JP2016084538A - Alloy for soft magnetic thin film layer and sputtering target material in perpendicular magnetic recording medium and perpendicular magnetic recording medium having soft magnetic thin film layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soft magnetic alloy for perpendicular magnetic recording medium exhibiting low Bs at room temperature and less in reduction width of Bs at high temperature and a sputtering target material for manufacturing a thin film of the alloy.SOLUTION: There are provided an alloy for soft magnetic thin film layer in a perpendicular magnetic recording medium containing, by at%, one or more kind of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Ni, Cu, Al, B, C, Si, P, Zn, Ga, Ge, Sn and the balance Co and Fe with inevitable impurities and satisfying following formulae (1) to (4) and a sputtering target material.(1)0.1≤Fe%/(Fe%+Co%)≤0.5 (2)5≤Ti%+Zr%+Hf%+V%+Nb%+Ta%+B%/2 (3)0.3≤0.813×Fe%/(Fe%+Co%)-0.062×TNM+1.751≤1.2 (4)Ni:1% or less and B:10% or less.SELECTED DRAWING: None

Description

  The present invention relates to an alloy for a soft magnetic thin film layer and a sputtering target material in a perpendicular magnetic recording medium, and a perpendicular magnetic recording medium having a soft magnetic thin film layer.

In recent years, the magnetic recording technology has been remarkably advanced, and the recording density of magnetic recording media has been increased to increase the capacity of the drive, realizing a higher recording density than the conventional in-plane magnetic recording media. A perpendicular magnetic recording system capable of being used has been put into practical use. The perpendicular magnetic recording system is a method suitable for high recording density, in which the easy magnetization axis is oriented in the perpendicular direction with respect to the medium surface in the magnetic film of the perpendicular magnetic recording medium. In the perpendicular magnetic recording system, a two-layer recording medium having a magnetic recording film layer and a soft magnetic film layer with improved recording sensitivity has been developed. A CoCrPt—SiO ₂ alloy is generally used for the magnetic recording film layer.

  On the other hand, a conventional soft magnetic film layer requires a high saturation magnetic flux density (hereinafter referred to as Bs) and a high amorphous forming ability (hereinafter referred to as amorphous). Depending on the usage environment, various properties such as high corrosion resistance and high hardness have been additionally required. Among the above required characteristics, it is important that Bs is particularly high. For example, JP 2008-299905 A (Patent Document 1), JP 2011-68985 A (Patent Document 2), and JP 2011-99166 A. No. 1 (Patent Document 3) also aims at high Bs, and since all the examples are 1.1T or more and 1.3T or more when limited to an amorphous state, sputtering is actually performed in a perpendicular magnetic recording medium. When used as a film, it can be seen that approximately 1.3 T or more of Bs is necessary.

  The reason why such a high Bs is required is that the Bs of a certain value or more is necessary to stabilize the magnetization of the recording film and that the magnetic anisotropy (hereinafter referred to as in-plane) is in the in-plane direction of the recording medium. This is considered to have a strong magnetic anisotropy (denoted as Hk). In particular, high Hk is an important factor for noise reduction, and it is generally known that when Bs of a soft magnetic film is high, a large value is obtained.

  However, there is an adverse effect caused by using a high Bs soft magnetic film. That is, when a soft magnetic film having a high Bs is used in a state of being magnetized by a writing head, the magnetic flux density is high, so that a magnetic influence is exerted on the surrounding area more than necessary. It is necessary to take a large space for writing, and there is a problem that it is difficult to increase the recording density. This phenomenon is also called “writing blur”.

JP 2008-299905 A JP 2011-68985 A JP 2011-99166 A

  From the background as described above, if the inventors can find a soft magnetic alloy having a high Hk even with a relatively low Bs while having a minimum Bs that stabilizes the magnetization of the recording film, noise reduction due to the high Hk can be achieved. Therefore, it was considered that high recording density can be achieved by suppressing “writing bleeding”. Therefore, influencing factors other than high Bs for increasing Hk were considered, and it was considered important to find a soft magnetic amorphous alloy capable of realizing this.

