JP4991981B2 - Manufacturing method of nano granular soft magnetic film - Google Patents

Manufacturing method of nano granular soft magnetic film Download PDF

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JP4991981B2
JP4991981B2 JP2004271178A JP2004271178A JP4991981B2 JP 4991981 B2 JP4991981 B2 JP 4991981B2 JP 2004271178 A JP2004271178 A JP 2004271178A JP 2004271178 A JP2004271178 A JP 2004271178A JP 4991981 B2 JP4991981 B2 JP 4991981B2
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magnetic field
soft magnetic
nanogranular
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magnetic film
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正人 大沼
繁弘 大沼
秀幸 大塚
啓安 藤森
和博 宝野
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National Institute for Materials Science
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この出願の発明は、ナノグラニュラー軟磁性膜の製造方法に関するものである。より詳しくは、この出願の発明は、高電気比抵抗で勝つ増幅された異方性磁場を有し、約１０ＧＨｚの超高周波領域での利用が可能であるナノグラニュラー軟磁性膜の製造方法に関するものである。
The invention of this application relates to a method for producing a nano granular soft magnetic film . More specifically, the invention of this application relates to a method for producing a nanogranular soft magnetic film having an amplified anisotropic magnetic field prevailing with a high electrical resistivity and being usable in an ultrahigh frequency region of about 10 GHz. is there.

磁場に対する応答に優れた軟磁性材料はトランスやチョークコイル、さらには電磁波吸収材料等、種々の電気・電子機器に必要不可欠な材料である。これら軟磁性材料には材料特有の共鳴周波数が必ず存在し、この共鳴周波数以上では軟磁気特性が失われる。通信機器や電算機の高速度化が急速に進んでいる現在、軟磁性材料の共鳴周波数の増大は極めて大きな社会的要請となっている。軟磁性材料の共鳴周波数を高めるためには飽和磁化の増大、高電気抵抗化、一軸異方性の付与による異方性磁場の向上が有効である。   Soft magnetic materials having excellent response to magnetic fields are indispensable materials for various electric and electronic devices such as transformers, choke coils, and electromagnetic wave absorbing materials. These soft magnetic materials always have a resonance frequency peculiar to the material, and the soft magnetic characteristics are lost above this resonance frequency. With the rapid increase in speed of communication equipment and computers, an increase in the resonance frequency of soft magnetic materials has become a very large social demand. In order to increase the resonance frequency of the soft magnetic material, it is effective to increase the saturation magnetization, increase the electrical resistance, and improve the anisotropic magnetic field by imparting uniaxial anisotropy.

ところで、酸化物または窒化物からなる母相（マトリクス）中に平均粒径がナノメートル・オーダーの強磁性粒子（グラニュール）が埋め込まれた組織を有するナノグラニュラー磁性膜が知られている。これらのうち強磁性粒子の体積分率が比較的大きな試料では強磁性粒子間の接触により磁気的な結合が生じ、磁気異方性が平均化され、軟磁気特性を示すことをすでに我々は知見している（特許文献１、特許文献２、非特許文献１〜非特許文献７）。   By the way, a nanogranular magnetic film having a structure in which ferromagnetic particles (granule) having an average particle diameter of nanometer order are embedded in a matrix (matrix) made of oxide or nitride is known. Among these, we have already found that samples with a relatively large volume fraction of ferromagnetic particles have magnetic coupling due to contact between the ferromagnetic particles, averaged magnetic anisotropy, and soft magnetic properties. (Patent Document 1, Patent Document 2, Non-Patent Document 1 to Non-Patent Document 7).

このナノグラニュラー軟磁性膜は、電気比抵抗が１０3μΩｃｍ以上と非常に大きく、
かつ軟磁性合金材料に付与可能な異方性磁場の最大値より５倍程度大きい異方性磁場Ｈｋを付与することが可能である。この結果、共鳴周波数がＧＨｚ領域に到達し、高周波領域で利用可能な軟磁性膜として極めて有用な材料である。
特開平１０−１８９３２２号公報 特開２００２−１５８４８６号公報 S. Ohnuma, H. Fujimori, S. Furukawa, S. Mitani and T. Matsumoto, J. Alloy and Compounds, 222, p.167 (1995) S. Ohnuma, H. Fujimori, S. Mitani and T. Matsumoto, J. Appl. Phys., 79, p.5130 (1996) S. Ohnuma and T. Masumoto, Scripta. Mater., 44, p.1309 (2001) S. Ohnuma, S. Mitani, H. Fujimori, T. Matsumoto, J. Magn. Soc. Jpm., 19, p.425 (1995) S. Ohnuma, N. Kobayashi, T. Matsumoto, S. Mitani and H. Fujimori, J. Magn. Soc. Jpm., 23, p.240 (1999) K. Hono and M. Ohnuma, book chapter of "Magnetic Nanostructure" edited by H. S. Nalwa, ASP, p.327 (2002) 大沼正人,日本学術振興会第１４７委員会第８１回研究会資料, p.11, (2003) This nanogranular soft magnetic film has a very large electrical resistivity of 10 3 μΩcm or more,
In addition, it is possible to apply an anisotropic magnetic field Hk that is approximately five times larger than the maximum value of the anisotropic magnetic field that can be applied to the soft magnetic alloy material. As a result, the resonance frequency reaches the GHz region, which is an extremely useful material as a soft magnetic film that can be used in the high frequency region.
JP-A-10-189322 JP 2002-158486 A S. Ohnuma, H. Fujimori, S. Furukawa, S. Mitani and T. Matsumoto, J. Alloy and Compounds, 222, p.167 (1995) S. Ohnuma, H. Fujimori, S. Mitani and T. Matsumoto, J. Appl. Phys., 79, p.5130 (1996) S. Ohnuma and T. Masumoto, Scripta. Mater., 44, p.1309 (2001) S. Ohnuma, S. Mitani, H. Fujimori, T. Matsumoto, J. Magn. Soc. Jpm., 19, p.425 (1995) S. Ohnuma, N. Kobayashi, T. Matsumoto, S. Mitani and H. Fujimori, J. Magn. Soc. Jpm., 23, p.240 (1999) K. Hono and M. Ohnuma, book chapter of "Magnetic Nanostructure" edited by HS Nalwa, ASP, p.327 (2002) Masato Onuma, The Japan Society for the Promotion of Science, 147th Committee Material, 81st Workshop, p.11, (2003)

