressure is 10 mmtorr, power is 300 W, and substrate temperature is 200.
The CrN layer was formed while changing the crystal orientation of CrN by changing the bias voltage applied to the substrate under the film forming condition of ° C.

The X-ray diffraction of CrN was measured by a thin film X-ray diffraction method at 20 ° <50 ° V and 250 mA.
The intensity ratio I (200) / I (11) of the peaks appearing in the vicinity of 2θ = 38 ° and 44 ° is performed in the range of θ <120 °
1) was sought. The adhesion was determined by measuring the applied load until the CrN layer was peeled from the surface of the base material with a scratch tester, and comparatively evaluating the sampling of Inventive Examples 1-5 and Comparative Examples 1-5. The obtained results are also shown in Table 1.

[0041]

[Table 1]

As is clear from the results of Table 1, the X-ray diffraction peak intensity ratio I (111) / I (200) is 0.5 or more and 4.0 in any CrN layer formed by any method.
It was shown that stable adhesion can be obtained in the following range. On the other hand, the X-ray diffraction peak intensity ratio I (111) / I (2
It was confirmed that when the value of (00) was less than 0.5 or more than 4.0, the adhesiveness was significantly reduced.

Example 2 Similar to Example 3 of Example 1, a Cr layer and a CrN layer were continuously formed on a substrate made of silica glass by the arc ion plating method. However, in this embodiment, Cr provided as an intermediate layer between the base material and the CrN layer.
The thickness of the layer was changed and the relationship between the thickness of the Cr layer and the adhesion of the CrN layer was investigated.

The thickness of the Cr layer was changed in the range of 0 to 6000Å, and the other conditions were the same. The adhesion was determined by measuring the applied load until the CrN layer was peeled from the surface of the base material with a scratch counter and making a comparative comparison. The obtained results are shown in Table 2.

[0045]

[Table 2]

As is clear from Table 2, C is used as the intermediate layer.
It was shown that the provision of the r layer clearly improves the adhesion of the CrN layer. It was also shown that the best adhesion can be obtained by setting the thickness of the Cr layer to about 1/10 of the thickness of the CrN layer.

Example 3 Similar to Example 3 of the invention of Example 1, the arc ion platey was used.
Substrate made of a material other than silica glass
Using a Cr layer with a thickness of 1000Å and a thickness of
A CrN layer of 3 μm was continuously formed. At this time Cr
X-ray diffraction peak intensity ratio of N I (111) / I (200)
Was set to 2.0. However, in this embodiment,
By using a base material made of
The adhesion of the CrN layer to be tested was examined. The base material is
Al as oxide ceramics ₂O₃, MgO, nitriding
SiN, AlN, BN, carbide as physical ceramics
SiC was used as the system ceramics. Close contact
Property is the applied load until the CrN layer peels from the substrate surface
Shall be measured with a scratch counter for comparative evaluation.
It was The results obtained are shown in Table 3.

[0048]

[Table 3]

As is clear from Table 3, by using the base material made of oxide ceramics, C having excellent adhesiveness was obtained.
It was shown that an rN layer was obtained.

Example 4 A 1000-Å-thick Cr layer and a 3 μm-thick CrN layer were continuously formed on the surface of an alumina disk having a diameter of 20 mm by the arc ion plating method. At this time, the CrN X-ray diffraction peak intensity ratio I (111) / I (2
00) was set to 2.0. When the specific resistance of the thin film thus obtained was examined, it was 2 × 10 ^-2 Ωcm. The thin film has a ball radius of 3 mm and a load of 10 N.
A ball-on-disk test was conducted at a sliding speed of 200 mm / sec and a sliding number of 10 ⁵ times. As a result, there was no peeling or adhesion and the abrasion amount of the CrN layer was 0.2 μm, which was extremely small. When the specific resistance of the thin film was examined after the sliding test,
It was 1.6 × 10 ^-2 Ωcm, and almost no change was observed compared to before sliding.

[0051]

INDUSTRIAL APPLICABILITY By using the wear resistant conductive thin film according to the present invention as a coating on the surface of a substrate made of at least one of ceramics and glass, AV or O
It is possible to provide a sliding member that is wear resistant and low in resistance, and can be used as a household electric appliance such as a device A, or an electric component member, which is sufficiently different from a conventional sliding member, and that dislikes electrification.

Front page continuation (72) Inventor Akira Nakayama 1-1-1 Kunyo Kita, Itami City, Hyogo Prefecture Sumitomo Electric Industries, Ltd. Itami Works (72) Inventor Tsuyoshi Yoshioka 1-1-1 Kunyo Kita, Itami City, Hyogo Prefecture Sumitomo Electric Industries, Ltd. Itami Works

Claims (7)

[Claims] 1. A conductive thin film for coating a surface of a base material made of at least one of ceramics and glass to impart abrasion resistance, which has a peak intensity of (200) with respect to a peak intensity of (200) in X-ray diffraction.
11) Peak intensity ratio I (111) / I (200)
CrN showing a crystal orientation of 0.5 to 4.0
Abrasion-resistant conductive thin film, comprising a layer consisting of. 2. A layer made of Cr in contact with the base material,
The wear-resistant conductive thin film according to claim 1, wherein the wear-resistant conductive thin film is formed by laminating the CrN layer. 3. The wear resistant conductive thin film according to claim 1, wherein the base material is made of oxide ceramics. 4. The abrasion-resistant conductive thin film according to claim 1, wherein the base material is made of silica glass. 5. A base material made of at least one of ceramics and glass, and provided on the base material and subjected to X-ray diffraction (200).
Ratio of (111) peak intensity to that of I
A thin film made of CrN having a crystal orientation of (111) / I (200) of 0.5 or more and 4.0 or less, the thin film being provided in a portion in contact with another member. A wear resistant member. 6. A base material made of at least one of ceramics and glass, a layer made of Cr and provided on the base material, and a layer provided so as to cover the layer made of Cr and subjected to X-ray diffraction (200). The ratio of the peak intensity of (111) to the peak intensity of () I (111) / I (200) is 0.5
A thin film formed by stacking a layer made of Cr and a layer made of CrN, the thin film being provided in a portion in contact with another member. A wear resistant member characterized by being 7. The wear resistant member according to claim 5, wherein the thin film is brought into contact with another member by sliding.