JPH02248328A - Formation of ferrite film - Google Patents
Formation of ferrite filmInfo
- Publication number
- JPH02248328A JPH02248328A JP1069673A JP6967389A JPH02248328A JP H02248328 A JPH02248328 A JP H02248328A JP 1069673 A JP1069673 A JP 1069673A JP 6967389 A JP6967389 A JP 6967389A JP H02248328 A JPH02248328 A JP H02248328A
- Authority
- JP
- Japan
- Prior art keywords
- ferrite film
- substrate
- ferrite
- solution
- solution containing
- 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.)
- Pending
Links
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 93
- 230000015572 biosynthetic process Effects 0.000 title claims description 4
- 239000000758 substrate Substances 0.000 claims abstract description 48
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 8
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 8
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 229910052738 indium Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- 229910052788 barium Inorganic materials 0.000 claims abstract description 7
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 52
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract description 12
- 239000011521 glass Substances 0.000 abstract description 6
- 235000010288 sodium nitrite Nutrition 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004744 fabric Substances 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229920001721 polyimide Polymers 0.000 abstract description 3
- 229910001035 Soft ferrite Inorganic materials 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000003822 epoxy resin Substances 0.000 abstract 1
- 229910052745 lead Inorganic materials 0.000 abstract 1
- 229920000647 polyepoxide Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 60
- 238000007747 plating Methods 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000002585 base Substances 0.000 description 22
- 239000007788 liquid Substances 0.000 description 19
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 235000005074 zinc chloride Nutrition 0.000 description 8
- 239000011592 zinc chloride Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- 235000019257 ammonium acetate Nutrition 0.000 description 5
- 229940043376 ammonium acetate Drugs 0.000 description 5
- 229960002089 ferrous chloride Drugs 0.000 description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 5
- -1 metal hydroxide ions Chemical class 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000011133 lead Substances 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
- 239000004071 soot Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-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
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 229940099607 manganese chloride Drugs 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
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- 239000011572 manganese Substances 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
- 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
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229930091051 Arenine Natural products 0.000 description 1
- 239000004859 Copal Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 241000782205 Guibourtia conjugata Species 0.000 description 1
- 101100404841 Leptosphaeria maculans NIIA gene Proteins 0.000 description 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- 229910003962 NiZn Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease 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
- 239000000945 filler Substances 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
- 238000000265 homogenisation Methods 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
- 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
- 229910021645 metal ion 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
- 229910052863 mullite Inorganic materials 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
- 230000001737 promoting effect 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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F10/00—Thin magnetic films, e.g. of one-domain structure
- H01F10/08—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers
- H01F10/10—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition
- H01F10/18—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being compounds
- H01F10/20—Ferrites
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ピネル型フェライト膜
の作製におけるフェライト膜の形成方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to spinel, which is widely applied to magnetic recording media, magneto-optical recording media, magnetic heads, magneto-optical elements, microwave elements, magnetostrictive elements, magnetoacoustic elements, etc. The present invention relates to a method for forming a ferrite film in the production of a type ferrite film.
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, FeOH" or other hydroxide metal ions are adsorbed onto the solid surface by contacting the solid surface with an aqueous solution, and then the adsorbed FeOH
FeOH2+ is obtained by oxidizing +, 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、この技術を基に膜の均質化９反応速度の向上等を
図ったもの（特開昭６０−１４０７１３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（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号公報）がある。Conventionally, attempts have been made to improve the film homogenization 9 reaction rate based on this technology (Japanese Unexamined Patent Publication No. 140713/1983), and to form ferrite films on various solids by imparting surface activity to the solid surface. (Japanese Unexamined Patent Publication No. 61-30674), or those related to improving the formation rate of ferrite film (Japanese Unexamined Patent Publications No. 61-179877 to 61 No. 61)
222924).
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、温度が比較的低温（水
溶液の沸点以下）でスピネル型フェライト膜を作製でき
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 is characterized in that a spinel-type ferrite film can be produced at a relatively low temperature (below the boiling point of the aqueous solution). Therefore, compared to other ferrite film manufacturing techniques, the limited range of solids is small.
発明が解決しようとする課題
しかし、前述したように、これまで膜の均質性、あるい
は膜の生成速度等に種々の改善が提案されているが、得
られる膜の磁気特性については前述した全ての方式とし
ても不十分であった。つまり、スピ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、各種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, although various improvements have been proposed in the homogeneity of the film or the production speed of the film, the magnetic properties of the resulting film cannot be improved by all of the above-mentioned methods. The method was also insufficient. In other words, sufficient magnetic properties as a spinel type ferrite, especially properties as a soft material, are not obtained. Therefore, there has been a major problem regarding its application to various electronic components and the like.
