JP5838416B2 - Method for manufacturing magnetic recording medium - Google Patents

Description

  The present invention relates to a method for manufacturing a magnetic recording medium, a magnetic recording medium, and a DLC film.

FIG. 8 is a cross-sectional view for explaining a conventional method of manufacturing a magnetic recording medium.
First, a deposition target substrate 100 in which at least a magnetic layer 102 is formed on a nonmagnetic substrate 101 is prepared, and a DLC (Diamond Like Carbon) film 103 having a thickness of 3 nm is formed on the deposition target substrate 100 by CVD (chemical). The film is formed by vapor deposition). Next, a CN film 104 having a thickness of 1 nm is formed on the DLC film 103 by sputtering.

  Next, fomblin oil is applied onto the CN film 104 by dipping the CN film 104 into fluorine-based fomblin oil. Next, the film formation substrate 100 is annealed at a temperature of 150 ° C. for 1 hour, whereby a 4 nm-thick fluorinated organic film 105 that functions as a solid lubricant is formed on the CN film 104. In addition, a vapor deposition method may be used as a method for forming the fluorinated organic film 105, and the vapor deposition temperature in that case is 110 ° C.

  When using the above magnetic recording medium, it is necessary to bring a media head (not shown) close to the fluorinated organic film 105, and it is required to shorten the distance between the media head and the magnetic layer 102. . For this reason, it is required to make the total film thickness of the DLC film 103, the CN film 104, and the fluorinated organic film 105 thinner.

  Therefore, it is conceivable to form the fluorinated organic film 105 on the DLC film 103 without the CN film 104. However, since the CN film 104 having a water contact angle of about 30 ° has a function of improving the adhesion between the DLC film 103 and the fluorinated organic film 105, the contact angle of water is 80 ° when the CN film 104 is eliminated. As a result, the adhesion between the DLC film 103 and the fluorinated organic film 105 is deteriorated, and the fluorinated organic film 105 is easily peeled off from the DLC film 103.

An object of one embodiment of the present invention is to provide a magnetic recording medium with improved adhesion between a DLC film and a fluorinated organic film, or a method for manufacturing the same.
An object of one embodiment of the present invention is to impart hydrophilicity to the surface of a DLC film without substantially reducing the film thickness.

In one embodiment of the present invention, a magnetic layer is formed over a nonmagnetic substrate,
Forming a DLC film on the magnetic layer;
By performing plasma treatment on the surface of the DLC film, the surface of the DLC film is shaved to a depth of 1 nm or less,
A method of manufacturing a magnetic recording medium in which a fluorinated organic film is formed on the DLC film,
The DLC film after the plasma treatment has a surface with a water contact angle of 50 ° or less,
The method of manufacturing a magnetic recording medium is characterized in that the processing gas supplied when performing the plasma processing includes at least one of nitrogen gas, oxygen gas, hydrogen gas and inert gas.

In one embodiment of the present invention, a magnetic layer is formed over a nonmagnetic substrate,
Forming a DLC film on the magnetic layer;
By performing plasma treatment on the surface of the DLC film, the decrease in the film thickness of the DLC film is suppressed to 0.3 nm or less, and the surface of the DLC film is nitrided,
A method of manufacturing a magnetic recording medium in which a fluorinated organic film is formed on the DLC film,
The DLC film after the plasma treatment has a surface with a water contact angle of 50 ° or less,
The method of manufacturing a magnetic recording medium is characterized in that the processing gas supplied when performing the plasma processing includes at least one of a mixed gas of nitrogen gas and inert gas and nitrogen gas.

In one embodiment of the present invention, when the plasma treatment is performed, the high frequency output when an inductively coupled plasma source is used is 200 W or less, and the density of the high frequency output when a parallel plate type plasma source is used is It is also possible to be 1 × 10 ⁻² W / cm ² or less.

  In one embodiment of the present invention, the frequency of the high-frequency power is preferably 100 kHz to 27 MHz.

  In one embodiment of the present invention, the pressure at the time of performing the plasma treatment may be 0.05 Pa or more and 10 Pa or less.

In one embodiment of the present invention, the fluorinated organic film includes a C _a F _b film, a C _a F _b N _c film, a C _a F _b H _d film, and a C formed by a CVD method using a source gas. _{an a} F _b O _e film, a C _a F _b O _e H _d film, a C _a F _b N _C O _e film, or a C _a F _b N _C O _e H _d film,
The source gas may include an organic source gas containing carbon and fluorine. However, a, b, c, d, and e are natural numbers.

