JPH0323226A - Formation of ferrite film and ferrite substrate - Google Patents
Formation of ferrite film and ferrite substrateInfo
- Publication number
- JPH0323226A JPH0323226A JP15869189A JP15869189A JPH0323226A JP H0323226 A JPH0323226 A JP H0323226A JP 15869189 A JP15869189 A JP 15869189A JP 15869189 A JP15869189 A JP 15869189A JP H0323226 A JPH0323226 A JP H0323226A
- Authority
- JP
- Japan
- Prior art keywords
- ferrite
- substrate
- ferrite film
- film
- solution
- 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
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 104
- 239000000758 substrate Substances 0.000 title claims abstract description 61
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- -1 iron ions Chemical class 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 230000005389 magnetism Effects 0.000 abstract description 4
- 229910001035 Soft ferrite Inorganic materials 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 72
- 239000000243 solution Substances 0.000 description 52
- 238000007747 plating Methods 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000007788 liquid Substances 0.000 description 25
- 239000002585 base Substances 0.000 description 20
- 239000011521 glass Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- 230000003746 surface roughness Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 5
- 239000005695 Ammonium acetate Substances 0.000 description 5
- 235000019257 ammonium acetate Nutrition 0.000 description 5
- 229940043376 ammonium acetate Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910003962 NiZn Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 210000000087 hemolymph Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は磁気記録媒体，光磁気記録媒体，磁気ヘッド，
磁気光学素子，マイクロ波素子，磁歪素子，磁気音響素
子などに広く応用されているスビネル型フェライト膜の
作製におけるフェライト嗅の形成方法およびその方法に
よりフェライト膜を形成したフェライト基板に関するも
のである。[Detailed description of the invention] Industrial application field The present invention is applicable to magnetic recording media, magneto-optical recording media, magnetic heads,
This invention relates to a method for forming a ferrite layer in the production of Subinel-type ferrite films, which are widely applied to magneto-optical devices, microwave devices, magnetostrictive devices, magnetoacoustic devices, etc., and a ferrite substrate on which a ferrite film is formed using the method.
従来の技術
フェライトめっきとは、例えば、特開昭５９〜１１１９
２９号公報に示されているように、固体表面に、金属イ
オンとして少なくとも第１鉄イオンを含む水溶液を接触
させて、固体表面にＦｅＯＨ＋またはこれと他の水酸化
金属イオンを吸着させ、次いで、吸着したＦｅＯＨ＋を
酸化させることによりＦｅＯＨ２＋を得、これが水溶液
中の水酸化金属イオンとの間でフェライト結晶化反応を
起こし、これによって固体表面にフェライト膜を形成す
ることをいう。Conventional technology ferrite plating is, for example, disclosed in Japanese Patent Application Laid-open No. 59-1119.
As shown in Publication No. 29, an aqueous solution containing at least ferrous ions as metal ions is brought into contact with a solid surface to adsorb FeOH+ or other hydroxide metal ions on the solid surface, and then, FeOH2+ is obtained by oxidizing the adsorbed FeOH+, which causes a ferrite crystallization reaction with metal hydroxide ions in an aqueous solution, thereby forming a ferrite film on the solid surface.
従来、この技術を基にフェライト膜の均質化、反応速度
の向上等を図ったもの（特開昭６０−１ ４０７ １
３号公報）、固体表面に界面活性を付与して種々の固体
にフェライト膜を形成しようとするものく特開昭６１−
３０６７４号公報）、あるいはフェライト膜の形成速度
の向上に関するもの（特開昭６１ １７９８７７号公
報ないし特開昭６１−２２２９２４公報）がある。Conventionally, based on this technology, the ferrite film was homogenized and the reaction speed was improved (Japanese Patent Application Laid-Open No. 1986-1407-1).
3), Japanese Patent Application Laid-Open No. 1986-61, which attempts to form ferrite films on various solids by imparting surface activity to the solid surface.
30674), or related to improving the formation rate of ferrite film (Japanese Patent Application Laid-Open Nos. 179877 to 222924 of 1982).
フェライトめっきは、膜を形成しようとする固体が前述
した水溶液に対して耐性があれば何でもよい。さらに、
水溶液を介した反応であるため、温度が比較的低音（水
溶液の沸点以下）でスビネル型フェライｌ・膜を作製で
きるという特徴がある。そのため、他のフェライト膜の
作製技術に比べて、固体の限定範囲が小さい。Any ferrite plating may be used as long as the solid on which the film is to be formed is resistant to the above-mentioned aqueous solution. moreover,
Since the reaction is carried out through an aqueous solution, it has the characteristic that Subinel-type ferrite films can be produced at relatively low temperatures (below the boiling point of the aqueous solution). Therefore, compared to other ferrite film manufacturing techniques, the limited range of solids is small.
各種の磁電変換素子（磁気抵抗素子あるいはホール素子
など）などの基板としては、磁気に対する感度を上げる
ためにフェライト基板を用いている。Ferrite substrates are used as substrates for various magnetoelectric conversion elements (magnetoresistive elements, Hall elements, etc.) in order to increase sensitivity to magnetism.
発明が解決しようとする課題
しかし、前述したようにこれまでフェライト膜の均質性
、あるいはフェライト膜の生成速度等に種々の改善が提
案されているが、得られるフェライト膜の磁気特性につ
いては前述した全ての方式とも不十分であった。つまり
、スビネル型フェライトとしての十分な磁気特性、特に
ソフト材料としての特性が得られていない。そのため、
各ｆ１電子部品等への応用あるいは適用等に関して大き
な課題があった。Problems to be Solved by the Invention However, as mentioned above, various improvements have been proposed to improve the homogeneity of the ferrite film or the production speed of the ferrite film, but the magnetic properties of the resulting ferrite film are not as described above. All methods were insufficient. In other words, sufficient magnetic properties as a Subinel type ferrite, especially properties as a soft material, are not obtained. Therefore,
There were major issues with regard to application or application to each f1 electronic component, etc.
