Forming method of intermediate layer formed between base material and DLC film, DLC film forming method, and intermediate layer formed between base material and DLC film

Abstract

An intermediate layer forming method to form an intermediate layer formed between a base material and a DLC film using a PVD method includes: a Ti layer film-forming step of film-forming a Ti layer on a base material; and a TiC layer film-forming step of film-forming a TiC layer on the Ti layer, in which in the Ti layer film-forming step, an Ar gas is supplied into a chamber into which the base material is carried and a film-forming pressure is set to a pressure in a range of not less than 0.4 Pa and not more than 1 Pa to film-form the Ti layer, and in the TiC layer film-forming step, an Ar gas and a CH.sub.4 gas are supplied into the chamber, a film-forming pressure is set to a pressure in a range of 0.2 Pa or more to less than 0.4 Pa, and a second bias voltage higher in bias voltage than a first bias voltage applied to the base material in the Ti layer film-forming step and higher in bias voltage than 100 V is applied to the base material to film-form the TiC layer.

Claims

1. An intermediate layer forming method to form an intermediate layer formed between a base material and a DLC film using a PVD method, the method comprising: a Ti layer film-forming step of film-forming a Ti layer on a base material; and a TiC layer film-forming step of film-forming a TiC layer on the Ti layer, wherein in the Ti layer film-forming step, an Ar gas is supplied into a chamber into which the base material is carried and a film-forming pressure is set to a pressure in a range of not less than 0.4 Pa nor more than 1 Pa to film-form the Ti layer, in the TiC layer film-forming step, an Ar gas and a CH.sub.4 gas are supplied into the chamber, a film-forming pressure is set to a pressure in a range of 0.2 Pa or more to less than 0.4 Pa, and a second bias voltage higher in bias voltage than a first bias voltage applied to the base material in the Ti layer film-forming step and higher in bias voltage than 100 V is applied to the base material to film-form the TiC layer, and the PVD method is an unbalanced magnetron sputter method.

2. The intermediate layer forming method according to claim 1, further comprising: between the Ti layer film-forming step and the TiC layer film-forming step, a graded layer film-forming step of film-forming a graded layer on the Ti layer, wherein in the graded layer film-forming step, an Ar gas and a CH.sub.4 gas are supplied into the chamber, the graded layer is film-formed while increasing a flow rate of the CH.sub.4 gas until a flow rate ratio between the Ar gas and the CH.sub.4 gas becomes a flow rate ratio between the Ar gas and the CH.sub.4 gas in the TiC layer film-forming step, and in the TiC layer film-forming step, the TiC layer is film-formed on the graded layer.

3. The intermediate layer forming method according to claim 2, wherein in the graded layer film-forming step, a bias voltage to be applied to the base material is changed from the first bias voltage to the second bias voltage.

4. The intermediate layer forming method according to claim 1, wherein in the Ti layer film-forming step, the Ti layer is film-formed so that a film thickness becomes 0.1 to 0.2 m.

5. The intermediate layer forming method according to claim 1, wherein in the TiC layer film-forming step, the TiC layer is film-formed so that a film thickness becomes 0.4 to 0.5 m.

6. The intermediate layer forming method according to claim 1, wherein in the Ti layer film-forming step, the first bias voltage is set to a voltage in a range of 500 V to 100 V to film-form the Ti layer.

7. The intermediate layer forming method according to claim 1, wherein in the TiC layer film-forming step, the second bias voltage is set to a voltage in a range of higher than 100 V and lower than 30 V to film-form the TiC layer.

8. A DLC film forming method to form a DLC film using a plasma CVD method on the intermediate layer formed by the intermediate layer forming method according to claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic diagram illustrating a film structure on a base material related to an embodiment of the present invention;

(2) FIG. 2 is a schematic diagram illustrating a film structure on a base material related to another embodiment of the present invention;

(3) FIG. 3 is a view illustrating an indentation peripheral portion after a Rockwell hardness test related to Comparative example 1;

(4) FIG. 4 is a view illustrating an indentation peripheral portion after a Rockwell hardness test related to Comparative example 2; and

(5) FIG. 5 is a view illustrating an indentation peripheral portion after a Rockwell hardness test related to Comparative example 3.