  Therefore, as a result of studying other influencing factors on Hk instead of obtaining high Hk with high Bs as in the past, it is estimated that the temperature characteristic (high Curie point) of high Bs is effective. Based on this, the inventors have found that by using an alloy having low Bs and high Bs and high temperature characteristics, both high Hk and reduction of writing bleeding can be achieved, leading to the invention. This makes it possible to provide a soft magnetic alloy for perpendicular magnetic recording media that exhibits a low saturation magnetic flux density at room temperature and a small decrease in the saturation magnetic flux density at high temperatures, and a sputtering target material for producing a thin film of this alloy. Is.

The gist of the invention is that
% Is at%, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Ni, Cu, Al, B, C, Si, P, Zn, Ga, Ge, Sn Alternatively, an alloy used for a soft magnetic thin film layer in a perpendicular magnetic recording medium, which is composed of two or more types, the balance Co, Fe, and inevitable impurities and satisfying all the following formulas (1) to (4).
(1) 0.1 ≦ Fe% / (Fe% + Co%) ≦ 0.5
(2) 5 ≦ Ti% + Zr% + Hf% + V% + Nb% + Ta% + B% / 2
(3) 0.3 ≦ 0.813 × Fe% / (Fe% + Co%) − 0.062 × TNM + 1.751 ≦ 1.2
(4) Ni: 1% or less, B: 10% or less However, Fe% / (Fe% + Co%) is the ratio of the content of Fe and the total content of Fe and Co. TNM is the amount of addition of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Ni, Cu, Al, B, C, Si, P, Zn, Ga, Ge, and Sn. Total%, and for B only, a value that is ½ times is used.

(2) A soft magnetic thin film layer made of an alloy having the amorphous structure according to (1).
(3) A perpendicular magnetic recording medium having the soft magnetic thin film layer according to (2).
(4) The sputtering target material is made of the alloy according to (1).

  As described above, according to the present invention, it is possible to provide a soft magnetic alloy for perpendicular magnetic recording media that exhibits low Bs at room temperature and has a small decrease in Bs at high temperature, and a sputtering target material for producing a thin film of this alloy. . By using the alloy of the present invention in a perpendicular magnetic recording medium, the magnetic properties of the soft magnetic alloy can be fully exhibited and the function of the soft magnetic thin film layer can be sufficiently enhanced. As a result, the perpendicular magnetic recording medium Can lead to improved performance.

Hereinafter, the present invention will be described in detail.
First, since the sputtered film is a thin film, it is expected that Hk is greatly influenced by the demagnetizing field, that is, the effects of the demagnetizing factor and the strength of magnetization are high. Here, the demagnetizing factor is an external factor determined by the shape of the thin film, and the strength of magnetization corresponds to Bs of the soft magnetic film. Therefore, as described above, Hk and Bs of the soft magnetic film have a correlation. However, this concept requires high Bs because of high Hk, which is the same as the need for conventional high Bs soft magnetic alloys.

  Then, the examination which discovers the factor which affects Hk besides Bs was performed. As will be described later in Examples and Comparative Examples, as a result of producing sputtered films and evaluating Hk for some soft magnetic amorphous alloy compositions, high Hk was obtained with high Bs as in the conventional concept. There was a phenomenon that Hk was extremely reduced in some compositions. When this result was analyzed in detail, it was found that Hk becomes extremely small as described above, particularly with a composition in which Bs is almost zero at the temperature of the substrate during film formation by sputtering.