フェライト膜の保磁力については、例えば、金属表面技
術ＶＯＬ．３８，Ｎｏ．９，１９８７ Ｐ．ｌに示され
ているように約１００ ０ｅ以上であり、マグネタイ
トもＭｎおよびＺｎを含んだ（ＭｎＺｎ系）フェライト
もほぼ同様の大きさである。Regarding the coercive force of ferrite film, for example, see Metal Surface Technology VOL. 38, No. 9, 1987 P. As shown in Fig. 1, it is approximately 1000e or more, and magnetite and ferrite containing Mn and Zn (MnZn type) are approximately the same size.
各種の磁電変換素子〈磁気抵抗素子あるいはホール素子
など〉などの基板としてフェライト基板を用いる場合、
例えば、焼結フェライト基板は多孔質であるため表面あ
らさが荒く、さらに、ビンホール等の欠陥も多くその表
面に薄膜素子を形成する場合には問題があった。When using a ferrite substrate as a substrate for various magnetoelectric conversion elements (such as magnetoresistive elements or Hall elements),
For example, since a sintered ferrite substrate is porous, its surface is rough, and it also has many defects such as via holes, which poses problems when forming thin film elements on its surface.
課題を解決するための手段
以上の課題を解決するために本発明は、鉄イオンを０．
Ｏ Ｏ ２ｔａｏｅ ／ｆ！以下含んだ溶液を基板に
接触させ、基板表面にフェライト膜を堆積させる方法と
したものである。Means for Solving the Problems In order to solve the above problems, the present invention provides iron ions at 0.
O O 2taoe /f! This method involves bringing a solution containing the following into contact with a substrate to deposit a ferrite film on the surface of the substrate.
種々の基体に本フェライト膜を形成してフェライト膜を
有するフェライト基板にしたものである。The ferrite film is formed on various substrates to obtain a ferrite substrate having a ferrite film.
作用
前述した方法によって、つまり鉄イオンを０．００２ｍ
ｏＱ ／２以下含んだ溶液を基体に接触させ、基体表面
にフェライト膜を形成することによって、前記の範囲外
の濃度の溶液を用いる方法では得られていなかった磁気
特性の優れた、しかも緻密で表面性の良好なフェライト
膜を形成することができる。そのため、種々の基体にフ
ェライト膜を形成したものは、基板として用いる場合、
緻密（ビンホールが少ない〉で表面性が良好（通常のガ
ラス並の表面あらさ）であり、さらにソフトフェライト
としての十分な磁気特性を有しているため例えば各種磁
電変換素子の磁気に対する感度を向上させることができ
る。Effect: By the method described above, iron ions are
By bringing a solution containing oQ /2 or less into contact with the substrate and forming a ferrite film on the surface of the substrate, it is possible to obtain excellent magnetic properties and a dense structure that could not be obtained using a method using a solution with a concentration outside the above range. A ferrite film with good surface properties can be formed. Therefore, when using various substrates with ferrite films as substrates,
It is dense (few holes) and has a good surface quality (surface roughness comparable to that of ordinary glass), and also has sufficient magnetic properties as a soft ferrite, so it can improve the magnetic sensitivity of various magnetoelectric conversion elements, for example. be able to.
実施例 以下、本発明の実施例について説明する。Example Examples of the present invention will be described below.
本発明のフェライト膜の形成方法の基本的な部分は、公
知の方法と大部分同じである。The basic parts of the method for forming a ferrite film of the present invention are mostly the same as known methods.
しかし、本発明では、鉄イオ゛ンをＯ． Ｏ Ｏ ２ｍ
ｏｅ ／ｆ！以下含んだ溶液を基体に供給するため、非
常に小さい保磁力（高い透磁率）のフェライト膜を得る
ことができる。しかも、得られるフェライト膜は、ビン
ホールが非常に少なく、通常のガラスと同等の表面あら
さである。これらの現象に対する原因は明確ではない。However, in the present invention, iron ions are O O 2m
oe/f! Since the solution containing the following is supplied to the substrate, a ferrite film with a very small coercive force (high magnetic permeability) can be obtained. Moreover, the resulting ferrite film has very few holes and has a surface roughness equivalent to that of ordinary glass. The causes for these phenomena are not clear.
結果的に、鉄イオン濃度を前記の範囲にすることによっ
て、得られるフェライト膜のソフト磁気特性〈低い保磁
力，高い透磁率〉あるいは優れた膜の緻密性．表面性に
なんらかの効果があるのではないかと思われる。As a result, by setting the iron ion concentration within the above range, the resulting ferrite film has soft magnetic properties (low coercive force, high magnetic permeability) or excellent film density. It seems that there may be some effect on superficiality.
本発明のフェライト膜の形成方法のいくつかの例を図を
用いて説明する。Some examples of the method of forming a ferrite film of the present invention will be explained with reference to the drawings.
例えば、一例の装置の概略図を第１図に示す。For example, a schematic diagram of an example device is shown in FIG.