ところが最近の高度情報社会における電気・電子機器の動作周波数は日進月歩で高まってきており、既存の高周波用軟磁性材料の中でも電気比抵抗が高く共鳴周波数の高いナノグラニュー軟磁性材料に対しても、さらなる情報の高密度化、高速処理化の社会的要請に
対応可能なものの開発が強く望まれている。 However, the operating frequency of electrical and electronic equipment in the recent advanced information society has been increasing steadily, and among the existing high-frequency soft magnetic materials, even for nanogranular soft magnetic materials with high electrical resistivity and high resonance frequency, There is a strong demand for the development of information that can meet social demands for higher information density and faster processing.

この出願の発明は、このような従来技術の実情に鑑みてなされたもので、高電気比抵抗でかつ増幅された異方性磁場を有し、約１０ＧＨｚの超高周波数領域での利用が可能であるナノグラニュラー軟磁性膜およびその製造方法を提供することを課題とする。   The invention of this application has been made in view of such a state of the art, has a high electrical resistivity and an amplified anisotropic magnetic field, and can be used in an ultrahigh frequency region of about 10 GHz. It is an object of the present invention to provide a nanogranular soft magnetic film and a method for producing the same.

この出願の発明は、上記課題を解決するため、第１には、ＦｅまたはＣｏの少なくとも１ 種を主構成成分とする（Ｃｏ，Ｆｅ）−（Ｎｉ，Ｐｄ，Ｐｔ）−Ｓｉ−Ｏ系のナノグ
ラニュラー軟磁性膜の製造方法であって、平均粒径が１０ｎｍ以下の強磁性粒子が、酸化物のセラミックスからなる母相中に埋め込まれた形態をなし、製膜後、真空中にて、０．１Ｔ以上の強磁場を面内方向に印加した状態で、熱処理を施すことにより異方性磁場を増幅させることを特徴とするナノグラニュラー軟磁性膜の製造方法を提供する。


In order to solve the above problems, the invention of this application is firstly based on a (Co, Fe)-(Ni, Pd, Pt) -Si-O system containing at least one of Fe and Co as a main constituent. A method for producing a nanogranular soft magnetic film, in which ferromagnetic particles having an average particle size of 10 nm or less are embedded in a parent phase made of an oxide ceramic, and after film formation , 0 Provided is a method for producing a nanogranular soft magnetic film characterized in that an anisotropic magnetic field is amplified by heat treatment in a state where a strong magnetic field of 1 T or more is applied in the in-plane direction.


また、第２は、上記第１の発明において、熱処理を、２０℃／ｍｉｎ以下の加熱速度で１ ００℃から５００℃の間の温度まで昇温させた後、その温度で０．１時間から５時間保持し、その後２０℃／ｍｉｎ以下の冷却速度で冷却することにより行うことを特徴とするナノグラニュラー軟磁性膜の製造方法を提供する。
The second aspect of the present invention is that in the first invention, after the heat treatment is performed at a heating rate of 20 ° C./min or less to a temperature between 100 ° C. and 500 ° C., the temperature is increased from 0.1 hour. Provided is a method for producing a nanogranular soft magnetic film, which is performed by holding for 5 hours and then cooling at a cooling rate of 20 ° C./min or less.

また、第３には、上記第１または第２の発明において、電磁石または超伝導磁石による磁場の印加を０．１Ｔから１０Ｔの範囲で行うことを特徴とするナノグラニュラー軟磁性膜の製造方法を提供する。
According to a third aspect of the present invention, there is provided a method for producing a nanogranular soft magnetic film according to the first or second invention, wherein the magnetic field is applied in the range of 0.1T to 10T by an electromagnet or a superconducting magnet. To do.

さらに、第４には、上記第１から第３の発明のいずれかにおいて、強磁性粒子中にＮｉ族元素が５原子％から３０原子％添加されていることを特徴とするナノグラニュラー軟磁性膜の製造方法を提供する。

According to a fourth aspect of the nanogranular soft magnetic film according to any one of the first to third inventions, the Ni group element is added to the ferromagnetic particles in an amount of 5 atomic% to 30 atomic%. A manufacturing method is provided.

