JPH03257191A - Plating method - Google Patents
Plating methodInfo
- Publication number
- JPH03257191A JPH03257191A JP2211259A JP21125990A JPH03257191A JP H03257191 A JPH03257191 A JP H03257191A JP 2211259 A JP2211259 A JP 2211259A JP 21125990 A JP21125990 A JP 21125990A JP H03257191 A JPH03257191 A JP H03257191A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- plated
- metal
- composition ratio
- iron
- 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
- 238000007747 plating Methods 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims description 49
- 230000007423 decrease Effects 0.000 claims description 21
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 abstract description 28
- 239000000956 alloy Substances 0.000 abstract description 28
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000008021 deposition Effects 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 55
- 229910052742 iron Inorganic materials 0.000 description 29
- 239000010408 film Substances 0.000 description 26
- 238000001556 precipitation Methods 0.000 description 7
- -1 iron ion Chemical class 0.000 description 5
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910000889 permalloy Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Thin Magnetic Films (AREA)
- Magnetic Heads (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は広く言って例えばニッケルー鉄合金（Ｎｉ
−Ｆｅ ）の電気めっきに関し、特定して言えば、例え
ば磁気記録ヘッド用の８０：２ＯＮｉ −Ｆｅ磁気コア
薄膜等のような磁性膜に均一なＮｉ −Ｆｅ威酸分の合
金膜を与えるためのめっき方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] Broadly speaking, this invention is applicable to nickel-iron alloys (Ni
-Fe) electroplating, specifically, for providing a uniform Ni-Fe alloy film on a magnetic film such as an 80:2ONi-Fe magnetic core thin film for a magnetic recording head. This relates to a plating method.
磁性膜として利用されるニッケルー鉄のめっき膜は、そ
の合金組成の違いによって、磁気特性が大きく左右され
る０合金組成を左右する要占の１つとして、第１図に示
すようにめっき液のＰＨ値がある。めっき液のＰｌ（値
を上げると、合金めっき中の鉄重量組成比は上昇し、Ｐ
Ｈｉ、で鉄重量組成比は極大値Ｆｅｍａｘをもつ。The magnetic properties of the nickel-iron plating film used as a magnetic film are greatly influenced by the difference in its alloy composition. One of the key factors that influences the alloy composition is the difference in plating solution as shown in Figure 1. There is a PH value. Pl of the plating solution (as the value increases, the iron weight composition ratio in the alloy plating increases,
At Hi, the iron weight composition ratio has a maximum value Femax.
合金組成比を最も安定した状態にするためには、めっき
液のＰＨ値の変動に対する鉄重量組成比の変動が最も少
ない点、すなわち、めっき液のＰＨＭｉ２を選択すれば
良い、従って従来のめっき方法は鉄重量組成比が極大に
な・７時のめっき液ＯＰＨ値を採用していた。In order to keep the alloy composition ratio in the most stable state, it is sufficient to select the point where the iron weight composition ratio changes least with respect to fluctuations in the pH value of the plating solution, that is, the plating solution PHMi2.Therefore, the conventional plating method The plating solution OPH value at 7 was used when the iron weight composition ratio was at its maximum.
従来のめっき方法において選定されためっき液のＰＨ値
により金属のめっきを行なう場合、めっき膜の析出の経
過とともに、めっき溶液中の鉄イオン濃度が減少するた
め、めっき膜の鉄重量組成比も同じように減少していた
ので、膜厚方向の酸分均−性を得るために、めっき中に
鉄イオンをめっき溶液中に補給しなければならず、高精
度な定量ポンプを使った滴下装置を付加することが必要
で、また、その運転にかかる手間も多大であり、膜厚方
向で成分均一化が得られたかどうかの信頼性、再現性に
も問題があった。When metal plating is performed using the pH value of the plating solution selected in the conventional plating method, the iron weight composition ratio of the plating film remains the same because the iron ion concentration in the plating solution decreases as the plating film deposits. Therefore, in order to achieve acid content uniformity in the film thickness direction, iron ions had to be replenished into the plating solution during plating, and a dripping device using a high-precision metering pump was used. In addition, the operation requires a lot of effort, and there are also problems in reliability and reproducibility as to whether or not the components have been made uniform in the film thickness direction.
