JPH0689476B2 - Microelectrode manufacturing method - Google Patents
Microelectrode manufacturing methodInfo
- Publication number
- JPH0689476B2 JPH0689476B2 JP62229711A JP22971187A JPH0689476B2 JP H0689476 B2 JPH0689476 B2 JP H0689476B2 JP 62229711 A JP62229711 A JP 62229711A JP 22971187 A JP22971187 A JP 22971187A JP H0689476 B2 JPH0689476 B2 JP H0689476B2
- Authority
- JP
- Japan
- Prior art keywords
- tip
- microelectrode
- curvature
- radius
- present
- 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.)
- Expired - Lifetime
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- Measuring Leads Or Probes (AREA)
- Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、筋肉活動電流測定用微小電極や、STM（Scann
ing Tunneling Microscope;走査型トンネル顕微鏡）の
探針などの微小電極、さらに詳しくは、電解研摩、切
削、塑性加工等により形成した微小電極よりもさらに微
細な先端径をもつ微小電極の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a microelectrode for measuring muscle activity current, an STM (Scann).
ing Tunneling Microscope; a microelectrode such as a probe of a scanning tunneling microscope, more specifically, a method for producing a microelectrode having a tip diameter smaller than that of a microelectrode formed by electrolytic polishing, cutting, plastic working or the like.
［開示の概要］ 本明細書および図面は、先鋭な導電性基体表面上に更に
電解めっきを施すことで、筋肉活動電流の測定や、STM
の探針などに適した微小電極を提供する技術を開示する
ものである。[Summary of Disclosure] This specification and the drawings show that a muscle conductive current is measured or STM is measured by further performing electrolytic plating on a sharp conductive substrate surface.
Disclosed is a technique for providing a microelectrode suitable for such a probe.
［従来の技術］ 人体などの筋肉の微小電流を測定するには、人体の単細
胞の大きさが約２μｍであるため、電極先端部の曲率半
径は１μｍ以下が要求される。また、STMの探針におい
ては、電極先端に１原子があることが理想であり、先端
部曲率半径は原子レベルの曲率半径をもつことが必要と
なってくる。これは、先端部曲率半径が小さいほど面内
分解能が向上するからである。このような微細先端部を
もつ電極の作製には、切削、塑性加工および電解研摩が
考えられている。その中で、例えば切削については時計
旋盤を用いて繊維状結晶の線材を切削し、５〜10μｍの
先端曲率半径が可能である。[Prior Art] In order to measure a minute current of a muscle such as a human body, since the size of a single cell of the human body is about 2 μm, the radius of curvature of the electrode tip is required to be 1 μm or less. Further, in the STM probe, it is ideal that there is one atom at the electrode tip, and it is necessary that the tip radius of curvature has an atomic level radius of curvature. This is because the in-plane resolution improves as the radius of curvature of the tip portion decreases. Cutting, plastic working, and electrolytic polishing have been considered for the production of electrodes having such fine tips. Among them, for cutting, for example, a fibrous crystal wire is cut by using a clock lathe, and a tip radius of curvature of 5 to 10 μm is possible.
電解研摩法については、例えば電解研摩液（シアン化ナ
トリウム10g、黄血塩10g、水100gの混合液）中に、直径
0.28mmの銀線を真直に矯正したものを入れ、銀線を陽
極、対向電極を陰極として、その極間に2.5〜3.0Vの直
流電圧を与える。すると電解研摩液中に浸されている銀
線は研摩されていき、やがて銀線の最大剪断応力と液中
部分の銀線重量の関係から、数分後に切断され微小電極
が形成される。For the electrolytic polishing method, for example, in an electrolytic polishing liquid (sodium cyanide 10 g, yellow blood salt 10 g, water 100 g),
Insert a straightened 0.28 mm silver wire, use the silver wire as the anode and the counter electrode as the cathode, and apply a DC voltage of 2.5 to 3.0 V between the electrodes. Then, the silver wire immersed in the electrolytic polishing solution is polished, and due to the relation between the maximum shear stress of the silver wire and the weight of the silver wire in the solution, the silver wire is cut after a few minutes to form a microelectrode.
このような電解研摩法による銀製微小電極の製作におい
ては、先端半径２μｍ以下のものが得られている。〔マ
イクロ加工技術（マイクロ加工技術編集委員会、第343
〜345頁）〕。In the production of silver microelectrodes by such an electrolytic polishing method, a tip radius of 2 μm or less has been obtained. [Micro Processing Technology (Micro Processing Technology Editorial Committee, No. 343
~ 345)]].
