JP2005251375A - Vertical magnetic recording medium and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To attain high performance, high recording density and mass production of a vertical magnetic recording medium having a granular structure, wherein low noise and thermal stability are made compatible. <P>SOLUTION: A material of a magnetic recording layer 15 and a material of an M component of a base layer 14 are correlated with each other to be selected and the magnetic recording layer 15 is constituted of ferromagnetic crystal grains 30 containing Ru and a non-magnetic crystal grain boundary 31, for example as CoPtRu-M(=SiO<SB>2</SB>). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a perpendicular magnetic recording medium mounted on various magnetic recording devices and a method for manufacturing the same.

As a technique for realizing high density magnetic recording, a perpendicular magnetic recording method in which the recording magnetization is perpendicular to the in-plane direction of the medium is drawing attention in place of the conventional longitudinal magnetic recording method.
The perpendicular magnetic recording medium mainly includes a magnetic recording layer of a hard magnetic material, an underlayer for orienting the magnetic recording layer in a desired direction, a protective film for protecting the surface of the magnetic recording layer, and It is composed of a backing layer of a soft magnetic material that plays a role of concentrating magnetic flux generated by a magnetic head used for recording.
The soft magnetic backing layer has a higher performance of the medium when formed, but may be omitted because it can be recorded without it. One having no soft magnetic underlayer is called a single-layer perpendicular magnetic recording medium, and one having a soft magnetic backing layer is called a two-layer perpendicular magnetic recording medium.
In the perpendicular magnetic recording medium as well as the longitudinal magnetic recording medium, it is essential to achieve both high thermal stability and low noise in order to increase the recording density. That is, to increase the thermal stability, the magnetocrystalline anisotropy Ku is increased, and to reduce the medium noise, the magnetic recording layer grain size is reduced and the magnetic intergranular interaction is reduced. It is necessary.

For conventional longitudinal magnetic recording media, various compositions and structures of magnetic recording layers and materials for nonmagnetic underlayers have been proposed so far. A widely used magnetic recording layer material is an alloy made of CoCr (hereinafter abbreviated as a CoCr alloy), and magnetically isolated magnetic particles are formed by segregating Cr at crystal grain boundaries.
As an example using a CoCr alloy, for example, Patent Document 1 is cited, and a segregation structure is formed by using CoCrPtX for the magnetic recording layer and increasing the ratio of Cr concentration at the grain boundaries to be higher than that in the grains.
As another magnetic recording layer material, a magnetic layer called a granular magnetic recording layer, which uses a nonmagnetic nonmetallic substance such as an oxide or nitride as a grain boundary phase has been proposed (Patent Document 2, Patent). Reference 3).

On the other hand, as an example of using a granular magnetic recording layer material for a perpendicular magnetic recording medium, a granular medium using a CoPtCr—SiO ₂ magnetic recording layer has been reported (see Non-Patent Document 1).
According to this, the granular medium can greatly reduce the medium noise and the crystal anisotropy constant Ku, which is an index of thermal stability, as compared with a perpendicular medium using a conventional CoCr alloy material as a magnetic recording layer. It has been confirmed that it is expected as a promising material in the future. In addition, examples of using a granular magnetic recording layer material include, for example, Patent Document 4 and Patent Document 5, and forming a segregation structure by performing heat treatment at 250 to 500 ° C. for 0.1 to 10 hours. Realized.
JP 2002-358615 A US Pat. No. 5,679,473 JP 2001-101651 A JP 2000-306228 A JP 2000-31329 A T.A. OiKaWa, M.M. Nakamura, H .; Uwazumi, T .; Shimatsu, H .; Muraoka, and Y.M. Nakamura, “Microstructure and Magnetic Properties of CoPtCr—SiO 2 Perpendicular Recording Media,” IEEE Trans. Magn. , Vol. 38, pp. 1976-1978, 2002

CoCr alloys or granular magnetic recording layer materials can also be applied to perpendicular magnetic recording media by causing perpendicular magnetic anisotropy, for example, by controlling crystal orientation with an underlayer. is there.
However, in the perpendicular magnetic recording medium, reducing the magnetic interaction between the magnetic particles is a problem of increasing the recording density.
In particular, the granular structure requires heat treatment at a high temperature for a long time, and is not suitable for mass production. When the segregation structure is formed by this method, there is a problem that the easy axis of magnetization becomes three-dimensional random.
In addition, a granular magnetic recording layer material is employed as the magnetic recording layer of the perpendicular magnetic recording medium, and in particular, a granular perpendicular magnetic recording medium having a CoPtCr-M structure (M is an oxide or a nitride) has been actively studied. It was.