この発明は上記のような問題点を解消するためになされ
たもので、めっき中に被めっき金属イオン（例えば鉄イ
オン）の補給をしなくても、膜厚方向の合金成分比の均
一化を行なうことができるめっき方法を得ることを目的
とする。This invention was made to solve the above problems, and it is possible to make the alloy component ratio uniform in the film thickness direction without replenishing the metal ions to be plated (for example, iron ions) during plating. The purpose is to obtain a plating method that can be used.
この発明に係るめっき方法は、めっき時に起こるめっき
溶液中のＰＨ値の増加（△Ｉ〉による被めっき金属（例
えば鉄）の重量組成比（Ｆ−ｔ）の増加（ΔＦ、）と、
めっき時の被めっき金属イオン（鉄イオン）濃度の減少
によって起こる被めっき金属の重量組成比（Ｆ、）の減
少（△Ｆ、）とを相殺するようなＰＨ値を選定し、この
選定されたＰＨ値のめっき液により被めっき金属をめっ
きするものである。The plating method according to the present invention includes an increase (ΔF,) in the weight composition ratio (F-t) of the metal to be plated (for example, iron) due to an increase in the pH value (ΔI) in the plating solution that occurs during plating,
A pH value that offsets the decrease (△F,) in the weight composition ratio (F,) of the metal to be plated caused by a decrease in the concentration of metal ions (iron ions) to be plated during plating was selected, and this value was selected. The metal to be plated is plated using a plating solution with a pH value.
例えばＰＨ値ｉｌのめっき液でめっきを行った場合、め
っき中の被めっき金属（鉄）の重量組成比（Ｆｌ）は、
ＰＨ値の増加（Δ■）による被めっき金属の重量組成比
（Ｆｌ）の増加（△Ｆ、）と、めっき溶液中の被めっき
金属イオン（鉄イオン）１度の減少による被めっき金属
の重量組成比（Ｆｌ）の減少（ΔＦ、）とで、相殺し合
い、めっき膜の析出方向では常に均一な被めっき金属の
重量組成比（Ｆｌ）となる。For example, when plating is performed using a plating solution with a pH value of il, the weight composition ratio (Fl) of the metal to be plated (iron) during plating is:
The weight of the metal to be plated increases due to an increase in the weight composition ratio (Fl) of the metal to be plated (△F, ) due to an increase in the pH value (Δ■), and the weight of the metal to be plated due to a decrease of 1 degree of metal ions (iron ions) in the plating solution. The decrease (ΔF, ) in the composition ratio (Fl) cancels each other out, and the weight composition ratio (Fl) of the metal to be plated is always uniform in the deposition direction of the plating film.
例えば磁性膜として利用されるニッケルー鉄のめっき膜
は、その合金組成の違いによって、磁気特性が大きく左
右される合金組成を左右する要因として前述した第１図
に示すようにめっき液のＰＨ値がある。又、第２図に示
すようにめっき溶液中のＰＨ値は、めっきの経過時間に
比例して増加する。又、第４図に示すように、めっき溶
液中のＦ０イオン（被めっき金属イオン）濃度は、めっ
きの経過時間に比例して減少し、その結果合金めっき中
の鉄重量組成比も減少する。For example, in the case of nickel-iron plating films used as magnetic films, the PH value of the plating solution, as shown in Figure 1 mentioned above, is a factor that influences the alloy composition, which has a large influence on the magnetic properties due to differences in the alloy composition. be. Further, as shown in FIG. 2, the pH value in the plating solution increases in proportion to the elapsed time of plating. Further, as shown in FIG. 4, the concentration of F0 ions (metal ions to be plated) in the plating solution decreases in proportion to the elapsed time of plating, and as a result, the iron weight composition ratio in the alloy plating also decreases.
例えば第４図において、めっき時間を七分とした時の、
めっき溶液中のＦ、イオン濃度減少における合金めっき
中の鉄重量組成比減少量がΔＦ。For example, in Figure 4, when the plating time is 7 minutes,
ΔF is the decrease in iron weight composition ratio in alloy plating due to decrease in F and ion concentration in the plating solution.