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． Ｎ１１９． １９８７ Ｐ、１１
．：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 films, see, for example, Metal Surface Technology VOL, 38. N119. 1987 P, 11
．． : As shown, it is approximately 1000e or more, and magnetite and ferrite containing Mn and Zn (MnZn type) are approximately the same size.
本発明は以上のような従来の欠点を除去し、磁気特性の
優れたフェライト膜の形成方法を提供することを目的と
するものである。An object of the present invention is to eliminate the above-mentioned conventional drawbacks and provide a method for forming a ferrite film with excellent magnetic properties.
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、第１鉄イオンを
含んだ溶液に、さらにバナジウム、インジウム、コバル
ト、銅、マグネシウム、リチウム、クロム、アルミニウ
ム、すず、鉛、チタン。Means for Solving the Problems In order to solve the problems above, the present invention provides a solution containing ferrous ions, which further contains vanadium, indium, cobalt, copper, magnesium, lithium, chromium, aluminum, tin, lead, Titanium.
イツトリウム、カルシウム、カリウム、カドミウム、サ
マリウム、ストロンチウム、セシウム、セリウム、ネオ
ジウム、パラジウム、モリブデン。Yttrium, calcium, potassium, cadmium, samarium, strontium, cesium, cerium, neodymium, palladium, molybdenum.
バリウムの１つないし２つ以上の元素を溶解し、この溶
液を基体に接触させ、基体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。This method involves dissolving one or more elements of barium, bringing this solution into contact with a substrate, and depositing a ferrite film on the surface of the substrate.
作用
前述した方法によって、つまり第１鉄イオン以外にさら
にバナジウム、インジウム、コバルト。Action: By the method described above, that is, in addition to ferrous ions, vanadium, indium, and cobalt are added.
銅、マクネシウム、リチウム、クロム、アルミニウム、
すす、鉛、チタン，イットリウム，カルシウム、カリウ
ム、カドミウム８サマリウム、ストロンチウム、セシウ
ム、セリウム、ネオジウム。Copper, magnesium, lithium, chromium, aluminum,
Soot, lead, titanium, yttrium, calcium, potassium, cadmium 8 samarium, strontium, cesium, cerium, neodymium.
パラジウム、モリブデン、バリウムの１つないし２つ以
上の元素を溶解した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、第１鉄イオン以
外の前記元素を含まない溶液を用いる方法では得られて
いなかった磁気特性（ソフト特性）の優れたフェライト
膜を形成することができる。A method using a solution that does not contain any of the above elements other than ferrous ions, by contacting a substrate with a solution in which one or more of the elements palladium, molybdenum, and barium are dissolved, and forming a ferrite film on the surface of the substrate. It is possible to form a ferrite film with excellent magnetic properties (soft properties) that could not be obtained previously.
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、第１鉄イオンを含んだ溶液に、さ
らにバナジウム、インジウム、コパル）、銅、マグネシ
ウム、リチウム、クロム、アルミニウム、すす、鉛、チ
タン，イットリウム，カルシウム、カリウム、カドミウ
ム、サマリウム。However, in the present invention, in the solution containing ferrous ions, vanadium, indium, copal), copper, magnesium, lithium, chromium, aluminum, soot, lead, titanium, yttrium, calcium, potassium, cadmium, and samarium are added.
ストロンチウム、セシウム、セリウム、ネオジウム、パ
ラジウム、モリブデン、バリウムの１つないし２つ以上
の元素を溶解させ、この溶液を基体に供給するため、非
常に小さい保磁力のフェライト膜を得ることができる。Since one or more elements of strontium, cesium, cerium, neodymium, palladium, molybdenum, and barium are dissolved and this solution is supplied to the substrate, a ferrite film with a very small coercive force can be obtained.
溶液中に第１鉄イオン以外の前記元素を同時に含めるこ
とが、得られるフェライト膜の磁気特性（ソフト特性化
）を優れたものにすることができる。これらの現象に対
する原因は明確ではない。By simultaneously including the above elements other than ferrous ions in the solution, the magnetic properties (soft properties) of the resulting ferrite film can be made excellent. The causes for these phenomena are not clear.
結果的に、第１鉄イオン以外の前記元素を含めることが
、得られるフェライト膜の磁気特性のソフト化（低い保
磁力）に何らかの効果があるのではないかと思われる。As a result, it seems that the inclusion of the above elements other than ferrous ions has some effect on softening the magnetic properties (lower coercive force) of the resulting ferrite film.
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、−例の装置の概略図を第１図に示す。For example, a schematic diagram of an example apparatus 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シ、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。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によって仕切り、非酸化
性（例えば窒素）ガスをケース内に送ることによって、
非酸化性雰囲気にする。タンク５には第１鉄イオンとさ
らにバナジウム、インジウム、コバルト、銅、マグネシ
ウム、リチウム、クロム、アルミニウム。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, to minimize variations in the properties of the obtained ferrite film, and to 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. In addition, as shown in the figure, the parts that undergo the ferrite plating reaction, such as the base 3 and the turntable 4, are partitioned by a case, and non-oxidizing gas (for example, nitrogen) is sent into the case.
