JPS61287032A - Production of thin magnetic material film - Google Patents
Production of thin magnetic material filmInfo
- Publication number
- JPS61287032A JPS61287032A JP12740685A JP12740685A JPS61287032A JP S61287032 A JPS61287032 A JP S61287032A JP 12740685 A JP12740685 A JP 12740685A JP 12740685 A JP12740685 A JP 12740685A JP S61287032 A JPS61287032 A JP S61287032A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- magnetic thin
- film according
- producing
- chemical formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000696 magnetic material Substances 0.000 title 1
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000010409 thin film Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 239000013522 chelant Substances 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 7
- -1 alkoxide compound Chemical class 0.000 claims 4
- 125000000217 alkyl group Chemical group 0.000 claims 4
- 239000011701 zinc Substances 0.000 claims 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 claims 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims 1
- 230000032258 transport Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000004642 Polyimide Substances 0.000 abstract description 8
- 229920001721 polyimide Polymers 0.000 abstract description 8
- 238000005268 plasma chemical vapour deposition Methods 0.000 abstract description 5
- 230000004907 flux Effects 0.000 abstract description 3
- GYIWFHXWLCXGQO-UHFFFAOYSA-N barium(2+);ethanolate Chemical compound [Ba+2].CC[O-].CC[O-] GYIWFHXWLCXGQO-UHFFFAOYSA-N 0.000 abstract 1
- 230000005587 bubbling Effects 0.000 abstract 1
- FRCRDSKTAZVJDU-UHFFFAOYSA-N cobalt(2+);ethanolate Chemical compound [Co+2].CC[O-].CC[O-] FRCRDSKTAZVJDU-UHFFFAOYSA-N 0.000 abstract 1
- MHKBQFNNFYZELC-UHFFFAOYSA-N ethanolate;iron(2+) Chemical compound [Fe+2].CC[O-].CC[O-] MHKBQFNNFYZELC-UHFFFAOYSA-N 0.000 abstract 1
- WXKZSTUKHWTJCF-UHFFFAOYSA-N zinc;ethanolate Chemical compound [Zn+2].CC[O-].CC[O-] WXKZSTUKHWTJCF-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 16
- 230000005415 magnetization Effects 0.000 description 16
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000010952 cobalt-chrome Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 244000005687 Poranopsis paniculata Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Chemical Vapour Deposition (AREA)
- Magnetic Record Carriers (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
- Thin Magnetic Films (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、高密度の垂直磁気記録を可能とする磁性体薄
膜の製造方法に関するものである。′従来の技術
近年磁気記録は、高密度化、ディジタル化の方向へ進み
つつある。磁気記録の方式として従来は、磁気記録媒体
の面内に磁化の容易軸を持っているいわゆる面内磁化に
よる磁気記録方式が主であった。しかしながら本方式で
は、記録密度を上げれば上げるほど澁気記録媒体内の磁
化方向が互いに反発し合うように並ぶため高密度化を計
るのが困難になってきている。そこで最近磁気記録の新
しい方式として、磁気記録媒体の面内に対して垂直方向
に磁化容易軸を持っているいわゆる垂直磁化による磁気
記録方式が開発され〔例えば 岩崎。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method of manufacturing a magnetic thin film that enables high-density perpendicular magnetic recording. ``Prior Art'' In recent years, magnetic recording has been moving toward higher density and digitalization. Conventionally, the main magnetic recording method has been a magnetic recording method using so-called in-plane magnetization, which has an easy axis of magnetization within the plane of a magnetic recording medium. However, in this method, as the recording density is increased, the magnetization directions within the recording medium are arranged so as to repel each other, making it difficult to achieve high density recording. Recently, a new method of magnetic recording, a magnetic recording method using so-called perpendicular magnetization, in which the axis of easy magnetization is perpendicular to the plane of the magnetic recording medium, has been developed [for example, by Iwasaki et al.