この出願の発明のナノグラニュラー軟磁性膜は、高電気比抵抗でかつ増幅された異方性磁場を有し、約１０ＧＨｚの超高周波数領域での利用が可能となる。   The nanogranular soft magnetic film of the invention of this application has a high electrical resistivity and an amplified anisotropic magnetic field, and can be used in an ultrahigh frequency region of about 10 GHz.

また、この出願の発明のナノグラニュラー軟磁性膜の製造方法は、ナノグラニュラー軟磁性膜に電磁石または超伝導磁石による０．１Ｔ以上の強磁場中熱処理を施すことにより、高電気比抵抗で増幅された異方性磁場を有するナノグラニュラー軟磁性膜を提供することが可能となり、極高電気抵抗でかつ巨大異方性磁場を有する超高周波数高透磁率軟磁性材料を得ることができる。   In addition, the method for producing a nano granular soft magnetic film of the invention of this application is that the nano granular soft magnetic film is subjected to a heat treatment in a strong magnetic field of 0.1 T or more by an electromagnet or a superconducting magnet, thereby differentiating with a high electrical resistivity. A nano granular soft magnetic film having a isotropic magnetic field can be provided, and an ultrahigh frequency high magnetic permeability soft magnetic material having a very high electric resistance and a giant anisotropic magnetic field can be obtained.

以下、この出願の発明について詳細に説明する。   Hereinafter, the invention of this application will be described in detail.

磁場中熱処理による一軸磁気異方性の付与は既に確立した技術として軟磁性材料の製造過程で用いられている。通常この効果は対象とする軟磁性材料の磁化を飽和させるだけ（言い換えると磁区を揃えるだけ）の比較的低い磁場で十分であり、それ以上の磁場を印加しても付与できる異方性磁場は増大しないとされている。これは、これまでに知られている軟磁性材料では、磁場中熱処理による一軸磁気異方性の誘導は、磁区内に自発的に存在
する数１００Ｔにも及ぶ巨大な内部磁場（別名、分子磁場）が駆動力になっているからである。すなわち、熱処理中に磁性原子対の磁気相互作用（擬双極子相互作用）が強い内部磁場の影響を受けて、磁性原子対が内部磁場の方向に再配列することが誘導磁気異方性の起源だからである。 Giving uniaxial magnetic anisotropy by heat treatment in a magnetic field is used as an established technique in the production process of soft magnetic materials. Usually, a relatively low magnetic field that saturates the magnetization of the target soft magnetic material (in other words, just aligns the magnetic domains) is sufficient for this effect, and an anisotropic magnetic field that can be applied even if a higher magnetic field is applied is It is said that it will not increase. This is because, in soft magnetic materials known so far, induction of uniaxial magnetic anisotropy by heat treatment in a magnetic field is caused by a huge internal magnetic field (also known as molecular magnetic field) of several hundred T that is spontaneously present in a magnetic domain. ) Is the driving force. That is, the magnetic interaction of magnetic atom pairs (pseudo-dipole interaction) is affected by a strong internal magnetic field during heat treatment, and the magnetic atom pairs rearrange in the direction of the internal magnetic field. That's why.

ところが、この出願の発明者らは、ナノグラニュー軟磁性材料に関する磁気異方性について鋭意研究を重ねた結果、ナノグラニュラー軟磁性材料に対し、飽和磁場を超えた強磁場（０．１Ｔ以上）中で熱処理を施すと、大きな一軸磁気異方性が誘導され、それによって異方性磁場が増大し、ひいては軟磁気特性の超高周波化に極めて有効であることを見出した。   However, the inventors of this application have conducted extensive research on the magnetic anisotropy of nanogranular soft magnetic materials, and as a result, compared with nanogranular soft magnetic materials, in a strong magnetic field (over 0.1 T) exceeding the saturation magnetic field. It has been found that when heat treatment is performed, a large uniaxial magnetic anisotropy is induced, thereby increasing the anisotropy magnetic field, and thus extremely effective in increasing the frequency of soft magnetic properties.

このような知見は、既存の合金軟磁性材料の磁場中熱処理やグラニュラー軟磁性材料の弱磁場熱処理では予想できなかったものであり、グラニュラー軟磁性材料の異方性磁場の起源に関して新しい概念を提示するものであるとともに、極高電気抵抗／巨大異方性磁場材料という新しい材料の作製に成功したものである。また、このことは、強磁場中熱処理を利用することで初めて明らかになったものである。このような現象は、軟磁性材料としてナノグラニュラー構造のものを用いたことと関係しているものと考えられる。現在のところその機構は未解明であるが、ナノグラニュラー軟磁性材料には従来とは異なる新しい誘導磁気異方性の発生機構が存在することは十分予想される。すなわち、ナノグラニュラー構造では、通常の弱磁場で磁化はほぼ飽和に近づくが十分ではなく、ナノ磁性粒子間の境界に存在する磁性原子の磁気モーメントは弱磁場では不飽和で、それらは強磁場が加わってはじめて飽和に近づくと考えられる。そのような磁性原子が強磁場下の熱処理によって再配列を起こし、結局、大きな磁気異方性が誘導されたものと推測される。   Such knowledge could not be anticipated by heat treatment in the magnetic field of existing alloy soft magnetic materials and weak magnetic field heat treatment of granular soft magnetic materials, and presented a new concept regarding the origin of anisotropic magnetic fields in granular soft magnetic materials. And succeeded in producing a new material called an extremely high electric resistance / giant anisotropic magnetic field material. This was also revealed for the first time by using heat treatment in a strong magnetic field. Such a phenomenon is considered to be related to the use of a nano granular structure as a soft magnetic material. At present, the mechanism is not yet elucidated, but it is fully expected that nanogranular soft magnetic materials have a new mechanism of induced magnetic anisotropy. In other words, in the nano-granular structure, the magnetization almost approaches saturation in a normal weak magnetic field, but it is not sufficient, and the magnetic moment of the magnetic atoms present at the boundary between nanomagnetic particles is unsaturated in the weak magnetic field, and they are subjected to a strong magnetic field. It is thought that it will approach saturation for the first time. It is presumed that such magnetic atoms undergo rearrangement by heat treatment under a strong magnetic field, and eventually a large magnetic anisotropy was induced.