Create a non-oxidizing atmosphere. Tank 5 contains ferrous ions, as well as vanadium, indium, cobalt, copper, magnesium, lithium, chromium, and aluminum.
スす、鉛、チタン，イットリウム，カルシウム。Soot, lead, titanium, yttrium, calcium.
カリウム、カドミウム、サマリウム、ストロンチウム、
セシウム、セリウム、ネオジウム、パラジウム、モリブ
デン、バリウムの１つないし２つ以上の元素を含む水溶
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ＮａＮＯ２を用い、さらに緩衝剤
として酢酸アンモニウムＣＨ３ＣＯＯＮ Ｈ４をいれた
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。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ＭｎＺ
ｎ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６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。potassium, cadmium, samarium, strontium,
Tank 6 is filled with an aqueous solution (reaction solution) containing one or more elements of cesium, cerium, neodymium, palladium, molybdenum, and barium. For example, sodium nitrite NaNO2 is used as an oxidizing agent, and a buffer is added. An aqueous solution (oxidizing liquid) containing ammonium acetate CH3COON H4 is put therein, and the liquid is supplied into the apparatus through nozzles 1 and 2 using a pump or the like. 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 contained is a MnZ-based ferrite film.
It is an n-type ferrite film. The six liquids are supplied to the base 3 while being rotated 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ｐ Ｈ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ＣＨ３ＣＯＯＮ Ｈ
＜を溶解した液（調整液）である。この液は、必要に応
じて、アンモニア水ＮＨ４０Ｈあるいは水酸化ナトリウ
ムＮａＯＨ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
す方法などがある。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 second liquid is a liquid (oxidizing liquid) in which only an oxidizing agent for oxidizing ferrous ions is dissolved. The third liquid contains ammonium acetate CH3COON H as a buffer or complexing agent to adjust the pH during the ferrite production reaction or to make it easier to incorporate other elements other than iron into the ferrite film.
This is a solution (adjusted solution) in which < is dissolved. The pH of this liquid may be adjusted by further dissolving an alkali such as aqueous ammonia NH40H or sodium hydroxide NaOH, if necessary. 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 are methods of repeatedly supplying liquid. What is required is to repeat supplying the reaction solution to the substrate 3 and then supplying the oxidizing solution to the substrate 3.
別の方法の一例の装置の概略図を第２図に示す。ノズル
１．基体３１回転台４．タンク５および６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
７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７は、２つのノズルから液を滴
下させ、ロートで混合して１つの口から流出させる方式
やあるいは２本の管を１本にしてノズルから液を出す方
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. Nozzle 1. Base body 31 rotating table 4. Tanks 5 and 6 are similar to those in FIG. However, in this method, unlike the method shown in FIG. 1, the plating solution prepared in two parts is mixed in the mixing section 7, and the mixed plating solution is supplied to the substrate 3 through the nozzle 1. For the mixing section 7, 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 combined into one and the liquid is discharged from the nozzle. Bye. 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１．基体３１回転台４．タンク５．６および混
合部７は第２図のものと同様である。予熱部８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８で５０℃
〜溶液の沸点以下に加熱した後、混合部７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７を除き、例え
ば、予熱部８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. Nozzle 1. Base body 31 rotating table 4. Tank 5.6 and mixing section 7 are similar to those in FIG. The preheating section 8 is the different part of the method. In other words, in this method, unlike the method shown in FIG.
~ After heating to below the boiling point of the solution, they are mixed in the mixing section 7, and the mixed plating solution is supplied to the substrate 3 through the nozzle 1. As a method of only preheating the solution, the mixing section 7 may be omitted, and after each plating solution is preheated in the preheating section 8, for example, the plating solution may be separately supplied to the substrate 3 using two nozzles.
磁場中でフェライト膜を形成する一例の装置の概略図を
第４図に示す。ノズル１．基体３９９回転４．タンク５
．６および混合部７は第２図のものと同様である。しか
し、本方法では、第２図に示した方法と異なり、基体３
を磁場中の条件下にするために磁石９を基体３のそばに
セットする。FIG. 4 shows a schematic diagram of an example of an apparatus for forming a ferrite film in a magnetic field. Nozzle 1. Base body 399 rotations4. tank 5
．． 6 and mixing section 7 are similar to those in FIG. However, in this method, unlike the method shown in FIG.
A magnet 9 is set near the substrate 3 in order to place the magnet 9 in a magnetic field.
