JP2016008334A - Production method of conductive diamond electrode - Google Patents
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Description
本発明は、導電性ダイヤモンド電極の製造方法および導電性ダイヤモンド電極に関する。 The present invention relates to a method for producing a conductive diamond electrode and a conductive diamond electrode.
ダイヤモンドは、機械的強度、化学的安定性に優れるが、電流を流せない難点がある。しかし、ダイヤモンドにホウ素を高濃度にドープしたホウ素ドープダイヤモンド（Boron Doped Diamond；以下、単にＢＤＤとも称する）は、金属的導電性が付与され、広い電位窓と、小さいバックグラウンド電流、ダイヤモンド由来の高い物理的・化学的安定性などの特徴を持ち、貴金属や炭素などの電極材料に比べ、電気化学分析や電気分解に有効な機能性電極材料として注目されている。そして、ＢＤＤ電極は、燃料電池用酸素還元電極やガスセンサの検出電極などへの応用が期待されている。さらに、ＢＤＤ電極は、電位窓が広く、バックグラウンド電流が小さいといった電気化学的特性を有することから、高感度な電気化学センサや高効率な電解用電極（例えば、水処理などで使用する電解用電極）としての利用が期待されている。しかしながら、この電極は、平滑な結晶面が表面に露出し、表面積が小さく、さらなる用途開発には表面積を増大させる技術が必要とされている。しかしながら、ダイヤモンドの機械的強度は極めて高いため、物理的処理が困難であり、化学的処理が主に用いられる。 Diamond is excellent in mechanical strength and chemical stability, but has a drawback that current cannot flow. However, boron doped diamond (hereinafter simply referred to as BDD) in which boron is doped at a high concentration in diamond is imparted with metallic conductivity, a wide potential window, a small background current, and a high diamond-derived diamond. It has features such as physical and chemical stability, and is attracting attention as a functional electrode material effective for electrochemical analysis and electrolysis compared to electrode materials such as precious metals and carbon. The BDD electrode is expected to be applied to an oxygen reduction electrode for fuel cells, a detection electrode of a gas sensor, and the like. Furthermore, since the BDD electrode has electrochemical characteristics such as a wide potential window and a small background current, a highly sensitive electrochemical sensor and a highly efficient electrolysis electrode (for example, for electrolysis used in water treatment, etc.) Use as an electrode is expected. However, this electrode has a smooth crystal face exposed on the surface and a small surface area, and a technique for increasing the surface area is required for further application development. However, since the mechanical strength of diamond is extremely high, physical treatment is difficult, and chemical treatment is mainly used.
従来、ダイヤモンド電極の表面処理方法には、気相法（特許文献１）、溶液法、および低圧プラズマ処理が知られている（特許文献２）。しかしながら、気相法では金属触媒が必要で処理が高温であり、かつ触媒の除去が必要であり；溶液法では、基板への影響が大きくなること、さらには含酸素官能基が多く生成し、親水性は向上するが、ダイヤモンド電極の特長である電位窓（ある電気化学系（溶媒・支持塩・電極の組み合わせ）において、有意義な電気化学測定が可能な電位領域）や安定性が大きく損なわれること；そして低圧プラズマ処理においては、酸素プラズマの場合は含酸素官能基が生成するため、親水性は向上するが、ダイヤモンド電極の特長である電位窓や安定性が大きく損なわれること、水素、フッ素終端ダイヤモンドを作製できる特徴もあるが、一般的には処理コストが大きいことが問題となる。 Conventionally, a gas phase method (Patent Document 1), a solution method, and a low-pressure plasma treatment are known as surface treatment methods for diamond electrodes (Patent Document 2). However, in the gas phase method, a metal catalyst is required, the treatment is at a high temperature, and the catalyst needs to be removed; in the solution method, the influence on the substrate is increased, and more oxygen-containing functional groups are generated. Although the hydrophilicity is improved, the potential window (potential region where meaningful electrochemical measurement is possible in a certain electrochemical system (a combination of solvent, supporting salt, and electrode)) and stability are greatly impaired. In the low-pressure plasma treatment, oxygen-containing functional groups are generated in the case of oxygen plasma, so that the hydrophilicity is improved, but the potential window and stability, which are the features of the diamond electrode, are greatly impaired, hydrogen, fluorine Although there is a feature that a terminal diamond can be produced, in general, a problem is that the processing cost is high.