In a granular perpendicular magnetic recording medium, it is necessary to form a segregation structure while making the easy axis of magnetization perpendicular. As a result of experiments using a Ru underlayer based on the references, it was confirmed that a relatively good separation structure of CoPtCr and M was formed.
However, in CoPtCr which is the main component of crystal grains having ferromagnetism in the granular perpendicular magnetic recording medium, Ku increases and the signal deterioration tends to increase as the Cr content ratio increases.
On the other hand, when the Cr content is reduced in order to prevent a decrease in Ku, it is also clear that the magnetic intergranular interaction between grains becomes strong and the medium noise increases.
To increase the density, it is necessary to break the trade-off relationship between such an improvement in Ku and a reduction in the interaction between crystal grains.

  Accordingly, an object of the present invention, a perpendicular magnetic recording medium suitable for high performance, high recording density, and mass production of the medium, which is compatible with low noise and thermal stability in a perpendicular magnetic recording medium having a granular structure, and It is in providing the manufacturing method.

The present invention is a perpendicular magnetic recording medium in which at least an underlayer, a magnetic recording layer, and a protective layer are sequentially laminated on a nonmagnetic substrate, and the magnetic recording layer includes ferromagnetic crystal grains containing a Ru component, and And a non-magnetic grain boundary made of an oxide or nitrogen containing M component, and the M component is selected from Cr, Al, Ti, Si, Ta, Hf, Zr, Y, and Ce. The perpendicular magnetic recording medium is made of an oxide or nitrogen of at least one element.
The magnetic recording layer has a structure of CoPtRu-M, and has a structure in which ferromagnetic crystal grains mainly composed of Co, Pt, and Ru are surrounded by nonmagnetic crystal grain boundaries mainly composed of M. Also good.
The underlayer may be made of Ru, Rh, Pd, Ir, Pt, or an alloy material containing at least these elements.

The crystal structure of the underlayer may be an hcp structure or a face-centered cubic lattice (fcc) structure considering the epitaxial growth of Co, which is the main component of the magnetic recording layer directly above and has a hexagonal close-packed (hcp) structure. Good.
A seed layer may be further provided immediately below the foundation layer.
The seed layer may include Ni or an alloy obtained by adding at least one element selected from Fe, B, Si, Nb, and Mo to Ni.
The seed layer may include Co or an alloy obtained by adding at least one element selected from Fe, B, Si, Nb, and Mo to Co.
The seed layer may include CoNi or an alloy obtained by adding at least one element selected from Fe, B, Si, Nb, and Mo to CoNi.

A soft magnetic backing layer may be further provided below the underlayer or the seed layer.
The present invention is a method of manufacturing a perpendicular magnetic recording medium in which at least an underlayer, a magnetic recording layer, and a protective layer are sequentially laminated on a nonmagnetic substrate, and includes Ru, Rh, Pd, Ir, Pt, or at least these. A step of forming the underlayer made of an alloy material containing an element, a ferromagnetic crystal grain containing a Ru component, and a nonmagnetic crystal grain boundary made of an oxide or nitrogen containing a M component, and The M component is made of an oxide or nitrogen of at least one element selected from Cr, Al, Ti, Si, Ta, Hf, Zr, Y, and Ce, and forms the magnetic recording layer. A method for manufacturing a perpendicular magnetic recording medium is provided.
Heat treatment may not be performed after the magnetic recording layer is formed.

  A step of performing a heat treatment after forming the magnetic recording layer may be further provided, wherein the heat treatment time may be 1 second to 10 minutes and the heat treatment temperature may be 250 ° C.

According to the present invention, the material of the magnetic recording layer and the M material of the underlayer are selected so as to have a correlation, and the magnetic recording layer is divided into ferromagnetic crystal grains including Ru and nonmagnetic crystal grain boundaries. Since the structure, for example, CoPtRu-M (= SiO ₂ ) is formed, the “crystallinity”, “orientation”, and “separation” of the ferromagnetic crystal grains are changed to the structure of the conventional CoPtCr-M. Compared with this, low noise and thermal stability can be achieved at the same time, and a perpendicular magnetic recording medium suitable for high performance, high recording density, and mass production of electromagnetic conversion characteristics can be produced. can do.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
[First example]
The first embodiment of the present invention will be described with reference to FIGS.
FIG. 1 shows a cross-sectional structure of a perpendicular magnetic recording medium according to the present invention.
(Media structure)
The perpendicular magnetic recording medium 1 has a structure in which at least an underlayer 14, a magnetic recording layer 15, a protective layer 16, and a liquid lubricant layer 17 are sequentially laminated on a nonmagnetic substrate 11.
As the nonmagnetic substrate 11, an Al alloy, tempered glass, crystallized glass, or the like that has been subjected to NiP plating, which is used for a normal magnetic recording medium, can be used.
Further, when the heat treatment after forming the magnetic recording layer 15 is not performed, a plastic substrate made of a resin such as polycarbonate or polyolefin can be used.

