JP2957620B2 - TiN film with uniform chromaticity and method for forming the same - Google Patents

Description

The present invention relates to a TiN film having uniform chromaticity and a method for forming the same.
In particular, the present invention relates to a method of forming a TiN film applied to accessories, ornaments, metal furniture, metal parts of house building materials, and the like, in which the characteristics of the TiN film are improved.

(Prior art and its problems) TiN has been widely used as a coating for accessories, ornaments, etc. due to its excellent physical properties.

Methods for providing a TiN coating on a substrate include CVD, PVD
The ion plating method is known, but the former uses a reaction gas such as TiCl ₄ as a source of Ti, which may be mixed into the formed film and impair the color tone of the film. There have been various inconveniences such as heat deformation of the material caused by the treatment.

The latter PVD method has a problem in that the TiN film formed is smooth and dense, but the color tone of the TiN changes as the source of the TiN film deteriorates, resulting in poor wraparound. Further, although the adhesion of TiN is good in the arc deposition method, there is a drawback that the particles of the coating are uniform and droplets are likely to be generated when forming a thick film.

The present invention has been made to solve these problems, and it is an object of the present invention to eliminate color variation of a TiN film and improve film quality.

(Means for Solving the Problems) In order to achieve the above object, the present inventor forms a TiN film of 1 μm or more by a multi-cathode method or the like, and a TiN film of 0.5 μm or less by an arc evaporation method to eliminate color variation. By superimposing on this, the number of droplets was extremely reduced and a composite film excellent in film quality, color tone, and productivity was successfully obtained. The ion plating of the multi-cathode method or the like and the arc deposition method in the present invention are conventionally known methods, and the present invention carries out these methods in the same vacuum chamber.

The gist of the present invention is to provide a TiN first layer having a film thickness of 1 μm or more, preferably 1 to 3 μm by ion plating such as a multi-cathode method, and a film thickness of 0.1 to 0.5 μm by ion plating of an arc evaporation method on the layer. A TiN film having a uniform chromaticity characterized by having a composite structure with a TiN second layer and a method for forming the same.

The formation method is such that only the Ti layer is formed on the substrate surface by ion plating such as a multi-cathode method in a thickness of 0.1 to 0.3 μm, and then a TiN film having a film thickness of 1 μm or more, preferably 1 to 3 μm is provided. And a TiN layer having a thickness of 0.1 to 0.5 μm is superposed on the layer.

 Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 exemplifies an apparatus used for carrying out the present invention. In a vacuum chamber 1, a workpiece 2 to be processed, a hearth 10 containing a TiN evaporation source, and a Ti target 4 for arc evaporation are arranged. . An electron beam gun 3 is provided in the vacuum chamber 1 as an evaporation source to increase the film thickness, and a filament as a thermoelectron supply source 6 and an anode electrode 5 of a positive bias voltage are provided to enhance the reaction with nitrogen. Cause
A mixed gas of Ar and N ₂ is introduced from the gas inlet 7 to generate TiN. The work 2 is revolved by applying a negative bias voltage. Multi-cathode method, hollow cathode method, film thickness of 1-3μ with one ion plating of high frequency method
After forming a first layer having a thickness of about m, the method is switched to arc deposition in which color reproducibility is excellent for each color distribution batch, and a second layer having a thickness of about 0.1 to 0.5 μm, in which a drop retlet is not noticeable, is formed.

In this case, it is preferable to provide a Ti layer between the substrate and the first layer to improve the adhesion to the substrate.

This film structure is dry-cleaned by a bombarding process as shown in FIG. 2, and a Ti layer 12 is formed on the surface of the substrate 11 as an adhesion layer to the substrate.
Only about 0.1 to 0.3 μm, then N ₂ is introduced, and Ti
An N layer 13 is formed in a thickness of 1 to 3 μm, and then 0.1 arc
TiN14 of about 0.5 .mu.m is formed.