本発明は、上記の課題を解決し、ダイヤモンド電極の表面積を増大させるとともに、ダイヤモンドへの窒素等の導入により高速な導電性のダイヤモンド電極を確実に得ることを目的とする。 An object of the present invention is to solve the above problems, increase the surface area of the diamond electrode, and reliably obtain a high-speed conductive diamond electrode by introducing nitrogen or the like into the diamond.
本発明は上記の課題を解決するために、以下の発明を提供するものである。
（１）大気圧下において、窒素を作動ガスとして、これにホウ素、水素および/または希ガスを含有させて窒素プラズマジェットを生成し、この窒素プラズマジェットをダイヤモンド薄膜の表面に照射してホウ素と窒素をドープするとともに表面積を増大させることを特徴とするダイヤモンド電極の製造方法。
（２）ダイヤモンド薄膜が、予めホウ素をドープされてなる上記（１）に記載のダイヤモンド電極の製造方法。
（３）上記（１）または（２）に記載の製造方法により得られたダイヤモンド電極。
In order to solve the above problems, the present invention provides the following inventions.
(1) Under atmospheric pressure, nitrogen is used as a working gas, and boron, hydrogen, and / or a rare gas is contained therein to generate a nitrogen plasma jet, and the surface of the diamond thin film is irradiated with this nitrogen plasma jet to form boron and A method for producing a diamond electrode, comprising doping nitrogen and increasing the surface area.
(2) The method for producing a diamond electrode according to (1), wherein the diamond thin film is previously doped with boron.
(3) A diamond electrode obtained by the production method according to (1) or (2) above.
本発明によれば、ダイヤモンド電極の表面積が増大し、さらにはダイヤモンドへの窒素等の導入を効率的に行い得る。たとえば、本発明によれば、ＢＤＤ電極の電位窓は安定し、電気化学的に測定されうる電気容量から見積もられる表面積が未処理に比較して好適には０．５Ｖ〜０．６Ｖの間で１．５〜４倍，０．２Ｖ〜１．２Ｖの間で２０〜３０倍程度まで向上し得る。 According to the present invention, the surface area of the diamond electrode is increased, and nitrogen or the like can be efficiently introduced into the diamond. For example, according to the present invention, the potential window of the BDD electrode is stable, and the surface area estimated from the electric capacity that can be measured electrochemically is preferably between 0.5V and 0.6V compared to untreated. It can be improved up to about 20 to 30 times between 1.5 to 4 times and 0.2 V to 1.2 V.
すなわち、本発明のダイヤモンド電極は、母材がホウ素ドープダイヤモンドの場合、大気圧下でプラズマジェットノズルに窒素、水素および/または希ガスを含有する作動ガスを供給して、電極間にパルス高電圧を印加してプラズマジェットを生成し、このプラズマジェット生成時に外気からの侵入酸素を水素で還元除去して窒素およびダイヤモンド電極の酸化を防止し、窒素主体のプラズマジェットとしてダイヤモンド薄膜の表面に照射することにより、ダイヤモンド薄膜の表面に微細な凹凸を形成して表面積を大幅に増大するとともに、既ドープＢに加えてＮを若干ドープして導電性を増大させる処理をするのである。これにより高速な導電性のダイヤモンド電極を確実に得ることができるものである。 That is, when the base material is boron-doped diamond, the diamond electrode of the present invention supplies a working gas containing nitrogen, hydrogen and / or a rare gas to the plasma jet nozzle under atmospheric pressure, and a pulse high voltage is applied between the electrodes. Is applied to generate a plasma jet, and when this plasma jet is generated, the invading oxygen from the outside air is reduced and removed with hydrogen to prevent oxidation of the nitrogen and diamond electrodes, and the surface of the diamond thin film is irradiated as a nitrogen-based plasma jet As a result, fine irregularities are formed on the surface of the diamond thin film to greatly increase the surface area, and in addition to the already doped B, a process of increasing the conductivity by slightly doping N is performed. As a result, a high-speed conductive diamond electrode can be obtained with certainty.