これによって、フェライト膜の堆積を磁場中で行うこと
ができる。図の場合、磁界方向は基体３の面内の１方向
にほぼ平行である。フェライト膜の堆積を磁場中で行う
と磁場のないときに比べて、ソフト特性が向上する−０
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。This allows the ferrite film to be deposited in a magnetic field. In the case of the figure, the direction of the magnetic field is approximately parallel to one direction within the plane of the base 3. If the ferrite film is deposited in a magnetic field, the soft characteristics will be improved compared to when there is no magnetic field. Oxygen may be oxidized by supplying a mixed gas of and oxygen or air.
別の方法の一例の装置の概略図を第５図に示す。基体３
．タンク５．６および混合部７はこれまでの方式と同様
である。めっき反応部１０およびウォーターパス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基体から隔離した状態で行うこと
ができる。さらに、基体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が組み込まれている。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７およびめっ
き反応部１０をウォーターパス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
．． The tank 5.6 and the mixing section 7 are the same as in the previous system. The plating reaction section 10 and water path 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 substrate. Furthermore, a ferrite film can be deposited on a portion of the base body 3. A substrate 3 on which a ferrite film is to be formed is incorporated 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. By setting the mixing section 7 and the plating reaction section 10 in the water path 11, they are 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６図に示す。ノズ
ル１．タンク５．６および混合部７は、これまでと同様
である。回転台あるいはウォーターパスなどを用いずに
、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. Nozzle 1. Tank 5.6 and mixing section 7 are the same as before. Instead of using a rotary table or a water path, 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 or air.
以上、示した例の反応液に第１鉄イオン以外にさらにバ
ナジウム、インジウム、コバルト、銅。In addition to ferrous ions, vanadium, indium, cobalt, and copper were added to the reaction solution in the example shown above.
マグネシウム、リチウム、クロム、アルミニウム、すず
、鉛、チタン，イットリウム，カルシウム、カリウム、
カドミウム、サマリウム、ストロンチウム、セシウム、
セリウム、ネオジウム、パラジウム、モリブデン、バリ
ウムの１つないし２つ以上の元素を含ませることによっ
て、第１鉄イオン以外の前記元素を含まないでフェライ
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。Magnesium, lithium, chromium, aluminum, tin, lead, titanium, yttrium, calcium, potassium,
Cadmium, samarium, strontium, cesium,
By including one or more of the elements cerium, neodymium, palladium, molybdenum, and barium, the soft magnetic properties of the ferrite film are improved compared to producing a ferrite film without containing any of the above elements other than ferrous ions. (coercive force decreases).
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、
つまり紙基材エポキシ、ガラス布基材エポキシ、ガラス
基材ポリエステル、ガラス布基材テフロン等の積層板な
ど、各種ガラス類、セラミックスなどがある。The material of the base body 3 is not particularly limited. To name a few, various plastics such as polyimide film and polyethylene terephthalate (PET), metals such as copper, nickel, silver, gold, tungsten, molybdenum, platinum, palladium, iron, and iron alloys, and various organic laminated layers. board,
That is, there are various glasses, ceramics, etc., such as laminates such as paper-based epoxy, glass cloth-based epoxy, glass-based polyester, and glass cloth-based Teflon.
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
生成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粗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 reaction, or ferrite crystallization reaction, allowing fine particles generated in the aqueous solution to be captured or gathered on the substrate surface, and further promoting or contributing to film growth. . It is also considered that by having a certain level of surface roughness, the substantial surface area of the base 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（Ａ ｌ ＝Ｏ：＋）
。This oxide includes alumina (A l =O:+)
.
ムライト（３Ａ ｌ ＝ Ｏｚ・２ＳｉＯ２’）、
ベリリア（Ｂｅｄ）、 ステアタイト（ＭｇＯ−８ｉ
０２） 。Mullite (3A l = Oz・2SiO2'),
beryllia (Bed), steatite (MgO-8i
02).
フォルステライト（２ＭｇＯ・ＳｉＯ：＋）、マグネシ
ア（ＭｇＯ）、チタニア（Ｔ ｉ Ｏ２） 、チタニア
士ジルコニア（ＺｒＯ２）、チタニア＋マグネシア等の
各種セラミックス、Ａｉ’２０：＋・５ｉｎ２Ｂ２０３
．Ａｉ’２０：＋・ＰｂＯ−８ｉＯ２・Ｂ２０：ｌ。Various ceramics such as forsterite (2MgO・SiO:+), magnesia (MgO), titania (T i O2), titanium zirconia (ZrO2), titania + magnesia, Ai'20:+・5in2B203
．． Ai'20:+.PbO-8iO2.B20:l.
