JPH03211269A - Tin film of uniform chromaticity and formation thereof - Google Patents

Abstract

PURPOSE:To allow the stabilization of color tones at the time of formation of films to a high thickness and the formation of the dense films of uniform color tones with good infiltrating by executing ion plating with a multicathode system, etc., and an arc vapor deposition system. CONSTITUTION:A work 2 of a material to be treated which is impressed with a negative bias voltage and is rotated and revolved, a hearth 10 contg. a Ti vapor source, and a Ti target 4 for arc evaporation are disposed in a vacuum chamber 1. An electron gun 3 is provided as an evaporating source for increasing the film thickness in the chamber 1. A thermion generating body 6 and an anode electrode 5 of a positive voltage are provided to induce plasma in order to enhance the reaction with nitrogen. A gaseous mixture composed of Ar and N2 is introduced from an introducing port 7 to form TiN. The 1st layer of >=1mu, more preferably 1 to 3mu film thickness is formed by the ion plating of one among a multicathode system, hollow cathode system and high-frequency system. The process is thereafter switched to an arc type vapor deposition having the excellent reproducibility of colors for each of color distribution batches, by which the 2nd layer of 0.1 to 0.5mu having inconspicuous droplets is formed.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a TiN film with uniform chromaticity and a method for forming the same.
In particular, the present invention relates to a film forming method that improves the properties of TiN films applied to accessories, ornaments, metal furniture, metal parts of housing materials, and the like.

(Prior Art and its Problems) Due to its excellent physical properties, T i N is widely used as a coating for jewelry, ornaments, and the like.

Methods for providing the TiN film on the substrate include CVD method,
Ion plating methods such as the PVD method are known, but since the former uses a reactive gas such as TiC1 as a source of Ti, there is a risk that this will mix into the produced film and impair the color tone of the film. There were various disadvantages such as thermal deformation of the material due to high temperature treatment.

In the latter PVD method, although the TiN film formed is smooth and dense, the color tone of the TiN changes as the source of the TiN film deteriorates, resulting in poor wraparound. In addition, in the arc evaporation method, TiN
Although the adhesion of the film is good, the particles in the film are non-uniform and droplets are likely to occur when forming a thick film.

The present invention was made to solve these problems, and aims to eliminate color variations in the TiN film and improve film quality.

(Means for Solving the Problems) In order to achieve the above object, the present inventor has developed a method using a multi-cathode method etc.
By forming a TiN film with a thickness of 1 μm or more and overlaying a TiN film with a thickness of 0.5 μm or less using an arc evaporation method to eliminate color variation, droplets can be extremely reduced and the film quality can be improved in one color tone and productivity. The ion plating methods used in the present invention, such as the multi-cathode method and the arc evaporation method, are conventionally known methods, and the present invention is a method in which these methods are carried out in the same vacuum chamber. It is something to do.

The gist of the present invention is to form a TiN first layer with a film thickness of 1 μm or more, preferably 1 to 3 μm, by ion plating using a multi-cathode method, and a film thickness of 0.1 to 0.0 μm by ion plating using an arc evaporation method on the first layer. The present invention provides a TiN film with uniform chromaticity, characterized by having a composite structure with a second TiN layer having a thickness of 5 μm, and a method for forming the same.

The formation method is to form only a Ti layer with a thickness of 0.1 to 0.3 μm on the surface of the base material by ion plating using a multi-cathode method, and then provide a TiN film with a thickness of 1 μm or more, preferably 1 to 3 μm. Then, by switching to ion plating using arc evaporation, a film thickness of 0.1 to 0.5 was deposited on the layer.
This is a stack of μ-sized TiN layers.

The present invention will be described in detail below based on the accompanying drawings.

FIG. 1 illustrates an apparatus used to carry out the present invention.
In the vacuum chamber 1, a workpiece 2 to be processed, a hearth 10 containing a Ti 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 6 as a source of thermionic electrons and an anode electrode 5 with a positive bias voltage are provided in order to enhance the reaction with nitrogen. Wake up plasma.

Introduce a mixed gas of Ar and N from the gas inlet 7,
Generate TiN. A negative bias voltage is applied to the work 2 to cause it to revolve. Multi-cathode method, hollow cathode method,
We use ion plating, one of the high-frequency methods, to create the first layer with a film thickness of about 1 to 3p, and then switch to arc evaporation, which has excellent color reproducibility for each batch of color distribution, making droplets less noticeable. A second layer having a thickness of approximately 0.1 to 0.5 is formed.

In this case, it is preferable to provide a Ti layer between the base material and the first layer in order to improve adhesion to the base material.