３はフェライト膜を形成しようとする基体である。４は
基体３を取り付けて、回転することができる回転台であ
る。１および２はめっき液を基体３に供給するためのノ
ズルである。適当なノズルを選択することによって、液
を滴下あるいは噴霧状等で供給することができる。めっ
き反応前の無駄な反応を極力おさえ、得られるフェライ
ト膜の特性のバラツキを小さくし、コントロールしやす
くするためにめっきに必要な液はいくつかに分割して準
備する方がよい。この図では２分割した場合を示す。５
および６は、各めっき液を貯蔵するタンクである。3 is a substrate on which a ferrite film is to be formed. Reference numeral 4 denotes a rotating table to which the base 3 can be attached and rotated. 1 and 2 are nozzles for supplying the plating solution to the substrate 3. By selecting an appropriate nozzle, the liquid can be supplied dropwise or in the form of a spray. In order to suppress wasteful reactions before the plating reaction as much as possible, reduce variations in the characteristics of the obtained ferrite film, and make it easier to control, it is better to prepare the solution necessary for plating in several parts. This figure shows a case where it is divided into two parts. 5
and 6 are tanks for storing each plating solution.
また、図に示すように基体３および回転台４等のフェラ
イトめっき反応を行う部分はケース７によって仕切り、
非酸化性（例えば窒素）ガスをケース７内に送ることに
よって、非酸化性雰囲気にする。タンク５には少なくと
も鉄イオンを０．００２ｗｏｅ ／ｅ以下含んだ水溶液
（反応液）を入れて、タンク６には、例えば酸化剤とし
て亜硝酸ナトリウムＮ ａ Ｎ Ｏ ２を用い、さらに
緩衝剤あるいは錯化剤として酢酸アンモニウムＣ Ｈ
３Ｃ Ｏ Ｏ Ｎ Ｈ ４を入れた水溶液（酸化液）を
入れ、ポンプ等で液を装置内にノズル１および２を通し
て供給する。In addition, as shown in the figure, the parts where the ferrite plating reaction is performed, such as the base body 3 and the turntable 4, are partitioned by a case 7.
A non-oxidizing atmosphere is created by sending a non-oxidizing (eg nitrogen) gas into the case 7. Tank 5 contains an aqueous solution (reaction solution) containing at least 0.002 woe/e or less of iron ions, and tank 6 contains, for example, sodium nitrite NaN O 2 as an oxidizing agent, and a buffer or complex. Ammonium acetate C H as a oxidizing agent
An aqueous solution (oxidizing liquid) containing 3C O O N H 4 is put in, and the liquid is supplied into the apparatus through nozzles 1 and 2 using a pump or the like.
反応液にさらにＮｉイオンおよびＺｎイオンが含まれる
と得られるフェライト膜はＮｉＺｎ系フェライト膜であ
り，ＭｎイオンおよびＺｎイオンが含まれると得られる
フェライト膜はＭｎＺｎ系フェライト膜である。基体３
には、回転台４により回転した状態で各液が供給される
。回転台４は、ヒーター等により５０〜１００℃に加熱
する。このようにして、基体３上でフェライト化反応を
行わせて、基体３にフェライト膜を形成する。The ferrite film obtained when the reaction solution further contains Ni ions and Zn ions is a NiZn-based ferrite film, and the ferrite film obtained when Mn ions and Zn ions are included is an MnZn-based ferrite film. Base body 3
Each liquid is supplied in a rotated state by a rotary table 4. The rotating table 4 is heated to 50 to 100°C using a heater or the like. In this way, the ferrite reaction is carried out on the base 3 to form a ferrite film on the base 3.
第１図では、めっきに必要な液を２つに分けた場合を示
したが、３液に分ける方法でもよい。３液に分割する方
法としては、例えば１つ目の液は前述した反応液で、２
つ目の液は第１鉄イオンを酸化するための酸化剤だけを
溶解した液（酸化液〉である。３つ目の液はフェライト
生成反応時のｐＨの調整あるいは鉄以外の他の元素をフ
ェライト膜中に取り込みやすくするための緩衝剤あるい
は錯化剤として酢酸アンモニウムＣＨｚＣＯＯＮＨｎを
溶解した液〈調整液〉である。この液は、必要に応して
、アンモニア水ＮＨ４０Ｈあるいは水酸化ナトリウムＮ
ａＯＨ等のアルカリをさらに溶解してｐＨを調整しても
よい。これらのめっき液の基体３への供給方法としては
、調整液を連続的に供給した状態で、さらに反応液と酸
化液を交互に繰り返し供給する方法あるいは反応液と調
整液を供給した後、酸化液を供給することを繰り返し供
給する方法などがある。必要なことは、反応液を基体３
に供給した後、次に酸化液を基体３に供給することを繰
り返すことである。Although FIG. 1 shows the case where the liquid necessary for plating is divided into two, it may be divided into three liquids. As a method of dividing into three liquids, for example, the first liquid is the above-mentioned reaction liquid, and the second liquid is the reaction liquid described above.
The first liquid is a liquid (oxidizing liquid) in which only an oxidizing agent for oxidizing ferrous ions is dissolved.The third liquid is used to adjust the pH during the ferrite production reaction or to add other elements other than iron. This is a liquid (adjustment liquid) in which ammonium acetate CHzCOONHn is dissolved as a buffer or complexing agent to make it easier to incorporate into the ferrite film.This liquid can be mixed with aqueous ammonia NH40H or sodium hydroxide N as necessary.
The pH may be adjusted by further dissolving an alkali such as aOH. These plating solutions can be supplied to the substrate 3 by continuously supplying the adjustment solution and then alternately and repeatedly supplying the reaction solution and the oxidation solution, or after supplying the reaction solution and the adjustment solution, the oxidation solution is There is a method of repeatedly supplying the liquid. All that is required is to transfer the reaction solution to the substrate 3.
After supplying the oxidizing liquid to the substrate 3, the process is repeated.