しかしながら、上記切削、塑性、電解研摩により従来例
では、原子レベルの先端径への適用には限度がある。However, due to the cutting, plasticity, and electrolytic polishing, there is a limit to the application to the tip diameter at the atomic level in the conventional example.
［本発明が解決しようとする問題点］ 本発明は以上の問題点に鑑みなされたもので、先端の曲
率半径が小さく、人体の筋肉活動電流測定や、STMの探
針に適した微小電極を提供することを目的としている。[Problems to be Solved by the Present Invention] The present invention has been made in view of the above problems, and a microelectrode suitable for measuring a muscle activity current of a human body and a probe for STM with a small radius of curvature at the tip. It is intended to be provided.
［問題点を解決するための手段］ 本発明は、先端が十数μｍ以下の曲率をもった円錐形状
を有する導電性基材表面上に電解めっき法により金属原
子を析出させることを特徴とする微小電極の製造方法で
ある。[Means for Solving Problems] The present invention is characterized in that metal atoms are deposited by electrolytic plating on the surface of a conductive base material having a conical shape with a tip having a curvature of a dozen μm or less. It is a manufacturing method of a microelectrode.
さらには、上記の電解めっき法が、パルス電圧、好まし
くは極性の異なる交番するパルス電圧を加える電解めっ
き法であることを特徴とする微小電極の製造方法であ
る。Furthermore, the above-mentioned electroplating method is a method for producing microelectrodes, which is an electroplating method in which a pulse voltage, preferably an alternating pulse voltage having different polarities is applied.
［作用］ 本発明の作用を第１図を用いて説明する。[Operation] The operation of the present invention will be described with reference to FIG.
第１図（ａ）において、１は金属の導電体であり、この
先端２は、ある曲率半径ρ1をもった円錐形状をしてい
る。この導電体１の表面に、電解めっき法により電析物
を生成させる。すると第１図（ｂ）に示すように、この
導電体１の先端部４には、ある曲率半径ρ2をもって電
析物３が析出する。ここでρ1が十数μｍ〜数μｍ以下
であると、ρ1とρ2を比較するとρ1＞ρ2という先端曲
率半径の関係をもつ微小電極を得られることとなる。In FIG. 1 (a), 1 is a metal conductor, and its tip 2 has a conical shape with a certain radius of curvature ρ 1 . An electrodeposit is formed on the surface of the conductor 1 by electrolytic plating. Then, as shown in FIG. 1 (b), the electrodeposit 3 is deposited on the tip 4 of the conductor 1 with a certain radius of curvature ρ 2 . Here, when ρ 1 is in the range of ten and several μm to several μm or less, when ρ 1 and ρ 2 are compared, it is possible to obtain a microelectrode having a relationship of the tip curvature radius of ρ 1 > ρ 2 .
［実施例］ 次に本発明を実施例に基づいて説明する。EXAMPLES Next, the present invention will be described based on examples.
第３図は本発明に用いられる電解めっき装置の模式図で
ある。ここで、11は陽極で、電析物となるタングステ
ン、白金、プラチナ等を用いる。この陽極11の形状は板
状、球状等でも実施可能であるが、点電極であることが
より好ましい。従って、陽極11には先端の曲率半径を数
μｍ程度に加工したものを用いる。12は陰極、即ち被加
工微小電極である。この被加工微小電極は、先端の曲率
半径が１μｍ程度になるように前加工する必要がある。
本発明が適用できる被加工微小電極の材質としては導電
性があれば限定されないが、タングステン、白金、プラ
チナ、等の微小電極に顕著な効果が得られる。13は電解
浴で、例えば亜硫酸金水溶液等が好ましい。14は直流電
源装置である。FIG. 3 is a schematic diagram of an electrolytic plating apparatus used in the present invention. Here, 11 is an anode, and tungsten, platinum, platinum or the like to be an electrodeposit is used. The shape of the anode 11 can be a plate, a sphere, or the like, but a point electrode is more preferable. Therefore, for the anode 11, a tip having a radius of curvature of several μm is used. Reference numeral 12 is a cathode, that is, a microelectrode to be processed. The microelectrode to be processed needs to be preprocessed so that the radius of curvature of the tip is about 1 μm.
The material of the microelectrode to be processed to which the present invention is applicable is not limited as long as it has conductivity, but a remarkable effect can be obtained for microelectrodes such as tungsten, platinum, and platinum. 13 is an electrolytic bath, for example, an aqueous solution of gold sulfite is preferable. 14 is a DC power supply device.
ここで、陽極11と陰極12は液面と水平で、さらに両者が
陽極の中心線上におかれ、先端が向かい合う形で設置さ
れるのが好ましい。Here, it is preferable that the anode 11 and the cathode 12 are horizontal with respect to the liquid surface, and both are placed on the center line of the anode so that the tips thereof face each other.