この出願の発明のナノグラニュラー軟磁性膜は、ＦｅまたはＣｏの少なくとも１種を主構成成分とする平均粒径が１０ｎｍ以下の強磁性粒子が、酸化物セラミックスからなる母相中に埋め込まれた形態をなし、異方性磁場が０．１Ｔ以上の面内方向の強磁場を印加した状態での熱処理により、製膜直後の軟磁性膜の異方性磁場に対して１．２倍から４倍に増幅されていることを特徴とする。このようなナノグラニュラー軟磁性膜は上記した方法により製造することができる。
The nanogranular soft magnetic film of the invention of this application has a form in which ferromagnetic particles having an average particle size of 10 nm or less and containing at least one of Fe or Co as a main constituent are embedded in a matrix made of oxide ceramics. None, heat treatment while applying a strong magnetic field in the in-plane direction with an anisotropic magnetic field of 0.1 T or more is 1.2 to 4 times the anisotropic magnetic field of the soft magnetic film immediately after film formation It is amplified. Such a nanogranular soft magnetic film can be manufactured by the method described above.

上記ナノグラニュラー軟磁性膜において、ＦｅまたはＣｏの少なくとも１種を主構成成分とする強磁性粒子の組成は６０原子％から９０原子％であることがすぐれた軟磁気特性の発現のために好ましい。   In the nanogranular soft magnetic film, the composition of the ferromagnetic particles containing at least one of Fe or Co as a main constituent is preferably 60 atom% to 90 atom% in order to exhibit excellent soft magnetic properties.

強磁性粒子の平均粒径は１０ｎｍ以下である。平均粒径が１０ｎｍより大きいと保磁力が大きくなり軟磁性体でなくなる。また、平均粒径の下限は超常磁性となる２ｎｍ程度である。   The average particle size of the ferromagnetic particles is 10 nm or less. When the average particle size is larger than 10 nm, the coercive force is increased and the soft magnetic material is lost. Further, the lower limit of the average particle diameter is about 2 nm which becomes superparamagnetic.

上記ナノグラニュラー軟磁性膜の異方性磁場Ｈｋは、弱磁場中製膜直後のナノグラニュラー軟磁性膜の異方性磁場の値に対して１．２倍から４倍、より好ましくは２倍から４倍に増幅したものとすることができる。異方性磁場Ｈｋの増幅率は、弱磁場中製膜直後のナノグラニュラー軟磁性膜の異方性磁場の値にもよるが、上記の範囲の増幅率であると、軟磁気特性の超高周波化に極めて有効となる。   The anisotropic magnetic field Hk of the nanogranular soft magnetic film is 1.2 to 4 times, more preferably 2 to 4 times the value of the anisotropic magnetic field of the nanogranular soft magnetic film immediately after film formation in a weak magnetic field. Can be amplified. The amplification factor of the anisotropic magnetic field Hk depends on the value of the anisotropic magnetic field of the nano-granular soft magnetic film immediately after film formation in a weak magnetic field. It will be extremely effective.

上記ナノグラニュラー軟磁性膜の電気比抵抗は２００μΩｃｍ以上、より好ましくは５００μΩｃｍ以上である。電気比抵抗の上限は、金属伝導からトンネル伝導へと変わるしいき値より１０4μΩｃｍ程度である。電気比抵抗が上記のような値であると上記の増幅
された異方性磁場Ｈｋと同様、超高周波領域への利用に大きく寄与することができる。 The electrical resistivity of the nanogranular soft magnetic film is 200 μΩcm or more, more preferably 500 μΩcm or more. The upper limit of the electrical resistivity is about 10 4 μΩcm from the threshold value that changes from metal conduction to tunnel conduction. If the electrical specific resistance is as described above, it can greatly contribute to the use in the ultra-high frequency region, similar to the amplified anisotropic magnetic field Hk.

上記ナノグラニュラー軟磁性膜の膜厚は、用途等に応じて適宜設定されるが、通常、０．１μｍから５μｍである。   The film thickness of the nanogranular soft magnetic film is appropriately set according to the application and the like, but is usually 0.1 μm to 5 μm.

また、上記ナノグラニュラー軟磁性膜において代表的な例を下記に示す。   A typical example of the nanogranular soft magnetic film is shown below.