別の方法の一例の装置の概略図を第２図に示す。ノズル
Ｉ，基体３，回転台４，タンク５および６，ケース７は
第１図のものと同様である。しかし、本方法では、第１
図に示した方法と異なり、２つに分けて準備しためっき
液を混合部８で混合し、混合しためっき液をノズル１を
介して、基体３に供給する。混合部８は、２つのノズル
から液を滴下させ、ロートで混合してｌつの口から流出
させる方法やあるいは２本の管をｌ本にしてノズル１か
ら液を出す方式など適当な方式を選択すればよい。適当
なノズル形状，構造を選択することによって、液を滴下
あるいは噴霧状等で基体３に供給することができる。A schematic diagram of an apparatus for an example of another method is shown in FIG. The nozzle I, base 3, rotary table 4, tanks 5 and 6, and case 7 are the same as those shown in FIG. However, in this method, the first
Unlike the method shown in the figure, the plating solution prepared in two parts is mixed in a mixing section 8, and the mixed plating solution is supplied to the substrate 3 through the nozzle 1. For the mixing section 8, an appropriate method can be selected, such as a method in which the liquid is dripped from two nozzles, mixed in a funnel, and then flowed out from one mouth, or a method in which two pipes are used and the liquid is discharged from the nozzle 1. do it. By selecting an appropriate nozzle shape and structure, the liquid can be supplied to the substrate 3 in the form of drops or spray.
さらに、別の方法の一例の装置の概略図を第３図に示す
。ノズルｌ，基体３，回転台４，タンク５，６，ケース
７および混合部８は第２図のものと同様である。予熱部
９が本方法の異なる部分である。つまり、本方法では、
第２図に示した方法と異なり、２つに分けた液を予熱部
９で５０℃〜溶液の沸点以下に加熱した後、混合部８で
混合し、混合しためっき液をノズル１を介して、基体３
に供給する。液を予熱だけする方式として、混合部８を
除き、例えば、予熱部９で各めっき液を予熱した後、２
つのノズルで別々にめっき液を基体３に供給してもよい
。Furthermore, a schematic diagram of an apparatus for an example of another method is shown in FIG. The nozzle 1, base 3, rotating table 4, tanks 5, 6, case 7 and mixing section 8 are the same as those shown in FIG. The preheating section 9 is the different part of the method. In other words, in this method,
Unlike the method shown in FIG. 2, the two divided solutions are heated in the preheating section 9 to 50°C to below the boiling point of the solution, then mixed in the mixing section 8, and the mixed plating solution is passed through the nozzle 1. , base 3
supply to. As a method that only preheats the solution, excluding the mixing section 8, for example, after preheating each plating solution in the preheating section 9,
The plating solution may be separately supplied to the substrate 3 using two nozzles.
前述した例は、酸化剤を用いる方法であるが、たとえば
酸化剤を用いずにケース７内に窒素と酸素の混合ガスあ
るいは空気を供給して、酸素によって酸化させてもよい
。Although the above-mentioned example is a method using an oxidizing agent, for example, a mixed gas of nitrogen and oxygen or air may be supplied into the case 7 without using an oxidizing agent to oxidize with oxygen.
別の方法の一例の装置の概略図を第４図に示す。基体３
，タンク５，６および混合部８はこれまでの方式と同様
である。めっき反応部１０およびウォーターバス１１が
本方法の異なる部分である。つまり、本方法では、これ
までに示した方法と異なり、回転台を使用せず、しかも
めっき反応部分などを気体から隔離した状態で行うこと
ができる。さらに、気体３の一部分にフェライト膜を堆
積させることができる。めっき反応部１０にはフェライ
ト膜を形成しようとする基体３が紹み込まれている。め
っき反応部１０では、物理的に基体３の表面上をめっき
液が均一に流れるようにしている。混合部８およびめっ
き反応部１０をウォーターバス１１内にセットすること
によって、５０〜１００℃に加熱する。このようにして
、めっき反応部１０にセットした基体３の表面にフェラ
イト膜を堆積させる。A schematic diagram of an apparatus for an example of another method is shown in FIG. Base body 3
, tanks 5, 6, and mixing section 8 are the same as in the previous system. The plating reaction section 10 and water bath 11 are the different parts of the method. That is, unlike the methods described above, this method does not use a rotating table and can be carried out in a state where the plating reaction area and the like are isolated from the gas. Furthermore, a ferrite film can be deposited on a portion of the gas 3. A substrate 3 on which a ferrite film is to be formed is introduced into the plating reaction section 10. In the plating reaction section 10, the plating solution is physically made to flow uniformly over the surface of the substrate 3. The mixing section 8 and the plating reaction section 10 are set in a water bath 11 and heated to 50 to 100°C. In this way, a ferrite film is deposited on the surface of the base 3 set in the plating reaction section 10.
さらに、別の方法の一例の概略図を第５図に示す。ノズ
ル１，タンク５，６および混合部８は、これまでと同様
である。回転台あるいはウォーターバスなどを用いずに
、その代わりに基体台１２を用いる。図に示すように、
基体台１２には基体３を傾斜させてセットしている。基
体３の表面上をめっき液が均一に流れるように基体３を
所定の角度に傾斜させ、内蔵したヒーターによって、５
０〜１００℃に基体３を加熱することができる。このよ
うにして、基体台１２にセットした基体３の表面にフェ
ライト膜を堆積させる。この方式では大気中，空気中で
行うこともできる。Furthermore, a schematic diagram of an example of another method is shown in FIG. The nozzle 1, tanks 5, 6, and mixing section 8 are the same as before. Instead of using a rotary table or a water bath, a base table 12 is used instead. As shown in the figure,
The base 3 is set on the base pedestal 12 in an inclined manner. The base body 3 is tilted at a predetermined angle so that the plating solution flows uniformly over the surface of the base body 3, and the built-in heater
The substrate 3 can be heated to 0-100°C. In this way, a ferrite film is deposited on the surface of the base 3 set on the base pedestal 12. This method can also be performed in the atmosphere.