  In one embodiment of the present invention, the organic material gas may contain three or more carbons.

In one embodiment of the present invention, the organic source gas in the case of forming the C _a F _b film on the DLC film is C ₃ F ₆ , C ₄ F ₆ , C ₆ F ₆ , C ₆ F _{12. , C 6 F 14, C 7} F 8, C 7 F 14, C 7 F 16, C 8 F 16, C 8 F 18, C 9 F 18, C 9 F 20, C 10 F 8, C 10 F 18 , C ₁₁ F ₂₀ , C ₁₂ F ₁₀ , C ₁₃ F ₂₈ , C ₁₅ F ₃₂ , C ₂₀ F ₄₂ , and C ₂₄ F ₅₀ ,
The organic material gas in the case of forming the C _a F _b N _C film on the DLC film is C ₃ F ₃ N ₃ , C ₃ F ₉ N, C ₅ F ₅ N, C ₆ F ₄ N ₂ , _{C 6 F 9 N 3, C} 6 F 12 N 2, C 6 F 15 N, C 7 F 5 N, C 8 F 4 N 2, C 9 F 21 N, C 12 F 4 N 4, C 12 F 27 N, C ₁₄ F ₈ N ₂ , C ₁₅ F ₃₃ N, C ₂₄ F ₄₅ N ₃ , and triheptafluoropropylamine,
In the case of forming the C _a F _b O _d film on the DLC film, the organic material gas is C ₃ F ₆ O, C ₄ F ₆ O ₃ , C ₄ F ₈ O, C ₅ F ₆ O ₃ , _{C 6 F 4 O 2, C} 6 F 10 O 3, C 8 F 4 O 3, C 8 F 8 O, C 8 F 8 O 2, C 8 F 14 O 3, C 13 F 10 O, C 13 F ₁₀ O ₃ and at least one of C ₂ F ₆ O (C ₃ F ₆ O) n (CF ₂ O) m,
The organic material gas in the case where the C _a F _b N _C O _d film is formed on the DLC film may include C ₇ F ₅ NO.

  In one embodiment of the present invention, perfluoroamines may be used as the organic material gas.

  In one embodiment of the present invention, the CVD method includes holding the DLC film on a holding electrode, disposing a counter electrode facing the DLC film held on the holding electrode, and holding the holding electrode and the counter electrode. It is preferable to use a plasma CVD method in which a DC voltage when forming DC plasma by supplying power to one of the electrodes or a DC voltage component when forming high-frequency plasma is + 150V to -150V.

One embodiment of the present invention includes a magnetic layer formed over a nonmagnetic substrate;
A DLC film formed on the magnetic layer;
A fluorinated organic film formed on the DLC film;
A magnetic recording medium comprising:

Also, in one aspect of the present invention, the composition of the interior of the DLC film is _{C 1-a H} a, and a 0 ≦ a ≦ 0.3, the interface between the DLC film and the fluorinated organic film The DLC film may have a composition in which H is replaced with N.

In one embodiment of the present invention, the fluorinated organic film includes a C _a F _b film, a C _a F _b N _c film, a C _a F _b H _d film, a C _a F _b O _e film, and a C _a F _b The film may be any of an O _{e Hd} film, a C _a F _b N _C O _e film, and a C _a F _b N _C O _e H _d film.
However, a, b, c, d, and e are natural numbers.

In one embodiment of the present invention, the C _a F _b film, the C _a F _b N _c film, the C _a F _b H _d film, the C _a F _b O _e film, the C _a F _b O _e H _d film, Each of the C _a F _b N _C O _e film and the C _a F _b N _C O _e H _d film may be an amorphous film.
However, a, b, c, d, and e are natural numbers.

  In one embodiment of the present invention, the thickness of any one of the films can be 3 nm or less.

One aspect of the present invention is a DLC film formed on a substrate,
The DLC film is a DLC film having a surface with a water contact angle of 50 ° or less.

  In one embodiment of the present invention, the surface having a water contact angle of 50 ° or less may be a surface after being etched to a depth of 1 nm or less from the surface of the DLC film by plasma treatment. .

Also, in one aspect of the present invention, within the composition _{C 1-a H} a of the DLC film, and a 0 ≦ a ≦ 0.3, the surface of the DLC film H is substituted with N It is also possible to have a composition.