MODE FOR CARRYING OUT THE INVENTION

(6) Hereinafter, there will be explained an embodiment related to the present invention based on a method of forming an intermediate layer 2 (a Ti layer 2a and a TiC layer 2b) on the surface of a base material 1 and forming a DLC film 3 on the intermediate layer 2 as illustrated in FIG. 1. Incidentally, in this embodiment, the intermediate layer 2 is formed by what is called a UBMS (unbalanced magnetron sputter) method being one example of a PVD method, and the DLC film 3 is formed by a plasma CVD method. The UBMS (unbalanced magnetron sputter) method is a sputtering method in which plasma emission to a base material is strengthened by making a magnetic field of a sputter cathode unbalanced intentionally and enables formation of a dense thin film. Further, as an apparatus used for forming the intermediate layer 2 and the DLC film 3, a UBMS apparatus capable of performing plasma CVD in the same chamber as that in which the intermediate layer 2 is formed is used. The UBMS apparatus is one well-known generally, so that the explanation of the apparatus constitution is omitted in this description. Further, in this description and the drawings, the same reference numerals and symbols are added to components having substantially the same functional constitutions, and thereby redundant explanations are omitted.

(7) First, as the base material 1, an iron-based material such as SCM415, SUS310, or SKD11 is carried into a chamber of the UBMS apparatus. Thereafter, the inside of the camber is vacuumed and the pressure is reduced to, for example, 2.610.sup.3 Pa or so. Subsequently, an Ar (argon) bombardment treatment is performed by heating a tungsten filament, and cleaning of the surface of the base material is performed. Incidentally, treatment conditions of the Ar bombardment treatment are that, for example, a chamber internal pressure is 1.3 to 1.4 Pa, a treatment time is 30 minutes, a filament discharge voltage is 40 V, a filament discharge current is 10 A, and a bias voltage is 300 to 400 V.

(8) Next, a Ti layer film-forming step of film-forming the Ti layer 2a on the base material 1 is started. At first, as a plasma-generating gas, an Ar gas is supplied into the chamber. At this time, the Ar gas is supplied so that the chamber internal pressure (film-forming pressure) becomes a pressure in a range of not less than 0.4 Pa and not more than 1.0 Pa. Further, a flow rate of the Ar gas is adjusted so as to make the chamber internal pressure become constant during the Ti layer film-forming step. A chamber internal temperature is adjusted to be 200 C. or lower. This chamber internal temperature is maintained to 200 C. or lower until film-formation of the DLC film 3 to be described later is finished.

(9) Thereafter, a pulse power supply for target is activated and a pulse power supply for bias is activated, to apply a bias voltage of 200 V, (which is a first bias voltage to be described later), to the base material 1. Thereby, the plasmatized Ar gas collides with a Ti target and Ti sputtered from the surface of the Ti target reaches the base material 1, and thereby the Ti layer 2a begins to be formed on the base material 1. Such film-forming processing of the Ti layer 2a is performed until a predetermined thickness (for example, 0.1 m) of the Ti layer 2a is obtained. Unless the Ti layer 2a exists, adhesiveness between the TiC layer 2b to be described later and the base material cannot be obtained.

(10) Incidentally, when the bias voltage in the Ti layer film-forming step is lower than 500 V, there is a risk that the base material 1 is damaged. On the other hand, when the bias voltage in the Ti layer film-forming step is higher than 100 V, energy of Ti to reach the base material 1 is small and a film does not become dense but becomes too smooth, therefore causing a risk that adhesiveness cannot be obtained. Therefore, the bias voltage in the Ti layer film-forming step is preferably 500 to 100 V. It is more preferably 400 to 200 V and further preferably 300 to 200 V. Incidentally, in this description, when levels of negative bias voltages are expressed, a bias voltage closer to 0 V is expressed to be high in bias voltage.

