Elsevier

Materials Letters

Volume 59, Issue 26, November 2005, Pages 3230-3233
Materials Letters

Wear behavior of DC unbalanced magnetron sputter deposited ZrCN films

https://doi.org/10.1016/j.matlet.2005.04.064Get rights and content

Abstract

For many years, TiN has been the most generally used film in every field of applications Another transition metal Zr, which belongs to the same periodic element group as Ti, is also an attractive material. There have been a lot of research reports discussing ZrN. However, knowledge on ZrCN is still limited. This paper presents initial experimental results on ZrCN films obtained with a DC unbalanced magnetron sputtering machine. The main purpose of this study is to understand the effects of variations in the ratio of C2H2 / N2 reactive gas flow rates and the additions of Ti and W on the hardness and wear performance of ZrCN series of films, while keeping the total of C2H2 and N2 flow rates constant at 15 sccm. The results showed that the hardness and wear behavior of ZrCN films were strongly dependent on the variations in the ratio of C2H2 / N2 reactive gas flow rates. The addition of Ti and W led to a significant enhancement in wear performance of ZrCN films, as well as in their hardness. The enhancement by Ti addition was greater than that by W addition. ZrCN, with and without Ti/W additions, showed much better wear behavior than TiN.

Introduction

Up to date, transition metal nitrides and carbonitride series of films have been widely used in industrial applications. Among the transition metals, besides Ti, Zr is another one attractive material for its excellent chemical and physical properties. For example, studies on ZrN films demonstrated that this compound has high chemical and thermal stability [1], high hardness [2], good machining/tribological performance [3], [4], low electrical resistivity [5], a gold-like color [6], etc.

In spite of the widespread studies on ZrN films, reports with regards to ZrCN are still limited. Most of the recent literatures concerning ZrCN films deal with the process details of plasma-aided chemical vapor deposition, mainly discussing how to grow ZrCN films at relatively low temperature [7], [8], [9], [10], [11], [12], [13]. As to the researches on applications of ZrCN films, not much has been reported. Hollstein et al. [14] deposited a group of ZrCN films by means of arc physical vapor deposition and investigated on their use for tools for minimal invasion surgery. The result indicated that ZrCN is a potential candidate for layers on surgical tools with regard to short-term biocompatibility to the human body. Rie et al. [15] deposited a group of Zr-based films and found good corrosive resistance of the ZrCN films. An analysis of ZrCN films revealed that they have lower coefficient of friction against various materials than a TiN film, with negligible degradation in mechanical and chemical properties [16].

Additives of Al, Cr and Si to TiN films have been reported to improve their mechanical properties [17], [18]. ZrN has similar structure and properties to TiN, as both Zr and Ti belong to the same periodic element group. Thus, similar addition effects may be expected to occur for Zr-based films. Mae et al. [19] deposited ZrN films using a RF reactive sputtering method and studied the influence of Si addition on ZrN. They found that with increasing Si content, the hardness of the films increases initially, attaining a maximum hardness at approximately 3%, and then decreases to lower hardness than that of Zr–N binary films. Although there is still not much knowledge with regard to the effect of addition on the mechanical behavior of Zr-based films, they seem to be promising.

This paper presents an initial experimental study of ZrCN films produced with DC unbalance magnetron deposition machine. The aim of this paper is to study the influence of variations in the ratio of C2H2 / N2 reactive gas flow rates and the Ti and W additions on the mechanical performance of ZrCN films, mainly the film hardness and wear performance, while keeping the total of C2H2 and N2 flow rates constant at 15 sccm. Considering the vast information on mechanical properties of TiN films, it was tested as well at identical conditions for comparison.

Section snippets

Experiment

The ZrCN films were synthesized using a TEER UDP-450 deposition machine, which employs reactive closed-field DC unbalanced magnetron sputtering method. A cross-sectional view show that the coating system comprises four vertical, orthogonally mounted magnetron cathodes which surround a rotational substrate holder. The target dimension is 300 × 110 × 10 mm.

Fig. 1 is a schematic drawing of the construction of ZrCN films studied here, in which three layers are seen to constitute a film. The three

Result and discussion

Table 2 lists the chemical composition and film thickness of ZrCN series of films. Considering ZrCN-4, ZrCN-2.75 and ZrCN-2, as the ratio of C2H2 / N2 flow rates decreased, the N content increased and the C content decreased. The relationship between the film thickness and the flow rate ratio was not explicit. ZrCN–W film had W content reaching as high as 20.3 at.% and its thickness was 1.7 μm. ZrCN–Ti had Ti content of only 13.8 at.% and a thickness of 1.1 μm.

Referring data in Table 2 to the

Conclusions

This paper presents initial experimental results on a series of ZrCN films deposited using a reactive four-target closed-field DC unbalance magnetron sputtering system. For growth of ZrCN films, four Zr targets were used. The additions of Ti/W to ZrCN films were achieved by using one Ti/W target and three Zr targets. The following conclusions were made under the conditions specified in this study:

  • No dependence of the variations in ratios of C2H2 / N2 reactive gas flow rates on the resulting

Acknowledgment

The authors wish to express their thanks for the financial support by the National Science Council under the contract of NSC92-2212-E-309-001.

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