“垂直磁化を用いた高密度磁気記録”日経エレクトロニ
クス（８，７）！１９２．ｐ、１００゜１９ア８．〕記
録密度が飛躍的に増大することが可能となった。この垂
直磁気記録方式にもちいられている記録媒体としては、
コバルト−クロム（Ｃｏ −Ｃｒ ）合金膜が主として
、スパッタ法、真空蒸着法〔例えば 岩崎、大内、′高
周波スパッタ法によるＣｏ−Ｃｘ垂直記録媒体”信学会
論文誌Ｖｏ１．６３−Ｃ，Ａ４． ｐｐ、 ２３８−２
４５゜Ａｐｒｉｌ、 １９８０．１等によって開発さ
れつつある。またＣｏ−Ｃｒ以外にもバリウムフェライ
ト（Ｂ ａｏ ・６ Ｆ ｅ ２０３ ）がスパッタ法
〔例えば 星、株間。“High-density magnetic recording using perpendicular magnetization” Nikkei Electronics (8, 7)! 192. p, 100°19a8. ] It has become possible to dramatically increase recording density. The recording media used in this perpendicular magnetic recording method are:
Cobalt-chromium (Co-Cr) alloy films are mainly produced by sputtering and vacuum evaporation methods [for example, Iwasaki, Ouchi, ``Co-Cx perpendicular recording medium by high-frequency sputtering'', Transactions of the IEICE, Vol. 1.63-C, A4. pp, 238-2
45° April, 1980.1, etc., is being developed. In addition to Co-Cr, barium ferrite (Bao 6 Fe 203) can also be produced using sputtering methods [e.g. Hoshi, Kusuma.
直性、山中；対向ターゲット式スノくツタによるＣ軸配
向！ａ−フェライト膜の構造と磁気特性、信学論（ｑ、
Ｔ ａｓ−Ｃ，１，Ｐ、ｅ−１ｅ （昭和５８−ｏｌ）
）により得られている。Straightness, Yamanaka; C-axis orientation by facing target type snow vine! a-Structure and magnetic properties of ferrite film, IEICE theory (q,
T as-C, 1, P, e-1e (Showa 58-ol)
) is obtained.
発明が解決しようとする問題点
これらの垂直磁気記録媒体において、Ｇｏ −Ｃｒ合金
膜は、低温で作成することが可能であるが、垂直磁化の
大きさの目安となる垂直磁気異方性がバリウムフェライ
トよりちいさい。そのため完全な垂直磁化膜とはならず
ある程度面内の磁化成分をものこすという問題があり、
しかも記録媒体が金属であるため、さびの問題や磁気ヘ
ッドが媒体面を走行中に金属（Ｃｏ−Ｃτ合金）がくっ
つく、いわゆる金属の焼き付き現象等がおこるという欠
点を有している。Problems to be Solved by the Invention In these perpendicular magnetic recording media, Go-Cr alloy films can be formed at low temperatures, but the perpendicular magnetic anisotropy, which is a measure of the magnitude of perpendicular magnetization, is lower than that of barium. Smaller than ferrite. Therefore, there is a problem that the film is not completely perpendicularly magnetized and retains some in-plane magnetization component.
Moreover, since the recording medium is made of metal, it has the drawbacks of rust and the so-called metal burn-in phenomenon, in which the metal (Co--Cτ alloy) sticks to the magnetic head while it runs on the medium surface.
一方バリウムフエライトは、はぼ完全なＣ軸配向の膜が
得られるため、その結晶磁気異方性からほぼ完全な垂直
磁化膜が作成できる。しかしながらバリウムフェライト
を含むヘキサゴナルフェライト膜を作成するのには、５
００”Ｃ以上の基板温度が必要である、そのためポリイ
ミドやアルミニウム上にバリウムフェライトやヘキサゴ
ナルフェライトを作成することが困難である。On the other hand, with barium ferrite, a film with almost perfect C-axis orientation can be obtained, and therefore a film with almost perfect perpendicular magnetization can be created due to its magnetocrystalline anisotropy. However, in order to create a hexagonal ferrite film containing barium ferrite,
A substrate temperature of 00''C or higher is required, which makes it difficult to create barium ferrite or hexagonal ferrite on polyimide or aluminum.