このような構成で陽極11と陰極12に電流を流すと、陽極
11の金属イオン化して電解浴13中にとけ出し、陰極12の
表面に電析していく。When current is applied to the anode 11 and the cathode 12 with such a configuration, the anode
The metal ions of 11 are melted out and dissolved in the electrolytic bath 13, and electrodeposited on the surface of the cathode 12.
電極に印加する電力については第４図（ａ）〜（ｃ）に
示すような直流が用いられるが、この中で特に、第４図
（ｂ）または（ｃ）に示すようなパルス電圧を印加する
のがより好ましい。さらに好ましくは、（ｃ）に示す極
性の異なるパルス電圧を印加するのがよい。As the electric power applied to the electrodes, a direct current as shown in FIGS. 4 (a) to 4 (c) is used. Among them, a pulse voltage as shown in FIG. 4 (b) or (c) is applied. More preferably. More preferably, pulse voltages having different polarities shown in (c) should be applied.
実施前の陰極12の先端の様子を第２図（ａ）に示す。５
は金属のワイヤーであり、前加工によって先端部６は１
μｍ程度の曲率半径を有している。この金属ワイヤー６
の先端部には、本発明の実施の結果、第２図（ｂ）に示
すような状態となる。ここで７は本発明の実施の結果析
出した電析物であり、その先端部８は第２図（ａ）の先
端６の曲率半径よりも小さな曲率半径を持つに至る。The state of the tip of the cathode 12 before execution is shown in FIG. 5
Is a metal wire, and the tip 6 is 1 by pre-processing.
It has a radius of curvature of about μm. This metal wire 6
As a result of the practice of the present invention, the tip portion of is in a state as shown in FIG. 2 (b). Here, 7 is an electrodeposit deposited as a result of the practice of the present invention, and its tip portion 8 has a radius of curvature smaller than the radius of curvature of the tip 6 in FIG. 2 (a).
実施例１ 本実施例は、電解研摩法によって得られたタングステン
ワイヤーの微小電極に本発明を適用した例である。本実
施例に用いた電解めっき装置は、基本的には第３図に示
したものと同一である。ここで、陰極12の被加工微小電
極には、0.5φのタングステンワイヤーを電解研摩法に
より先端曲率半径を0.1μｍ程度としたものを、陽極11
には白金の点電極を用いた。電解浴13としては亜硫酸金
水溶液を用い、温度は55℃、pH3.7であった。電極には
第４図（ｃ）に示すような電圧波形をもった50V、デュ
ーティー比60％、オフセットプラスマイナス50％のパル
ス電圧を印加した。通電時間は約３分である。通電の
間、マグネティックスターラーで電解浴を攪拌した。Example 1 This example is an example in which the present invention is applied to a microelectrode of a tungsten wire obtained by electrolytic polishing. The electroplating apparatus used in this example is basically the same as that shown in FIG. Here, as the microelectrode to be processed of the cathode 12, a 0.5φ tungsten wire having a tip curvature radius of about 0.1 μm formed by electrolytic polishing is used as the anode 11.
A platinum point electrode was used for this. An aqueous gold sulfite solution was used as the electrolytic bath 13, and the temperature was 55 ° C. and the pH was 3.7. A pulse voltage of 50 V having a voltage waveform as shown in FIG. 4 (c), a duty ratio of 60% and an offset of ± 50% was applied to the electrodes. The energization time is about 3 minutes. While energizing, the electrolytic bath was stirred with a magnetic stirrer.
この結果得られた陰極12の先端部は、曲率半径が0.05μ
ｍとなり、電解研摩法よりもさらに50％程度微小な微小
電極を短時間のうちに得ることができた。The tip of the cathode 12 obtained as a result has a radius of curvature of 0.05 μm.
m, and it was possible to obtain a microelectrode which is about 50% smaller than that of the electrolytic polishing method in a short time.
さらに実験条件を適宜選択し実施することにより、最小
で0.01μｍ程度の先端部曲率半径をもった微小電極の製
造が可能であった。Furthermore, it was possible to manufacture a microelectrode having a tip radius of curvature of at least about 0.01 μm by appropriately selecting the experimental conditions and carrying out the experiment.
実施例２ 本実施例は、グラインダーを用いた機械研摩により得ら
れたタングステン、銀ワイヤー微小電極に本発明を適用
した例である。Example 2 This example is an example in which the present invention is applied to tungsten and silver wire microelectrodes obtained by mechanical polishing using a grinder.