Ａｉ！ｚＯ：＋・ＭｇＯ・５ｉｎ２・Ｂ２０：１．ＡＪ
２０３・ＣａＯ−ＭｇＯ−３ｉＯ＝ −Ｂ２０３ な
どのガラスセラミックス、Ｃｕｂ、ＮｉＯなどの金属酸
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。Ai! zO:+・MgO・5in2・B20:1. A.J.
Examples include glass ceramics such as 203.CaO-MgO-3iO=-B203, metal oxides such as Cub and NiO, and iron-containing oxides such as ferrite.
さらに、フェライト膜を堆積させた基体に１５０℃以上
で熱処理を施すことによって、軟質磁気特性のさらに改
善が図られる。Furthermore, by subjecting the substrate on which the ferrite film is deposited to a heat treatment at 150° C. or higher, the soft magnetic properties can be further improved.
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。）２１に塩化第１鉄
５ｇ、塩化ニッケル４ｇ、塩化亜鉛１００■および元素
Ｘを表１および表２に示す量をそれぞれ溶解した水溶液
（反応液）を作製した。さらに別の溶液として、水２１
に亜硝酸ナトリウム０．５ｇおよび酢酸アンモニウム１
０ｇを溶解した水溶液（酸化液）を作製した。(Example 1) An aqueous solution in which 5 g of ferrous chloride, 4 g of nickel chloride, 100 μm of zinc chloride, and element reaction solution) was prepared. As another solution, water 21
0.5 g of sodium nitrite and 1 part of ammonium acetate
An aqueous solution (oxidizing solution) was prepared by dissolving 0 g.
これらの溶液を用いて、第１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１．５１
で送り非酸化性雰囲気を得、回転台をヒータにより９０
℃一定にした。回転台は毎分３００回転の速度で回転さ
せた。各溶液は毎分４０ｍ１の流量で噴霧状にして供給
した。基体はアルミナ基板である。Using these solutions, a ferrite film was produced using an apparatus as shown in FIG. The device is supplied with nitrogen gas at a rate of 1.51 per minute.
to obtain a non-oxidizing atmosphere, and heat the rotary table to 90°C using a heater.
The temperature was kept constant. The turntable was rotated at a speed of 300 revolutions per minute. Each solution was supplied in the form of a spray at a flow rate of 40 ml/min. The base is an alumina substrate.
（以 下 余 白）
表１
元素、添加量および磁気特性
表２
元素、添加量および磁気特性
鉄、塩化ニッケルおよび塩化亜鉛だけを溶解した液を用
いて、先に示した条件と同様に、フェライト膜をアルミ
ナ基板に形成した。［比較品］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
性を測定したところ、表１および表２の右の欄に示した
結果が得られ、本発明の方法で得たフェライト膜の方が
保磁力が非常に小さい値を示した。(Margins below) Table 1 Elements, additive amounts, and magnetic properties Table 2 Elements, additive amounts, and magnetic properties Using a solution containing only iron, nickel chloride, and zinc chloride, ferrite was prepared under the same conditions as described above. A film was formed on an alumina substrate. [Comparative product] When the magnetic properties of the ferrite film obtained by the method of the present invention and the ferrite film prepared for comparison were measured, the results shown in the right column of Tables 1 and 2 were obtained, and the results showed that the ferrite film of the present invention was The ferrite film obtained by this method showed a much smaller coercive force.
（実施例２） 水２１に塩化第１鉄５ｇ、塩化ニッケル４ｇ。(Example 2) 5 g of ferrous chloride and 4 g of nickel chloride in water 21.
塩化亜鉛９０■および実施例１と同じＮａＡから魔Ｗま
での元素Ｘの内、ＮＩＩＡとり、ＮａＥとＨおよびＮｌ
１ＮとＴの２元素を複合添加して、実施例１と同様にそ
れぞれ溶解した水溶液（反応液）を作製した。さらに別
の溶液として、水２１に亜硝酸ナトリウム０．５ｇおよ
び酢酸アンモニウム１０ｇを溶解し、さらにアンモニア
水でｐＨ＝８に調整した水溶液（酸化液）を作製した。Zinc chloride 90■ and the same elements X from NaA to W as in Example 1, NIIA, NaE, H and Nl
Two elements, 1N and T, were added in combination to prepare an aqueous solution (reaction solution) in which they were dissolved in the same manner as in Example 1. As another solution, an aqueous solution (oxidizing solution) was prepared by dissolving 0.5 g of sodium nitrite and 10 g of ammonium acetate in water 21 and adjusting the pH to 8 with aqueous ammonia.
これらのめっき液を用いて、実施例１と同様にフェライ
トめっきを行った。用いた基体はアルミナ基板である。Ferrite plating was performed in the same manner as in Example 1 using these plating solutions. The substrate used was an alumina substrate.
比較のために、前述した反応液として塩化第１鉄、塩化
ニッケルおよび塩化亜鉛だけを溶解した液を用いて、同
様にめっきを行った。For comparison, plating was performed in the same manner using a solution in which only ferrous chloride, nickel chloride, and zinc chloride were dissolved as the reaction solution described above.