(11) Next, a TiC layer film-forming step of film-forming the TiC layer 2b on the Ti layer 2a is started. First, a CH.sub.4 (methane) gas is further supplied into the chamber into which the Ar gas has been supplied. At this time, the CH.sub.4 gas is supplied so that a flow rate ratio between the Ar gas and the CH.sub.4 gas becomes about 95:5 constantly. Further, flow rates of the individual gases are adjusted so that the chamber internal pressure (film-forming pressure) becomes a pressure in a range of 0.2 Pa or more to less than 0.4 Pa. The chamber internal pressure is adjusted to be constant during the TiC layer film-forming step. Further, the bias voltage to be applied to the base material 1 is changed to 50 V from 200 V.

(12) The above-described film-forming conditions are applied, and thereby the TiC layer 2b begins to be formed on the Ti layer 2a. Such film-forming processing of the TiC layer 2b is performed until a predetermined film thickness (for example, 0.45 m) of the TiC layer 2b is obtained.

(13) Incidentally, when the bias voltage in the TiC layer film-forming step, (which is a second bias voltage to be described later), is 100 V or lower, the TiC layer 2b to be formed becomes too smooth, thereby making it impossible to secure the adhesiveness sufficiently. Therefore, the bias voltage in the TiC layer film-forming step needs to be higher than 100 V. On the other hand, when the bias voltage in the TiC layer film-forming step becomes 30 V or higher, mixture of Ti and carbon does not advance, to thus cause a risk that hardness decreases. Therefore, the bias voltage in the TiC layer film-forming step is preferably set to be higher than 100 V and lower than 30 V. It is further preferably 75 to 50 V.

(14) By the Ti layer film-forming step and the TiC layer film-forming step described above, the intermediate layer 2 is formed on the surface of the base material 1.

(15) Thereafter, as a gas for film-forming the DLC film 3, a C.sub.2H.sub.2 (acetylene) gas is supplied into the same chamber as that in which the above-described intermediate layer 2 is formed. Then, the DLC film 3 is film-formed on the TiC layer 2b of the intermediate layer 2 by a conventionally well-known plasma CVD method.

(16) By undergoing the above-described series of steps, the intermediate layer 2 (the Ti layer 2a and the TiC layer 2b) and the DLC film 3 are formed on the base material. When the film-forming pressure of the TiC layer 2b is set to be lower than that of the Ti layer 2a and the bias voltage in the film-forming step of the TiC layer 2b (second bias voltage) is set to be higher than that in the film-forming step of the Ti layer 2a (first bias voltage) as described in this embodiment, the adhesiveness between the base material 1 and the DLC film 3 can be improved as will be described in Examples to be described later. This makes it difficult for the DLC film 3 to peel off, to thus be able to improve performance as the DLC film 3

(17) In the foregoing, the preferred embodiment of the present invention has been described, but the present invention is not limited to such an example. It is apparent that those skilled in the art are able to devise various variation or modification examples within the scope of the technical spirit described in the claims, and it should be understood that such examples belong to the technical scope of the present invention as a matter of course.

(18) For example, in the above-described embodiment, as the plasma-generating gas, the Ar gas is used, but the plasma-generating gas is not limited to this. Further, the formation of the intermediate layer 2 is not limited to using the Ti target. Further, the gases to be supplied into the chamber are not also limited to the CH.sub.4 gas and the C.sub.2H.sub.2 gas.

Formation of Graded Layer 2c

(19) Further, the above-described embodiment is designed that the Ti layer 2a and the TiC layer 2b are film-formed as the intermediate layer 2, but as illustrated in FIG. 2, a graded layer 2c may also be film-formed between the Ti layer 2a and the TiC layer 2b. The graded layer 2c means a layer rich in Ti on the Ti layer 2a side and having a large content of C on the TiC layer 2b side as compared to the Ti layer 2a side. As will be explained in Examples to be described later, the graded layer 2c is provided, thereby making it possible to improve the adhesiveness between the base material 1 and the DLC film 3.

