JPH02116625A - Formation of ferrite film - Google Patents
Formation of ferrite filmInfo
- Publication number
- JPH02116625A JPH02116625A JP26637188A JP26637188A JPH02116625A JP H02116625 A JPH02116625 A JP H02116625A JP 26637188 A JP26637188 A JP 26637188A JP 26637188 A JP26637188 A JP 26637188A JP H02116625 A JPH02116625 A JP H02116625A
- Authority
- JP
- Japan
- Prior art keywords
- ferrite
- substrate
- film
- solution
- ferrite film
- 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 69
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 239000000758 substrate Substances 0.000 claims abstract description 45
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 35
- 238000009835 boiling Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 230000008021 deposition Effects 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract description 6
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 229910001035 Soft ferrite Inorganic materials 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 3
- 235000010288 sodium nitrite Nutrition 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 57
- 238000007747 plating Methods 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 150000002500 ions Chemical class 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 235000019257 ammonium acetate Nutrition 0.000 description 5
- 229940043376 ammonium acetate Drugs 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229930091051 Arenine Natural products 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003962 NiZn Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 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
- 239000003570 air Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 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
- 208000014617 hemorrhoid Diseases 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 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
- 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
- 239000010453 quartz Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
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、磁気へ、ラ
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／１／型フェラ
イト膜の作製におけるフェライト１僕の形成方法に関す
るものである。[Detailed Description of the Invention] Industrial Application Field The present invention is widely applied to magnetic recording media, magneto-optical recording media, magnetism, RAD, magneto-optical elements, microwave elements, magnetostrictive elements, magneto-acoustic elements, etc. The present invention relates to a method for forming ferrite 1 in the production of a spinane/1/type ferrite film.
従来の技術
フェライトめっきとは１例えば、特開昭６９−１１１９
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
合４イオンを吸着させ。What is conventional technology ferrite plating?
As disclosed in Japanese Patent 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 4-hydroxide ions on the solid surface.
次いで、吸着したＦｅＯＨ＋ を竣化させることにより
ＦｅＯＨを得、これが水溶液中の水酸化金屑イオンとの
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。Next, FeOH is obtained by completing the adsorbed FeOH+, which causes a ferrite crystallization reaction with hydroxide scrap ions in the aqueous solution, thereby forming a ferrite film on the solid surface.
従来、この技術を基にめっき膜の均質化１反応速度の向
と等を図ったもの（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, based on this technique, the method aimed at homogenizing the plating film, improving the reaction rate, etc. (Japanese Patent Application Laid-open No. 140713/1983)
, attempts to form ferrite films on various solids by imparting surface activity to the solid surface (Japanese Patent Laid-Open No. 61-30674)
JP-A-61-179877 to JP-A-61-222924 relate to improvements in the formation rate of ferrite films.
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
５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１弗点以下）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。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. Furthermore, since the reaction is carried out through an aqueous solution, a spinel-type ferrite film can be produced at a relatively low temperature (below the temperature of the aqueous solution).
そのため、他のフェライト膜作製技術に比べて。Therefore, compared to other ferrite film fabrication techniques.
固体の限定範囲が小さい。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、これまで模の均質性あるいは
膜の生成速度等に種４の改善が提案されているが、潜ら
れる１摸の軟質磁気特性あるいは生産性に対しては、ま
だまだ不十分である。そのため、各種電子部品等への応
用・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 Type 4 improvements have been proposed in terms of pattern homogeneity or film formation speed, none of them have been able to improve the soft magnetic properties or productivity of the model. However, it is still insufficient. Therefore, there have been major issues regarding its application to various electronic components, etc.
課題を解決するだめの手段
以上の課題を解決するために本発明は、溶液中に金属イ
オンとして少な（とも第１鉄イオンを含んだ溶液を６０
′Ｃ〜沸点以下に加熱した後、順欠溶液を基体に供給し
て、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。In order to solve the problem which is more than just a means to solve the problem, the present invention aims to solve the problem by adding a solution containing a small amount of metal ions (in other words, ferrous ions) to 60% of the solution.
After heating the solution to below the boiling point, a sequential solution is supplied to the substrate to deposit a ferrite film on the surface of the substrate.