According to one embodiment of the present invention, a magnetic recording medium with improved adhesion between a DLC film and a fluorinated organic film or a method for manufacturing the magnetic recording medium can be provided.
Further, according to one embodiment of the present invention, it is possible to provide a DLC film having hydrophilicity on the surface of the DLC film without substantially reducing the film thickness.

It is sectional drawing for demonstrating the manufacturing method of the magnetic-recording medium which concerns on 1 aspect of this invention. It is sectional drawing which shows typically the plasma processing apparatus using the inductively coupled plasma source for performing a plasma processing on the surface of the DLC film 13 shown in FIG. FIG. 2 is a cross-sectional view schematically showing a plasma processing apparatus using a parallel plate type plasma source for performing plasma processing on the surface of the DLC film 13 shown in FIG. 1, and forming a fluorinated organic film according to one embodiment of the present invention. It is sectional drawing which shows typically the plasma CVD apparatus for film-forming. It is sectional drawing which shows typically the plasma CVD apparatus for forming the fluorinated organic film | membrane which concerns on 1 aspect of this invention. It is a graph which shows the plasma processing time characteristic in ICP input electric power 200W, Comprising: It is a figure which shows the relationship between processing time and the contact angle of water. It is a graph which shows the substrate bias application characteristic in ICP input electric power 200W, Comprising: It is a figure which shows the relationship between DC bias voltage and the contact angle of water. It is a diagram showing the relationship between deposition rate of Vdc and _C a _{F b} membrane of Example 3. It is sectional drawing for demonstrating the manufacturing method of the conventional magnetic recording medium.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description, and it will be easily understood by those skilled in the art that modes and details can be variously changed without departing from the spirit and scope of the present invention. Therefore, the present invention should not be construed as being limited to the description of the embodiments below.

(First embodiment)
FIG. 1 is a cross-sectional view for explaining a method of manufacturing a magnetic recording medium according to one embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a plasma processing apparatus using an inductively coupled plasma source for performing plasma processing on the surface of the DLC film 13 shown in FIG. FIG. 3 is a cross-sectional view schematically showing a plasma processing apparatus using a parallel plate type plasma source for performing plasma processing on the surface of the DLC film 13 shown in FIG.

  First, as shown in FIG. 1, a film formation substrate 2 having at least a magnetic layer 12 formed on a nonmagnetic substrate 11 is prepared, and a DLC film 13 having a thickness of about 3 nm is formed on the film formation substrate 2. A film is formed by a CVD method. The deposition target substrate 2 is, for example, a bird disk substrate or a media head.

Next, at least one processing gas of nitrogen gas, oxygen gas, hydrogen gas, inert gas, and mixed gas thereof is supplied to the surface of the DLC film 13 at a pressure of 0.05 Pa or more and 10 Pa or less, and is 100 kHz or more and 27 MHz. When the plasma processing apparatus shown in FIG. 2 is used, high-frequency power of 200 W or less is supplied at the following frequencies, and when the plasma processing apparatus shown in FIG. 3 is used, high-frequency power of 1 × 10 ⁻² W / cm ² or less is supplied. By supplying, the surface of the DLC film 13 is subjected to plasma treatment. Thereby, the DLC film 13 is shaved from the surface to a depth of 1 nm or less (more preferably, a depth of 0.3 nm or less, more preferably 0.1 nm), and the contact angle of water on the surface of the DLC film 13 is 50. It is less than ° (more preferably less than 30 °).

  Thereafter, the DLC film 13 is dipped into the fluorine-based fomblin oil, so that the fomblin oil is applied on the DLC film 13. Next, the film-formed substrate 10 is annealed at a temperature of 150 ° C. for 1 hour, whereby a 4 nm-thick fluorinated organic film 15 that functions as a solid lubricant is formed on the DLC film 13. In addition, you may use a vapor deposition method as a preparation method of the fluorinated organic film | membrane 15, and the vapor deposition temperature in that case is 110 degreeC.

Here, the plasma processing apparatus shown in FIGS. 2 and 3 will be described.
The plasma processing apparatus shown in FIG. 2 is an apparatus capable of performing plasma processing on both surfaces of a film formation substrate 2 having a DLC film 13 formed on both surfaces, and is symmetrical with respect to the film formation substrate 2. It is configured. However, in FIG. 2, only the left side with respect to the deposition target substrate 2 is shown.