であるとき、第２図においてめっき時間の七分における
ＰＨ上昇量がΔ■であったならば、第３図においてめっ
き時間の七分におけるＰＨ上昇における合金めっき中の
鉄重量組成比増加量が上記鉄重量組成比減少量ΔＦ、と
同じになる鉄重量組成比Ｆ１を選び、第１図よりその鉄
重量組成比Ｆｌｌ＋におけるＰＨ値ｉｌを選定する。If the amount of PH increase at 7 minutes of plating time is Δ■ in Figure 2, then the amount of increase in iron weight composition ratio in alloy plating due to PH increase at 7 minutes of plating time in Figure 3 is An iron weight composition ratio F1 that is the same as the iron weight composition ratio reduction amount ΔF is selected, and a PH value il at that iron weight composition ratio Fll+ is selected from FIG.
第１図において選定したＰＨ値ｉ、でめっき時間七分め
っきを行う場合、△■だけＰＨ値が上昇する。その時の
合金めっき中の鉄重量組成比の増加量ΔＦ０とＦ、イオ
ン濃度減少における合金めっき中の鉄重量組成比の減少
量ΔＦ、とが同じ量であるため、膜厚方向の合金成分比
は均一化される。When plating is performed for 7 minutes at the PH value i selected in FIG. 1, the PH value increases by Δ■. Since the amount of increase ΔF0 in the iron weight composition ratio in the alloy plating at that time and F and the decrease amount ΔF in the iron weight composition ratio in the alloy plating due to the decrease in ion concentration are the same, the alloy composition ratio in the film thickness direction is Equalized.
ここで、ニッケルー鉄合金の電気メツキにおいて、合金
めっき中の鉄重量組成比の増加量ΔＦ。Here, in electroplating of nickel-iron alloy, increase amount ΔF of iron weight composition ratio in alloy plating.
と、Ｆ、イオン濃度減少における合金めっき中の鉄重量
組成比の減少量ΔＦ、とが相殺し合うことにより、均一
なめっきが得られる合理的根拠について説明する。めっ
き中のめっき液のＰＨは微少だが上昇する。その結果、
ＰＨ依存性の強いＦ。The rational basis for obtaining uniform plating by canceling out F and the amount of decrease ΔF in the iron weight composition ratio in alloy plating due to decrease in ion concentration will be explained. The pH of the plating solution during plating increases, albeit slightly. the result,
F with strong PH dependence.
の析出速度が増大する。このときＮｉ２＋はＦ、２＋は
どのＰＨ依存性はないので、Ｎ、の析出速度は殆んど変
わらない、よってＦ％＋の補給があり、Ｆ、１＋が一定
に保たれておれば、Ｆ１組成比は増大する（上記ΔＦ、
に相当）、ところが、本発明のように、あえてＦ、２＋
の補給をしない場合にはめっきの進行と共にＦ、ｔ＋濃
度の減少が起こる。The precipitation rate increases. At this time, Ni2+ does not depend on F and 2+ has no pH dependence, so the precipitation rate of N hardly changes.Therefore, if F%+ is supplied and F,1+ is kept constant, F1 The composition ratio increases (the above ΔF,
However, as in the present invention, F, 2+
If the F and t+ concentrations are not replenished, the F and t+ concentrations will decrease as plating progresses.
例えば１１のめっき重量があり、Ｆ、析出量（ｇ） ／
１７ （１） （７）Ｆ、 ”？ＩＩｔ減少トナル。For example, there is a plating weight of 11, F, precipitation amount (g) /
17 (1) (7)F, ``?IIt decreasing tonal.
この濃度減少の結果、上記のようなＦ、！＋依存のＰＨ
依存性がなければ、Ｆ、の析出速度はＮ１のそれより落
ちる所であるが（１７Ｉｌのめっき重量の場合にΔＦ、
となる）、このＰＨ依存性があるために、＋ΔＦ、−△
Ｆ、−０となり、Ｆ１組成比は変化しない結果になる。As a result of this concentration reduction, F,!, as shown above. + dependent PH
If there were no dependence, the precipitation rate of F would be lower than that of N1 (ΔF, in the case of a plating weight of 17Il,
), and due to this PH dependence, +ΔF, -Δ
F becomes -0, resulting in no change in the F1 composition ratio.