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、優れたソフト磁気特性を示し
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 superior soft magnetic properties.
（実施例３） 水２１に塩化第１鉄４ｇ、塩化マンガン８ｇ。(Example 3) 4 g of ferrous chloride and 8 g of manganese chloride in water 21.
塩化亜鉛６０■および実施例１と同じＮａＡから魔Ｗま
での元素Ｘを実施例１と同様にそれぞれ溶解した水溶液
（反応液）を作製した。さらに別の溶液として、水２１
に亜硝酸ナトリウム０．５ｇおよび酢酸アンモニウム１
０ｇを溶解し、さらにアンモニア水でｐＨ＝９に調整し
た水溶液（酸化液）を作製した。Aqueous solutions (reaction liquids) were prepared in which 60 ml of zinc chloride and elements X from NaA to W were dissolved in the same manner as in Example 1. As another solution, water 21
0.5 g of sodium nitrite and 1 part of ammonium acetate
An aqueous solution (oxidizing solution) was prepared by dissolving 0 g of the oxidizing agent and adjusting the pH to 9 with aqueous ammonia.
これらのめっき液を用いて、第２図に示した装置で、フ
ェライトめっきを行った。用いた基体はアルミナ基板で
ある。Using these plating solutions, ferrite plating was performed using the apparatus shown in FIG. The substrate used was an alumina substrate.
比較のために、前述した反応液として塩化第１鉄、塩化
マンガンおよび塩化亜鉛だけを溶解した液を用いて、同
様にめっきを行った。For comparison, plating was performed in the same manner using a solution in which only ferrous chloride, manganese chloride, and zinc chloride were dissolved as the reaction solution described above.
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。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.
（実施例４）
実施例１のＮＩＩＢ、ＮおよびＷと同一のめっき液を用
いて、第３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・Ｓ ｉｏ２．ＭｇＯ
，Ｂｅｄ、Ａｌ２Ｏ３・Ｓ ｉ０２・Ｂ２Ｏ３ガラスセ
ラミックス基体１石英ガラス板。(Example 4) Ferrite plating was performed using the same plating solution as NIIB, N, and W in Example 1 using the apparatus shown in FIG. The substrate used was mainly MgO.Sio2. MgO
, Bed, Al2O3/S i02/B2O3 glass ceramic substrate 1 quartz glass plate.
ポリイミドフィルム、ステンレス板、銅板、銅張りガラ
ス布基材エポキシの９種類である。There are nine types: polyimide film, stainless steel plate, copper plate, and copper-clad glass cloth base epoxy.
比較のために、前述した反応液として填化第１鉄、塩化
ニッケルおよび塩化亜鉛だけを溶解した液を用いて、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 similarly plated using a solution in which only ferrous filler, nickel chloride, and zinc chloride were dissolved as the reaction 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、優れたソフト磁気特性を示し
ｔ二。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 is almost the same as the result of Example 1, and the ferrite film obtained by the method of the present invention exhibits superior soft magnetic properties.
（実施例５）
実施例３と同じ反応液および酸化液を各２１作製し、こ
れらの溶液を用いて、第４図に示した装置を使って、ア
ルミナ基板に１時間のフェライトめっきを行った。(Example 5) 21 each of the same reaction solution and oxidation solution as in Example 3 were prepared, and using these solutions, ferrite plating was performed on an alumina substrate for 1 hour using the apparatus shown in Fig. 4. .
比較のために、前述した反応液として墳化第１鉄、塩化
マンガンおよび塩化亜鉛だけを溶解した液を用いて、同
様にめっきを行った。For comparison, plating was performed in the same manner using a solution in which only ferrous iron, manganese chloride, and zinc chloride were dissolved as the reaction solution described above.
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。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 3, and the ferrite film obtained by the method of the present invention showed superior soft magnetic properties.
（実施例６）
実施例３と同じ反応液および酸化液をそれぞれ２Ｉ！作
製し、第５図に示した装置を用いて、フェライトめっき
を行った。基体はアルミナ基板を用い、１時間のめっき
を行った。(Example 6) The same reaction solution and oxidation solution as in Example 3 were used at 2I each! Ferrite plating was performed using the apparatus shown in FIG. An alumina substrate was used as the base, and plating was performed for 1 hour.
得られたフェライト膜は、実施例３で得られた膜と同様
の磁気特性を示した。The obtained ferrite film exhibited magnetic properties similar to those of the film obtained in Example 3.