  The plasma processing apparatus shown in FIG. 2 has a holding mechanism (not shown) for holding the deposition target substrate 2 in the chamber 21, and applies a DC voltage or high frequency power to the substrate held by the holding mechanism. A first power supply 22 is provided. A high frequency coil 23 is disposed in the chamber 21 so as to face the film formation substrate 2. A high frequency power having a frequency of 13.56 MHz, for example, is applied to the high frequency coil 23 by a second power source 24. It is like that. A processing gas is introduced into the chamber 21 by a gas introduction mechanism 25. Further, the chamber 21 is provided with an exhaust port for evacuating the inside of the chamber 21. This exhaust port is connected to an exhaust pump (not shown).

The plasma processing apparatus shown in FIG. 3 has a chamber 1, and a holding electrode 4 that holds a deposition target substrate 2 is disposed below the chamber 1. The holding electrode 4 is electrically connected to a high frequency power source 6 having a frequency of 13.56 MHz, for example, and the holding electrode 4 also functions as an RF application electrode (RF cathode). The high frequency output density of the holding electrode 4 to which a high frequency is applied by the high frequency power source 6 is 1 × 10 ⁻² W / cm ² or less as described above.

  A gas shower electrode (counter electrode) 7 is disposed above the chamber 1 at a position parallel to the holding electrode 4. These are a pair of parallel plate electrodes. The gas shower electrode is connected to the ground potential. On the lower surface of the gas shower electrode 7, a plurality of supply ports for supplying a shower-like process gas to the side where the piezoelectric film of the substrate 2 is formed (the space between the gas shower electrode 7 and the holding electrode 4) (see FIG. (Not shown) is formed.

  A gas introduction path (not shown) is provided inside the gas shower electrode 7. One side of the gas introduction path is connected to the supply port, and the other side of the gas introduction path is connected to the processing gas supply mechanism 3. Further, the chamber 1 is provided with an exhaust port for evacuating the inside of the chamber 1. This exhaust port is connected to an exhaust pump (not shown).

  According to this embodiment, the surface of the DLC film 13 is subjected to plasma treatment, and the DLC film 13 is shaved by 1 nm or less from the surface, so that the contact angle of water on the surface of the DLC film 13 is 50 ° or less. Even if the fluorinated organic film 15 is directly formed on the film 13, sufficient adhesion between the fluorinated organic film 15 and the DLC film 13 can be secured, and the fluorinated organic film 15 is peeled off from the DLC film 13. Can be suppressed.

Why can thus on the surface of the DLC film 13 without hardly reducing a thickness having a hydrophilic property, the internal composition of the DLC film 13 is C _1-a H _a, and, 0 ≦ a ≦ The DLC film at the interface between the DLC film 13 and the fluorinated organic film 15 is considered to have a composition in which H is replaced with N or the like.

  In this embodiment, the plasma treatment is performed on the DLC film formed on the deposition substrate. However, the plasma treatment is performed on the organic film or the inorganic film other than the DLC film deposited on the deposition substrate. Alternatively, plasma treatment may be performed on a resin film formed on the deposition target substrate.

  In the present embodiment, a deposition target substrate 10 having at least the magnetic layer 12 formed on the nonmagnetic substrate 11 is prepared, and the DLC film 13 deposited on the deposition target substrate 10 is subjected to plasma treatment. However, the present invention is not limited to this, and the DLC film 13 formed on another substrate may be subjected to plasma treatment. The other substrate in this case may be, for example, an electronic device, and even when a DLC film is laminated on the electronic device and subjected to plasma treatment, the electronic device is rarely broken by plasma. Further, plasma treatment may be performed on an organic film or an inorganic film formed on another base material.

(Second Embodiment)
The manufacturing method of the magnetic recording medium according to the present embodiment is the same as that of the first embodiment until the surface of the DLC film 13 shown in FIG. The process of forming the fluorinated organic film 15 on the DLC film 13 using the plasma processing apparatus as a plasma CVD apparatus will be described. This embodiment is the same as the first embodiment except for the step of forming the fluorinated organic film 15.

  FIG. 3 is a cross-sectional view schematically illustrating a plasma CVD apparatus for forming a fluorinated organic film according to one embodiment of the present invention.

  The plasma CVD apparatus has a chamber 1, and a holding electrode 4 that holds a substrate 2 having a piezoelectric film is disposed below the chamber 1. As the piezoelectric film, for example, a ferroelectric film such as a PZT film can be used.