以上、示した例の反応液に少なくとも鉄イオンがＯ．Ｏ
Ｏ２ｍｏｅ／ｉ！以下含んでいることによって、前記以
外の濃度の反応液を用いてフェライト膜を作製するより
フェライト膜の軟質磁気特性が向上（保磁力が低下）す
る。As mentioned above, at least iron ions were added to the reaction solution of the example shown. O
O2moe/i! By containing the following, the soft magnetic properties of the ferrite film are improved (the coercive force is reduced) compared to producing a ferrite film using a reaction solution with a concentration other than the above.
基体３の材質としては、特に限定はない。いくつか例を
あげると、ポリイミドフィルム，ポリエチレンテレフタ
レート（ＰＥＴ）などの各種プラスチック類，銅，ニッ
ケル，銀，金，タングステン，モリブデン，白金，パラ
ジウム，鉄，鉄合金などの金属類、各種の有機積層板、
つまり紙基材エボキシ，ガラス布基材エボキシ，ガラス
基材ポリエステル、ガラス布基材テトラフルオロエチレ
ン等の積層板など、各社ガラス類、セラミックスなどが
ある。The material of the base body 3 is not particularly limited. Some examples include polyimide films, various plastics such as polyethylene terephthalate (PET), metals such as copper, nickel, silver, gold, tungsten, molybdenum, platinum, palladium, iron, and iron alloys, and various organic laminated materials. board,
In other words, there are laminates made of paper-based epoxy, glass cloth-based epoxy, glass-based polyester, glass cloth-based tetrafluoroethylene, glasses of various companies, ceramics, and the like.
さらに、基体３の表面が、中心線平均あらさ（Ｒａ）で
０．０１μｍ以上であれば、膜の堆積速度の向上が図れ
る。これは、ＦｅＯＨ＋の吸着や酸化反応あるいはフェ
ライト結晶化反応に対して、プラスに働き、水溶液中で
生威した微粒子が基体表面にとらえられたり、あるいは
集まり、さらには膜成長を促進・加担すると考えられる
。また、ある程度以上の表面あらさを有していることに
よって、実質的な基体３の表面積が増加して、吸着等の
反応に携わる面積の増加も影響を与えているとも考えら
れる。Furthermore, if the surface of the substrate 3 has a center line average roughness (Ra) of 0.01 μm or more, the film deposition rate can be improved. This is thought to have a positive effect on FeOH+ adsorption, oxidation reactions, or ferrite crystallization reactions, allowing fine particles that have grown in the aqueous solution to be captured or gathered on the substrate surface, and furthermore to promote and aid film growth. It will be done. It is also considered that by having a certain level of surface roughness, the substantial surface area of the substrate 3 increases, and the increase in the area involved in reactions such as adsorption also has an effect.
実験的に、特にフェライト膜形成に対して相性がよかっ
たものが、酸素，窒素あるいは硫黄のいずれか１つ以上
を含むものあるいは特に酸化物類である。Experimentally, materials that are particularly compatible with ferrite film formation are those containing one or more of oxygen, nitrogen, or sulfur, or especially oxides.
この酸化物としては、アルミナ（Ａｅ ２０．），ムラ
イト（３Ａｅ ２０３ ・２Ｓ ｉ０２）ｒベリリア（
Ｂｅｄ），ステアタイト（ＭｇＯ−Ｓ ｉ ０２）．フ
ォルステライト（２ＭｇＯ−Ｓ ｉｏ２），マグネシア
（Ｍｇ○），チタニア（ＴｉＱ２）．チタニア＋ジルコ
ニア（ＺｒＯ２），チタニア＋マグネシア等の各種セラ
ミックス．Ａｅ２０３ ｓｉ０２・Ｂ２０３，Ａｔ！
２０３−Ｐｂｏ−Ｓ ｉ○２” Ｂ２０３，Ａｅ２０３
−ＭｇＯ ・Ｓ ｉ ０２ ・Ｂ２０３．Ａｅ ２０３
ＣａＯ−ＭｇＯ−Ｓｉ０２・Ｂ２０３などのガラスセラ
ミックス、ＣｕＯ．ＮｉＯなとの金属酸化物あるいはフ
ェライト等の鉄を含んだ酸化物などがある。Examples of this oxide include alumina (Ae 20.), mullite (3Ae 203 ・2S i02) r beryllia (
Bed), steatite (MgO-S i 02). forsterite (2MgO-S io2), magnesia (Mg○), titania (TiQ2). Various ceramics such as titania + zirconia (ZrO2) and titania + magnesia. Ae203 si02・B203, At!
203-Pbo-S i○2” B203, Ae203
-MgO ・S i 02 ・B203. Ae 203
Glass ceramics such as CaO-MgO-Si02/B203, CuO. Examples include metal oxides such as NiO, and oxides containing iron such as ferrite.
各種の薄膜磁電返還素子（磁気抵抗素子あるいはホール
素子など〉などの磁気に対する感度を向上させるために
、前記素子を形成するのに適した基板としてはそれぞれ
のデバイスに適した基体材料を選択すればよいが、基体
の表面あらさば平滑なほど、当然その表面に形成したフ
ェライト膜の表面も平滑になる。非磁性の各種の基体を
用いても、十分なソフト特性を有するフェライト膜を付
加した基板であるため、素子の磁気に対する感度が向上
し、さらにＮｉＺｎ系フェライト膜を形成すれば、高抵
抗であるという特徴をも加えて、導体を直接フェライト
膜上に形成できる。つまり、絶縁層なしにＷ１々のデバ
イスを作製することができる。In order to improve the sensitivity to magnetism of various thin film magnetoresistive elements (magnetoresistive elements, Hall elements, etc.), it is necessary to select a substrate material suitable for each device as a substrate for forming the element. However, the smoother the surface of the substrate, the smoother the surface of the ferrite film formed on that surface will naturally be.Even if various non-magnetic substrates are used, a substrate with a ferrite film added that has sufficient soft characteristics can be used. Therefore, the sensitivity of the element to magnetism is improved, and if a NiZn-based ferrite film is formed, a conductor can be formed directly on the ferrite film with the added feature of high resistance.In other words, a conductor can be formed directly on the ferrite film without an insulating layer. W1 devices can be manufactured.