・Ｃｏ−Ｐｄ−Ｓｉ−Ｏ系、Ｃｏ−Ｎｉ−Ｓｏ−Ｏ系、Ｃｏ−Ａｌ−Ｏ系、Ｃｏ−Ｐｔ−Ａｌ−Ｏ系、Ｃｏ−Ｚｒ−Ｏ系、Ｃｏ−Ａｌ−Ｎ系、Ｃｏ−Ｍｇ−Ｆ系
・Ｆｅ−Ａｌ−Ｏ系、Ｆｅ−Ｂ−Ｎ系、Ｆｅ−Ｚｒ−Ｏ系
・Ｃｏ−Ｆｅ−Ｍｇ−Ｆ系、Ｃｏ−Ｆｅ−Ａｌ−Ｏ系、Ｃｏ−Ｆｅ−ＲＥ−Ｈ系、Ｃｏ−Ｆｅ−ＲＥ−Ｏ系；ただし、ＲＥは希土類元素である。 Co-Pd-Si-O, Co-Ni-So-O, Co-Al-O, Co-Pt-Al-O, Co-Zr-O, Co-Al-N, Co -Mg-F system -Fe-Al-O system, Fe-BN system, Fe-Zr-O system -Co-Fe-Mg-F system, Co-Fe-Al-O system, Co-Fe-RE -H system, Co-Fe-RE-O system; provided that RE is a rare earth element.

次にこの出願の発明によるナノグラニュラー軟磁性膜の製造方法について述べる。   Next, a method for producing a nano granular soft magnetic film according to the invention of this application will be described.

この出願の発明によるナノグラニュラー軟磁性膜の製造方法は、ＦｅまたはＣｏの少なくとも１種を主構成成分とする平均粒径が１０ｎｍ以下の強磁性粒子が、酸化物セラミックスからなる母相に埋め込まれた形態をなすナノグラニュラー軟磁性膜を作製し、その後、真空中にて、０．１Ｔ以上の面内方向の磁場を印加した状態で、熱処理を施すことを特徴とする。 In the method for producing a nanogranular soft magnetic film according to the invention of this application, ferromagnetic particles having an average particle size of 10 nm or less, the main component of which is at least one of Fe or Co, are embedded in a parent phase made of oxide ceramics. A nano-granular soft magnetic film having a form is prepared, and then heat treatment is performed in a state of applying a magnetic field in an in-plane direction of 0.1 T or more in a vacuum.

また、上記ナノグラニュラー軟磁性膜における強磁性粒子中には、５原子％から３０原子％のＮｉ族元素、すなわちＮｉ、Ｐｄ、Ｐｔを添加させてもよい。このようにすると、より広範な組成範囲において請求項１の条件を満たすナノグラニュラー軟磁性膜の製造方法が提供される。   Further, 5 atomic% to 30 atomic% of Ni group elements, that is, Ni, Pd, and Pt may be added to the ferromagnetic particles in the nano granular soft magnetic film. This provides a method for producing a nanogranular soft magnetic film that satisfies the conditions of claim 1 in a wider composition range.

先ず、この出願の発明における強磁場中熱処理をする前のナノグラニュラー軟磁性膜を作製する方法について述べる。   First, a method for producing a nanogranular soft magnetic film before heat treatment in a strong magnetic field in the invention of this application will be described.

この場合の成膜法としては、たとえばスパッタ法を用いることができる。スパッタ製膜する際に、作製されるナノグラニュラー軟磁性膜に一軸磁気異方性を付与するために永久磁石で５０Ｏｅから５００Ｏｅ程度の弱磁場を磁性膜面内方向に印加することが望ましい。また、スパッタ製膜は０．１Ｐａから１×１０-4Ｐａ程度の真空中で行うことが好ましい。 As a film forming method in this case, for example, a sputtering method can be used. It is desirable to apply a weak magnetic field of about 50 Oe to 500 Oe with a permanent magnet in the in-plane direction of the magnetic film in order to impart uniaxial magnetic anisotropy to the produced nano granular soft magnetic film during sputtering film formation. Sputter film formation is preferably performed in a vacuum of about 0.1 Pa to 1 × 10 −4 Pa.

この出願の発明の製造方法では、以上のようにして弱磁場中製膜されたナノグラニュラー軟磁性膜に対して、強磁場中熱処理を施す。   In the manufacturing method of the invention of this application, a heat treatment in a strong magnetic field is performed on the nanogranular soft magnetic film formed in a weak magnetic field as described above.

この場合、電磁石または超伝導磁石を用い、０．１Ｔ以上の磁場を印加する。印加する磁場の強度が弱すぎると異方性磁場Ｈｋの増幅が十分でなくなる。また、印加する磁場の強度の上限は簡便に発生可能な定常磁場の上限より１０Ｔ程度である。   In this case, an electromagnet or a superconducting magnet is used and a magnetic field of 0.1 T or more is applied. If the strength of the applied magnetic field is too weak, the anisotropic magnetic field Hk will not be sufficiently amplified. The upper limit of the strength of the applied magnetic field is about 10 T from the upper limit of the steady magnetic field that can be easily generated.

また、熱処理は真空中で行うが、その真空度は０．１Ｐａから１×１０-4Ｐａ程度であることが好ましい。 The heat treatment is performed in a vacuum, and the degree of vacuum is preferably about 0.1 Pa to 1 × 10 −4 Pa.