またバリウムフェライト単独では、垂直磁気異方性が大
きく、磁気記録媒体としての保磁力（抗磁力）が、２０
００〜３０００エールステツド（Ｏｅ）と高くなるため
、例えばフェライトヘッド（Ｍｎ−Ｚｎ ７エライト
ヘツド）のごときヘッドでは、その飽和磁束密度（１３
ｇ ）がちいさいため、媒体を十分に磁化することが困
難である。〔例えば、スパッタ合金膜ヘッドによる高抗
磁力媒体への記録。In addition, barium ferrite alone has a large perpendicular magnetic anisotropy, and has a coercive force (coercive force) of 20
For example, in a head such as a ferrite head (Mn-Zn 7-elite head), the saturation magnetic flux density (13
g) Because the medium is small, it is difficult to sufficiently magnetize the medium. [For example, recording on a high coercive force medium using a sputtered alloy film head.
信学技報ＭＲ７７−２（１９７７）Ｐ、１１）７エ２イ
トヘツドで記録再生を行なうためには、抗磁力を下げな
ければならない、そのためにバリウムフェライトにコバ
ルト（Ｃ，）とチタン（Ｔｉ）を添加し抗磁力を下げる
試みがなされているが、バリウムフェライトの飽和磁化
も下げるという問照点を有している。IEICE Technical Report MR77-2 (1977) P, 11) In order to perform recording and reproduction with a 782-bit head, it is necessary to lower the coercive force, and for this purpose, cobalt (C,) and titanium (Ti) are added to barium ferrite. Attempts have been made to lower the coercive force by adding barium ferrite, but this has the problem of also lowering the saturation magnetization of barium ferrite.
問題点を解決するための手段
本発明は、前記問題点を解決するため、従来のスパッタ
法や真空蒸着法ではなく、プラズマ中に反応ガスを流し
、プラズマの活性さを利用した、プラズマＣＶＤ法によ
って３５０”Ｃ以下の低温でバリウムフェライト単相よ
り保磁力（抗磁力）がちいさく、しかも飽和磁束密度（
Ｍｓ ）の大きいベキサゴナルフェライトを製造する方
法を提供するものである。Means for Solving the Problems In order to solve the above-mentioned problems, the present invention provides a plasma CVD method that utilizes the activity of plasma by flowing a reactive gas in the plasma, instead of the conventional sputtering method or vacuum evaporation method. Therefore, at low temperatures below 350"C, the coercive force (coercive force) is smaller than that of barium ferrite single phase, and the saturation magnetic flux density (
The present invention provides a method for producing a bexagonal ferrite having a large Ms ).
作 用
発明者らは、プラズマＣＶＤ法を用いることによって３
６０℃以下の低温で保磁力がちいさく、Ｍｓ の大き
いベキサゴナルフェライトが得られることを見いだした
。すなわち、Ｆｅ、 Ｂａ、 Ｇｏ、 Ｚｎを含有
する金属アルコオキサイド、あるいは、Ｆｅ、 Ｂａ、
Ｃｏ、 Ｚｎ を含有するβ−ジケトン金属キレート
を加熱し気化しやすくさせてアルゴン（Ａｒ）をキャリ
アガスとし、酸素を反応ガスとして、高周波プラズマ（
周波数１３．５６ ＭＨｚ ）中にこれらを導入して、
３５０”Ｃ以下の基板上で分解析出させることによりベ
キサゴナルフェライトを生成させるものである。Effect The inventors achieved 3 by using the plasma CVD method.
It has been found that a vexagonal ferrite with a low coercive force and a large Ms can be obtained at a low temperature of 60°C or lower. That is, metal alkoxide containing Fe, Ba, Go, Zn, or Fe, Ba,
A β-diketone metal chelate containing Co and Zn is heated to facilitate vaporization, and is then treated with high-frequency plasma (Argon) as a carrier gas and oxygen as a reaction gas.