次に本発明の更に具体的な実施例について説明する。Next, more specific embodiments of the present invention will be described.
（実施例１）
イオン交換水（以下単に水とする。）５ｅに塩化第１鉄
，塩化ニッケルおよび塩化亜鉛をそれぞれ第１表に示し
た量を溶解した水溶液（反応液）を作製した。さらに別
の溶液として、水５ｅに亜硝酸ナトリウムおよび酢酸ア
ンモニウムをそれぞれ第１表に示した量を溶解した水溶
液（酸化液〉を作製した。(Example 1) An aqueous solution (reaction solution) was prepared by dissolving ferrous chloride, nickel chloride, and zinc chloride in amounts shown in Table 1 in ion-exchanged water (hereinafter simply referred to as water) 5e. As another solution, an aqueous solution (oxidizing solution) was prepared by dissolving sodium nitrite and ammonium acetate in the amounts shown in Table 1 in water 5e.
これらの溶液を用いて、第３図に示すような装置でフェ
ライト膜を作製した。装置には窒素ガスを毎分１．５ｅ
で送り非酸化性雰囲気を得、回転台をヒータにより１０
０℃一定にした。回転台は毎分４００回転の速度で回転
させた。各溶液は毎分４０ｍｅの流量で噴霧状にして供
給した。基体はガラス基板である。Using these solutions, a ferrite film was produced using an apparatus as shown in FIG. The equipment is supplied with nitrogen gas at a rate of 1.5e per minute.
A non-oxidizing atmosphere was obtained by sending the rotary table with a heater.
The temperature was kept constant at 0°C. The turntable was rotated at a speed of 400 revolutions per minute. Each solution was supplied in the form of a spray at a flow rate of 40 me/min. The base is a glass substrate.
（以下
余
白
）
これらのフェライト膜の磁気特性を測定した結果を第１
表に示す。試料ｆｆｉＡの保磁力Ｈｅを１００としたと
きの比較値であり、試料ＮｃｔＤ−Ｊの保磁力は試料Ｎ
ｎＡの半分以下であり、非常にソフト性が優れている。(Left below) The results of measuring the magnetic properties of these ferrite films are shown in the first section.
Shown in the table. This is a comparison value when the coercive force He of sample ffiA is set to 100, and the coercive force of sample NctD-J is
It is less than half of nA, and has excellent softness.
つまり、本発明の方法で得たフェライト膜の保磁力は通
常これまで得られていたフェライト膜の保磁力の半分以
下であり、保磁力が非常に小さい値を示した。That is, the coercive force of the ferrite film obtained by the method of the present invention was usually less than half of the coercive force of the ferrite film obtained hitherto, and the coercive force showed a very small value.
さらに、本発明の方法で得たフェライト膜は、ビンホー
ルが少なく、ガラス基板と同等の表面あらさであった。Furthermore, the ferrite film obtained by the method of the present invention had fewer vials and a surface roughness equivalent to that of a glass substrate.
（実施例２〉
反応液および酸化液として実施例１のＦと同じ液を作製
した。この酸化液をさらにアンモニア水でｐＨ＝８に調
整した。(Example 2) The same liquid as F in Example 1 was prepared as a reaction liquid and an oxidizing liquid. This oxidizing liquid was further adjusted to pH=8 with aqueous ammonia.
これらのめっき液を用いて、第１図および第２図に示し
た装置で、フェライトめっきを行った。Ferrite plating was performed using these plating solutions in the apparatus shown in FIGS. 1 and 2.
用いた基体はアルミナ基板にガラスグレーズを施したも
のである。The substrate used was an alumina substrate coated with glass glaze.
比較のために、実施例１のＡと同じ液を作製し、同様に
めっきを行った。For comparison, the same solution as A in Example 1 was prepared and plating was performed in the same manner.
本発明の方法で得たフェライト膜と比較のために作製し
たフェライト膜の磁気特性を比較したところ、両者のＨ
ｅは実施例１の桔果とほぼ同様であり、本発明の方法で
得たフェライト膜の方が、優れたソフト磁気特性を示し
た。さらに、ビンホ−ノＬが少なく、表面も平滑であっ
た。Comparing the magnetic properties of the ferrite film obtained by the method of the present invention and the ferrite film prepared for comparison, the H
e was almost the same as that of Example 1, and the ferrite film obtained by the method of the present invention showed superior soft magnetic properties. Furthermore, there was less Vinho-no L and the surface was smooth.
（実施例３）
水５ｅに塩化第１鉄０．３ｇ．塩化マンガン１．３ｇお
よび塩化亜鉛８山をそれぞれ溶解した反応液を作製した
。さらに酸化液として、水５ｅに亜硝酸ナトリウム６０
町および酢酸アンモニウム２ｇを溶解し、さらにアンモ
ニア水でｐＨ＝９に調整した液を作製した。(Example 3) 0.3g of ferrous chloride in 5e of water. A reaction solution was prepared in which 1.3 g of manganese chloride and 8 mounds of zinc chloride were dissolved respectively. Furthermore, as an oxidizing liquid, 60% of sodium nitrite is added to 5e of water.