As a material for the underlayer 14, Ru, Rh, Pd, Ir, Pt, or an alloy containing at least these is used.
When such a material is applied, since the crystal grain boundary of the underlayer 14 is relatively large at 0.2 nm or more, an oxide or nitride that is a grain boundary component is formed when the magnetic recording layer 15 is formed. Easy to place on the grain boundary.
Furthermore, since Ru contained in the magnetic recording layer 15 is preferentially arranged on the crystal grains of the underlayer 14, it is a grain boundary component in the ferromagnetic crystal grains, particularly in the thin film region of the magnetic recording layer 15. Intrusion of oxides or nitrides can be suppressed.
In order to sufficiently exhibit the effect of forming the separation structure of the magnetic recording layer 15 as described above, the total content of Ru, Rh, Pd, Ir, and Pt in the underlayer 14 is preferably 50 atomic% or more. More preferably, it is 80 atomic% or more.

Further, the crystal structure of the underlayer 14 is the main component of the magnetic recording layer directly above, and promotes the epitaxial growth of Co having a hexagonal close packed (hcp) structure. A face-centered cubic lattice (fcc) structure is preferable.
In the case of the hcp structure, it is preferable that the mismatch between the a-axis lattice constant and the value of the a-axis lattice constant of the magnetic recording layer is smaller. In the case of the fcc structure, {(a-axis lattice constant) × 1 / √2} and the a-axis lattice constant value of the magnetic recording layer are preferably smaller.
The thickness of the underlayer 14 is preferably thin, but is preferably 3 nm or more at which sufficient crystal growth is observed and a relatively large grain boundary width as described above is formed.
Moreover, the seed layer 13 can be provided directly under the underlayer for the purpose of improving the orientation of the underlayer 14 and controlling the crystal grain size.

The seed layer 13 may be non-magnetic. However, when the soft magnetic backing layer 12 is disposed below the seed layer 13, the seed layer 13 exhibits a soft magnetic characteristic so as to function as a part of the soft magnetic backing layer. More preferred materials are used. As the crystal structure, in consideration of lattice matching with the hcp structure or the fcc structure of the underlayer 14, it is preferable to take the crystal structure of the hcp structure or the fcc structure like the underlayer 14.
From the above, examples of the seed layer 13 include Ni, an alloy obtained by adding at least one element selected from Fe, B, Si, Nb, and Mo to Ni, Co, or Fe to Co, Alloy in which at least one element selected from B, Si, Nb, and Mo is added, or CoNi, or alloy in which at least one element selected from B, Si, Nb, Mo, and Fe is added to CoNi Is preferred.

Further, the Co, Ni content, or the total CoNi content is preferably 80 atomic% or more, and more preferably 90 atomic% or more.
When the seed layer 13 is provided below the underlayer 14 in order to concentrate the magnetic flux generated by the magnetic head and assist recording, the soft magnetic backing layer 12 can be provided below the underlayer 14.
As the soft magnetic backing layer 12, for example, crystalline NiFe alloy, Sendust (FeSiAl) alloy, CoFe, etc., microcrystalline FeTaC, CoTaZr, CoFeNi, CoNiP, amorphous Co alloy CoZrNb, etc. can be used. .
The optimum value of the thickness of the soft magnetic underlayer 12 varies depending on the structure and characteristics of the magnetic head using recording. However, in the case where the soft magnetic underlayer 12 is formed by continuous film formation with other layers, the balance between productivity and It is desirable that the thickness is approximately 10 nm to 500 nm.

In the case where the film is formed on the non-magnetic substrate in advance before the formation of the other layers to be continuously formed by plating or the like, the thickness may be as thick as several μm.
The material composition of the magnetic recording layer 15 is a CoPtRu-M structure, that is, Co, Pt, Ru, and M, where M is selected from Cr, Al, Ti, Si, Ta, Hf, Zr, Y, and Ce. It is an oxide or nitride of at least one selected element.
Further, the magnetic recording layer 15 has a structure in which a nonmagnetic crystal grain boundary mainly containing M is surrounded by ferromagnetic crystal grains mainly containing Co, Pt and Ru.
As described in the explanation of the underlayer 14, Ru contained in the crystal grains having ferromagnetism is preferentially arranged on the crystal grains of the underlayer 14, and thus has an effect of promoting the segregation structure. In addition, since the same hcp structure as Co is adopted, the orientation and crystallinity are improved as compared with the case where the material composition is CoPtCr-M.

For example, a thin film mainly composed of carbon is used for the protective layer 16.
For the liquid lubricant layer 17, for example, a perfluoropolyether lubricant can be used.
(Correlation between magnetic recording layer / underlayer)
Next, the structural relationship between the magnetic recording layer 15 and the underlayer 14 will be described.
FIG. 2 shows an enlarged cross-sectional structure of each crystal grain and crystal grain boundary in the magnetic recording layer 15 and the underlayer 14.
The material of the magnetic recording layer 15 is established by the correlation with the material of the underlayer 14.
The material of the magnetic recording layer 15 is made of a CoPtRu-M structure (M is an oxide or a nitride) having a granular structure. The material of the underlayer 14 is made of Ru, Rh, Pd, Ir, Pt, or an alloy containing at least these.