By introducing these into the frequency (13.56 MHz),
Vexagonal ferrite is produced by fractional deposition on a substrate of 350''C or less.
このように低温でベキサゴナルフェライトの析出が可能
となるのは、プラズマ中においては、化学反応を低温で
引きおこす活性なラジカルやイオン等の化学種が多く存
在し、通のＣＶＤ（熱による分解析出をおこなうＣＶＤ
）では、エネルギー的におこりえない反応がプラズマ中
では可能であるためである。〔例えば、薄膜ハンドブッ
ク ２２６ページ、オーム社 昭和５８年１２月１０日
〕また一般にプラズマＣＶＤ法は、通常の熱ＣＶＤ法に
くらべて、低温で酸化物、炭化物、窒化物等の高融点物
質が合成できるばかりでなく、熱分解析出反応を伴うた
めに低温においても高純度でしかも結晶性の良い膜が得
られる。そのためへキサゴナルフェライトのような結晶
の配向性の良いことが必要でしかもそれを低温で合成す
るのには最適の方法であると考えられる。The reason why it is possible to precipitate bexagonal ferrite at such low temperatures is that there are many chemical species such as active radicals and ions that cause chemical reactions at low temperatures in the plasma, which is common in CVD (thermal separation). CVD for analysis
), reactions that cannot occur energetically are possible in plasma. [For example, Thin Film Handbook, page 226, Ohmsha, December 10, 1982] In general, plasma CVD methods can synthesize high melting point substances such as oxides, carbides, and nitrides at lower temperatures than normal thermal CVD methods. Not only is this possible, but since it involves a thermal decomposition reaction, a film with high purity and good crystallinity can be obtained even at low temperatures. Therefore, it is necessary to have crystals with good orientation, such as hexagonal ferrite, and this is considered to be the optimal method for synthesizing them at low temperatures.
実施例
以下、本発明の一実施例について、図面にもとづいて説
明する。図は、本発明の一実施例におけるプラズマＣＶ
Ｄ装置の概略図を示すものである。）同図において、１
１は反応チャンバー、１２は高周波電極、１３は高周波
電源、１４は基板加熱ホルダー、１６は基板、１６はＦ
ｅ （ＯＲ）ｓあるいはＦ ｅ （Ｃ５Ｈ−、Ｏ）３の
バブラー、１７はＢ ａ （ＯＲ）２ あるいは、Ｂａ
（Ｃ６−０）２のバブラー、１８はＣｏ （ＯＲ）ｓ
アルイハＣ０（Ｃ５Ｈ７ｏ）３ツバフラー、１９ ハＺ
ｎ（ＯＲ）４匁あるいは、Ｚｎ（Ｃ６Ｈ７Ｑ）２のバブ
ラー、２０はキャリアガス（Ａｒ）のボンベ、２１は反
応ガス（Ｃ゜）のボンベ、２２はロータリーポンプであ
る。EXAMPLE Hereinafter, an example of the present invention will be described based on the drawings. The figure shows a plasma CV in one embodiment of the present invention.
D shows a schematic diagram of the device. ) In the same figure, 1
1 is a reaction chamber, 12 is a high frequency electrode, 13 is a high frequency power source, 14 is a substrate heating holder, 16 is a substrate, 16 is F
e (OR)s or F e (C5H-,O)3 bubbler, 17 is B a (OR)2 or Ba
(C6-0)2 bubbler, 18 is Co(OR)s
Aruiha C0 (C5H7o) 3 Tsubafura, 19 HaZ
n(OR)4 momme or Zn(C6H7Q)2 bubbler, 20 a carrier gas (Ar) cylinder, 21 a reaction gas (C°) cylinder, and 22 a rotary pump.