一方、母材がホウ素をドープしていないダイヤモンドの場合は大気圧下でプラズマジェットノズルに窒素、ホウ素、水素および/または希ガスを含有する作動ガスを供給して、窒素主体のプラズマジェットを生成すればよい。 On the other hand, when the base material is diamond that is not doped with boron, a working gas containing nitrogen, boron, hydrogen and / or a rare gas is supplied to the plasma jet nozzle at atmospheric pressure to generate a nitrogen-based plasma jet. do it.
本発明のダイヤモンド電極は、大気圧下において、窒素を作動ガスとして、これにホウ素、水素および/または希ガスを含有させた混合ガスで、窒素プラズマジェットを生成し、この窒素プラズマジェットをダイヤモンド薄膜の表面に照射してホウ素と窒素をドープするとともに表面積を大幅に増大させることにより得られる。 The diamond electrode of the present invention generates a nitrogen plasma jet at a atmospheric pressure, using nitrogen as a working gas, and a mixed gas containing boron, hydrogen and / or a rare gas. It is obtained by irradiating the surface of the substrate with boron and nitrogen and greatly increasing the surface area.
ダイヤモンド薄膜の製造には、ＣＶＤ（化学蒸着）法や、ＰＶＤ（物理蒸着）法等を使用し得るが、マイクロ波プラズマ化学蒸着（ＭＰＣＶＤ）法が好適である。 For the production of the diamond thin film, a CVD (chemical vapor deposition) method, a PVD (physical vapor deposition) method or the like can be used, but a microwave plasma chemical vapor deposition (MPCVD) method is preferable.
窒素プラズマジェットを生成する窒素、ホウ素、水素および/または希ガスを含有する混合ガスは、窒素80%〜99.9%，混入酸素還元用の水素0.1%〜20%の窒素／水素混合ガスをベースとし，そこにホウ素含有物質や希ガスを微量添加するのが好適である。 The mixed gas containing nitrogen, boron, hydrogen and / or noble gas that generates a nitrogen plasma jet is based on a nitrogen / hydrogen mixed gas of 80% to 99.9% nitrogen and 0.1% to 20% hydrogen for mixed oxygen reduction. It is preferable to add a small amount of a boron-containing substance or a rare gas thereto.
窒素源としては、アンモニア、窒素／水素混合ガスが好適であり、ホウ素源としては、ジボラン（Ｂ２Ｈ６）、ホウ酸、固体ホウ素等が挙げられる。 As the nitrogen source, ammonia and a nitrogen / hydrogen mixed gas are suitable, and as the boron source, diborane (B 2 H 6 ), boric acid, solid boron and the like can be mentioned.
また、希ガスの添加により放電が生じやすくなるペニング効果が誘発され，生成される活性種やラジカル種密度を上昇し得る。 In addition, the addition of a rare gas induces a Penning effect that tends to cause discharge, and the generated active species and radical species density can be increased.
ダイヤモンド薄膜として、予めホウ素がドープされた、ホウ素ドープダイヤモンド（ＢＤＤ）を用いてもよく、この場合には、窒素、水素および/または希ガスを含有する混合ガスで窒素プラズマジェットを生成する。窒素プラズマジェットは、プラズマ発生量を増加させて効率的処理をおこなうために、大気圧（常圧）窒素プラズマジェットが好適である。ダイヤモンド薄膜の昇温も同時に達成する熱プラズマ，例えばアーク型プラズマ，パルスアーク型プラズマが用いられ得る。非熱プラズマである誘電体バリア放電プラズマを用いることもでき，ダイヤモンド薄膜の温度制御は外部ヒーターにより達成し得る。 As the diamond thin film, boron-doped diamond (BDD) doped with boron in advance may be used. In this case, a nitrogen plasma jet is generated with a mixed gas containing nitrogen, hydrogen and / or a rare gas. The nitrogen plasma jet is preferably an atmospheric pressure (normal pressure) nitrogen plasma jet in order to increase the amount of plasma generated and perform efficient processing. Thermal plasma, such as arc-type plasma or pulsed arc-type plasma, that simultaneously achieves temperature rise of the diamond thin film can be used. Dielectric barrier discharge plasma which is non-thermal plasma can also be used, and the temperature control of the diamond thin film can be achieved by an external heater.