次にめっき方法の具体例を説明する。めっき浴としては
、硫酸ニッケル、塩化ニッケル〈Ｎム”濃度、１０ｇ／
ｌ）、硫酸鉄（Ｆ、′＋濃度、 ０．２５ｇ／ｊ！以下
）、ＰＨ緩衝材としての硼酸、その他の添加剤より成る
酸性浴を用いる。めっき重量は例えば１７１とし、めっ
き温度は室温近辺の一定温度に設定する。めっき液の撹
拌強度がめつき膜の析出組成や膜厚分布等の析出状態に
与える影響は大きいので、厳密に制御する必要がある。Next, a specific example of the plating method will be explained. As a plating bath, nickel sulfate, nickel chloride (Num) concentration, 10g/
1), iron sulfate (F, '+ concentration, 0.25 g/j! or less), boric acid as a PH buffer, and other additives. The plating weight is, for example, 171, and the plating temperature is set to a constant temperature around room temperature. Since the stirring intensity of the plating solution has a large influence on the deposition state such as the deposited composition and film thickness distribution of the plated film, it is necessary to strictly control it.
ここでは被めっき物であるウェハ表面に近接して平行に
往復運動する撹拌棒を利用する。めっき電流密度は極力
低くし、５ｍＡ／−程度以下とする。Here, a stirring rod is used that moves back and forth in parallel to the surface of the wafer, which is the object to be plated. The plating current density should be as low as possible, about 5 mA/- or less.
このような条件でめっきを行なった結果のデータを第５
図に示す、第５図によれば、被めっき金属である鉄の重
量組成比Ｆ１は１７．５ （ｗ ｔ％〕、重量組成比Ｆ
□の増加量又は減少量ΔＦ、は０．１（ｗｔ％）、めっ
き時に起こるめっき溶液中のＰＨ値の増加量ΔＩは０．
０８（ＰＨ）となる。The data of the results of plating under these conditions are summarized in the fifth column.
According to FIG. 5, the weight composition ratio F1 of iron, which is the metal to be plated, is 17.5 (wt%), and the weight composition ratio F1 is 17.5 (wt%).
The amount of increase or decrease ΔF in □ is 0.1 (wt%), and the amount of increase ΔI in the PH value in the plating solution that occurs during plating is 0.
08 (PH).
次にこの実施例のめっき方法を計真機用８インチ固定デ
ィスク装置に適用した場合を説明する。Next, a case will be described in which the plating method of this embodiment is applied to an 8-inch fixed disk device for a measuring machine.
第６図は８インチ固定ディスク装置における薄膜ヘッド
の素子拡大構造図である。この薄膜ヘッドの素子は、厚
さ４ｍ＋のＡ ｌ ｚ Ｏｓ ／ Ｔｉ Ｃ（アルミナ
チタンカーバイト）の３インチウェハ１０にコア（上部
コア１２、下部コア１１）、ギャップ層１３、コイル１
４、保護膜１５などを積層して作成される。この素子中
心部にある上部コア１２と下部コア１１はパーマロイめ
っき（Ｎ、とＦ。FIG. 6 is an enlarged structural diagram of a thin film head in an 8-inch fixed disk device. The element of this thin film head consists of a 3-inch wafer 10 of AlzOs/TiC (alumina titanium carbide) with a thickness of 4m+, a core (upper core 12, lower core 11), a gap layer 13, and a coil 1.
4. It is created by laminating a protective film 15 and the like. The upper core 12 and lower core 11 in the center of this element are permalloy plated (N, F).
の合金メツキ〉でＩｉ膜されている。It is coated with an alloy plating of Ii.
この上部コア１２と下部コア１１のＦ０組組成比び膜厚
は、ヘッドの電気特性に大きく影響すると考えられてい
る。従ってヘッドの電気特性の歩留りを向上させるため
に、パーマロイめっきのＦ０組組成比び膜厚の均一化を
図るために本発明のめっき方法が採用される。It is believed that the F0 group composition ratio and film thickness of the upper core 12 and lower core 11 greatly affect the electrical characteristics of the head. Therefore, in order to improve the yield of the electrical characteristics of the head, the plating method of the present invention is adopted to make the F0 group composition and film thickness of permalloy plating uniform.
ところで、第６図の上部コア１２の膜厚方向の合金組成
比は第８図に示すようになり、第１図に示す１３ＯＰＨ
値でめっきを行なう場合、第７図に示すように上部コア
の膜厚が３．３μｍの場合ではその下側と上側のＦ０組
酸比差は１７．５０−１７．３２＝０．１８ （ｗ ｔ
％〕となる。ところが、上記実施例のめっき方法を用い
てめっきを行なうと、組成比差はほぼ０となる。By the way, the alloy composition ratio in the film thickness direction of the upper core 12 in FIG. 6 is as shown in FIG.