まずジェトキシ鉄（Ｆｅ （Ｃ−０２Ｈ６）３〕、ジェ
トキシバリウム（Ｂａ （Ｃ・Ｃ２Ｈ６）２〕、ジェト
キシコバルト（： Ｃｏ （Ｃ−Ｃ２Ｈ５）３’］ 、
ジェトキシ亜鉛ＣＺ２１１ＣＯ−Ｃ２Ｈ６）４］の入っ
たバブラー１６．１７．１８．１９を１６０℃に加熱し
、これらのバブラーにバブル用のアルゴンガス２ｏをそ
れぞれ２ ｅｓ ｏ ｃｃ／分、８０ＣＣ／分。First, jetoxyiron (Fe (C-02H6)3), jetoxybarium (Ba (C・C2H6)2), jetoxycobalt (: Co (C-C2H5)3'),
Bubblers 16, 17, 18, 19 containing jetoxyzinc CZ211CO-C2H6)4] were heated to 160°C, and 2 o of argon gas for bubbles was added to these bubblers at 2 es o cc/min and 80 cc/min, respectively.
１０ｃｃ／分、１０ａｃ／分の流量で流し、これらの蒸
気をロータリーポンプ２２によって減圧状態になった反
応チャンバー１１内の３４５℃に加熱されたポリイミド
基板上に導入する。次に同じく、反応ガスである酸素２
１を２５０ｃｃ／分の流量で同じくポリイミド基板上に
流す。この時のガス圧は１０Ｔｏｒｒであった。次いで
高周波電力（１３，５６ＭＨｚ ）をｓ ｏ ｏ Ｗ
（６Ｗ／ｃｉ）で６０分間印加し、反応させた。These vapors were introduced at a flow rate of 10 cc/min and 10 ac/min onto a polyimide substrate heated to 345° C. in the reaction chamber 11, which was brought into a reduced pressure state by the rotary pump 22. Next, similarly, the reactive gas oxygen 2
1 was also flowed onto the polyimide substrate at a flow rate of 250 cc/min. The gas pressure at this time was 10 Torr. Next, the high frequency power (13,56MHz) is
(6 W/ci) was applied for 60 minutes to cause a reaction.
次にこの時ポリイミド基板上に析出したベキサゴナルフ
ェライトの膜厚は、約２．４μｍであった。Next, the film thickness of the bexagonal ferrite deposited on the polyimide substrate at this time was about 2.4 μm.
次にこの膜について、Ｘ線解析、およびＶＳＭ（振動試
料型磁力計）による膜の磁気的特性を測定した。結果は
、第−表、試料番号１に示す。Next, the magnetic properties of this film were measured using X-ray analysis and a VSM (vibrating sample magnetometer). The results are shown in Table 1, sample number 1.
以下余白
以下同様にして、基板温度、金属アルコオキサイドの種
類、およびβ−ジケトン金属キレートの種類、バブラー
量（Ａｒ の流量）、反応チャンバー内の圧力、高周波
電力等を変化させた時のＸ線解析、ＶＳＭの結果を第−
表試料番号２〜１２に示す。また試料番号１３〜１９は
本願発明外の比較例である。Below are the margins. In the same way, X-rays were obtained by changing the substrate temperature, the type of metal alkoxide, the type of β-diketone metal chelate, the amount of bubbler (flow rate of Ar), the pressure in the reaction chamber, the high-frequency power, etc. Analysis, VSM results
Shown in table sample numbers 2-12. Moreover, sample numbers 13 to 19 are comparative examples other than the present invention.
ここでＸ線解析は、ヘキサゴナルフェライトの単相でＣ
軸配向が得られたかどうかを調べた。またＶＳＭの結果
からヘキサゴナルフェライトの飽和磁化と、ヒステリシ
ス曲線（Ｂ−Ｈカーブ）を求めヘキサゴナルフエライト
の垂直方向（薄膜の膜面に対して垂直の方向）の残留磁
化と保磁力、および水平方向の残留磁化と保磁力を求め
た。（垂直方向の残留磁化および保磁力が水平方向の残
留磁化および保磁力にくらべて大きければ大きいほどよ
りすぐれた垂直磁化膜である。）
基板温度を３６０℃以下にするのがのぞましく、３５０
℃以上になると基板材料として使用されるポリイミドや
Ｍ等において熱的変形や劣化がおこり良質のへキサゴナ
ルフェライト膜が得られないためである。Here, the X-ray analysis shows that C is a single phase of hexagonal ferrite.