In FIG. 2, 20 is a crystal grain of the underlayer 14. Reference numeral 21 denotes a crystal grain boundary of the underlayer 14. Reference numeral 30 denotes ferromagnetic crystal grains of the magnetic recording layer 15. Reference numeral 31 denotes a nonmagnetic crystal grain boundary of the magnetic recording layer 15. When the magnetic recording layer 15 is configured as CoPtCr-M, the crystal grains 30 are CoPtCr, and M (oxide or nitride) is the crystal grain boundary 31.
Here, the correlation between the materials of the magnetic recording layer 15 and the underlayer 14 will be described.
Compared with the structure of CoPtCr-M, which is a conventional magnetic recording layer material, the CoPtRu-M structure of the present invention has a composition of ferromagnetic crystal grains 30 in the thin film region of the magnetic recording layer 15 and a grain boundary. Excellent separation from 31 components.
As a result, the magnetic recording layer 15 can form a good segregation structure in which individual crystal grains 30 are separated from the thin film region (that is, the interface with the underlayer 14) to the surface of the magnetic recording layer 15.

In addition, the ferromagnetic crystal grains 30 can be epitaxially grown on the underlayer 14 in association with the above-described effects such as separability and segregation structure, and the “crystallinity” and “orientation” of the ferromagnetic crystal grains 30 can be obtained. Property "can be further improved.
When the underlayer 14 is made of a specific material, Ru and M tend to be very easily separated on the surface of the underlayer 14. As a result, the “separability” of the Co particles that are the ferromagnetic crystal grains 30 is further improved, and the penetration of M (oxide or nitride) that hinders crystal orientation into the grains is suppressed.
On the other hand, the conventional structure of CoPtCr-M not containing Ru, or CoCrPtRu described in claim 5 of Patent Document 1 that does not contain M, has a segregated structure and a grain boundary as in the present invention. The effect on the separability is not obtained.

Specifically, when the underlayer 14 is composed of Ti, Ni, Ta, or Zr, the grain boundary width of the crystal grain boundary 21 on the surface of the layer is small, so that the magnetic recording layer 15 that is an upper layer thereof. This segregation structure is difficult to form. As a result, in the magnetic recording layer 15, since the grain boundary width of the nonmagnetic crystal grain boundary 31 is narrow or the ferromagnetic crystal grain 30 is connected, the grain size increases, the grain boundary component is mixed into the grain, etc. Occurs.
Furthermore, the structure of the magnetic recording layer 15 is used even when Ru, Rh, Pd, Ir, Pt, or an alloy containing at least these is used as the material of the underlayer 14 on which a good separation structure is formed on the surface. It depends on the material.
From the above, the material of the magnetic recording layer 15 and the material of M of the underlayer 14 are selected with correlation, and the magnetic recording layer 15 is selected from the ferromagnetic crystal grains 30 containing Ru and the nonmagnetic crystal grain boundaries 31. For example, CoPtRu-M (= SiO ₂ ), so that the “crystallinity”, “orientation”, and “separation” of the ferromagnetic crystal grains 30 can be compared with the conventional CoPtCr-M. Compared to the structure, it can be remarkably improved.

[Second example]
Next, a second embodiment of the present invention will be described. In addition, about the same part as the 1st example mentioned above, the description is abbreviate | omitted and the same code | symbol is attached | subjected.
This example is an example of the manufacturing method of the perpendicular magnetic recording medium 1 shown in FIG.
(Prototype example 1)
A prototype example 1 of the perpendicular magnetic recording medium 1 will be described.
As the non-magnetic substrate 11, a chemically strengthened glass substrate (for example, N-5 glass substrate manufactured by HOYA) having a smooth surface is used.
After cleaning this nonmagnetic substrate 11, it was introduced into a sputtering apparatus, and using a Co ₉₂ Ta ₃ Zr ₅ target (here, the numerical value represents atomic%, the same applies hereinafter), under an Ar gas pressure of 5 mTorr. Then, CoTaZr is formed to 180 nm to form the soft magnetic backing layer 12.

Thereafter, the NiFeNbSi seed layer 13 is formed by 15 nm under an Ar gas pressure of 35 mTorr using a Ni ₈₄ Fe ₁₂ Nb ₂ Si ₂ target which is a soft magnetic Ni-based alloy.
Further, using a Ru target, the Ru underlayer 14 is formed by 20 nm under an Ar gas pressure of 25 mTorr.
Then, CoPtRu—SiO ₂ using a 91 mol% (Co ₇₆ Pt ₁₄ Ru ₁₀ ) -9 mol% (SiO ₂ ) [hereinafter referred to as (Co ₇₆ Pt ₁₄ Ru ₁₀ ) ₉₁ (SiO ₂ ) ₉ ] target. A magnetic recording layer 15 made of 12 nm is formed at an Ar gas pressure of 40 mTorr.
Finally, a protective layer 16 made of carbon was formed by 4 nm, and then taken out from the vacuum apparatus.