  From the above, it was considered important not to reduce Bs at room temperature as in the prior art, but to reduce the amount of decrease in Bs from room temperature at the temperature during film formation. That is, by applying an alloy having a low Bs at room temperature but a low Bs drop from room temperature at a temperature of about 150 ° C., which is the temperature at the time of sputtering film formation, it has a high Hk and at the same time, It was suggested that it can be reduced. Based on this idea, Bs at room temperature is 0.3-1.2T, which is lower than that of conventional soft magnetic films, and an alloy having a small decrease in Bs at 150 ° C. with respect to Bs at room temperature is studied. Invented.

  Note that (150 ° C. Bs) / (room temperature Bs) × 100% was used as an index for evaluating the decrease width of Bs at 150 ° C. with respect to Bs at room temperature. That is, as the Bs ratio is a large value close to 100%, the decrease width of Bs due to the temperature increase is small. Hereinafter, it is simply referred to as “Bs ratio”.

Below, the reason for limitation of this invention alloy is demonstrated.
0.1 ≦ Fe% / (Fe% + Co%) ≦ 0.5
In this alloy, Fe and Co are elements for providing the minimum necessary magnetization for stabilizing the magnetization of the recording film, and the behavior of Bs and Fe% / (Fe% + Co%) is a so-called slater boring curve. Etc. The most important finding in the present invention is that a high Hk can be obtained even with a soft magnetic film having a relatively low Bs at room temperature by setting a high Bs ratio as described above. Further, Fe% / (Fe% + Co%) ) Is low, the Bs ratio can be kept high.

  Although the detailed cause of this phenomenon in the present alloy having an amorphous structure is unknown, it is considered that the orbital distribution of 3d electrons of Fe atom and Co atom is related. In particular, when Fe% / (Fe% + Co%) exceeds 0.5, a sufficient Bs ratio cannot be obtained. In general, a thin Ru film is inserted between soft magnetic films in a perpendicular magnetic recording medium. Due to antiferromagnetic coupling between the soft magnetic film and the Ru film, a weak noise magnetic field from the outside in the hard disk use environment is used. Resistant to Since Fe may be used to improve the antiferromagnetic coupling, it is often preferable to include a certain amount of Fe. However, it is preferable to reduce Fe for a high Bs ratio. Therefore, the preferable range of Fe% / (Fe% + Co%) is preferably 0.1% or more and 0.40% or less.

5 ≦ Ti% + Zr% + Hf% + V% + Nb% + Ta% + B% / 2
In this alloy, Ti, Zr, Hf, V, Nb, Ta, and B are elements for enhancing the amorphousness. If the total of these is less than 5, sufficient amorphousness cannot be obtained. When a crystalline alloy is used, noise is generated from the magnetic recording medium. However, B is an element that has a particularly high amorphous promoting effect, and an effect that is almost equivalent can be obtained with an addition amount that is half that of the other elements. Therefore, only a value of 1/2 is used in the total equation. In order to obtain sufficient amorphousness, it is preferably 9% or more, more preferably 13% or more.

0.3 ≦ 0.813 × Fe% / (Fe% + Co%) − 0.062 × TNM + 1.751 ≦ 1.2
In this alloy, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Ni, Cu, Al, B, C, Si, P, Zn, Ga, Ge, and Sn are all Bs. It is an element that reduces The Bs of this alloy system is approximately approximated by “0.813 × Fe% / (Fe% + Co%) − 0.062 × TNM + 1.751”. In this example, Bs obtained in the range of 0.1 ≦ Fe% / (Fe% + Co%) ≦ 0.50 is overlapped with Fe% / (Fe% + Co%) and TNM. As a result of regression analysis, it is an equation obtained with a high correlation coefficient. By setting the value of this equation in the range of 0.3 to 1.2, 0.3 to 1.2 T, which is higher than that of the conventional soft magnetic film A soft magnetic alloy having a relatively low Bs. However, if H is less than 0.3, sufficient Hk cannot be obtained, and if it exceeds 1.2, “writing bleeding” increases as in the conventional soft magnetic film having a high Bs. In addition, since the effect of reducing Bs by B is about half that of other elements, only a value of 1/2 is used for calculating TNM. In addition, Preferably it is 0.4-1.1, More preferably, it is 0.5-1.0.