真空装置の不使用，取り回しの良さ，活性種やラジカル種の高密度生成の観点から、大気圧窒素プラズマジェットが最適に用いられる。すなわち、窒素プラズマジェット吹き付けを組み込んだライン処理により，高速な導電性ダイヤモンド電極の生成が可能となる。 An atmospheric pressure nitrogen plasma jet is optimally used from the viewpoint of non-use of a vacuum apparatus, good handling, and high density generation of active species and radical species. That is, a high-speed conductive diamond electrode can be generated by a line process incorporating nitrogen plasma jet spraying.
たとえば、大気圧窒素プラズマジェットは、好適には、次のような条件で実施される。プラズマ生成電力が１０Ｗ〜１ｋＷ，照射時間は1 秒〜1 時間，窒素に水素を１％〜２０％混合することにより，プラズマ内でＮＨラジカルが生成される。 For example, the atmospheric pressure nitrogen plasma jet is preferably performed under the following conditions. When the plasma generation power is 10 W to 1 kW, the irradiation time is 1 second to 1 hour, and 1% to 20% of hydrogen is mixed with nitrogen, NH radicals are generated in the plasma.
本発明において、得られるダイヤモンド電極は、最も好ましくは窒素およびホウ素をドープされてなる。 In the present invention, the resulting diamond electrode is most preferably doped with nitrogen and boron.
ダイヤモンド薄膜の厚さは、用途等により異なるが、通常２０ｎｍ〜５０μｍ程度から選択される。 Although the thickness of a diamond thin film changes with uses etc., it is normally selected from about 20 nm-50 micrometers.
ダイヤモンド薄膜にドープするホウ素および窒素の量は、用途等により異なるが、通常、少なくともダイヤモンドの炭素に対してホウ素を１００ｐｐｍ以上、好ましくは、１０００ｐｐｍ以上、さらに好ましくは５０００ｐｐｍ以上である。 The amount of boron and nitrogen to be doped in the diamond thin film varies depending on the application and the like, but is usually 100 ppm or more, preferably 1000 ppm or more, more preferably 5000 ppm or more with respect to at least carbon of diamond.
本発明により得られるダイヤモンド電極は、各種電解反応に用いられ、たとえばフッ化物イオンを含有する電解浴を用いた電解フッ素化反応や食塩電解のような無機電解反応、電解めっき等が挙げられる。 The diamond electrode obtained by the present invention is used in various electrolytic reactions, and examples thereof include an electrolytic fluorination reaction using an electrolytic bath containing fluoride ions, an inorganic electrolytic reaction such as salt electrolysis, and electrolytic plating.
以下、実施例により本発明をさらに詳細に説明する。
実施例１
ペルメレック電極株式会社製ボロンドープダイヤモンド薄膜(Nb-BDD，ボロン濃度9000ppm)の表面に，大気圧窒素プラズマ発生装置を用いて、5，10，20，25，および30分間、窒素を含有する雰囲気中で、プラズマジェットと接触させて賦活化処理を行った。基盤温度：５２０℃、アーク電圧：４．５ｋＶ/Ａ，パルスアーク：２１ｋＨＺ，ガス：窒素２０slmおよび水素０．２２sccmであった。三極式セルを用い、電解液として０．５Ｍ硫酸水溶液を用いた。処理後に、得られたダイヤモンド薄膜を、顕微レーザーラマン分光測定(Ｒａｍａｎ)，電界放出型走査電子顕微鏡(ＦＥ−ＳＥＭ)，エネルギー分散型蛍光X線分析装置(ＥＤＳ)，およびＸ線光電子分光分析(ＸＰＳ)で評価した。また、電気化学特性を0.5Ｍ硫酸水溶液中でのサイクリックボルタンメトリー(ＣＶ)により試験した。
Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
In an atmosphere containing nitrogen for 5, 10, 20, 25, and 30 minutes on the surface of a boron-doped diamond thin film (Nb-BDD, boron concentration 9000 ppm) manufactured by Permerek Electrode Co., Ltd. using an atmospheric pressure nitrogen plasma generator Then, the activation treatment was performed in contact with the plasma jet. Base temperature: 520 ° C., arc voltage: 4.5 kV / A, pulsed arc: 21 kHZ, gas: nitrogen 20 slm and hydrogen 0.22 sccm. A tripolar cell was used, and a 0.5 M aqueous sulfuric acid solution was used as the electrolytic solution. After the treatment, the obtained diamond thin film was subjected to microscopic Raman spectroscopy (Raman), field emission scanning electron microscope (FE-SEM), energy dispersive X-ray fluorescence spectrometer (EDS), and X-ray photoelectron spectroscopy ( XPS). The electrochemical properties were also tested by cyclic voltammetry (CV) in 0.5M aqueous sulfuric acid.