(20) Here, there will be explained a film-forming step of the graded layer 2c. First, the Ti layer 2a is film-formed on the base material 1 by the Ti layer film-forming step explained in the above-described embodiment. Thereafter, a CH.sub.4 gas is supplied into the chamber into which the Ar gas has been supplied. A flow rate is a volume basis such as m.sup.3(1000 L)/minute. At this time, the flow rate of the CH.sub.4 gas is increased gradually so that a flow rate ratio between the Ar gas and the CH.sub.4 gas changes gradually from 100:0 to 95:5. Further, the bias voltage to be applied to the base material 1 is gradually increased from 200 V in the Ti layer film-forming step to 50 V in the TiC layer film-forming step according to the flow rate. Incidentally, the flow rate ratio between the Ar gas and the CH.sub.4 gas and the bias voltage are adjusted to change continuously until the graded layer film-forming step is finished. For example, when a processing time in the graded layer film-forming step is 10 minutes, it is designed so that the flow rate ratio between the Ar gas and the CH.sub.4 gas is changed continuously for 10 minutes and the flow rate ratio becomes 95:5 when 10 minutes elapse. The same is applied also to the bias voltage.

(21) Thereby, the graded layer 2c whose composition has been changed continuously is formed on the Ti layer 2a. Incidentally, the film-forming pressure in the graded layer film-forming step is set to the same as the pressure in the Ti layer film-forming step, or set to a pressure lower than the film-forming pressure in the Ti layer film-forming step and higher than the film-forming pressure of the TiC layer. Further, even in the case when the bias voltage is set to be constant and the flow rate of the CH.sub.4 gas is increased gradually, the graded layer 2c can be formed.

(22) Thereafter, the graded layer 2c is formed so as to have a predetermined film thickness (for example, 0.05 m), and then the TiC layer 2b is film-formed on the graded layer 2c by the TiC layer film-forming step explained in the above-described embodiment. Then, by the plasma CVD method, the DLC film 3 is film-formed on the TiC layer 2b.

Example

(23) Under conditions illustrated in Table 1 below, intermediate layers were each formed on a base material by the UBMS method, and DLC films were film-formed on the individual intermediate layers by the plasma CVD method. Then, differences in adhesiveness among the DLC films at this time were evaluated. Evaluation results of the DLC films are illustrated also in Table 1.

(24) In this example, as the base material, one in which a SCM415 was subjected to a carburizing and quenching treatment and was subjected to a tempering treatment at 200 C. to be polished to a surface roughness of Ra=0.01 m was used. Further, in order to suppress a decrease in hardness of the base material, the chamber internal temperature was adjusted to be 200 C. or lower from start of the Ti layer film-forming step until finish of the DLC film-forming step. Further, the number of targets was set to one and an output of the pulse power supply for target was set to 6 kW. Further, a distance between the base material and the Ti target was set to about 15 cm, a base material rotation number was set to a self-revolving motion at 2 rpm, a frequency was set to 25 kHz, and a Duty ratio was set to 75%. Incidentally, FILM-FORMING PRESSURE in Table 1 means the chamber internal pressure during film-forming processing.

(25) Further, in this example, a Ti layer and a TiC layer were designed to be film-formed as the intermediate layer. Incidentally, in Examples 3 to 8 and Comparative examples 1 to 4, a graded layer was also further film-formed. As for each film-forming time of the individual layers, it is 15 minutes in the Ti layer, it is 7.5 minutes in the graded layer, and it is 105 minutes in the TiC layer. Further, the DLC film was film-formed so as to have a film thickness of 1.8 m, and a film hardness was adjusted to be about HV 1600 using a microhardness tester (FISCHERSCOPE H100C manufactured by Fischer Instruments).

(26) Further, as for the adhesiveness evaluation of the DLC film, a scratch test and an indentation observation by a Rockwell hardness tester were performed, and comparisons were performed with individual samples.

(27) The scratch test was performed on the surface of the sample with a scratch length of 10 mm, at a scratch speed of 10 mm/min, and with a scratch load of 0 to 100 N using a Rockwell C-scale indenter (in conformity with JIS Z 2245: diamond with a pointed end of 0.2 mm in radius of curvature and with a cone angle of 120, and after scratch, the load with which peeling occurred was recorded by observation of an attached microscope. In this example, in terms of usefulness, ones with a peeling occurrence load being 35 N or more are set to be accepted.