  The holding electrode 4 is electrically connected to a high frequency power source 6 having a frequency of 13.56 MHz, for example, and the holding electrode 4 also functions as an RF application electrode. The periphery and the lower part of the holding electrode 4 are shielded by an earth shield 5. In the present embodiment, the high frequency power source 6 is used, but another power source, for example, a DC power source or a microwave power source may be used.

  A gas shower electrode (counter electrode) 7 is disposed above the chamber 1 at a position parallel to the holding electrode 4. These are a pair of parallel plate electrodes. The gas shower electrode is connected to the ground potential. In this embodiment, a power source is connected to the holding electrode 4 and a ground potential is connected to the gas shower electrode. However, a ground potential may be connected to the holding electrode 4 and a power source may be connected to the gas shower electrode. .

  On the lower surface of the gas shower electrode 7, a plurality of supply ports for supplying a shower-like source gas to the side where the piezoelectric film of the substrate 2 is formed (the space between the gas shower electrode 7 and the holding electrode 4) (see FIG. (Not shown) is formed. As the source gas, one having an organic source gas containing carbon and fluorine can be used. This organic source gas preferably contains three or more carbons.

  A gas introduction path (not shown) is provided inside the gas shower electrode 7. One side of the gas introduction path is connected to the supply port, and the other side of the gas introduction path is connected to the source gas supply mechanism 3. Further, the chamber 1 is provided with an exhaust port for evacuating the inside of the chamber 1. This exhaust port is connected to an exhaust pump (not shown).

  Further, the plasma CVD apparatus has a control unit (not shown) for controlling the high-frequency power source 6, the source gas supply mechanism 3, the exhaust pump, and the like, and this control unit performs a CVD film forming process to be described later. It controls the plasma CVD apparatus.

  Next, a process of forming the fluorinated organic film 15 on the DLC film 13 shown in FIG. 1 using the plasma CVD apparatus shown in FIG. 3 will be described.

In the present embodiment, any one of a C _a F _b film, a C _a F _b N _C film, a C _a F _b O _d film, and a C _a F _b N _C O _d film is used as the fluorinated organic film 15. However, a, b, c, and d are natural numbers.

The film formation of any of the C _a F _b film, the C _a F _b N _C film, the C _a F _b O _d film, and the C _a F _b N _C O _d film will be described in detail below.
The deposition target substrate 2 is inserted into the chamber 1 shown in FIG. 3, and the deposition target substrate 2 is held on the holding electrode 4 in the chamber 1.

Next, the inside of the chamber 1 is evacuated by an exhaust pump. Next, a shower-like source gas is introduced into the chamber 1 from the supply port of the gas shower electrode 7 and supplied to the surface of the deposition target substrate 2. The supplied source gas passes between the holding electrode 4 and the earth shield 5 and is exhausted to the outside of the chamber 1 by an exhaust pump. Then, the inside of the chamber 1 is made a source gas atmosphere by controlling the supply pressure of the source gas and the exhaust gas to a predetermined pressure and a source gas flow rate, and a high frequency (RF) of 13.56 MHz, for example, is applied by the high frequency power source 6. Then, _a C _a F _b film 15 is formed on the DLC film 13 of the deposition target substrate 2 by generating plasma. The film forming conditions at this time are a pressure of 0.01 Pa to atmospheric pressure, a processing temperature of room temperature, and a DC voltage component when forming a high frequency plasma is +150 V to −150 V (more preferably +50 V to −50 V). It is preferable to carry out at By suppressing the DC voltage component in this way, plasma damage to the film below the fluorinated organic film 15 can be suppressed.

  Next, the power supply from the high frequency power source 6 is stopped, the supply of the source gas from the supply port of the gas shower electrode 7 is stopped, and the film forming process is finished.

  As said source gas, it is preferable to use what has organic source gas containing carbon and a fluorine.

Specific examples of the organic material gas are as follows.
The organic raw material gas for forming a C _a F _b film as the film 15 is C ₃ F ₆ , C ₄ F ₆ , C ₆ F ₆ , C ₆ F ₁₂ , C ₆ F ₁₄ , C ₇ F ₈ , C _{7 F 14, C 7 F 16} , C 8 F 16, C 8 F 18, C 9 F 18, C 9 F 20, C 10 F 8, C 10 F 18, C 11 F 20, C 12 F 10, C _It has at least one of ₁₃ F ₂₈ , C ₁₅ F ₃₂ , C ₂₀ F ₄₂ , and C ₂₄ F ₅₀ .