Ni: 1% or less, B: 10% or less Ni is an element that reduces Bs. Particularly, when Ni exceeds 1%, the effect cannot be sufficiently obtained, so the content was set to 1% or less. B, like Ni, is an element that reduces Bs. In particular, if B exceeds 10%, the effect cannot be obtained sufficiently, so the content was made 10% or less.

Hereinafter, the present invention will be specifically described with reference to examples.
Alloy powders having the compositions shown in Table 1 were prepared by gas atomization. The molten base material was induction-melted in an Ar atmosphere decompressed at 25 kg, and the molten alloy was discharged from a nozzle with a diameter of 8 mm, and immediately after that, high-pressure Ar gas was sprayed and atomized. This powder was classified to 500 μm or less and used as a raw material powder for HIP molding (hot isostatic pressing). The billet for HIP molding was prepared by filling a raw material powder into a carbon steel can having a diameter of 200 mm and a length of 100 mm, followed by vacuum degassing and sealing. The billet filled with this powder was subjected to HIP molding under the conditions of a molding temperature of 1000 ° C., a pressure of 120 MPa, and a holding time of 2 hours. Thereafter, a sputtering target material having a diameter of 95 mm and a thickness of 2 mm was produced from the molded body. A thin film was produced using this sputtering target material.

The inside of the chamber was evacuated to 1 × 10 ⁻⁴ Pa or less, and Ar gas having a purity of 99.99% was added to 0.6 Pa to perform sputtering. The thin film was formed on a glass substrate with a thickness of 1.5 μm. At the time of sputtering, the temperature of the substrate during thin film formation was about 150 ° C. due to the plasma irradiation of the sputtering gas. For this thin film sample, Bs was measured at room temperature (30 ° C.) and 150 ° C. using a VSM (sample vibration type magnetometer), and Bs at 30 ° C. relative to Bs at 150 ° C. (hereinafter referred to as “Bs ratio” or “(Bs at 150 ° C.) / (Bs at 30 ° C.) × 100%”) was evaluated.

  Furthermore, BH curves magnetized in the vertical direction and in-plane direction with respect to the thin film surface are also measured, and the difference in the applied magnetic field necessary for saturating the magnetization in each direction, that is, required in the vertical direction. A value obtained by subtracting the necessary applied magnetic field in the in-plane direction from the applied magnetic field was evaluated as an anisotropic magnetic field Hk depending on the magnetization direction. The crystal structure was evaluated by X-ray diffraction. The X-ray source was Cu-kα ray, and measurement was performed at a scan speed of 4 ° / min. In this diffraction pattern, the crystal structure was not observed, and the crystal structure peak was evaluated as x.

As shown in Table 1, no. Nos. 1 to 17 are examples of the present invention. 18-30 are comparative examples.

  First, the value of the formula (3) “0.813 × Fe% / (Fe% + Co%) − 0.062 × TNM + 1.751” in the example shows a good agreement with Bs at room temperature. It is effective, and by setting the value of this formula to 0.3 to 1.2, it is confirmed that an alloy having Bs of 0.3 to 1.2 T, which is lower than the conventional soft magnetic film, can be obtained. . Comparative Example No. For compositions such as 20 and 21, where Fe% / (Fe% + Co%) is large and deviates from the scope of the present invention, this formula is not effective.

  Next, Invention Example No. 2 to 11, with Fe% / (Fe% + Co%) fixed at 0.3, TNM for lowering Bs was changed to 13 to 27, and Bs at room temperature was changed from 0.34 to 1.18. It is the sample made to do. The Hk of these samples changes with Bs, and the conventionally known “phenomenon that high Hk can be obtained at high Bs” is recognized even in the Bs range lower than the conventional one of less than 1.2T as in the present invention. .