Thereafter, a liquid lubricant layer 17 made of perfluoropolyether was formed by a dip method by 2 nm to constitute the perpendicular magnetic recording medium 1.
The magnetic recording layer 15 made of CoPtRu—SiO ₂ is formed by an RF sputtering method, the carbon protective film is formed by an ion beam deposition method, and all other layers are formed by a DC magnetron sputtering method. It was.
The above manufacturing method does not require heat treatment for a long time at a high temperature. Therefore, it is possible to manufacture a high recording density perpendicular magnetic recording medium 1 which is excellent in mass productivity and has both low noise and high thermal stability. it can.
Further, in this example, since heat treatment is not particularly required and high performance is exhibited, non-heat deposition may be performed.

[Third example]
Next, a third embodiment of the present invention will be described with reference to FIG. In addition, about the same part as each example mentioned above, the description is abbreviate | omitted and the same code | symbol is attached | subjected.
This example is a modification regarding the manufacturing method of the second example described above.
Here, Prototype Examples 2 to 5 were produced as the perpendicular magnetic recording medium 1 and compared with Comparative Examples 1 to 3 produced as conventional media. In all of prototype examples 2 to 5, no heat treatment was performed.
(Prototype example 2)
As the perpendicular magnetic recording medium 1, the Rh underlayer 14 was formed using an Rh target instead of the Ru underlayer 14. In addition, all other layers were formed in the same manner as in Prototype Example 1 described above.

(Prototype example 3)
As the perpendicular magnetic recording medium 1, a Pd underlayer 14 was formed using a Pd target instead of the Ru underlayer 14. In addition, all other layers were formed in the same manner as in Prototype Example 1 described above.
(Prototype example 4)
As the perpendicular magnetic recording medium 1, an Ir underlayer 14 was formed using an Ir target instead of the Ru underlayer 14. In addition, all other layers were formed in the same manner as in Prototype Example 1 described above.
(Prototype example 5)
As the perpendicular magnetic recording medium 1, a Pt underlayer 14 was formed using a Pt target instead of the Ru underlayer 14. In addition, all other layers were formed in the same manner as in Prototype Example 1 described above.

(Comparative Example 1)
As the perpendicular magnetic recording medium 1, a Ti underlayer 14 was formed using a Ti target instead of the Ru underlayer 14. In addition, all other layers were formed in the same manner as in Prototype Example 1 described above.
(Comparative Example 2)
As the perpendicular magnetic recording medium 1, the NiTaZr underlayer 14 was formed using a Ni ₈₂ Ta ₁₀ Zr ₈ target instead of the Ru underlayer 14. In addition, all other layers were formed in the same manner as in Prototype Example 1 described above.
(Comparative Example 3)
The perpendicular magnetic recording medium 1 was formed in the same manner as in Prototype Example 2, except that after the process of Comparative Example 2, heat treatment was performed at 500 ° C. for 30 minutes in a vacuum other than 1 × 10 ⁻⁶ Torr.

For prototype examples 1 to 5 and comparative examples 1 and 2, samples having a configuration in which the magnetic recording layer 15 made of CoPtRu—SiO ₂ was omitted for the structural analysis of the underlayer 14.
First, planar observation by TEM and X-ray diffraction evaluation were performed on samples in which the CoPtRu—SiO ₂ magnetic recording layer 15 of prototype examples 1 to 5 and comparative examples 1 and ₂ was omitted.
From the TEM observation, the average grain boundary width on the surface of the underlayer was calculated from the obtained image. In X-ray diffraction, the crystal structure of the underlayer 14 was evaluated.
For the sample in which the magnetic recording layer 15 of CoPtRu—SiO ₂ was formed, the magnetic characteristics were evaluated using a Kerr effect measuring apparatus. In the case of the vertical direction, the coercive force Hc and the squareness ratio S were measured from the hysteresis loop obtained by applying the magnetic field H in the range of ± 20 kOe using the pole Kerr effect.

Here, S is defined as S = θkr / θks, where the saturation value of the Kerr rotation angle θk is θks and the residual rotation angle when the applied magnetic field H = 0 (kOe) is θkr. In the case of the in-plane direction, a hysteresis loop was obtained by using the in-plane Kerr effect and applying a magnetic field in the range of ± 20 kOe in the in-plane direction.
<Characteristic comparison>
FIG. 3 shows the underlayer material 40, the crystal structure 41, the average grain boundary width 42, and the magnetic properties (Hc, S) 43 and 44 of the underlayer 14 in prototype examples 1 to 5 and comparative examples 1 and 2.
The crystal structures of Ru, Rh, Pd, Ir, and Pt of the underlayer 14 of prototype examples 1 to 5 were hcp or fcc, and the average grain boundary width was 0.30 to 0.38 nm.
Moreover, these magnetic characteristics were as favorable as Hc = 4900-5220Oe and S was 0.95 or more.