The organic raw material gas for forming a C _a F _b N _C film as the film 15 is C ₃ F ₃ N ₃ , C ₃ F ₉ N, C ₅ F ₅ N, C ₆ F ₄ N ₂ , C ₆ F ₉ N ₃ , C ₆ F ₁₂ N ₂ , C ₆ F ₁₅ N, C ₇ F ₅ N, C ₈ F ₄ N ₂ , C ₉ F ₂₁ N, C ₁₂ F ₄ N ₄ , C ₁₂ F ₂₇ N, C _It has at least one of ₁₄ F ₈ N ₂ , C ₁₅ F ₃₃ N, C ₂₄ F ₄₅ N ₃ , and triheptafluoropropylamine.

The organic raw material gas when forming a C _a F _b O _d film as the film 15 is C ₃ F ₆ O, C ₄ F ₆ O ₃ , C ₄ F ₈ O, C ₅ F ₆ O ₃ , C ₆ F ₄ O ₂ , C ₆ F ₁₀ O ₃ , C ₈ F ₄ O ₃ , C ₈ F ₈ O, C ₈ F ₈ O ₂ , C ₈ F ₁₄ O ₃ , C ₁₃ F ₁₀ O, C ₁₃ F ₁₀ O ₃ , And C ₂ F ₆ O (C ₃ F ₆ O) n (CF ₂ O) m.

The organic raw material gas in the case of forming a C _a F _b N _C O _d film as the film 15 has C ₇ F ₅ NO.

  In the present embodiment, the high frequency power source 6 is used, but a DC power source or a microwave power source may be used. Thus, it is preferable that the direct-current voltage at the time of forming direct-current plasma by using a direct-current power supply is + 150V to −150V (more preferably + 50V to −50V).

In this way, a C _a F _b film, a C _a F _b N _c film, a C _a F _b H _d film, a C _a F _b O _e film formed on the DLC film 13 of the deposition target substrate 2, The film 15 of any one of the C _a F _b O _e H _d film, the C _a F _b N _C O _e film, and the C _a F _b N _C O _e H _d film has a film thickness of 3 nm or less (more preferably 1 nm). The water contact angle is large and water repellent, and functions as a solid lubricant. This film 15 is preferably an amorphous film. The Young's modulus of the film 15 is preferably 0.1 to 30 GPa.

(Third embodiment)
4 is a cross-sectional view schematically showing a plasma CVD apparatus for forming a fluorinated organic film according to one embodiment of the present invention. The same parts as those in FIG. Only explained.

  The holding electrode 4 is electrically connected to the high frequency power source 6a and the ground potential via the changeover switch 8a, and high frequency power or ground potential is applied to the holding electrode 4 by the changeover switch 8a. The gas shower electrode 7 is electrically connected to the high frequency power source 6b and the ground potential via the changeover switch 8b, and the high frequency power or the ground potential is applied to the gas shower electrode 7 by the changeover switch 8b. ing. In the present embodiment, the high frequency power supplies 6a and 6b are used. However, other power supplies such as a DC power supply or a microwave power supply may be used.

  The plasma CVD apparatus also includes a control unit (not shown) for controlling the changeover switches 8a and 8b, the high frequency power supplies 6a and 6b, the plasma forming gas supply mechanism 3, the exhaust pump, and the like. Controls the plasma CVD apparatus to perform the CVD film forming process.

  Next, the process of forming the fluorinated organic film 15 on the DLC film 13 shown in FIG. 1 using the plasma CVD apparatus shown in FIG. 4 will be described, but the description of the same parts as those in the second embodiment will be omitted. .

(1) The high frequency power supplies 6a and 6b and the ground potential are connected to the holding electrode 4 and the gas shower electrode 7 according to the first connection state, and the C _a F _b film and C _a are formed on the DLC film 13 of the deposition target substrate 2. F _b N _c film, C _a F _b H _d film, C _a F _b O _e film, C _a F _b O _e H _d film, C _a F _b N _C O _e film and C _a F _b N _C O _e film first connection state when forming one of the film 15 H _d membrane connects the holding electrode 4 a high frequency power source 6a by switching switch 8a, and connected to ground potential and the gas shower electrode 7 by switching the switch 8b State. A specific method for forming the film 15 in this state is the same as that in the first embodiment, and a description thereof will be omitted.