A solution was prepared by dissolving 2 g of ammonium acetate and adjusting the pH to 9 with aqueous ammonia.
これらのめっき液を用いて、第３図に示した装置で、フ
ェラ−ｒトめっきを行った。用いた基体はガラス基板で
ある。Using these plating solutions, ferrite plating was performed using the apparatus shown in FIG. The substrate used was a glass substrate.
比較のために、水５ｅに塩化第１鉄４ｇ，塩化マンガン
２６ｇおよび塩化亜鉛１３０ｍｇをそれぞれ溶解した反
応液を作製した。さらに酸化液として、水５ｅに亜硝酸
ナトリウム１．５ｍｇおよび酢酸アンモニウム２０ｇを
溶解し、さらにアンモニア水でｐＨ＝９に調整した液を
作製した。For comparison, a reaction solution was prepared by dissolving 4 g of ferrous chloride, 26 g of manganese chloride, and 130 mg of zinc chloride in water 5e. Further, as an oxidizing solution, 1.5 mg of sodium nitrite and 20 g of ammonium acetate were dissolved in water 5e, and the solution was further adjusted to pH=9 with aqueous ammonia.
本発明の方法で得たフェライト膜と比較のために作製し
たフェライト膜の磁気特性を比較したところ、両者のＨ
ｅは実施例１の結果とほぼ同様であり、本発明の方法で
得たフェライト膜の方が、優れたソフト磁気特性を示し
た。さらに、緻密さあるいは表面あらさも優れた膜であ
った。Comparing the magnetic properties of the ferrite film obtained by the method of the present invention and the ferrite film prepared for comparison, the H
e was almost the same as the result of Example 1, and the ferrite film obtained by the method of the present invention showed superior soft magnetic properties. Furthermore, the film had excellent density and surface roughness.
（実施例４）
実施例１のＩｔＤ，ＦおよびＨと同一のめっき液を用い
て、第４図に示した装置で、フェライトめっきを行った
。用いた基体は主としてＭｇＯ・Ｓｉ○２，Ｍｇ○，Ｂ
ｅｄ．Ａｅ ２０３−Ｓ ｉ Ｏ２・Ｂ２０３ガラスセ
ラミックス基体，石英ガラス板，ポリイミドフィルム，
ステンレス板，鋼板，ｆｌＡ張りガラス布基材エボキシ
の９種類である。(Example 4) Using the same plating solution as ItD, F, and H in Example 1, ferrite plating was performed using the apparatus shown in FIG. The substrates used were mainly MgO・Si○2, Mg○, B
ed. Ae 203-S i O2/B203 glass ceramics substrate, quartz glass plate, polyimide film,
There are 9 types: stainless steel plate, steel plate, and flA clad glass cloth base material epoxy.
比較のために、実施例１のｒｔＡと同ヒ液を用いて、同
様に各９種類の基体についてめっきを行った。For comparison, nine types of substrates were plated in the same manner using rtA of Example 1 and the same hemolymph solution.
本発明の方法で得たフェライト膜と比較のために作製し
たフェライト膜の磁気特性を比較したところ、両者のＨ
ｃは実施例１の結果とほぼ同様であり、本発明の方法
で得たフェライト膜の方が、潰れたソフト磁気特性を示
した。さらに、本発明のフェライト膜は緻密でしかも表
面あらさの小さい非常に平滑な膜であった。Comparing the magnetic properties of the ferrite film obtained by the method of the present invention and the ferrite film prepared for comparison, the H
c was almost the same as the result of Example 1, and the ferrite film obtained by the method of the present invention showed more crushed soft magnetic properties. Furthermore, the ferrite film of the present invention was dense and very smooth with small surface roughness.
（実施例５）
実施例３と同し反応液および酸化液を各５ｅ作製し、こ
れらの溶液を用いて、第５図に示した装置を使って、ア
ルミナ基板にガラスグレーズを施した基板に２時間のフ
ェライトめっきを行った。(Example 5) The same reaction solution and 5e of oxidation solution as in Example 3 were prepared, and these solutions were used to coat an alumina substrate with glass glaze using the apparatus shown in FIG. Ferrite plating was performed for 2 hours.
比較のために、実施例３の比較と同じ液を用いて、同様
にめっきを行った。For comparison, plating was performed in the same manner as in Example 3 using the same solution.
本発明の方法で得たフェライト膜と比較のために作製し
たフェライト膜の磁気特性を比較したところ、両者のＨ
ｃは実施例３の結果とほぼ同様であり、本発明の方法
で得たフェライト膜の方が、優れたソフト磁気特性を示
した。さらに、本発明のフェライト膜は緻密でしがち表
面あらさの小さい非常に平滑な膜であった。Comparing the magnetic properties of the ferrite film obtained by the method of the present invention and the ferrite film prepared for comparison, the H
c was almost the same as the result of Example 3, and the ferrite film obtained by the method of the present invention showed superior soft magnetic properties. Furthermore, the ferrite film of the present invention was dense and very smooth with little surface roughness.
（実施例６）
実施例１のＦと同じ反応液および酸化液をそれぞれ５ｅ
作製し、第３図に示した装置を用いて、実施例１と同様
にフェライトめっきを行った。基体はガラス基板を用い
、２時間のめっきを行った。［本発明品】
比較のために、焼結フェライトをラッピングして鏡面仕
上げした。［比較品１
本発明によって得たフェライト膜をつけた基板と比較の
焼結体フェライトを比較すると、ビンホール密度は比較
品の１／１万以下であり、表面あらさは中心線平均あら
さ（Ｒａ）で１ ／ １ ０以下の値であった。つまり
、本発明のフェライト基板はビンホーＪＬが非常に少な
く、しかも、表面が非常に平滑であるため、鏡面仕上げ
などまったく必要とせず、そのまま各種のデバイス形或
に用いることができる。(Example 6) The same reaction solution and oxidation solution as F in Example 1 were added to 5e each.