(28) Further, the indentation by the Rockwell hardness tester was formed by applying an initial test force of 98.07 N and a total test force of 1471 N onto the surface of the sample by the above-described Rockwell C-scale indenter. Then, whether or not peeling of the DLC film exists in an indentation peripheral portion was observed. In this example, ones without peeling of the DLC film are set to be accepted.

(29) That is, in this example, as long as the peeling occurrence load of the DLC film is 35 N or more in the scratch test and the state where peeling of the DLC film does not exist in the indentation peripheral portion is found in a Rockwell hardness test, the adhesiveness between the base material and the DLC film is determined to be improved.

(30) TABLE-US-00001 TABLE 1 INTERMEDIATE LAYER GRADED LAYER Ti LAYER FILM- FILM-FORMING FLOW RATE FILM BIAS FORMING FLOW RATE FILM BIAS VOLTAGE PRESSURE RATIO THICKNESS VOLTAGE PRESSURE RATIO THICKNESS (V) (Pa) AR:CH.sub.4 (M) (V) (Pa) AR:CH.sub.4 (M) EXAMPLE 1 200 0.4 100:0 0.15 EXAMPLE 2 200 0.4 100:0 0.1 EXAMPLE 3 200 0.4 100:0 0.1 200 .fwdarw. 50 0.4 100:0 .fwdarw. 95:5 0.05 EXAMPLE 4 200 1 100:0 0.1 200 .fwdarw. 50 0.4 100:0 .fwdarw. 95:5 0.05 EXAMPLE 5 200 0.4 100:0 0.1 200 .fwdarw. 75 0.4 100:0 .fwdarw. 95:5 0.05 EXAMPLE 6 300 0.4 100:0 0.1 300 .fwdarw. 50 0.4 100:0 .fwdarw. 95:5 0.05 EXAMPLE 7 400 0.4 100:0 0.1 400 .fwdarw. 50 0.4 100:0 .fwdarw. 95:5 0.05 EXAMPLE 8 200 0.4 100:0 0.2 200 .fwdarw. 75 0.4 100:0 .fwdarw. 95:5 0.05 COMPARATIVE 200 0.4 100:0 0.1 200 .fwdarw. 50 0.4 100:0 .fwdarw. 95:5 0.05 EXAMPLE 1 COMPARATIVE 100 0.2 100:0 0.1 100 0.2 100:0 .fwdarw. 95:5 0.05 EXAMPLE 2 COMPARATIVE 200 1 100:0 0.1 200 .fwdarw. 50 1 100:0 .fwdarw. 95:5 0.05 EXAMPLE 3 COMPARATIVE 200 0.4 100:0 0.1 200 .fwdarw. 100 0.4 100:0 .fwdarw. 90:10 0.05 EXAMPLE 4 ADHESIVENESS INTERMEDIATE LAYER EVALUATION OF DLC FILM TiC LAYER INTERMED- PEELING FILM- FLOW IATE LAYER OCCURRENCE PEELING OF INDENTATION BIAS FORMING RATE FILM FILM LOAD OF PERIPHERAL PORTION VOLTAGE PRESSURE RATIO THICKNESS THICKNESS SCRATCH AFTER ROCKWELL (V) (Pa) AR:CH.sub.4 (M) (uM) TEST (N) HARDNESS TEST EXAMPLE 1 50 0.2 95:5 0.45 0.6 44 NONE EXAMPLE 2 50 0.2 95:5 0.5 0.6 50 NONE EXAMPLE 3 50 0.2 95:5 0.45 0.6 61 NONE EXAMPLE 4 50 0.2 95:5 0.45 0.6 37 NONE EXAMPLE 5 75 0.2 95:5 0.45 0.6 43 NONE EXAMPLE 6 50 0.2 95:5 0.45 0.6 44 NONE EXAMPLE 7 50 0.2 95:5 0.45 0.6 39 NONE EXAMPLE 8 75 0.2 95:5 0.4 0.6 47 NONE COMPARATIVE 50 0.4 95:5 0.35 0.5 33 EXISTENCE EXAMPLE 1 COMPARATIVE 100 0.2 95:5 0.45 0.6 27 EXISTENCE EXAMPLE 2 COMPARATIVE 50 1 95:5 0.45 0.6 30 EXISTENCE EXAMPLE 3 COMPARATIVE 100 0.2 90:10 0.45 0.6 32 EXISTENCE EXAMPLE 4