また、熱処理において加熱速度は２０℃／ｍｉｎ以下であることが好ましい。加熱速度が速すぎると熱処理温度の下限における温度制御が困難となる。加熱速度の下限は、一定加熱速度を安定に保持できる下限により１℃／ｍｉｎ程度である。熱処理温度は１００℃から５００℃の間の温度が好ましい。熱処理温度が高すぎるグラニュラー組織が粗大化し、熱処理温度が低すぎると磁壁の移動が困難となる。加熱時間（保持時間）は０．１時間から５時間が好ましい。加熱時間が上記の範囲外であると異方性磁場Ｈｋの増幅が十分でなくなる。冷却速度は２０℃／ｍｉｎ以下であることが好ましい。冷却速度が速すぎると
磁壁の固着が困難となる。冷却速度の下限は、実効的な熱処理時間への影響より１℃／ｍｉｎ程度である。 Further, in the heat treatment, the heating rate is preferably 20 ° C./min or less. If the heating rate is too high, temperature control at the lower limit of the heat treatment temperature becomes difficult. The lower limit of the heating rate is about 1 ° C./min due to the lower limit capable of stably maintaining a constant heating rate. The heat treatment temperature is preferably between 100 ° C. and 500 ° C. If the heat treatment temperature is too high, the granular structure becomes coarse, and if the heat treatment temperature is too low, the domain wall becomes difficult to move. The heating time (holding time) is preferably 0.1 to 5 hours. When the heating time is out of the above range, the anisotropic magnetic field Hk is not sufficiently amplified. The cooling rate is preferably 20 ° C./min or less. If the cooling rate is too fast, it becomes difficult to fix the domain wall. The lower limit of the cooling rate is about 1 ° C./min due to the effect on the effective heat treatment time.

製膜に使用する基板としては、ガラス基板、ＳｉやＧｅ等の半導体基板等を用いることができる。   As a substrate used for film formation, a glass substrate, a semiconductor substrate such as Si or Ge, or the like can be used.

次に、この出願の発明の実施例を述べる。もちろん、この出願の発明は以下の例に限定されるものではなく、細部については様々な態様が可能であることは言うまでもない。   Next, examples of the invention of this application will be described. Of course, the invention of this application is not limited to the following examples, and it goes without saying that various aspects are possible in detail.

＜ナノグラニュラー軟磁性薄膜の弱磁場製膜＞
試料１
下記の条件でＣｏ−Ｐｄ−Ｓｉ−Ｏ系ナノグラニュラー軟磁性薄膜の弱磁場製膜を行った。 <Nano-granular soft magnetic thin film with weak magnetic field>
Sample 1
Under the following conditions, a Co—Pd—Si—O nanogranular soft magnetic thin film was formed into a weak magnetic field.

製法：ＲＦマグネトロンスパッタ法
基板：コーニング７０５９石英ガラス
真空度：０．６７Ｐａ
磁場：１００Ｏｅ（永久磁石により磁性膜面内方向に印加）
ターゲット：Ｃｏ−Ｓｉ合金上にＰｄチップを載せた複合ターゲット
電力：２００Ｗ
酸素分圧：２ｓｃｃｍ
得られたナノグラニュラー軟磁性膜の組成はＣｏ56Ｐｄ13Ｓｉ8Ｏ23であり、異方性磁
場Ｈｋは３００Ｏｅ、膜厚は２．５μｍであった。 Manufacturing method: RF magnetron sputtering method Substrate: Corning 7059 quartz glass Vacuum degree: 0.67 Pa
Magnetic field: 100 Oe (applied in the in-plane direction of the magnetic film by a permanent magnet)
Target: Composite target with Pd chip on Co-Si alloy Power: 200W
Oxygen partial pressure: 2 sccm
The composition of the obtained nanogranular soft magnetic film was Co 56 Pd 13 Si 8 O 23 , the anisotropic magnetic field Hk was 300 Oe, and the film thickness was 2.5 μm.

試料２
上記試料１の作製において、Ｃｏ−Ｓｉ上のターゲット上のＰｄチップ数と酸素分圧を変えた以外は同様にして、Ｃｏ−Ｐｄ−Ｓｉ−Ｏ系ナノグラニュラー軟磁性薄膜の弱磁場製膜を行った。 Sample 2
In the production of Sample 1, a Co-Pd-Si-O nanogranular soft magnetic thin film was formed in a weak magnetic field in the same manner except that the number of Pd chips on the target on Co-Si and the oxygen partial pressure were changed. It was.

得られたナノグラニュラー軟磁性膜の組成はＣｏ55Ｐｄ6Ｓｉ8Ｏ31であり、異方性磁場Ｈｋは５０Ｏｅ、膜厚は２．１μｍであった。 The composition of the obtained nanogranular soft magnetic film was Co 55 Pd 6 Si 8 O 31 , the anisotropic magnetic field Hk was 50 Oe, and the film thickness was 2.1 μm.

［実施例１］
上記の弱磁場中で製膜した試料１のナノグラニュラー軟磁性膜に対して下記の条件で加熱処理を施し、実施例１とした。 [Example 1]
The nano-granular soft magnetic film of Sample 1 formed in the weak magnetic field was subjected to a heat treatment under the following conditions, and Example 1 was obtained.