When plating is carried out at the same temperature, as shown in Figure 7, when the film thickness of the upper core is 3.3 μm, the difference in F0 group acid ratio between the lower and upper sides is 17.50-17.32=0.18 ( wt
%]. However, when plating is performed using the plating method of the above embodiment, the difference in composition ratio becomes almost zero.
このように上記実施例によれば、めっき析出膜の析出方
向での鉄重量組成比が均一となり、磁気特性の均一なニ
ッケルー鉄めつき膜を得ることができる。As described above, according to the above embodiment, the iron weight composition ratio in the deposition direction of the plated deposited film becomes uniform, and a nickel-iron plated film with uniform magnetic properties can be obtained.
なお、上記実施例では、ニッケルー鉄合金の電気めっき
の場合について説明したが他の同様のめっきによる磁性
膜成膜の場合であってもよく、この場合も上記実施例と
同様の効果を奏する。In the above embodiment, the electroplating of nickel-iron alloy was described, but the magnetic film may be formed by other similar plating, and in this case, the same effects as in the above embodiment can be obtained.
ここで、ニッケルー鉄合金めっき以外の例を述べておく
、この発明のめっき方法は類似の電解析出機構を有する
他の合金めっきにも十分に応用できる。上記実施例のニ
ッケルー鉄合金めっきにおけるＦ、の析出は以下のよう
に２段階に進行すると考えられている。Here, an example other than nickel-iron alloy plating will be described; the plating method of the present invention can be sufficiently applied to other alloy plating having a similar electrolytic deposition mechanism. It is believed that the precipitation of F in the nickel-iron alloy plating of the above example proceeds in two stages as follows.
（ｘｌＦ、 ” ” ２０ Ｈ−−Ｆａ （ＯＨ）ｚ
（２）Ｆｌｌ （ＯＨ：ｈ＋２Ｈ”→Ｆ＠＋２Ｈ！
○（Ｈ”は水素発生機からの水素）
このように、上記実施例のめっき方法はめっきの過程に
おいて一旦水酸化物が生成されるという考えの元で行な
われ、これが他の一般のめっき方法と異なる点である。(xlF, ” 20 H--Fa (OH)z
(2)Fll (OH:h+2H”→F@+2H!
○ (H" is hydrogen from the hydrogen generator) In this way, the plating method in the above example is performed based on the idea that hydroxide is once generated during the plating process, and this is similar to other general plating methods. This is a different point.
したがって、本めっき方法はＦ、の析出速度のＰＨ依存
性が高いわけである。Therefore, in this plating method, the precipitation rate of F is highly dependent on pH.
同様な反応により行なわれる合金めっきとして、Ｎ、−
Ｚ、合金めっきにおけるＺ、 、Ｎ、−Ｃ。As alloy plating performed by a similar reaction, N, -
Z, Z, , N, -C in alloy plating.
合金めっきにおけるＣ、 、Ｆ、−Ｚ１１合金めっきに
おける２１％などをあげることができる。これらにおい
ても、ＰＨ−析出速度の関係における上り匂配の領域で
合金組成の精密制御が可能である。Examples include C, , F in alloy plating, and 21% in -Z11 alloy plating. In these cases as well, the alloy composition can be precisely controlled in the upward slope region of the PH-precipitation rate relationship.
以上のように本発明によれば、めっき時に起こるめっき
溶液中のＰＨ値の増加による被めっき金属の重量組成比
の増加と、めっき時の被めっき金属イオン濃度の減少に
よって起こる被めっき金属の重量組成比の減少とを相殺
するようなＰＨ値を選定し、この選定されたＰＨ値のめ
っき液により被めっき金属をめっきするようにしたので
、めっき中に被めっき金属イオンの補給をしなくても、
めっき析出膜の析出方向での被めっき金属重量組成比が
均一となり、したがって膜厚方向の合金成分比の均一化
された合金膜を提供できるという効果が得られる。As described above, according to the present invention, the weight composition ratio of the metal to be plated increases due to an increase in the pH value in the plating solution that occurs during plating, and the weight of the metal to be plated occurs due to a decrease in the ion concentration of the metal to be plated during plating. A pH value that offsets the decrease in composition ratio was selected, and the metal to be plated was plated with a plating solution having this selected pH value, so there was no need to replenish metal ions during plating. too,
The weight composition ratio of the metal to be plated in the direction of deposition of the plating deposit becomes uniform, and therefore an alloy film having a uniform alloy component ratio in the film thickness direction can be provided.