We checked whether axial orientation was obtained. In addition, from the VSM results, the saturation magnetization and hysteresis curve (B-H curve) of hexagonal ferrite were determined, and the residual magnetization and coercive force in the vertical direction (direction perpendicular to the film surface of the thin film) of hexagonal ferrite, as well as the horizontal direction. The residual magnetization and coercive force were determined. (The larger the residual magnetization and coercive force in the vertical direction are compared to the residual magnetization and coercive force in the horizontal direction, the better the perpendicularly magnetized film is.) It is preferable to keep the substrate temperature below 360°C. 350
This is because if the temperature exceeds .degree. C., thermal deformation and deterioration occur in the polyimide, M, etc. used as the substrate material, making it impossible to obtain a good quality hexagonal ferrite film.
またプラズマ電力を０．６Ｗ〜１０Ｗと限定したのはα
ｓＷ／７以下のプラズマ電力では、十分に気相中で単相
のへキサゴナルフエライトが合成できないためでおり、
１ｏｗ／ＣＩＬ以上では、電力が強すぎて気相中で出来
たヘキサゴナルフエライトが再分解されヘキサゴナルフ
ェライト以外の相（Ｆｅ３０． （ＣｏＦｅ２０４）等
）が析出するためである。In addition, the plasma power was limited to 0.6W to 10W because α
This is because single-phase hexagonal ferrite cannot be sufficiently synthesized in the gas phase with a plasma power of sW/7 or less.
This is because at 1 ow/CIL or more, the electric power is too strong and the hexagonal ferrite formed in the gas phase is re-decomposed and phases other than hexagonal ferrite (Fe30. (CoFe204), etc.) are precipitated.
またプラズマを維持する時の圧力をα１〜１０Ｔａｒτ
に限定したのは、ｏ、１Ｔｏττ以下では、反応生成物
（ヘキサゴナルフエライト）の製膜速度が遅く、実用上
問題があるためであり、１０ Ｔｏｒｒ以上では、基板
上に膜として成虫せず、空間でパウダー状物質となるた
めである。Also, the pressure when maintaining the plasma is α1~10Tarτ
The reason for this is that at o,1Toττ or less, the film formation rate of the reaction product (hexagonal ferrite) is slow, which poses a practical problem; This is because it becomes a powder-like substance.
発明の効果
以上述べてきたように、本発明によれば、プラズマの活
性さを巧みに利用して、３６０℃以下の比較的低温で垂
直方向の残留磁化が大きく垂直方向の保磁力の比較的ち
いさいヘキサゴナルフェライト膜が作成できる方法であ
って、高密度の磁気記録を達成するのにきわめて有益な
発明である。Effects of the Invention As described above, according to the present invention, by skillfully utilizing the activity of plasma, the residual magnetization in the perpendicular direction is large and the coercive force in the perpendicular direction is relatively low at a relatively low temperature of 360°C or less. This invention is a method for producing a small hexagonal ferrite film, and is extremely useful for achieving high-density magnetic recording.
図は、本発明の一実施例におけるプラズマＣＶＤ装置の
概略図である。
１１・・・・・・反応チャンバー、１２・・・・・・高
周波電極、１３・・・・・・高周波電源、１４・・・・
・・基板加熱ホルダー、１６・・・・・・基板、１６・
・・・・・Ｆ ｅ （ＯＲ）ｓのバブラー、１７・・・
・・・Ｂａ（ＯＲ）２のバブラー、１８・・・・・・Ｃ
０ｐＲ）３のバブラー、１９・・・・・・Ｚｎ （ＯＲ
）４のバブラー、に・・・・・・Ａｒ キャリアガスボ
ンベ、２１・・・・・・反応ガス（Ｏ２）ボンベ、２２
・・・・・・ロータリーホンプ。The figure is a schematic diagram of a plasma CVD apparatus in one embodiment of the present invention. 11... Reaction chamber, 12... High frequency electrode, 13... High frequency power supply, 14...