(2) The high frequency power sources 6a and 6b and the ground potential are connected to the holding electrode 4 and the gas shower electrode 7 according to the second connection state, and the C _a F _b film and C _a are formed on the DLC film 13 of the deposition target substrate 2. F _b N _c film, C _a F _b H _d film, C _a F _b O _e film, C _a F _b O _e H _d film, C _a F _b N _C O _e film and C _a F _b N _C O _e film second connection state when forming one of the film 15 H _d membrane connects the holding electrode 4 and the ground potential by switching the switch 8a, RF power supply was connected to 6b and the gas shower electrode 7 by switching the switch 8b State. A specific method for forming the film 15 in this state is as follows.

The chamber 1 is evacuated by an exhaust pump. Next, a shower-like source gas is introduced into the chamber 1 from the supply port of the gas shower electrode 7 and supplied to the surface of the DLC film 13 of the deposition target substrate 2. The supplied source gas passes between the holding electrode 4 and the earth shield 5 and is exhausted to the outside of the chamber 1 by an exhaust pump. Then, by controlling the supply pressure of the source gas and the exhaust gas to a predetermined pressure and a source gas flow rate, the inside of the chamber 1 is made a source gas atmosphere, and a radio frequency (RF) of, for example, 13.56 MHz is gas showered by the high frequency power source 6b. A C _a F _b film, a C _a F _b N _c film, a C _a F _b H _d film, and a C _a F _b are formed on the DLC film 13 of the deposition target substrate 2 by being applied to the electrode 7 and generating plasma. A film 15 of any one of an O _e film, a C _a F _b O _e H _d film, a C _a F _b N _C O _e film, and a C _a F _b N _C O _e H _d film is formed. The film forming conditions at this time are a pressure of 0.01 Pa to atmospheric pressure, a processing temperature of room temperature, and a DC voltage component when forming a high frequency plasma is +150 V to −150 V (more preferably +50 V to −50 V). It is preferable to carry out at

  Next, the power supply from the plasma power supply is stopped, the supply of the source gas from the supply port of the gas shower electrode 7 is stopped, and the film forming process is ended.

  In this embodiment, the same effect as that of the second embodiment can be obtained.

<Example 1>
A DLC film is formed on the substrate, and the contact angle of water on the surface of the DLC film is measured. Thereafter, the surface of the DLC film is subjected to plasma nitriding, and then the contact angle of water on the surface of the DLC film is measured. The plasma processing time characteristics were confirmed.

(Experimental conditions)
Substrate: Si
Plasma source used: Inductively coupled plasma source (ICP source) shown in FIG.
Gas used: N ₂
Gas flow rate: 5sccm
Pressure: 1Pa
ICP input power: 200W
ICP frequency: 13.56 MHz
Processing time: 5, 10, 30, 60 sec
Contact angle of water on DLC film surface before treatment: about 80 °

(Experimental result)
FIG. 5 is a graph showing the plasma processing time characteristics at an ICP input power of 200 W, showing the relationship between the processing time and the contact angle of water.
As shown in Table 1 and FIG. 5, the contact angle of water on the surface of the DLC film can be reduced to 20 ° or less by setting the ICP input power to 200 W and applying the nitrogen plasma treatment for 60 seconds to the surface of the DLC film. it can.

<Example 2>
A DLC film is formed on the substrate, and the contact angle of water on the surface of the DLC film is measured. Thereafter, the surface of the DLC film is subjected to plasma nitriding, and then the contact angle of water on the surface of the DLC film is measured. The substrate bias application characteristics were confirmed.

(Experimental conditions)
Substrate: Si
Plasma source used: Inductively coupled plasma source (ICP source) shown in FIG.
Gas used: N ₂
Gas flow rate: 5sccm
Pressure: 1Pa
ICP input power: 200W
ICP frequency: 13.56 MHz
Processing time: 5 sec
Substrate bias: DC bias DC bias voltage: 0, 50, 100V
Contact angle of water on DLC film surface before treatment: about 80 °

(Experimental result)
FIG. 6 is a graph showing the substrate bias application characteristics at an ICP input power of 200 W, and showing the relationship between the DC bias voltage and the contact angle of water.
As shown in Table 2 and FIG. 6, when the ICP input power is 200 W and the processing time is 5 seconds, the contact angle of water can be lowered by applying a substrate bias, and water can be reduced by applying a bias of 100 V. The contact angle can be about 24 °.