(31) As Examples 1 to 8 in Table 1, when the intermediate layer was formed in a manner to make the film-forming pressure of the TiC layer lower than that of the Ti layer, results of the scratch test and the Rockwell hardness test both reached the acceptance criterion.

(32) As Comparative examples 1 to 3, on the other hand, when the film-forming pressure of the intermediate layer was set to be always constant, the result of the scratch test fell below the acceptance criterion (the peeling occurrence load of 35 N or more). Further, in the indentation peripheral portion after the Rockwell hardness test, peeling of the DLC film occurs as illustrated in FIG. 3 (Comparative example 1), FIG. 4 (Comparative example 2), and FIG. 5 (Comparative example 3), to thereby find that the adhesiveness of the DLC film is not good.

(33) Next, when focusing on the film-forming conditions of Examples 1 to 3, the film-forming pressure of the Ti layer is 0.4 Pa and the film-forming pressure of the TiC layer is 0.2 Pa, resulting in that the conditions of the film-forming pressures are the same. However, the peeling occurrence load of the scratch test in Example 3 having the graded layer became larger than that in Examples 1 and 2 each having no graded layer as a result. That is, it is found that when the graded layer is film-formed as the intermediate layer, the effect of improving the adhesiveness of the DLC film is increased.

(34) Further, even though Comparative example 1 had the graded layer capable of improving the adhesiveness of the DLC film, the evaluation result of the DLC film resulted in rejection. On the other hand, the evaluation result of the DLC film in Examples 1 and 2 each having no graded layer is good. That is, making a comparison between Examples 1 and 2 and Comparative example 1 supports that it is better when the film-forming pressures of the Ti layer and the TiC layer are not constant.

(35) Next, when focusing on the film-forming conditions of Example 3 and Example 4, Examples 3 and 4 both have the graded layer, but differ only in the film-forming pressure of the Ti layer because they are 0.4 Pa and 1 Pa. Making a comparison between the evaluation result of the DLC film in Example 3 and the evaluation result of the DLC film in Example 4 revealed that the peeling occurrence load in the scratch test becomes larger in Example 3 as a result. Therefore, the film-forming pressure of the Ti layer is found to be preferable when it is lower.

(36) Besides, in consideration of the fact that only the film-forming pressure of the Ti layer is different between Example 3 and Example 4 in terms of the film-forming condition and the evaluation result of the DLC film reached the acceptance criterion both in Example 3 and Example 4, it is obvious that even when the film-forming pressure of the Ti layer is, for example, 0.7 Pa being a pressure higher than 0.4 Pa in Example 3 and lower than 1 Pa in Example 4, the evaluation result of the DLC film becomes good.

(37) Further, the film-forming pressures of the Ti layer and the TiC layer in Comparative example 1 are 0.4 Pa constantly, and under this condition, the evaluation result of the DLC film results in rejection. On the other hand, in Example 3, the film-forming pressure of the Ti layer is 0.4 Pa and the film-forming pressure of the TiC layer is 0.2 Pa, resulting in that the film-forming pressure of the TiC layer becomes smaller than that of the Ti layer. In consideration of the fact that the evaluation result of the DLC film results in acceptance under this condition, it is found that the film-forming pressures of the Ti layer and the TiC layer are not constant and it is better when the film-forming pressure of the TiC layer is a little lower than that of the Ti layer.

(38) Accordingly, when considering the results of Examples 3 and 4 and Comparative example 1, it is conceivable that as long as the film-forming pressure of the Ti layer is set to a pressure in a range of not less than 0.4 Pa and not more than 1 Pa and the film-forming pressure of the TiC layer is set to a pressure in a range of 0.2 Pa or more to less than 0.4 Pa, the adhesiveness of the DLC film can be improved.