第１図はＰＨ値に対する鉄重量酸比比の変化を表わした
図、第２図はめっきの経過時間に対するＰＨの変化を表
わした図、第３図はめっきの経過時間に対するＰＨ上昇
における合金めっき中の鉄重量酸比比の変化を表わした
図、第４図はめっきの経過時間に対するＦ、イオン濃度
減少における合金めっき中の鉄重量組成比の変化を表わ
した図、第５図は上部コアめっきにおいてＰＨとＦ１組
成である。
Ｆ、・・・鉄重量組戒比（被めっき金属の重量組成比〉
、ΔＦ、・・・鉄重量組戒比減少量又は鉄重量組成比増
加量、△■・・・ＰＨ上昇量、１１・・・下部コア、１
２・・・上部コア、１３・・・ギャップ層、１４・・・
コイル、１５・・・保護膜。Figure 1 is a diagram showing the change in the iron weight/acid ratio with respect to the PH value, Figure 2 is a diagram showing the change in PH with respect to the elapsed time of plating, and Figure 3 is a diagram showing the change in PH with respect to the elapsed time of plating during alloy plating. Fig. 4 shows the change in the iron weight composition ratio in alloy plating as the F and ion concentration decreases with respect to the elapsed plating time. PH and F1 composition. F,... Iron weight composition ratio (weight composition ratio of metal to be plated)
, ΔF, ... amount of decrease in iron weight composition ratio or amount of increase in iron weight composition ratio, △■ ... amount of increase in PH, 11 ... lower core, 1
2... Upper core, 13... Gap layer, 14...
Coil, 15...protective film.
Claims (1)
き金属をめっきするためのめっき方法において、めっき
時に起こるめっき溶液中のＰＨ値の増加による被めっき
金属の重量組成比の増加と、めっき時の被めっき金属イ
オン濃度の減少によって起こる被めっき金属の重量組成
比の減少とを相殺するようなＰＨ値を選定し、この選定
されたＰＨ値のめっき液により被めっき金属をめっきす
ることを特徴とするめっき方法。In a plating method for plating a metal to be plated so that the component ratio of the plated part is uniform, an increase in the weight composition ratio of the metal to be plated due to an increase in the pH value in the plating solution that occurs during plating, and Select a pH value that offsets the decrease in the weight composition ratio of the metal to be plated caused by a decrease in the concentration of metal ions to be plated, and plate the metal to be plated with a plating solution having this selected pH value. Characteristic plating method.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP91100754A EP0440071B1 (en) | 1990-01-23 | 1991-01-22 | Plating process |
| DE69121597T DE69121597T2 (en) | 1990-01-23 | 1991-01-22 | Plating process |
| US07/644,824 US5182009A (en) | 1990-01-23 | 1991-01-23 | Plating process |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-13080 | 1990-01-23 | ||
| JP1308090 | 1990-01-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03257191A true JPH03257191A (en) | 1991-11-15 |
Family
ID=11823190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2211259A Pending JPH03257191A (en) | 1990-01-23 | 1990-08-08 | Plating method |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH03257191A (en) |
| KR (1) | KR930009993B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5650899B2 (en) * | 2009-09-08 | 2015-01-07 | 上村工業株式会社 | Electroplating equipment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5582793A (en) * | 1978-12-18 | 1980-06-21 | Ibm | Nickelliron plating method |
| JPS61159594A (en) * | 1985-01-07 | 1986-07-19 | Hitachi Ltd | Plating solution for forming nickel-iron film containing boron |
-
1990
- 1990-08-08 JP JP2211259A patent/JPH03257191A/en active Pending
-
1991
- 1991-01-21 KR KR1019910000942A patent/KR930009993B1/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5582793A (en) * | 1978-12-18 | 1980-06-21 | Ibm | Nickelliron plating method |
| JPS61159594A (en) * | 1985-01-07 | 1986-07-19 | Hitachi Ltd | Plating solution for forming nickel-iron film containing boron |
Also Published As
| Publication number | Publication date |
|---|---|
| KR930009993B1 (en) | 1993-10-13 |
| KR910021498A (en) | 1991-12-20 |
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