On the other hand, the Ti underlayer 14 of Comparative Example 1 has the same hcp structure as Ru of the prototype 1 but has an average grain boundary width as small as 0.1 nm or less. The magnetic properties are low Hc and low S.
Since the NiTaZr underlayer 14 of Comparative Example 2 has an amorphous structure, the grain boundary width cannot be calculated. Regarding magnetic properties, both Hc and S are extremely bad.
From the above results, it can be seen that when the underlayer 14 has an amorphous structure such as NiTaZr, the magnetic recording 15 is not vertically aligned and vertical anisotropy does not appear.
It can also be seen that even in the Ti underlayer having the hcp structure, the grain boundary width is very small, so that it is difficult to form a segregation structure and the magnetic properties are lowered.
In Comparative Example 3 in which heat treatment was performed on Comparative Example 2, Hc and S were improved, but Hc was low and S was small.

Furthermore, with respect to Comparative Example 3, in-plane magnetic characteristics were also evaluated. As a result, Hc and S were almost the same values as in the vertical direction.
This shows that although the segregation structure is slightly improved by heating, the easy magnetization axis is random.
Accordingly, it has been clarified that in the magnetic recording layer 15 having the granular structure, it is important to form a segregation structure simultaneously with the crystal orientation when the magnetic recording layer 15 is formed.
Moreover, even if the crystal structure is the same, the magnetic properties differ greatly depending on the difference in grain boundary width, and it can be seen that Ru, Rh, Pd, Ir, and Pt can achieve both crystal orientation formation and segregation structure formation even without heating. .
The above comparison results are summarized.

In the magnetic recording layer 15, among CoPtCr, which is a main component of crystal grains having ferromagnetism, when using Ru instead of Cr and having a CoPtRu structure, signal deterioration in electromagnetic conversion characteristics is reduced compared to Cr, In addition, the present inventors have found an effect of reducing medium noise and improving SNR (signal to noise ratio) which is an index of recording density.
That is, in the magnetic recording layer 15, since the ferromagnetic crystal grains have better crystallinity and orientation than CoPtCr, the Ku has a large effect and the effect of reducing the magnetic intergranular interaction equivalent to or better than that of Cr. It was found that it has excellent separability.
It was also clarified at the same time that the effects of crystallinity, orientation, and separability are strongly dependent on the structure of the underlayer 14 disposed immediately below the granular magnetic recording layer 15.
[Fourth example]
Next, a fourth embodiment of the present invention will be described with reference to FIG. In addition, about the same part as each example mentioned above, the description is abbreviate | omitted and the same code | symbol is attached | subjected.

This example is a modification regarding the manufacturing method of the second example described above.
(Prototype example 6)
A magnetic recording layer 15 made of CoPtRu—SiO ₂ was formed as the perpendicular magnetic recording medium 1, and then heat treatment was performed before the protective layer 16 was formed. That is, as the heat treatment, the substrate was heated at a substrate temperature of 200 ° C. for 10 seconds using a lamp heater in a heating chamber. All the processes other than the heat treatment were made in the same manner as in Prototype Example 1.
The heat treatment after the formation of the magnetic recording layer 15 is preferably not less than 1 second and not more than 10 minutes in consideration of mass productivity. If the heating temperature is too high, the segregation structure may be disturbed. Is preferred.
Here, the reason for performing the heat treatment will be described.

In the manufacturing method of the present invention, heat treatment is performed for the purpose of ensuring a certain degree of crystal orientation and segregation structure in advance mainly due to the effect of the underlayer 14 and bringing it closer to an ideal structure.
The post-heating treatment after forming the magnetic recording layer 15 changes the fine structure of the magnetic recording layer 15. The reason is that the lattice defects are improved and non-magnetic grain boundary component elements that remain in the grains without becoming oxides or nitrides (for example, Si and O when the grain boundary components are SiO ₂ ). Is bonded and segregated to the grain boundary. Thereby, crystallinity improves and segregation is promoted. As a result, signal degradation is improved and the magnetic cluster size is reduced.
In contrast, in conventional heat treatment, the structure is finally realized by high-temperature and long-time heat treatment from the state where the ferromagnetic crystal grain component and the nonmagnetic grain boundary component are not separated at all. The orientation is close to random.

(Comparative Example 4)
As the perpendicular magnetic recording medium 1, a CoPtCr—SiO ₂ magnetic recording layer 15 was formed using a (Co ₈₀ Pt ₁₅ Cr ₅ ) ₉₁ (SiO ₂ ) ₉ target. In addition, all other layers were formed in the same manner as in Prototype Example 1 described above.
(Comparative Example 5)
As the perpendicular magnetic recording medium 1, a CoPtCr—SiO ₂ magnetic recording layer 15 was formed by using a (Co ₇₆ Pt ₁₄ Cr ₁₀ ) ₉₁ (SiO ₂ ) ₉ target. In addition, all other layers were formed in the same manner as in Prototype Example 1 described above.
(Comparative Example 6)
As the perpendicular magnetic recording medium 1, a CoPtCr—SiO ₂ magnetic recording layer 15 was formed by using a (Co ₇₂ Pt ₁₃ Cr ₁₅ ) ₉₁ (SiO ₂ ) ₉ target. In addition, all other layers were formed in the same manner as in Prototype Example 1 described above.