When coating a large-sized workpiece, a large workpiece, or a workpiece having a complicated shape with a film having a thickness of 1 to 3 μm as in the past, the processing time takes about 1 to 3 hours, and the Ti base material as the evaporation source is N _2. , And the periphery of the Ti base material is nitrided, which affects the deposition rate distribution and the like, and the color distribution becomes unstable for each batch and for the rotation, but the film obtained by the present invention is equivalent to 10 lots. As a result of color and chromaticity measurement, the chromaticity difference is ΔE ^* (0.5 to 1.2)
The uniform chromaticity was obtained within the range of the degree. The chromaticity difference in the conventional method is ΔE ^* = 1.5 to 8. In particular, the chromaticity difference when forming a high film thickness was large.

(Example) The inside of the vacuum chamber 1 was evacuated to 1.5 × 10 ^-3 pa or more, and while the watch case was revolved next time, Ar gas was introduced into the vacuum chamber from the gas inlet of 7 at 1 to 5 × 10 ^-1 pa. To generate thermoelectrons from the thermionic body 6, apply 30 V to 50 V from the positive bias generator 5, and apply a negative bias of −10 to −200 V to the work 2, thereby generating plasma. The surface is cleaned, then the Ti is melted and evaporated by the electron beam 3, the shutter 9 is opened, and in order to improve the adhesion of the base material, only the Ti bath is formed to a thickness of about 0.1 to 0.3 μm, and then N ₂ and Ar are mixed. Gas was introduced from 7 to form TiN about 1 to 3 μm, then the shutter 9 was closed, and the thermionic generator 6, the positive bias generator 5,
Turn off the electron beam 3, change the conductance valve and the flow rate of N ₂ , adjust the pressure to 4 to 4 × 10 ¹ Pa, and use the arc deposition method 4
To form a TiN film having a thickness of about 0.1 to 0.5 μm. FIG. 3 shows the results of the measurement of the chromaticity, together with the results of the comparative example.

(Effects of the Invention) In the present invention, by performing ion plating by a multi-cathode method and an arc deposition method, it is possible to stabilize the color tone and to form a dense film when forming a thick film. This coating is excellent in abrasion resistance and is an indispensable method for coating metal parts of residential building materials with an emphasis on functionality. Furthermore, TiN coatings with a uniform color tone and good wraparound can be made even for those that require a film thickness of several thousand mm, such as decorations, so that the field of application is wide.

[Brief description of the drawings]

1 is an explanatory cross-sectional view illustrating an apparatus used for carrying out the present invention, FIG. 2 is a cross-sectional view of a work, and FIG. 3 is a graph showing a relationship between a film thickness and a chromaticity difference in Examples and Comparative Examples of the present invention. It is. DESCRIPTION OF SYMBOLS 1 ... Vacuum tank, 2 ... Work, 3 ... Electron beam, 4 ... Target, 5 ... Anode electrode, positive bias generator, 6 ... Thermoelectron generator, 7 ... Gas inlet, 8 ... ... Shahei board, 9 ... Shutter, 10 ... Heath.

Claims (2)

(57) [Claims] 1. A Ti film intermediate layer having a thickness of 0.1 to 0.3 μm on a substrate surface, a TiN first layer having a thickness of 1 to 3 μm formed by multi-cathode ion plating on a surface of the intermediate layer, Thickness of 0.1 on one layer by arc evaporation type ion plating
A TiN film having a uniform chromaticity, having a composite structure with a second layer of a TiN film having a thickness of about 0.5 μm. 2. A Ti layer is formed on the surface of the substrate in a thickness of 0.1 to 0.3 μm,
Furthermore, the multi-cathode ion plating
After providing a TiN film having a thickness of 1 to 3 μm on the surface of the Ti layer, switching to ion plating of an arc evaporation method, and then stacking a TiN layer having a thickness of 0.1 to 0.5 μm by the same method on the surface of the TiN film. Forming a TiN film having a uniform chromaticity.