磁場強度：１Ｔから１０Ｔ（電磁石により軟磁性膜の面内方向に磁場を印加）
真空度：０．４Ｐａ
加熱速度：２℃／ｍｉｎ
熱処理温度：２００℃
保持時間：１時間
冷却速度：２℃／ｍｉｎ
実施例１のナノグラニュラー軟磁性膜の電気比抵抗は１．５×１０3μΩｍ、飽和磁束
密度Ｂｓは９．５ｋＧ、保磁力Ｈｃは９Ｏｅであった。異方性磁場Ｈｋの磁場依存性を図１（ａ）に示す。また、磁場が１０Ｔの場合のナノグラニュラー軟磁性膜の磁化曲線を図２（ａ）に示す。 Magnetic field strength: 1T to 10T (applying a magnetic field in the in-plane direction of the soft magnetic film with an electromagnet)
Degree of vacuum: 0.4 Pa
Heating rate: 2 ° C / min
Heat treatment temperature: 200 ° C
Holding time: 1 hour Cooling rate: 2 ° C / min
The electrical resistivity of the nanogranular soft magnetic film of Example 1 was 1.5 × 10 3 μΩm, the saturation magnetic flux density Bs was 9.5 kG, and the coercive force Hc was 9 Oe. The magnetic field dependence of the anisotropic magnetic field Hk is shown in FIG. Further, FIG. 2A shows the magnetization curve of the nanogranular soft magnetic film when the magnetic field is 10T.

［実施例２］
実施例１において、試料１の代わりに試料２を用いた以外は同様にして加熱処理を施し
、実施例２とした。 [Example 2]
In Example 1, heat treatment was performed in the same manner except that Sample 2 was used instead of Sample 1, and Example 2 was obtained.

実施例２のナノグラニュラー軟磁性膜の電気比抵抗は９．６×１０4μΩｍ、飽和磁束
密度Ｂｓは７ｋＧ、保磁力Ｈｃは３．５Ｏｅであった。異方性磁場Ｈｋの磁場依存性を図１（ｂ）に示す。また、磁場が１０Ｔの場合のナノグラニュラー軟磁性膜の磁化曲線を図２（ｂ）に示す。 The electrical resistivity of the nanogranular soft magnetic film of Example 2 was 9.6 × 10 4 μΩm, the saturation magnetic flux density Bs was 7 kG, and the coercive force Hc was 3.5 Oe. The magnetic field dependence of the anisotropic magnetic field Hk is shown in FIG. Further, FIG. 2B shows the magnetization curve of the nanogranular soft magnetic film when the magnetic field is 10T.

［比較例１］
実施例１において、磁場を印加しないこと以外は同様にして加熱処理を施し、比較例１とした。 [Comparative Example 1]
In Example 1, heat treatment was performed in the same manner except that no magnetic field was applied, and Comparative Example 1 was obtained.

比較例１のナノグラニュラー軟磁性膜の電気比抵抗は１．５×１０3μΩｍ、飽和磁束
密度Ｂｓは９．５ｋＧ、保磁力Ｈｃは９Ｏｅであった。異方性磁場Ｈｋは３００Ｏｅであった。比較例１のナノグラニュラー軟磁性膜の磁化曲線を図３（ａ）に示す。 The electrical resistivity of the nanogranular soft magnetic film of Comparative Example 1 was 1.5 × 10 3 μΩm, the saturation magnetic flux density Bs was 9.5 kG, and the coercive force Hc was 9 Oe. The anisotropic magnetic field Hk was 300 Oe. The magnetization curve of the nanogranular soft magnetic film of Comparative Example 1 is shown in FIG.

［比較例２］
実施例２において、磁場を印加しないこと以外は同様にして加熱処理を施し、比較例２とした。 [Comparative Example 2]
In Example 2, heat treatment was performed in the same manner except that no magnetic field was applied, and Comparative Example 2 was obtained.

比較例２のナノグラニュラー軟磁性膜の電気比抵抗は９．６×１０4μΩｍ、飽和磁束
密度Ｂｓは７ｋＧ、保磁力Ｈｃは３．５Ｏｅであった。異方性磁場Ｈｋは５０Ｏｅであった。比較例２のナノグラニュラー軟磁性膜の磁化曲線を図３（ｂ）に示す。 The electrical resistivity of the nanogranular soft magnetic film of Comparative Example 2 was 9.6 × 10 4 μΩm, the saturation magnetic flux density Bs was 7 kG, and the coercive force Hc was 3.5 Oe. The anisotropic magnetic field Hk was 50 Oe. The magnetization curve of the nanogranular soft magnetic film of Comparative Example 2 is shown in FIG.

図１より、また図２と図３との比較により、強磁場印加による異方性磁場Ｈｋの増大が明瞭に観察される。このように弱磁場中製膜の状態で２００Ｏｅ以上（３００Ｏｅ程度）の大きな異方性磁場Ｈｋを示すナノグラニュラー軟磁性膜および弱磁場中製膜の状態で１００Ｏｅ以下（５０Ｏｅ程度）の異方性磁場Ｈｋを示すナノグラニュラー軟磁性膜のどちらにおいても強磁場印加による異方性磁場Ｈｋの増大が認められた。特に弱磁場中製膜の状態で１００Ｏｅ以下（５０Ｏｅ）の異方性磁場Ｈｋを示す試料では初期値（弱磁場中製膜後の値）と比較して異方性磁場Ｈｋの大きさが３倍にも達し、増大量でも１００Ｏｅ以上であった。   From FIG. 1 and a comparison between FIG. 2 and FIG. 3, an increase in the anisotropic magnetic field Hk due to the application of a strong magnetic field is clearly observed. As described above, the nano-granular soft magnetic film showing a large anisotropic magnetic field Hk of 200 Oe or more (about 300 Oe) in the state of film formation in a weak magnetic field and the anisotropic magnetic field of 100 Oe or less (about 50 Oe) in the state of film formation in a weak magnetic field. In any of the nanogranular soft magnetic films showing Hk, an increase in the anisotropic magnetic field Hk was observed due to the application of a strong magnetic field. In particular, in a sample showing an anisotropic magnetic field Hk of 100 Oe or less (50 Oe) in the state of film formation in a weak magnetic field, the magnitude of the anisotropic magnetic field Hk is 3 as compared with the initial value (value after film formation in the weak magnetic field). Doubled and the increase amount was over 100 Oe.