作用
前述した方法によって、つまり溶液中に金属イオンとし
て少なくとも第１鉄イオンを含んだ溶液を５０’Ｃ〜沸
点以下に加熱した後、溶液を順欠基体に供給して、基体
表面にフェライト膜を形成することによって、これまで
に潜られていない高い生産性（膜の堆積速友が大きい）
あるいは膜の均一性およびソフトフェライト膜としての
十分な軟質磁気特性（小さい保磁力あるいは高い透磁率
）を得ることができる。Function: After heating a solution containing at least ferrous ions as metal ions to 50'C to below the boiling point by the method described above, the solution is sequentially supplied to the substrate to form a ferrite film on the surface of the substrate. High productivity that has not been achieved so far (the speed of film deposition is large) by forming
Alternatively, uniformity of the film and sufficient soft magnetic properties (low coercive force or high magnetic permeability) as a soft ferrite film can be obtained.
実施例 以下１本発明の実施例について説明する。Example An embodiment 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１本発明では、金属イオンとして少なくとも第１
鉄イオンを含んだ溶液を６０℃〜溶液の沸点以下に加熱
した後、順欠溶液を基体に供給して、フェライト膜を形
成するため、これまでの方法に比べると速い堆積速度、
均一なフェライト膜あるいはソフトフェライトとしての
十分な軟質磁気特性（小さい保磁力あるいは高い透磁率
）を有する膜を得ることができる。However, in the present invention, at least the first metal ion is
After heating the solution containing iron ions to 60°C to below the boiling point of the solution, the solution is sequentially supplied to the substrate to form a ferrite film, resulting in a faster deposition rate than previous methods.
A uniform ferrite film or a film having sufficient soft magnetic properties (low coercive force or high magnetic permeability) as soft ferrite can be obtained.
基体に接触させる前に、めっき液を所定の温度内に加熱
することが、基体表面でのフェライト膜の形成反応を兄
進し、しかも基体に分布の小さい均一なフェライト膜を
形成することができる。しかも、痔られるフェライト、
寞の磁気特性は、これまでの方法では認められていない
軟質磁性材料としての十分な磁気特性を示す。これらの
現象に対する原因は明確ではない。Heating the plating solution to a predetermined temperature before contacting the substrate accelerates the ferrite film formation reaction on the substrate surface, and can form a uniform ferrite film with a small distribution on the substrate. . Moreover, the ferrite that causes hemorrhoids,
The magnetic properties of the material show sufficient magnetic properties as a soft magnetic material, which has not been recognized by conventional methods. The causes for these phenomena are not clear.
第１銖イオンを酸化させるために、酸化剤を用いる場合
でも、第１鉄イオンと酸化剤の両者を基体に供給する前
に所定の温度に加熱すればよい。Even when an oxidizing agent is used to oxidize the ferrous ions, both the ferrous ions and the oxidizing agent may be heated to a predetermined temperature before being supplied to the substrate.
つまり、めっきに必・要な液をすべて６０℃〜溶液の沸
点以下に加熱した後、ｌｌｌｉ次、溶液を基体に供給す
ればよい。That is, after all the liquids necessary for plating are heated to 60° C. to below the boiling point of the solution, the solution is then supplied to the substrate.
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。3 is a substrate on which a ferrite film is to be formed.
４は基体３を取り付けて１回転することができる回転台
である。この図の場合、基体３にめっき液を供給する時
点ではめっき液は１液であるが、得られるフェライト膜
の特性のバラツキを小さくシ。Reference numeral 4 denotes a rotating table to which the base 3 can be attached and rotate once. In the case of this figure, only one plating solution is used at the time of supplying the plating solution to the substrate 3, but variations in the properties of the resulting ferrite film are minimized.
コントロールしやすくするためには、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。For easier control, it is better to prepare the solution necessary for plating by dividing it into several parts.
この図では２分割した場合を示す。これらの液を予熱部
７で６０℃〜溶液の沸点以下に加熱した後、混合部１で
混合し、混合しためっき液をノズ／Ｌ／２を介して、基
体３に供給する。混合部１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。ノズル２の形状・
構造は適当なもの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。This figure shows a case where it is divided into two parts. These solutions are heated to 60° C. to below the boiling point of the solution in the preheating section 7, then mixed in the mixing section 1, and the mixed plating solution is supplied to the substrate 3 through the nozzle/L/2. For the mixing section 1, select an appropriate method, 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. Shape of nozzle 2
By selecting an appropriate structure, the liquid can be supplied to the substrate 3 in the form of drops or spray.