<Characteristic comparison>
FIG. 4 shows magnetic recording layer material 50, SNR (signal-to-noise ratio) 51, signal deterioration ratio 52, magnetic cluster size obtained from evaluation of electromagnetic conversion characteristics in prototype examples 1 and 6 and comparative examples 4 to 6. 53. The SNR is a value with a linear recording density of 400 kFCl, and the signal degradation is a value evaluated with a linear recording density of 50 kFC1.
Electromagnetic conversion characteristic evaluation results and magnetic cluster size evaluation will be described for the perpendicular magnetic recording media 1 of prototype examples 1 and 6 and comparative examples 4 to 6.
The electromagnetic conversion characteristic evaluation was performed by a spin stand tester using a single magnetic pole / GMR head. In addition, the magnetic cluster size is a value obtained by approximating a magnetic cluster to a cylinder from an image obtained by MFM observation of an AC demagnetized medium.

In Comparative Examples 4 to 6, the proportion of SiO _{2 which} is the main component of the nonmagnetic crystal grain boundary is constant at 9 mol% with respect to the total composition of the magnetic recording layer, and the ferromagnetic crystal grains excluding this ratio In CoPtCr as the main component, the ratio of Co: Pt is constant and the amount of Cr is changed between 5 and 15 at%.
From FIG. 4, it can be seen that as the Cr concentration increases, the SNR increases, the rate of signal degradation increases, and the magnetic cluster size decreases. From this result, when the Cr concentration is high, the magnetic intergranular interaction is reduced and the magnetic cluster size is reduced. As a result, the SNR is improved. However, as the Cr concentration is increased, the signal deterioration is increased and the thermal stability is increased. It turns out that gets worse.
From the above results, it can be seen that Cr has a trade-off relationship between low noise and high thermal stability.

On the other hand, Prototype Example 1 of the present invention has a smaller magnetic cluster size and superior SNR than Comparative Example 6 which has the smallest magnetic cluster size and superior SNR among Comparative Examples 4-6.
In addition, it can be seen that the prototype example 1 has the same signal degradation as the comparative example 4 in which the signal degradation was the smallest among the comparative examples 4 to 6, and is excellent in thermal stability.
As a result, comparing Prototype Example 1 and Comparative Example 5 having the same Ru or Cr content, Prototype Example 1 has excellent SNR, small signal degradation, and a small magnetic cluster size.
Further, regarding Prototype Example 1 and Comparative Example 5, in order to clarify the effect of Ru, composition analysis of the magnetic recording layer 15 was performed using TEM / EDX.

As a result, in the case of CoPtRu—SiO ₂ of Prototype Example 1, the Ru concentration ratio of intragranular: grain boundary was 9: 1 and the Si concentration ratio was 2: 8, whereas CoPtCr— of Comparative Example 5 In the SiO ₂ grains: the Cr concentration ratio at the grain boundary was 5: 5, and the Si concentration ratio was 3: 7.
Therefore, Ru in the magnetic recording layer 15 of CoPtRu—SiO ₂ is preferentially disposed on the crystal grains of the underlayer 14 unlike the case of Cr in the CoPtCr—SiO ₂ magnetic layer, and as a result, the SiO ₂ It became clear that segregation was promoted.
Next, comparing Prototype Example 1 and Prototype Example 6, Prototype Example 6 has a smaller magnetic cluster size, better SNR, and a lower signal degradation rate. From this result, it became clear that the performance of the perpendicular magnetic recording medium 1 can be further improved by heat treatment at a relatively low temperature for a short time.

In the prototype examples 1 and 6, the underlayer 14 is made of Ru. However, even if this is made of Rh, Pd, Ir, Pt, or an alloy containing at least Ru, Rh, Pd, Ir, Pt, the prototype example 1 6, the same effect as in the case of the Ru underlayer 14 was observed.
That is, compared to the CoPtCr-M structure, when the CoPtRu-M structure is used, the ratio of SNR and signal degradation is greatly improved, the magnetic cluster size is reduced, and the respective characteristics are reduced by post-heating treatment. Further improved.
Further, when Ti and NiTaZr are used as the underlayer 14, there is no difference between the CoPtCr-M structure and the CoPtRu-M structure, and the low magnetic properties Hc and S shown in FIG. 3 are reflected. The SNR was 5 dB or less, the Decay was 10% or more, and the magnetic cluster size was 100 nm or more.

In each trial example, the case where the grain boundary component M is SiO ₂ is shown, but M is at least one selected from Cr, Al, Ti, Ta, Hf, Zr, Y, and Ce. The same effect can be obtained even when an oxide of a kind of element or a nitride of at least one kind of element selected from Cr, Al, Ti, Si, Ta, Hf, Zr, Y, and Ce is used. I was able to confirm that.