従って、この出願の発明の手法を利用することで大きな電気比抵抗を示すナノグラニュラー軟磁性膜の中でも特に電気比抵抗の大きなものにおいて異方性磁場Ｈｋの増大が達成できることがわかる。大きな電気比抵抗、大きな異方性磁場Ｈｋのどちらも共鳴周波数を高くする効果があるために、この出願の発明の手法は数１０ＧＨｚの超高周波領域まで適用可能な軟磁性材料の開発手法として利用可能である。   Therefore, it can be seen that by using the method of the invention of this application, an increase in the anisotropic magnetic field Hk can be achieved in a nanogranular soft magnetic film exhibiting a large electrical resistivity, particularly in a film having a large electrical resistivity. Since both the large electrical resistivity and the large anisotropic magnetic field Hk have the effect of increasing the resonance frequency, the method of the invention of this application is used as a method for developing a soft magnetic material that can be applied up to several tens of GHz. Is possible.

（ａ）は実施例１の異方性磁場Ｈｋの磁場強度依存性を示す図、（ｂ）は実施例２の異方性磁場Ｈｋの磁場強度依存性を示す図である。(A) is a figure which shows the magnetic field strength dependence of the anisotropic magnetic field Hk of Example 1, (b) is a figure which shows the magnetic field strength dependence of the anisotropic magnetic field Hk of Example 2. FIG. （ａ）は実施例１の磁化曲線を示す図、（ｂ）は実施例２の磁化曲線を示す図である。(A) is a figure which shows the magnetization curve of Example 1, (b) is a figure which shows the magnetization curve of Example 2. FIG. （ａ）は比較例１の磁化曲線を示す図、（ｂ）は比較例２の磁化曲線を示す図である。(A) is a figure which shows the magnetization curve of the comparative example 1, (b) is a figure which shows the magnetization curve of the comparative example 2.

Claims (4)

ＦｅまたはＣｏの少なくとも１種を主構成成分とする（Ｃｏ，Ｆｅ）−（Ｎｉ，Ｐｄ，Ｐｔ）−Ｓｉ−Ｏ系のナノグラニュラー軟磁性膜の製造方法であって、平均粒径が１０ｎｍ以下の強磁性粒子が、酸化物のセラミックスからなる母相中に埋め込まれた形態をなし、製膜後、真空中にて、１T以上の強磁場を面内方向に印加した状態で、熱処理を施すことにより異方性磁場を１．２倍から4倍に増幅させることを特徴とするナノグラニュラー軟磁性膜の製造方法 A method for producing a (Co, Fe)-(Ni, Pd, Pt) -Si-O-based nanogranular soft magnetic film having at least one of Fe and Co as a main component, wherein the average particle size is 10 nm or less The ferromagnetic particles are embedded in a matrix of oxide ceramics, and after film formation , heat treatment is performed in a vacuum with a strong magnetic field of 1 T or more applied in the in-plane direction. Method for amplifying an anisotropic magnetic field from 1.2 times to 4 times by the method 熱処理を、２０℃／ｍｉｎ以下の加熱速度で１００℃ から５００℃ の間の温度まで昇温させた後、その温度で０．１時間から５時間保持し、その後２０℃／ｍｉｎ以下の冷却速度で冷却することにより行うことを特徴とする請求項１記載のナノグラニュラー軟磁性膜の製造方法。   The temperature of the heat treatment is raised to a temperature between 100 ° C. and 500 ° C. at a heating rate of 20 ° C./min or less, then held at that temperature for 0.1 to 5 hours, and then a cooling rate of 20 ° C./min or less. The method for producing a nanogranular soft magnetic film according to claim 1, wherein the method is performed by cooling at a temperature. 電磁石または超伝導磁石による磁場の印加を１Ｔから１０Ｔの範囲で行うことを特徴とする請求項１または２に記載のナノグラニュラー軟磁性膜の製造方法。   3. The method for producing a nanogranular soft magnetic film according to claim 1, wherein the magnetic field is applied by an electromagnet or a superconducting magnet in the range of 1T to 10T. 強磁性粒子中にＮｉ族元素が５原子％ から３０原子％添加されていることを特徴とす
る請求項１から３のいずれかに記載のナノグラニュラー軟磁性膜の製造方法。
The method for producing a nanogranular soft magnetic film according to any one of claims 1 to 3, wherein a Ni group element is added to the ferromagnetic particles in an amount of 5 atomic percent to 30 atomic percent.
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