前述した混合部１は特に必要はない。例えば、予熱部７
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。６および６は、各めっ
き液を貯蔵するタンクである。The mixing section 1 described above is not particularly necessary. For example, preheating section 7
After preheating each plating solution, the plating solutions may be separately supplied to the substrate 3 using two nozzles. 6 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にょって仕切シ、場
合によっては、非酸化：生（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ことがで
きる。タンク６には、例えば酸化剤として亜硝酸す）
ＩＪウムＮＩＬＮＯ２を用い。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 the case, and in some cases, non-oxidizing: raw (e.g. nitrogen) gas is sent into the case. A non-oxidizing atmosphere can be created. Tank 6 contains, for example, nitrite as an oxidizing agent)
Using IJum NILNO2.
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、Ｃ００ＮＨ４をいれた水溶液（酸化液）を入れ、タ
ンク５に少なくとも第１秩イオンを含む水溶液（反応液
）を入れて、ポンプ等で液を予熱部７へ送り、混合部１
に供給する。反応液にさらにＮ１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
ライト膜であシ。Additionally, ammonium acetate C as a buffer or complexing agent.
Pour an aqueous solution containing H, C00NH4 (oxidizing solution) into the tank 5, put an aqueous solution (reaction solution) containing at least the first Chichi ions into the tank 5, send the solution to the preheating section 7 using a pump, etc., and mix the solution into the mixing section 1.
supply to. When the reaction solution further contains N1 ions and Zn ions, the resulting ferrite film is a NiZn-based ferrite film.
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系フェラフェライト膜。The ferrite film obtained when Mn ions and Zn ions are contained is a MnZn-based ferrite film.
基体３には１回転台４によシ回転した状態で多液が供給
される。回転台４は、ヒーターを内蔵しているため６０
〜１ｏｏ℃に加熱することができる。A large amount of liquid is supplied to the substrate 3 while being rotated by a one-turn table 4. Turntable 4 has a built-in heater, so
It can be heated to ~100°C.
このようにして、基体３上でフェライト結晶化反応を行
わせて、基本３にフェライト膜を形成する。In this manner, a ferrite crystallization reaction is performed on the base 3 to form a ferrite film on the base 3.
前述した例は、酸化剤を用いる方法であるが。The example described above is a method using an oxidizing agent.
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。For example, instead of using an oxidizing agent, a mixed gas of nitrogen and oxygen or air may be supplied into the case to cause oxidation with oxygen.
さらに、別の方法の一例の装置の概略図を第２図に示す
。混合部１．タンク５およびｅは、第１図のものと同様
である。めっき反応部８およびウォーターバス９が本方
法の異なる部分である。つまシ１本方法では、第１図に
示した方法と異なり回転台を使用せずにしかもめっき反
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
。めっき反応部８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８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１およびめっき反応部８をウォーターバス
９内にセットすることによって、混合部１にめっき液が
到達する前にめっき液を６０〜溶液の沸点以下に加熱す
ることができる。Furthermore, a schematic diagram of an apparatus for an example of another method is shown in FIG. Mixing section 1. Tanks 5 and e are similar to those in FIG. The plating reaction section 8 and the water bath 9 are the different parts of the method. Unlike the method shown in FIG. 1, the single pick method does not require the use of a rotating table and can be carried out in a state in which the plating reaction area is isolated from the gas. A substrate 3 on which a ferrite film is to be formed is incorporated in the plating reaction section 8. In the plating reaction section 8, the plating solution is physically made to flow uniformly over the surface of the substrate 3. By setting the mixing section 1 and the plating reaction section 8 in the water bath 9, the plating solution can be heated to 60°C to below the boiling point of the solution before the plating solution reaches the mixing section 1.
このようにすれば、混合部１およびめっき反応部８等も
所定の温度に保持することができる。このようにして、
１６つき反応部８にセットした基体３０表面にフェライ
ト膜を堆積させる。In this way, the mixing section 1, the plating reaction section 8, etc. can also be maintained at a predetermined temperature. In this way,
A ferrite film is deposited on the surface of the substrate 30 set in the reaction section 8 with a ferrite film.
さらに、別の方法の一例の装置の概略図を第３図に示す
。これは先に示した第２図の方法とほぼ同様であるが、
基体３の一平面のある部分だけにフェライトめっきする
のに適した方法である。それ以外は先に説明した第２図
の方法と同様である。Furthermore, a schematic diagram of an apparatus for an example of another method is shown in FIG. This is almost the same as the method shown in Figure 2 above, but
This method is suitable for ferrite plating only on a certain portion of one plane of the base body 3. Other than that, the method is the same as the method shown in FIG. 2 described above.