This film structure is dry cleaned by bombardment treatment as shown in Fig. 2, and only a Ti layer 12 of about 0.1 to 0.3p is formed on the surface of the base material 11 as an adhesive layer with the base material, and then N2 is introduced. Then, a TiN layer 13 of 1 to 3 IjM is formed, and then a TiN layer 14 of about 0.1 to 0.5t3 is formed by arc evaporation.

Conventionally, when coating a large amount of workpieces, large workpieces, or workpieces with complex shapes with a film of 1 to 3 IjM, the processing time is about 1 to 3 hours, and the Ti base material of the evaporation source is exposed to N2. As a result, the area around the Ti base material is nitrided, which affects the deposition rate distribution, etc., and the color distribution becomes unstable from batch to batch and from round to round.
As a result of measuring the chromaticity of one color in a lot, the difference in chromaticity of one color is ΔE” (0
, 5 to 1.2), and uniform chromaticity was obtained. The chromaticity difference in the conventional method is ΔE"=1.5 to 8.The chromaticity difference was especially large when forming a high film thickness (Example) Exhaust to more than 1
While rotating the watch case, Ar gas is introduced into the vacuum chamber from the gas inlet 7 to a pressure of 1 to 5 x 10-1 pa, the thermionic body 6 generates thermoelectrons, and the positive bias generator 5 generates 30V. ~50V is applied and a negative bias of -10 to -200V is applied to the workpiece 2 to generate plasma and perform bombardment surface cleaning. Next, the electron beam 3 is used to melt and evaporate Ti, and the shutter 9 is opened. , in order to improve the adhesion of the base material, only the Ti layer has a thickness of 0.1 to 0.3
After the formation of about .mu., a mixed gas of N2 and Ar is introduced from 7 to form about 1 to 31 of TiN, and then the shutter 9 is closed, and thermionic generator 6, positive bias generator 5. Turn off the electron beam 3, change the conductance valve and N2 flow rate, and set the pressure to 4 to 4XIO-''Pa for arc evaporation method 4.
TiN was formed with a film thickness of about 0.1 to 0.5 μM. The results of measuring the chromaticity of this are shown in FIG. 3 together with the results of the comparative example.

(Effects of the Invention) In the present invention, by performing ion plating using a multi-cathode method and an arc evaporation method, it is possible to stabilize the color tone and form a dense film when forming a high film thickness. This coating has excellent wear resistance and is an essential method for coating metal parts of housing construction materials with emphasis on functionality. Furthermore, it is possible to create a TiN film with a uniform color tone and good wraparound, even for items such as decorative items that require a film thickness of several thousand layers, so it has a wide range of applications.

[Brief explanation of drawings]

Fig. 1 is an explanatory cross-sectional view illustrating the apparatus used to carry out the present invention, Fig. 2 is a cross-sectional view of a workpiece, and Fig. 3 is a graph showing the relationship between film thickness and chromaticity difference in an example of the present invention and a comparative example. It is. 1...Vacuum chamber, 2...Workpiece, 3...Electron beam gun, 4...Target. 5... Anode electrode, positive bias generator, 6... Thermionic generator, 7... Gas inlet, 8... Shahei plate, 9... Shutter 10... Hearth.

Claims (4)

[Claims] 1. Film thickness 1 by ion plating on the surface of the base material using one of the multi-cathode method, hollow cathode method, and high-frequency method
It is characterized by having a composite structure of a first TiN layer with a thickness of 1 to 3 μm, preferably 1 to 3 μm, and a second TiN layer with a thickness of 0.1 to 0.5 μm formed by ion plating using an arc evaporation method on the layer. TiN film with uniform chromaticity. 2. The TiN film according to claim 1, further comprising a Ti film intermediate layer having a thickness of 0.1 to 0.3 μm between the base material and the first layer. 3. Ti is applied to the surface of the base material by ion plating using one of the multi-cathode method, hollow cathode method, and high frequency method.
An N layer is provided to a thickness of 1 μm or more, preferably 0.1 to 3 μm, and then the arc evaporation method is switched to ion plating to form a TiN film with a thickness of 0.1 to 0.5 μm or more on the layer. A method for forming a TiN film of uniform chromaticity on a substrate, characterized by forming a layered composite structure. 4. A Ti layer with a thickness of 0.1 to 3 μm was formed on the surface of the base material, and a TiN film with a thickness of 1 μm or more, preferably 1 to 3 μm was provided by ion plating using one of the multi-cathode method, hollow cathode method, and high frequency method. 4. The method according to claim 3, further comprising switching to ion plating using an arc evaporation method, and then overlaying the layer with a TiN layer having a thickness of 0.1 to 0.5 μm using the same method.