陰極12にグラインダーを用いて機械研摩したタングステ
ンおよび銀ワイヤーを用いた以外は、電解装置および条
件は実施例１と同様に行った。The electrolysis apparatus and conditions were the same as in Example 1 except that tungsten and silver wires that were mechanically polished using a grinder were used for the cathode 12.
実施前と実施後の陰極12の先端形状を顕微鏡観察した模
式図を第５図（ａ）および（ｂ）に示す。第５図（ｂ）
に示すように、ワイヤー51の先端部の凸凹の電析物の白
金52が析出して、先端形状がなめらかとなった。即ち本
発明を用いることにより、従来、機械研摩のみでは先端
形状凸凹であった微小電極の表面をなめらかにすること
が可能となった。Schematic views of the tip shape of the cathode 12 before and after the observation under a microscope are shown in FIGS. 5 (a) and 5 (b). Fig. 5 (b)
As shown in (1), platinum 52, which is an electrodeposited material having irregularities on the tip of the wire 51, was deposited, and the tip shape was smooth. That is, by using the present invention, it has become possible to smooth the surface of the microelectrode, which has been uneven in the shape of the tip in the past only by mechanical polishing.
［発明の効果］ 以上説明したように、本発明によれば、従来の微小電極
の製造方法に比較して、さらに先端の曲率半径の小さ
な、またなめらかな先端部をもつ微小電極を得ることが
できる。また、本発明の微小電極は、生物細胞などの微
小領域の電流測定や、STMの探針などに極めて有用であ
ると言える。[Effects of the Invention] As described above, according to the present invention, it is possible to obtain a microelectrode having a tip with a smaller radius of curvature and a smooth tip as compared with the conventional method for producing a microelectrode. it can. Further, it can be said that the microelectrode of the present invention is extremely useful for current measurement in a micro area such as a biological cell, STM probe, and the like.
第１図（ａ）および（ｂ）は本発明の作用の説明図、第
２図（ａ）および（ｂ）は本発明の一実施例図、第３図
は本発明の実施例に用いた電解めっき装置の模式図、第
４図は実施例で印加した電圧波形図、第５図は本発明の
一実施例図である。 １…金属の導電体、2,6…先端部、 3,7,52…電析物、 4,8…電析物の先端部、 5,51…ワイヤー、11…陽極、 12…陰極、13…電解浴、 14…電源装置。1 (a) and 1 (b) are explanatory views of the operation of the present invention, FIGS. 2 (a) and 2 (b) are one embodiment of the present invention, and FIG. 3 is used in the embodiment of the present invention. FIG. 4 is a schematic diagram of an electrolytic plating apparatus, FIG. 4 is a voltage waveform diagram applied in the examples, and FIG. 5 is an example of the present invention. DESCRIPTION OF SYMBOLS 1 ... Metal conductor, 2,6 ... Tip part, 3,7,52 ... Electrodeposit, 4,8 ... Electrodeposit tip, 5,51 ... Wire, 11 ... Anode, 12 ... Cathode, 13 … Electrolysis bath, 14… Power supply.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０１Ｒ 1/067 Ｍ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location G01R 1/067 M
Claims (3)
状を有する導電性基材表面上に電解めっき法により金属
原子を析出させることを特徴とする微小電極の製造方
法。1. A method for producing a microelectrode, which comprises depositing metal atoms on a surface of a conductive base material having a conical shape with a tip having a curvature of not less than 10 μm by electrolytic plating.
電解めっき法であることを特徴とする特許請求の範囲第
１項記載の微小電極の製造方法。2. The method for producing a microelectrode according to claim 1, wherein the electrolytic plating method is an electrolytic plating method for applying a pulse voltage.
ルス電圧であることを特徴とする特許請求の範囲第２項
記載の微小電極の製造方法。3. The method of manufacturing a microelectrode according to claim 2, wherein the pulse voltage is an alternating pulse voltage having different polarities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62229711A JPH0689476B2 (en) | 1987-09-16 | 1987-09-16 | Microelectrode manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62229711A JPH0689476B2 (en) | 1987-09-16 | 1987-09-16 | Microelectrode manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6473097A JPS6473097A (en) | 1989-03-17 |
| JPH0689476B2 true JPH0689476B2 (en) | 1994-11-09 |
Family
ID=16896500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62229711A Expired - Lifetime JPH0689476B2 (en) | 1987-09-16 | 1987-09-16 | Microelectrode manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0689476B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5917860U (en) * | 1982-07-24 | 1984-02-03 | 日本電子材料株式会社 | Measuring probe |
-
1987
- 1987-09-16 JP JP62229711A patent/JPH0689476B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6473097A (en) | 1989-03-17 |
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