タンク５および６よりポンプを介して、各めっき液を混
合部１に供給し、その部分でめっき液を混合して、めっ
き反応部８へ送シ込む。めっき反応部８にはフェライト
膜を形成しようとする基体３の一部の部分が組み込まれ
ている。めっき反応部８では、第２図に示した方法と同
様に、物理的に基体３の表面上をめっき液が薄く均一に
流れるようにしている。各めっき液の供給パイプ、混合
部１、めっき反応部８および基体３をウォーターバス９
内にセットすることによって、５０〜溶液の沸点以下に
加熱する。このようにして、めっき反応部８にセットし
た基体３０表面にフェライト膜を堆積させる。Each plating solution is supplied from tanks 5 and 6 to mixing section 1 via pumps, where the plating solutions are mixed and sent to plating reaction section 8 . A part of the base 3 on which a ferrite film is to be formed is incorporated into the plating reaction section 8 . In the plating reaction section 8, the plating solution is physically made to flow thinly and uniformly over the surface of the substrate 3, similarly to the method shown in FIG. Supply pipes for each plating solution, mixing section 1, plating reaction section 8 and substrate 3 are placed in a water bath 9.
By setting the temperature within 50℃, the solution is heated to below the boiling point. In this way, a ferrite film is deposited on the surface of the base 30 set in the plating reaction section 8.
以上、示してきた３種類の方法とも２つのめっき液を加
熱した後、１液に混合して基体３に供給する方法を示し
たが、多液を分離して基体３に供給する方式でもよい。In the three methods shown above, two plating solutions are heated and then mixed into one solution and then supplied to the substrate 3. However, a method may also be used in which multiple solutions are separated and supplied to the substrate 3. .
基体の材質としては、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、ポリエチレンテンフタレ
ート（Ｐｉ！：Ｔ）などの各種フラスチック類、銅、ニ
ッケル、銀、金、タングステン。There are no particular limitations on the material of the base. To name a few: polyimide film, various plastics such as polyethylenethenephthalate (Pi!:T), copper, nickel, silver, gold, and tungsten.
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、ガラヌ
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。Metals such as molybdenum, platinum, palladium, iron, and iron alloys, various organic laminates, such as paper-based epoxy, galanic cloth-based epoxy, glass-based polyester, glass-based Teflon, etc.
各種ガラス類、セラミックスなどがある。There are various types of glass and ceramics.
さらに、基体３の表面あらさが、中心線平均粗さ（Ｒａ
）で０．０１μｍ以上であれば、膜の堆蹟速度あるいは
限界膜厚（めっき膜の厚みが厚くなると剥離する）の向
上が図れる。この堆積速度の向上は、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、特
に吸着等に対してプラスに働らき、水溶液中で生成した
微粒子が基体表面、つまりフェライト結晶化反応をして
いる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。まだ、ある程度
以上の表面粗さを有していることによって。Furthermore, the surface roughness of the base 3 is determined by the center line average roughness (Ra
) is 0.01 μm or more, it is possible to improve the deposition rate of the film or the critical film thickness (the thicker the plated film is, the more it will peel off). This increase in deposition rate has a positive effect on FeOH+ adsorption, oxidation reaction, or ferrite crystallization reaction, especially against adsorption, and the fine particles generated in the aqueous solution are transferred to the substrate surface, that is, the ferrite crystallization reaction. They are thought to be trapped or gathered on the surface of the film, and further promote or assist in film growth. By still having a certain level of surface roughness.
実質的な基体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。It is also thought that an increase in the surface area of the substrate, which increases 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（ム１２０． ）、
ムライト（３ム１２０． ＋＋ ２５ｉｏ２） 、ベリ
リア（Ｂｏｏ）。Examples of this oxide include alumina (mu120.),
Mullite (3 ml 120. ++ 25 io2), beryllia (Boo).
ステアタイト（ＭｇＯ・５ｉｎ２）、フォμステライト
（２Ｍｇｏ・５ｉｎ２）、マグネシア（ＭｇＯ）、チタ
ニア（ＴｉＯ２）、チタニア＋ジルコニア（ｚｒＯ□）
、チタニア＋マグネシア等の各岨セラミックス。Steatite (MgO・5in2), phostellite (2Mgo・5in2), magnesia (MgO), titania (TiO2), titania + zirconia (zrO□)
, titania + magnesia, and other ceramics.