<Example 3>
A DLC film is formed on a Si substrate, the surface of the DLC film is subjected to plasma nitriding, and then a DLC film is formed on the DLC film with a fluorinated organic film using the plasma CVD apparatus shown in FIG. A certain C _a F _b film was formed.

(Deposition conditions)
Deposition pressure: 2Pa
RF power: 50W
RF frequency: 13.56 MHz
DC voltage component (Vdc) for forming high-frequency plasma: −1 to −2 V
C _a F _b film thickness: 181.2 nm
Deposition rate: 18.1 nm / min
Source gas: Perfluoroamine triheptafluoropropylamine represented by the following chemical formula (1) (tertiary amines)

(Water contact angle)
When the contact angle of water of the above C _a F _b film was measured, it was 104.3 °, and it was confirmed that sufficient water repellency could be secured. Therefore, the C _a F _b film easily repels moisture and functions as a solid lubricant.

(Relationship between Vdc and deposition rate)
In this example, when the film formation rate of the C _a F _b film was measured by changing Vdc, the relationship shown in FIG. 7 was obtained. FIG. 7 is a diagram showing the relationship between Vdc and the film formation rate of the C _a F _b film when forming the C _a F _b film on the DLC film formed on the Si substrate.

According to FIG. 7, it was confirmed that the C _a F _b film can be formed with Vdc in the range of more than −0 V to −150 V. Further, it was confirmed that a practically sufficient film formation rate of 12 nm / min or more can be obtained when Vdc is in the range of more than −0 V to −50 V. Note that when the film formation rate is 0 nm / min or less, the DLC film on the Si substrate is etched.

DESCRIPTION OF SYMBOLS 1 ... Chamber 2 ... Film-forming substrate 3 ... Source gas supply mechanism 4 ... Holding electrode 5 ... Earth shield 6, 6a, 6b ... High frequency power supply 7, 7a, 7b ... Gas shower electrode (counter electrode)
8a, 8b ... changeover switch 11 ... nonmagnetic substrate 12 ... magnetic layer 13 ... DLC film 15 ... fluorinated organic _film, C a _{F b film,} C _a F b _{N c film,} C _a F b _{H d} film, _{C a} F _b O _{e film, C a F b O e H} d _{film, C a F b N C O} e film and _{C a F b N C O e} H d of either film layer 21 ... chamber 22 ... first Power source 23 ... High frequency coil 24 ... Second power source 25 ... Gas introduction mechanism

Claims (4)

Forming a magnetic layer on a non-magnetic substrate;
Forming a DLC film on the magnetic layer;
By performing plasma treatment on the surface of the DLC film, the decrease in the film thickness of the DLC film is suppressed to 0.3 nm or less, and the surface of the DLC film is nitrided,
A method of manufacturing a magnetic recording medium in which a fluorinated organic film is formed on the DLC film,
The DLC film after the plasma treatment has a surface with a water contact angle of 50 ° or less,
The processing gas supplied when performing the plasma processing has at least one of a mixed gas of nitrogen gas and inert gas and nitrogen gas,
The fluorinated organic film includes a C _a F _b film, a C _a F _b N _c film, a C _a F _b H _d film, a C _a F _b O _e film, a C _a formed by a CVD method using a source gas. An F _b O _e H _d film, a C _a F _b N _C O _e film, or a C _a F _b N _C O _e H _d film,
The method of manufacturing a magnetic recording medium, wherein the source gas contains triheptafluoropropylamine (tertiary amine) of perfluoroamines.
However, a, b, c, d, and e are natural numbers. Oite to claim 1,
When performing the plasma treatment, the high frequency output when an inductively coupled plasma source is used is 200 W or less, and the density of the high frequency output when a parallel plate type plasma source is used is 1 × 10 ⁻² W / cm ^2. A method for manufacturing a magnetic recording medium, characterized by the following. In claim 2 ,
The method of manufacturing a magnetic recording medium, wherein the frequency of the high-frequency power is 100 kHz or more and 27 MHz or less. In any one of Claims 1 thru | or 3 ,
The method for producing a magnetic recording medium, wherein a pressure at the time of performing the plasma treatment is 0.05 Pa or more and 10 Pa or less.

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