Ferrite plating was performed in the same manner as in Example 1 using the fabricated device shown in FIG. A glass substrate was used as the base, and plating was performed for 2 hours. [Product of the present invention] For comparison, sintered ferrite was lapped to give it a mirror finish. [Comparative product 1 Comparing the substrate with the ferrite film obtained according to the present invention and the comparative sintered ferrite, the bin hole density is less than 1/10,000 of that of the comparative product, and the surface roughness is the center line average roughness (Ra) The value was less than 1/10. In other words, since the ferrite substrate of the present invention has very little Binho JL and has a very smooth surface, it does not require any mirror finishing and can be used as it is in various device shapes.
発明の効果
本発明によって、前述したように鉄イオンを０． ０
０ ２ｍｏｅ／ｅ以下含んだ溶液を用いることによって
、前記範囲外の液を用いるより優れたソフトフェライト
としての磁気特性を示すフェライト膜を作製することが
できる。しかも、得られる膜の緻密性および平滑性は非
常に優れている。Effects of the Invention According to the present invention, as described above, iron ions can be reduced to 0. 0
By using a solution containing 0.02 moe/e or less, it is possible to produce a ferrite film that exhibits better magnetic properties as a soft ferrite than using a solution outside the above range. Furthermore, the resulting film has excellent density and smoothness.
これによって、各種電子部品等への適用に十分な磁気特
性を有するフェライト膜を得ることができる。さらに、
各種のデバイス形成に非常に有効なフェライト基板であ
る。This makes it possible to obtain a ferrite film having sufficient magnetic properties for application to various electronic components and the like. moreover,
This is a ferrite substrate that is extremely effective for forming various devices.
第１図，第２図，第３図，第４図および第５図は、本発
明のフェライト膜の形或方法の実施例に用いた装置の概
略図である。
１，２・・・・・・ノズル、３・・・・・・基体、４・
・・・・・回転台、５．６・・・・・・タンク、７・・
・・・・ケース、８・・・・・・混合部、９・・・・・
・予熱部、１０・・・・・・めっき反応部、ＩＩ・・・
・・・ウォーターバス、１２・・・・・・基体台。FIGS. 1, 2, 3, 4, and 5 are schematic diagrams of apparatuses used in embodiments of the ferrite film formation and method of the present invention. 1, 2...Nozzle, 3...Base, 4.
... Rotating table, 5.6 ... Tank, 7...
...Case, 8...Mixing section, 9...
・Preheating section, 10...Plating reaction section, II...
...Water bath, 12...Base base.
Claims (4)
を基板に接触させ、基板表面にフェライト膜を堆積させ
ることを特徴とするフェライト膜の形成方法。(1) A method for forming a ferrite film, which comprises bringing a solution containing 0.002 mol/l or less of iron ions into contact with a substrate to deposit a ferrite film on the surface of the substrate.
めの酸化剤を含んだ溶液を基体に接触させる前に混合し
た後、基体に接触させる請求項１記載のフェライト膜の
形成方法。(2) The method for forming a ferrite film according to claim 1, wherein the solution containing iron ions and the solution containing an oxidizing agent for oxidizing ferrous ions are mixed before contacting the substrate, and then contacted with the substrate.
を基体に接触させる請求項１記載のフェライト膜の形成
方法。(3) The method for forming a ferrite film according to claim 1, wherein the solution is heated to a temperature of 50° C. to below the boiling point and then brought into contact with the substrate in sequence.
イト膜を形成したフェライト基板。(4) A ferrite substrate in which a ferrite film is formed on the surface of the substrate by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15869189A JP2792115B2 (en) | 1989-06-21 | 1989-06-21 | Method of forming ferrite film and ferrite substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15869189A JP2792115B2 (en) | 1989-06-21 | 1989-06-21 | Method of forming ferrite film and ferrite substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0323226A true JPH0323226A (en) | 1991-01-31 |
| JP2792115B2 JP2792115B2 (en) | 1998-08-27 |
Family
ID=15677248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15869189A Expired - Lifetime JP2792115B2 (en) | 1989-06-21 | 1989-06-21 | Method of forming ferrite film and ferrite substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2792115B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009267288A (en) * | 2008-04-30 | 2009-11-12 | Nec Tokin Corp | Method of manufacturing ferrite film |
| JP2013203637A (en) * | 2012-03-29 | 2013-10-07 | Mitsubishi Materials Corp | Composition for forming ferrite thin film, method of forming ferrite thin film, and ferrite thin film formed by the method |
| JP2020050895A (en) * | 2018-09-25 | 2020-04-02 | 日本特殊陶業株式会社 | Method for producing composite particle |
-
1989
- 1989-06-21 JP JP15869189A patent/JP2792115B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009267288A (en) * | 2008-04-30 | 2009-11-12 | Nec Tokin Corp | Method of manufacturing ferrite film |
| JP2013203637A (en) * | 2012-03-29 | 2013-10-07 | Mitsubishi Materials Corp | Composition for forming ferrite thin film, method of forming ferrite thin film, and ferrite thin film formed by the method |
| US9228091B2 (en) | 2012-03-29 | 2016-01-05 | Mitsubishi Materials Corporation | Ferrite thin film-forming composition material, method of forming ferrite thin film, and ferrite thin film formed using the same |
| JP2020050895A (en) * | 2018-09-25 | 2020-04-02 | 日本特殊陶業株式会社 | Method for producing composite particle |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2792115B2 (en) | 1998-08-27 |
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