ム１２ｏ、 −５ｉｏ２ ・Ｂ２０． Ｓ・ム１２０．
− ＰｂＯ拳ＳｉＯ２・Ｂ２０．．１１２０３−ＭｇＯ
−５ｉｎ２− Ｂ２０． 、 ム１２０３ＣａＯ−Ｍ
ｇＯ−５ｉｎ２− Ｂ２０． などのカラスセラミッ
クス、 （ＵＯｌＮｉＯ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。Mu12o, -5io2 ・B20. S. Mu120.
- PbO fist SiO2・B20. ．． 11203-MgO
-5in2- B20. , Mu1203CaO-M
gO-5in2- B20. There are glass ceramics such as (UOlNiO) and iron-containing oxides such as ferrite.
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。）２βに塩化第１鉄
４１．塩化マンガン６１および塩化亜鉛５０、％をそれ
ぞれ溶解した水＠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１２と酢酸アン
モニウム１０１を溶解した水溶液（腹化液）を作製した
。(Example 1) Ion exchange water (hereinafter simply referred to as water) 2β and ferrous chloride 41. A water solution (reaction solution) was prepared in which 61% manganese chloride and 50% zinc chloride were dissolved. As another solution, an aqueous solution (abdominating liquid) was prepared by dissolving 12 sodium nitrite and 101 ammonium acetate in water 21.
これらの溶液を用いて、第１図に示すような装置でフェ
ライトめっきを行った。ただし、混合部１を用いずに２
つのノズルを用いて液を別々に供給した。装置には窒素
ガスを毎分１．６４で送り込み非酸化性雰囲気を得１回
転台をヒータにより９０℃一定にした。回転台４は毎分
３００回転の速度で回転させた。各溶液はウォーターバ
スによって約８０℃に加熱した。各溶液を毎分８０−の
流量で噴霧して、基体３に供給した。めっきに用いた基
体３はアルミナ基板である。Using these solutions, ferrite plating was performed using an apparatus as shown in FIG. However, without using mixing section 1,
The liquid was supplied separately using two nozzles. Nitrogen gas was fed into the apparatus at a rate of 1.64 per minute to create a non-oxidizing atmosphere, and the rotating table was kept at a constant temperature of 90° C. using a heater. The rotating table 4 was rotated at a speed of 300 revolutions per minute. Each solution was heated to approximately 80°C by a water bath. Each solution was supplied to the substrate 3 by spraying at a flow rate of 80-min. The substrate 3 used for plating is an alumina substrate.
比較のために、第１図に示した装置の予熱部７を除いて
、２つのめつき液を責霧状にして、基体３に供給し、先
に示しだ条件と同様に、フェライトめっきを行った。For comparison, except for the preheating section 7 of the apparatus shown in FIG. went.
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・膜厚測定、微小部分の狙Ｊ文分析お
よび磁気測定をしたところ、・膜厚は本発明の形成方法
で得た。貞の方が厚く約１．６倍であり、 Ｈａの値
：は１／６であり、微小部分の＠成変化は本発明の方法
による膜では、±０．５π内であり、比較品は±８に内
であった。つまり、本発明の形成方法による・漠の方が
厚みが厚く、膜の均一性が高く、シかもソフト特性の優
れたフェライト膜である。When we conducted film thickness measurements, targeted analysis of minute portions, and magnetic measurements of the ferrite film obtained by the method of the present invention and the ferrite film prepared for comparison, we found that the film thickness was that of the ferrite film obtained by the method of the present invention. . The film made by the method of the present invention is approximately 1.6 times thicker, and the value of Ha is 1/6. It was within ±8. In other words, the ferrite film produced by the formation method of the present invention is thicker, more uniform, and has excellent soft characteristics.
（実施例２）
水２１に塩化第１鉄４ｙ、塩化ニッケ／Ｌ／４Ｆおよび
塩化亜鉛１００キ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２４に亜硝酸ナトリウム０．
６ｇと酢酸アンモニウム１ｇを溶解した液を作製した。(Example 2) A reaction solution was prepared by dissolving 4y of ferrous chloride, nickel chloride/L/4F, and 100kg of zinc chloride in 21 water. Furthermore, as an oxidizing liquid, sodium nitrite is added to 24% of water.