...Substrate heating holder, 16...Substrate, 16.
...F e (OR)s bubbler, 17...
...Ba(OR)2 bubbler, 18...C
0pR) 3 bubbler, 19...Zn (OR
) 4 bubbler, Ar carrier gas cylinder, 21... Reactant gas (O2) cylinder, 22
・・・・・・Rotary homp.
Claims (11)
）および亜鉛（Ｚｎ）を含有する金属アルコオキサイド
、あるいはβ−ジケトン金属キレートと、これらの蒸気
を輸送するガスとしてのアルゴン（Ａｒ）および反応ガ
スとしての酸素（Ｏ＿２）をプラズマ中で分解させ、加
熱された基板上にヘキサゴナルフェライトを析出させる
ことを特徴とする磁性体薄膜の製造方法。(1) Iron (Fe), barium (Ba), cobalt (Co)
) and zinc (Zn), or β-diketone metal chelate, argon (Ar) as a gas that transports these vapors, and oxygen (O_2) as a reactive gas, are decomposed in a plasma, A method for producing a magnetic thin film, which comprises depositing hexagonal ferrite on a heated substrate.
学式がＦｅ（ＯＲ）＿３（ただしＲはアルキル基）、で
示されることを特徴とする特許請求の範囲第１項記載の
磁性体薄膜の製造方法。(2) A method for producing a magnetic thin film according to claim 1, characterized in that the alkoxide compound containing iron is represented by the chemical formula Fe(OR)_3 (where R is an alkyl group). .
化学式がＦｅ（Ｃ＿５Ｈ＿７Ｏ）＿３で示されることを
特徴とする特許請求の範囲第１項記載の磁性体薄膜の製
造方法。(3) As a β-diketone metal chelate containing iron,
2. The method for producing a magnetic thin film according to claim 1, wherein the chemical formula is Fe(C_5H_7O)_3.
て、化学式がＢａ（ＯＲ）＿２（ただし、Ｒはアルキル
基）で示されることを特徴とする特許請求の範囲第１項
記載の磁性体薄膜の製造方法。(4) The method for producing a magnetic thin film according to claim 1, wherein the alkoxide compound containing barium has a chemical formula of Ba(OR)_2 (where R is an alkyl group). .
して、化学式がＢａ（Ｃ＿５Ｈ＿７Ｏ）＿２で示される
ことを特徴とする特許請求の範囲第１項記載の磁性体薄
膜の製造方法。(5) The method for producing a magnetic thin film according to claim 1, wherein the barium-containing β-diketone metal chelate has a chemical formula of Ba(C_5H_7O)_2.
て化学式がＣｏ（ＯＲ）＿３（ただし、Ｒはアルキル基
）で示されることを特徴とする特許請求の範囲第１項記
載の磁性体薄膜の製造方法。(6) The method for producing a magnetic thin film according to claim 1, wherein the alkoxide compound containing cobalt has a chemical formula of Co(OR)_3 (where R is an alkyl group).
して、化学式がＣｏ（Ｃ＿５Ｈ＿７Ｏ）＿３で示される
ことを特徴とする特許請求の範囲第１項記載の磁性体薄
膜の製造方法。(7) The method for producing a magnetic thin film according to claim 1, wherein the β-diketone metal chelate containing cobalt has a chemical formula of Co(C_5H_7O)_3.
学式がＺｎ（ＯＲ）＿２（ただし、Ｒはアルキル基）で
示されることを特徴とする特許請求の範囲第１項記載の
磁性体薄膜の製造方法。(8) The method for producing a magnetic thin film according to claim 1, wherein the alkoxide compound containing zinc has a chemical formula of Zn(OR)_2 (where R is an alkyl group).