  Here, the important points of the present invention are shown in the present invention example and the comparative example. Invention Example No. 1, 7, 13, 16 and Comparative Example No. 18-24 show Bs around 0.7T which is lower than the conventional soft magnetic film at room temperature. However, the invention example No. While Hk of 1, 7, 13, and 16 is as large as 550 A / m or more, Comparative Example No. Hk of 18-24 is remarkably low as 90 A / m or less, and comparative example No. in which Bs becomes almost zero at 150 ° C. The Hk of 21 is extremely low.

  Further, the magnitude of Hk of these samples clearly has an inverse correlation with Fe% / (Fe% + Co%), and a positive correlation with the Bs ratio is recognized. The reason for this phenomenon is not clear, but since the thin film receives an external magnetic field during sputtering, it is presumed that there is an influence of the magnetization behavior when the film is formed at a temperature of around 150 ° C. . Thus, in addition to the conventionally known “phenomenon in which high Bk is obtained at high Bs”, it has been found that “high Hk can be obtained by setting a large Bs ratio”. It was also clarified that an alloy having a high Bs ratio can be obtained by setting Fe% / (Fe% + Co%) low.

  Hereinafter, individual comparative examples will be described. Comparative Example No. As for 18-24, since Fe% / (Fe% + Co%) is over 0.50, Bs ratio is low and Hk is low. Comparative Example No. From 25 to 27, since the total of amorphous promoting elements was low, a crystal peak was observed as a result of X-ray diffraction. Comparative Example No. No. 28 has a low Bs ratio and a low Hk because Bs at room temperature is low.

  Further, Comparative Example No. 29 and 30 will be described in detail. Invention Example No. 2, 5, 7 and Comparative Example No. Measuring the residual magnetization with a gauss meter on the surface of the thin film 10 mm away from the position where the ferrite magnet was in contact with the end of the rod-shaped ferrite magnet with a diameter of 1 mm and a length of 10 mm. As a result, Invention Example No. 7 is assumed to be 1.0, the present invention example No. 5 is 1.2 and the invention example No. 2 is 1.5, Comparative Example No. 29 and 30 were both 2.5. Thus, Comparative Example No. Nos. 29 and 30 have a high Bs at room temperature, and thus have a magnetic influence over a wide range even after the external magnetic field is removed, indicating that “writing blur” is large.

On the other hand, the present invention example No. Nos. 1 to 17 have a high Hk because Bs at room temperature is 0.3 to 1.2 T, which is lower than the soft magnetic film in the conventional perpendicular magnetic recording medium, and the ratio of Bs at 150 ° C. to Bs at room temperature is high. You can see that it has.


Patent Applicant Sanyo Special Steel Co., Ltd.
Attorney: Attorney Shiina

Claims (4)

at%
Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Ni, Cu, Al, B, C, Si, P, Zn, Ga, Ge, Sn, one or more, the balance An alloy used for a soft magnetic thin film layer in a perpendicular magnetic recording medium, which is made of Co, Fe, and inevitable impurities and satisfies all of the following formulas (1) to (4).
(1) 0.1 ≦ Fe% / (Fe% + Co%) ≦ 0.5
(2) 5 ≦ Ti% + Zr% + Hf% + V% + Nb% + Ta% + B% / 2
(3) 0.3 ≦ 0.813 × Fe% / (Fe% + Co%) − 0.062 × TNM + 1.751 ≦ 1.2
(4) Ni: 1% or less, B: 10% or less However, Fe% / (Fe% + Co%) is the ratio of the content of Fe and the total content of Fe and Co. TNM is the amount of addition of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Ni, Cu, Al, B, C, Si, P, Zn, Ga, Ge, and Sn. Total%, and for B only, a value that is ½ times is used. A soft magnetic thin film layer comprising the alloy having an amorphous structure according to claim 1. A perpendicular magnetic recording medium having the soft magnetic thin film layer according to claim 2. A sputtering target material comprising the alloy according to claim 1.