A solution was prepared by dissolving 6 g of ammonium acetate and 1 g of ammonium acetate.
これらの溶液を用いて、第１図に示した装置でフェライ
トめっきを行った。めっきに用いた基体３はアルミナ基
板である。Using these solutions, ferrite plating was performed using the apparatus shown in FIG. The substrate 3 used for plating is an alumina substrate.
めっき時のめっき液の加熱温度と得られた膜の厚み（μ
ｍ単位）と堆積速度を表１に示す。表１の値は、基体３
内の１４Ｘ２１！１ｆｆの部分の平均膜厚である。めっ
き液の加熱温度が５０℃以上（基体ＡＣ以降）では速い
堆積速度で、膜厚の均一なフェライト膜を得ることがで
きた。The heating temperature of the plating solution during plating and the thickness of the obtained film (μ
(in m) and deposition rate are shown in Table 1. The values in Table 1 are for substrate 3
This is the average film thickness of the 14×21!1ff portion. When the heating temperature of the plating solution was 50° C. or higher (after the substrate AC), a ferrite film with a uniform thickness could be obtained at a high deposition rate.
表１ 各基体の予熱温度と膜厚（μｍ）、堆積速度（μ
ｍ／ｗｉｎ）さらに、得られた各めっき膜の８磁気特性
を測定したところ、予熱温度５０℃以下の膜ではＢ−Ｈ
カーブの縦（Ｂ）の値が小さかった。Table 1 Preheating temperature, film thickness (μm), and deposition rate (μm) for each substrate
Furthermore, when we measured the 8 magnetic properties of each plated film obtained, it was found that the B-H
The vertical (B) value of the curve was small.
（実施例３）
水２１に塩化第１秩４２と塩化ニッケｔＶ４？および塩
化亜鉛８０ηをそれぞれ溶解し、反応液を作製した。さ
らに、水２１に酢酸アンモニウム１ｇを溶解して酸化液
を作製した。(Example 3) Water 21, Daiichi Chloride 42 and Nickel Chloride tV4? A reaction solution was prepared by dissolving 80η of zinc chloride and 80η of zinc chloride. Further, 1 g of ammonium acetate was dissolved in water 21 to prepare an oxidizing solution.
これらの溶液を用いて、実施例１と同様にフェライトめ
っきを行った。ただし、装置には空気を毎分１．６１の
量を供給し、空気中でめっきを行った。用いた基体３は
主としてＭｇＯ・５ｉｎ２． ＭｇＯ。Ferrite plating was performed in the same manner as in Example 1 using these solutions. However, air was supplied to the apparatus at a rate of 1.61 per minute, and plating was performed in air. The substrate 3 used was mainly MgO・5in2. MgO.
ＢｅＯ、ムｌ Ｏ−８ｉ、０２−Ｂ２Ｏ，ガラ７、セラ
ミックス基板、石英ガラヌ板、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。得られたフェライト膜の膜厚は９種類の基体
ともほぼ同じで約１．３μｍ（堆積速度でｏ、ｏｒｓ
ｐｙｎ／分）であυ、膜厚が均一で、十分な付着強度を
有した膜が得られた。There are nine types: BeO, Mul O-8i, 02-B2O, Gala 7, ceramic substrate, quartz galanium plate, polyimide film, stainless steel plate, copper plate, and copper-clad glass cloth base epoxy. The thickness of the obtained ferrite film was approximately the same for all nine types of substrates, approximately 1.3 μm (deposition rate: o, ors).
pyn/min), a film with a uniform thickness and sufficient adhesion strength was obtained.
比較のだめに、第１図に示した装置の加熱部７を除いて
、同様にめっきを行った。各９種類の基体についてめっ
きを行い、得られたフェライト膜と先に示した本発明の
方法によるフェライト膜とを比較評価した。For comparison, plating was performed in the same manner as in the apparatus shown in FIG. 1 except for the heating section 7. Nine types of substrates were each plated, and the obtained ferrite film was compared and evaluated with the ferrite film produced by the method of the present invention 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
ａの比は１：４〜６であり、本発明の方法で得たフェラ
イト庚の方が、Ｈａが小さかった。さらに、膜厚は本発
明の方法で得たフェライト膜の方が、厚く１．５〜２．
６倍であった。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
The ratio of a was 1:4 to 6, and the ferrite core obtained by the method of the present invention had a smaller Ha. Furthermore, the film thickness of the ferrite film obtained by the method of the present invention is 1.5 to 2.