(39) However, in Comparative example 4, even though the film-forming pressure of the TiC layer was lower than that of the Ti layer, the adhesiveness evaluation of the DLC film fell below the acceptance criterion. On the other hand, in Examples 3 and 5 in which the graded layer is provided similarly to Comparative example 4 and the film-forming pressures and the film thicknesses of the individual layers are also the same, the evaluation result of the DLC film reaches the acceptance criterion. Here, when focusing on the bias voltages of Examples 3 and 5 and Comparative example 4, the bias voltages in the TiC layer film-forming step are different from one another. That is, the reason why the adhesiveness of the DLC film in Comparative example 4 became bad is conceivably because the bias voltage in the TiC layer film-forming step was 100 V, and thereby the formed TiC layer became too smooth and the adhesiveness became insufficient.

(40) Accordingly, in order to improve the adhesiveness of the DLC film, it is necessary to set the film-forming pressure of the Ti layer to a pressure in a range of not less than 0.4 Pa and not more than 1 Pa and set the film-forming pressure of the TiC layer to a pressure in a range of 0.2 Pa or more to less than 0.4 Pa, and further make the bias voltage in the TiC layer film-forming step become higher than 100 V.

(41) Next, in a state where the TiC layers were formed under the conditions of Examples, 3, 5, 6, and 8 and Comparative examples 1, 3, and 4, X-ray diffraction was performed on the individual surfaces of the base materials by a focusing method using an X-ray diffractometer (RINT2000 manufactured by Rigaku Corporation). As an X-ray tube, a Cu tube was used, a voltage was set to 40 kV, a current was set to 20 mA, a scan angle 2 was set to 20 to 80, and a scan step was set to 3/min. In an X-ray diffraction peak intensity ITiC(111) of the (111) crystal plane of TiC appearing near 2:36.3 degrees and an X-ray diffraction peak intensity IFe(110) of the (111) crystal plane of Fe appearing near 20:44.6 degrees, which were measured in an X-ray diffraction (XRD) profile at this time, an intensity ratio expressed by ITiC(111)/IFe(110) was calculated. Results are illustrated in Table 2.

(42) TABLE-US-00002 TABLE 2 TiC/Fe INTENSITY RATIO TiC Fe (Fe IS SET TO 100) INTENSITY INTENSITY ITiC (111)/ ITiC (111) IFe (110) IFe (110) 100 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 506 461 109 EXAMPLE 4 EXAMPLE 5 450 439 102 EXAMPLE 6 582 537 108 EXAMPLE 7 EXAMPLE 8 836 496 168 COMPARATIVE 129 529 24 EXAMPLE 1 COMPARATIVE EXAMPLE 2 COMPARATIVE 62 351 17 EXAMPLE 3 COMPARATIVE 249 429 58 EXAMPLE 4

(43) As illustrated in Table 2, in Comparative examples 1, 3, and 4, ITiC(111) was smaller than IFe(110) and the intensity ratio between TiC and Fe was about 58 at the maximum. On the other hand, in Examples 3, 5, 6, and 8, ITiC(111) was large as compared to that in Comparative examples 1, 3, and 4, and the intensity ratio between TiC and Fe exceeded 100 in all of Examples 3, 5, 6, and 8.

(44) When considering the adhesiveness evaluation results of the DLC film illustrated in Table 1 and the results of the XRD measurement illustrated in Table 2, it is found that what is necessary is to form such an intermediate layer that the intensity ratio expressed by ITiC(111)/IFe(110)100 becomes 60 or more in order to improve the adhesiveness of the DLC film. Further, the more preferable intensity ratio is 80 or more, and the still more preferable intensity ratio is 100 or more.

INDUSTRIAL APPLICABILITY

(45) The present invention can be applied to DLC film coating of a base material.

EXPLANATION OF CODES

(46) 1 base material 2 intermediate layer 2a Ti layer 2b TiC layer 2c graded layer 3 DLC film