発明の効果
本発明によって、前述したように、めっき液に第１鉄イ
オン以外にさらにバナジウム、インジウム、コバルト、
銅、マグネシウム、リチウム、クロム、アルミニウム、
すす、鉛、チタン，イットリウム，カルシウム、カリウ
ム、カドミウム、サマリウム、ストロンチウム、センウ
ム、セリウム、ネオジウム、パラジウム、モリブデン、
ノ望すウムの１つないし２つ以上の元素を混入すること
によって、第１鉄イオン以外の前記元素を含まない液を
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。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。Effects of the Invention According to the present invention, as described above, in addition to ferrous ions, vanadium, indium, cobalt,
copper, magnesium, lithium, chromium, aluminum,
Soot, lead, titanium, yttrium, calcium, potassium, cadmium, samarium, strontium, cenium, cerium, neodymium, palladium, molybdenum,
To produce a ferrite film exhibiting better magnetic properties as a soft ferrite than using a liquid containing no elements other than ferrous ions by mixing one or more of the desired elements. I can do it. This makes it possible to obtain a ferrite film having sufficient magnetic properties for application to various electronic components and the like.
第１図、第２図、第３図、第４図、第５図および第６図
は本発明のフェライト膜の形成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・・
・・・・混合部、８・・・・・・予熱部、９・・・・・
・磁石、１０・・・・・・めっき反応部、１１・・・・
・・ウォーターパス、１２・・・・・・基体台。
代理人の氏名 弁理士 粟野重孝 ほか１名第１図
第
図
第
図
偽
図
第
図
つ１−ターバスFIG. 1, FIG. 2, FIG. 3, FIG. 4, FIG. 5, and FIG. 6 are schematic diagrams of an apparatus used in an embodiment of the method for forming a ferrite film of the present invention. 1.2...Nozzle, 3...Base, 4.
... Rotating table, 5.6 ... Tank, 7...
...Mixing section, 8...Preheating section, 9...
・Magnet, 10...Plating reaction part, 11...
...Water path, 12...Base stand. Name of agent: Patent attorney Shigetaka Awano and one other person Figure 1 Figure Figure False Figure Figure 1 - Turbus
Claims (8)
インジウム，コバルト，銅，マグネシウム，リチウム，
クロム，アルミニウム，すず，鉛，チタン，イットリウ
ム，カルシウム，カリウム，カドミウム，サマリウム，
ストロンチウム，セシウム，セリウム，ネオジウム，パ
ラジウム，モリブデン，バリウムの１つないし２つ以上
の元素を溶解した溶液を基体に接触させ、基体表面にフ
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) Vanadium is added to the solution containing ferrous ions,
Indium, cobalt, copper, magnesium, lithium,
Chromium, aluminum, tin, lead, titanium, yttrium, calcium, potassium, cadmium, samarium,
A method for forming a ferrite film, the method comprising depositing a ferrite film on the surface of a substrate by contacting a solution containing one or more of the following elements: strontium, cesium, cerium, neodymium, palladium, molybdenum, and barium. .
液を第１鉄イオンを含んだ溶液と同時に基体に接触させ
、非酸化性雰囲気でフェライト膜を堆積させ、基体表面
の表面あらさが中心線平均粗さ（Ｒａ）で０．０１μｍ
以上である請求項１記載のフェライト膜の形成方法。(2) A solution containing an oxidizing agent for oxidizing ferrous ions is brought into contact with the substrate at the same time as the solution containing ferrous ions, and a ferrite film is deposited in a non-oxidizing atmosphere to improve the surface roughness of the substrate surface. The center line average roughness (Ra) is 0.01 μm
The method for forming a ferrite film according to claim 1, which is the above.
するた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。(3) The ferrite film according to claim 1, wherein the solution containing ferrous ions and the solution containing an oxidizing agent for oxidizing the ferrous ions are mixed before contacting the substrate and then contacted with the substrate. Formation method.
表面の表面あらさが中心線平均粗さ（Ｒａ）で０．０１
μｍ以上である請求項１記載のフェライト膜の形成方法
。(4) The ferrite film is deposited in an oxidizing atmosphere, and the surface roughness of the substrate surface is 0.01 in center line average roughness (Ra).
The method for forming a ferrite film according to claim 1, wherein the ferrite film has a thickness of μm or more.
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。(5) The method for forming a ferrite film according to claim 1, wherein the solution is heated to 50° C. to below the boiling point and then brought into contact with the substrate in sequence.
のフェライト膜の形成方法。(6) The method for forming a ferrite film according to claim 1, wherein the ferrite film is deposited in a magnetic field.
イト膜を堆積させた基体に１５０℃以上で熱処理を施す
請求項１記載のフェライト膜の形成方法。(7) The method for forming a ferrite film according to claim 1, wherein after depositing the ferrite film on the surface of the substrate, the substrate on which the ferrite film is deposited is subjected to heat treatment at 150° C. or higher.