It was 6 times more.
（実施例４）
実施例１と同じ反応液および嘴化液をそれぞれ２１作環
し、これらの溶液を用いて、第２図に示した装置を使用
して、フェライトめっきを行った。(Example 4) Twenty-one rings were each made of the same reaction solution and beaking solution as in Example 1, and these solutions were used to perform ferrite plating using the apparatus shown in FIG.
めっき時間は１時間であり、アルミナ基板を使用した。The plating time was 1 hour, and an alumina substrate was used.
得られたフェライト膜は、実施例１で得られたフェライ
ト膜と同瑳の膜厚および磁気特性を示した。The obtained ferrite film exhibited the same film thickness and magnetic properties as the ferrite film obtained in Example 1.
（実施例５）
実施例２と同じ反応液および酸化液を各２４作製し、第
３図に示した装置を用いて、フェライトめっきを行った
。１時間のめっきを行い、基体３はアルミナ基板を用い
た。(Example 5) 24 each of the same reaction solution and oxidation solution as in Example 2 were prepared, and ferrite plating was performed using the apparatus shown in FIG. Plating was performed for one hour, and an alumina substrate was used as the substrate 3.
得られたフェライト膜は、実施例２で得られた膜と同様
の膜厚および磁気特性を示した。The obtained ferrite film exhibited the same film thickness and magnetic properties as the film obtained in Example 2.
発明の効果
本発明によって、前述したように、めっき液を基体に供
給する前に所定の温変に予熱することによって、これま
でのフェライト膜の形成方法では達成されなかった高い
生産性（堆積速度）および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。Effects of the Invention As described above, the present invention enables high productivity (deposition rate ) and a ferrite film that exhibits magnetic properties as soft ferrite can be produced. by this.
各輝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。A ferrite film having magnetic properties sufficient for application to various bright electronic components can be obtained.
第１図、第２図および第３図は本発明のフェライト膜漠
の形成方法の実施例に用いた装置の概略図である。
１・・・・・・混合部、２・・・・・ノズル、３・・・
・・・基体、４・・・・・回転台、６．６・・・・・・
タンク、７・・・・・・予熱部。
８・・・・・・めっき反応部、９・・・・・・ウォータ
ーバヌ。
代理人の氏名 弁理士 粟 計重 孝 ほか１名第１図
第
図
ウォーターバス
第
図
ウォーターバスFIGS. 1, 2, and 3 are schematic diagrams of an apparatus used in an embodiment of the method for forming a ferrite film desert of the present invention. 1...Mixing section, 2...Nozzle, 3...
... Base body, 4 ... Rotating table, 6.6 ...
Tank, 7... Preheating section. 8...Plating reaction section, 9...Water vane. Name of agent: Patent attorney Takashi Awa Keishige and one other person Figure 1 Figure Water Bath Figure Water Bath
Claims (2)
だ溶液を５０℃〜沸点以下に加熱した後、順欠溶液を基
体に供給して、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) A ferrite characterized in that a solution containing at least ferrous ions as metal ions is heated to 50°C to below the boiling point, and then the sequential solution is supplied to a substrate to deposit a ferrite film on the surface of the substrate. How to form a film.
酸化剤を含んだ請求項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 further contains an oxidizing agent for oxidizing ferrous ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26637188A JPH02116625A (en) | 1988-10-21 | 1988-10-21 | Formation of ferrite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26637188A JPH02116625A (en) | 1988-10-21 | 1988-10-21 | Formation of ferrite film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02116625A true JPH02116625A (en) | 1990-05-01 |
Family
ID=17430014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26637188A Pending JPH02116625A (en) | 1988-10-21 | 1988-10-21 | Formation of ferrite film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02116625A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6130674A (en) * | 1984-07-20 | 1986-02-12 | Nippon Paint Co Ltd | Formation of ferrite film |
| JPS6342378A (en) * | 1986-08-08 | 1988-02-23 | Nippon Paint Co Ltd | Formation of ferrite film |
-
1988
- 1988-10-21 JP JP26637188A patent/JPH02116625A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6130674A (en) * | 1984-07-20 | 1986-02-12 | Nippon Paint Co Ltd | Formation of ferrite film |
| JPS6342378A (en) * | 1986-08-08 | 1988-02-23 | Nippon Paint Co Ltd | Formation of ferrite film |
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