1 is a cross-sectional view showing a structure of a perpendicular magnetic recording medium according to a first embodiment of the present invention. It is sectional drawing which expands and shows each crystal grain and the part of a crystal grain boundary in a magnetic recording layer and a base layer. It is explanatory drawing which shows the layer structure and magnetic characteristic which are the 3rd Embodiment of this invention. It is explanatory drawing which shows the electromagnetic conversion characteristic which is the 4th Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Nonmagnetic base | substrate 12 Soft magnetic backing layer 13 Seed layer 14 Underlayer 15 Magnetic recording layer 16 Protective layer 17 Liquid lubricant layer 20 Underlayer crystal grain 21 Underlayer crystal grain boundary 30 Ferromagnetic grain of magnetic recording layer 31 Nonmagnetic grain boundaries in magnetic recording layers

Claims (17)

A perpendicular magnetic recording medium in which at least an underlayer, a magnetic recording layer, and a protective layer are sequentially laminated on a nonmagnetic substrate,
The magnetic recording layer comprises ferromagnetic crystal grains containing a Ru component and nonmagnetic crystal grain boundaries made of an oxide or nitride containing an M component, and
The perpendicular magnetic recording characterized in that the M component is an oxide or nitride of at least one element selected from Cr, Al, Ti, Si, Ta, Hf, Zr, Y, and Ce. Medium. The magnetic recording layer has a CoPtRu-M structure, and
2. The perpendicular magnetic recording medium according to claim 1, wherein a ferromagnetic crystal grain mainly composed of Co, Pt, and Ru is surrounded by a nonmagnetic crystal grain boundary mainly composed of M.   3. The perpendicular magnetic recording medium according to claim 1, wherein the underlayer is made of Ru, Rh, Pd, Ir, Pt, or an alloy material containing at least these elements. The perpendicular magnetic recording medium according to claim 3, wherein the total content of Ru, Rh, Pd, Ir, and Pt in the underlayer is 50 atomic% or more.   The crystal structure of the underlayer is an hcp structure or a face-centered cubic lattice (fcc) structure in consideration of epitaxial growth of Co, which is the main component of the magnetic recording layer directly above and has a hexagonal close-packed (hcp) structure. The perpendicular magnetic recording medium according to claim 1, wherein the perpendicular magnetic recording medium is a magnetic recording medium.   6. The perpendicular magnetic recording medium according to claim 1, further comprising a seed layer provided immediately below the underlayer.   7. The perpendicular magnetic recording medium according to claim 6, wherein the seed layer is Ni or an alloy obtained by adding at least one element selected from Fe, B, Si, Nb, and Mo to Ni. 7. The perpendicular magnetic recording medium according to claim 6, wherein the seed layer is an alloy obtained by adding at least one element selected from Fe, B, Si, Nb, and Mo to Co or Co. The perpendicular magnetic recording medium according to claim 6, wherein the seed layer is an alloy obtained by adding at least one element selected from Fe, B, Si, Nb, and Mo to CoNi or CoNi.   The perpendicular magnetic recording medium according to claim 7, wherein the seed layer has a Ni, Co content, or a CoNi total content of 80 atomic% or more.   11. The perpendicular magnetic recording medium according to claim 1, further comprising a soft magnetic backing layer below the underlayer or the seed layer. A method of manufacturing a perpendicular magnetic recording medium in which at least an underlayer, a magnetic recording layer, and a protective layer are sequentially laminated on a nonmagnetic substrate,
Forming the base layer made of Ru, Rh, Pd, Ir, Pt, or an alloy material containing at least these elements;
It consists of a ferromagnetic crystal grain containing a Ru component and a nonmagnetic crystal grain boundary made of an oxide or nitride containing an M component, and the M component contains Cr, Al, Ti, Si, Ta, Hf And forming the magnetic recording layer comprising an oxide or nitride of at least one element selected from Zr, Y, and Ce, and a method of manufacturing a perpendicular magnetic recording medium, comprising: . The magnetic recording layer has a CoPtRu-M structure, and
13. The perpendicular magnetic recording medium according to claim 12, wherein the nonmagnetic crystal grain boundary mainly comprising M is surrounded by ferromagnetic crystal grains mainly containing Co, Pt, and Ru. Manufacturing method.   The crystal structure of the underlayer is an hcp structure or a face-centered cubic lattice (fcc) structure in consideration of epitaxial growth of Co, which is a main component of the magnetic recording layer directly above and has a hexagonal close packed (hcp) structure. 14. The method of manufacturing a perpendicular magnetic recording medium according to claim 12 or 13.   15. The method of manufacturing a perpendicular magnetic recording medium according to claim 12, wherein no heat treatment is performed after the magnetic recording layer is formed.   15. The method of manufacturing a perpendicular magnetic recording medium according to claim 12, further comprising a step of performing a heat treatment after forming the magnetic recording layer. In the step of performing the heat treatment,
The method of manufacturing a perpendicular magnetic recording medium according to claim 16, wherein the heat treatment time is 1 second or more and 10 minutes or less, and the heat treatment temperature is 250 ° C or less.

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