、次に酸化剤を含んだ溶液を基体に接触させることを繰
り返す請求項１記載のフェライト膜の形成方法。(8) The method for forming a ferrite film according to claim 1, wherein the step of repeatedly bringing a solution containing ferrous ions into contact with the substrate and then contacting the solution containing an oxidizing agent with the substrate is repeated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1069673A JPH02248328A (en) | 1989-03-22 | 1989-03-22 | Formation of ferrite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1069673A JPH02248328A (en) | 1989-03-22 | 1989-03-22 | Formation of ferrite film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02248328A true JPH02248328A (en) | 1990-10-04 |
Family
ID=13409604
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1069673A Pending JPH02248328A (en) | 1989-03-22 | 1989-03-22 | Formation of ferrite film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02248328A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6257392B1 (en) * | 1995-02-16 | 2001-07-10 | S. Neal Graham | Vibratory bowl and associated parts orienting tooling with pivotal top confinement |
| EP1403886A2 (en) * | 2002-09-13 | 2004-03-31 | Nec Tokin Corporation | Ferrite thin film, method of manufacturing the same and electromagnetic noise suppressor using the same |
| JP2009267288A (en) * | 2008-04-30 | 2009-11-12 | Nec Tokin Corp | Method of manufacturing ferrite film |
| WO2010055597A1 (en) * | 2008-11-12 | 2010-05-20 | Ｎｅｃトーキン株式会社 | Body with magnetic film attached and manufacturing method therefor |
-
1989
- 1989-03-22 JP JP1069673A patent/JPH02248328A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6257392B1 (en) * | 1995-02-16 | 2001-07-10 | S. Neal Graham | Vibratory bowl and associated parts orienting tooling with pivotal top confinement |
| EP1403886A2 (en) * | 2002-09-13 | 2004-03-31 | Nec Tokin Corporation | Ferrite thin film, method of manufacturing the same and electromagnetic noise suppressor using the same |
| EP1403886A3 (en) * | 2002-09-13 | 2004-06-09 | Nec Tokin Corporation | Ferrite thin film, method of manufacturing the same and electromagnetic noise suppressor using the same |
| US7438946B2 (en) | 2002-09-13 | 2008-10-21 | Nec Tokin Corporation | Ferrite thin film, method of manufacturing the same and electromagnetic noise suppressor using the same |
| US7648774B2 (en) | 2002-09-13 | 2010-01-19 | Nec Tokin Corporation | Ferrite thin film, method of manufacturing the same and electromagnetic noise suppressor using the same |
| JP2009267288A (en) * | 2008-04-30 | 2009-11-12 | Nec Tokin Corp | Method of manufacturing ferrite film |
| WO2010055597A1 (en) * | 2008-11-12 | 2010-05-20 | Ｎｅｃトーキン株式会社 | Body with magnetic film attached and manufacturing method therefor |
| CN102209997A (en) * | 2008-11-12 | 2011-10-05 | Nec东金株式会社 | Body with magnetic film attached and manufacturing method therefor |
| US9991051B2 (en) | 2008-11-12 | 2018-06-05 | Tokin Corporation | Body with magnetic film attached and manufacturing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0111869B1 (en) | Process for forming a ferrite film | |
| EP0259975B1 (en) | Method for forming ferrite film | |
| US6183828B1 (en) | Plating on nonmetallic disks | |
| JPH02116631A (en) | Formation of ferrite film | |
| JPH02248328A (en) | Formation of ferrite film | |
| JP2629896B2 (en) | Method of forming ferrite film | |
| JP2841568B2 (en) | Method of forming ferrite film | |
| JPH02248329A (en) | Formation of ferrite film | |
| JP2668998B2 (en) | Method of forming ferrite film | |
| JP2792115B2 (en) | Method of forming ferrite film and ferrite substrate | |
| JPH02116627A (en) | Formation of ferrite film | |
| JP2595691B2 (en) | Method of forming ferrite film | |
| JPH02116628A (en) | Formation of ferrite film | |
| JPH0338006A (en) | Anisotropic ferrite film and forming method thereof | |
| EP0442022A2 (en) | Method of forming ferrite coatings | |
| JPH02116625A (en) | Formation of ferrite film | |
| JPH02116629A (en) | Formation of ferrite film | |
| JP2008108901A (en) | Manufacturing device and manufacturing method of ferrite thin film | |
| JPS61222924A (en) | Method for forming ferrite film | |
| JPH01246149A (en) | Formation of ferrite film | |
| JPS6196522A (en) | Manufacture of magnetic recording body | |
| JPS6181608A (en) | Preparation of powder of hexagonal ferrite particle | |
| JPS6218006A (en) | Manufacture of hexagonal ferrite particle powder | |
| JPH0456779B2 (en) | ||
| JPS60140713A (en) | Manufacture of ferrite film |