、化学式がＺｎ（Ｃ＿５Ｈ＿７Ｏ）＿２で示されること
を特徴とする特許請求の範囲第１項記載の磁性体薄膜の
製造方法。(9) The method for producing a magnetic thin film according to claim 1, wherein the β-diketone metal chelate containing zinc has a chemical formula of Zn(C_5H_7O)_2.
．５Ｗ／ｃｍ＾２〜１０Ｗ／ｃｍ＾２（Ｗはワット）で
あることを特徴とする特許請求の範囲第１項記載の磁性
体薄膜の製造方法。(10) The electric power (power) when generating plasma is 0
．． 2. The method of manufacturing a magnetic thin film according to claim 1, wherein the heating voltage is 5 W/cm^2 to 10 W/cm^2 (W is watt).
ｏｒｒであることを特徴とする特許請求の範囲第９項記
載の磁性体薄膜の製造方法。(11) Pressure when maintaining plasma is 0.1-10T
10. The method of manufacturing a magnetic thin film according to claim 9, wherein the magnetic thin film is orr.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12740685A JPH0664738B2 (en) | 1985-06-12 | 1985-06-12 | Method for manufacturing magnetic thin film |
| US06/826,386 US4717584A (en) | 1985-02-07 | 1986-02-05 | Method of manufacturing a magnetic thin film |
| DE8686300848T DE3685346D1 (en) | 1985-02-07 | 1986-02-07 | MAGNETIC THIN FILM AND METHOD FOR THE PRODUCTION THEREOF. |
| EP86300848A EP0194748B1 (en) | 1985-02-07 | 1986-02-07 | Magnetic thin film and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12740685A JPH0664738B2 (en) | 1985-06-12 | 1985-06-12 | Method for manufacturing magnetic thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61287032A true JPS61287032A (en) | 1986-12-17 |
| JPH0664738B2 JPH0664738B2 (en) | 1994-08-22 |
Family
ID=14959192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12740685A Expired - Lifetime JPH0664738B2 (en) | 1985-02-07 | 1985-06-12 | Method for manufacturing magnetic thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0664738B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01208468A (en) * | 1988-02-15 | 1989-08-22 | Riken Corp | Barium-based thin film manufacturing method |
| JPH0296916A (en) * | 1988-10-03 | 1990-04-09 | Matsushita Electric Ind Co Ltd | Magnetic medium and production thereof |
| EP1221709A2 (en) * | 1995-12-15 | 2002-07-10 | Matsushita Electric Industrial Co., Ltd. | Plasma display panel suitable for high-quality display and production method |
| JP2008088511A (en) * | 2006-10-03 | 2008-04-17 | Adeka Corp | Raw material for depositing thin film, method for producing thin film, and zinc compound |
-
1985
- 1985-06-12 JP JP12740685A patent/JPH0664738B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01208468A (en) * | 1988-02-15 | 1989-08-22 | Riken Corp | Barium-based thin film manufacturing method |
| JPH0296916A (en) * | 1988-10-03 | 1990-04-09 | Matsushita Electric Ind Co Ltd | Magnetic medium and production thereof |
| EP1221709A2 (en) * | 1995-12-15 | 2002-07-10 | Matsushita Electric Industrial Co., Ltd. | Plasma display panel suitable for high-quality display and production method |
| USRE40647E1 (en) | 1995-12-15 | 2009-03-10 | Matsushita Electric Industrial Co., Ltd. | Method of producing plasma display panel with protective layer of an alkaline earth oxide |
| USRE41503E1 (en) | 1995-12-15 | 2010-08-17 | Panasonic Corporation | Method of producing plasma display panel with protective layer of an alkaline earth oxide |
| JP2008088511A (en) * | 2006-10-03 | 2008-04-17 | Adeka Corp | Raw material for depositing thin film, method for producing thin film, and zinc compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0664738B2 (en) | 1994-08-22 |
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