１）ＳＥＭ画像（表面形態観察）
図１に窒素プラズマ処理を１０〜３０分間行った試料のSEM画像を示す。窒素プラズマ処理されていない試料との比較から，処理によって，ダイヤモンド構造由来の三角錐の形態が壊され，未処理では確認されなかった孔が確認された。その孔の径は，処理時間が長くなるにつれ大きくなった．よって，窒素プラズマ処理で，表面が微細に凹凸形成され表面積が増大することが示された。
1) SEM image (surface morphology observation)
FIG. 1 shows an SEM image of a sample subjected to nitrogen plasma treatment for 10 to 30 minutes. From the comparison with the sample that was not treated with nitrogen plasma, the shape of the triangular pyramid derived from the diamond structure was destroyed by the treatment, and holes that were not confirmed without treatment were confirmed. The diameter of the hole increased as the processing time increased. Thus, nitrogen plasma treatment showed that the surface was finely formed with irregularities and the surface area increased.
２）Ｒａｍａｎ測定（微細構造の評価）
図２のスペクトルにおいて、４８０ｃｍ−１におけるピークは、基盤に由来し、１２００ｃｍ−１におけるピークは、不規則なダイヤモンド構造に由来するピークである。ＩＤ/ＩＧは,ｓｐ３炭素に起因するＤバンド（１３００ｃｍ−１）強度/ｓｐ２炭素に起因するＧバンド（１５２０ｃｍ−１）強度比を示す。
2) Raman measurement (evaluation of microstructure)
In the spectrum of FIG. 2, the peak at 480 cm −1 is derived from the base, and the peak at 1200 cm −1 is a peak derived from an irregular diamond structure. I D / I G indicates a D band (1300 cm −1 ) intensity attributed to sp 3 carbon / G band (1520 cm −1 ) intensity ratio attributed to sp 2 carbon.
Ｒａｍａｎ測定から，プラズマ処理後もダイヤモンド構造由来のピークであるＤバンドが確認されたので、ダイヤモンド構造が維持されていることがわかった。 From the Raman measurement, it was found that the diamond structure was maintained because the D band, which is a peak derived from the diamond structure, was confirmed even after the plasma treatment.
３）ＸＰＳ測定（結合状態の評価）
図３のＸＰＳ測定結果から、５分間の窒素プラズマ処理で窒素が導入されたことが確認された。
3) XPS measurement (assessment of binding state)
From the XPS measurement result of FIG. 3, it was confirmed that nitrogen was introduced by the nitrogen plasma treatment for 5 minutes.
４）ＥＤＳ測定（元素分析）
図４は、ＥＤＳ測定結果を示す。５分間の窒素プラズマ処理で窒素の含有量が最大であった。
4) EDS measurement (elemental analysis)
FIG. 4 shows the EDS measurement results. The nitrogen content was maximum after 5 minutes of nitrogen plasma treatment.
５）ＣＶ測定（表面積の評価）
図５は、ＣＶ測定結果を示す。二重層容量を用いて比較した結果、窒素プラズマ処理で表面積が増大したことが確認された。二重層容量の増加率（未処理に対する）は、０．５Ｖ〜０．６Ｖの間で５分間：１７４％；１０分間：１４３％；２０分間：２６３％、２５分間：１４８％；および３０分間：３８９％、であった。
5) CV measurement (surface area evaluation)
FIG. 5 shows the CV measurement results. As a result of comparison using the double layer capacity, it was confirmed that the surface area was increased by the nitrogen plasma treatment. The rate of increase in double layer capacity (vs. untreated) is between 0.5V and 0.6V for 5 minutes: 174%; 10 minutes: 143%; 20 minutes: 263%, 25 minutes: 148%; and 30 minutes : 389%.
また、０．２Ｖ〜１．２Ｖの間で５分間：１１２％；１０分間：１３４０％；２０分間：２９３０％；２５分間：２９３０％；３０分間：１９４０％であった。 Moreover, it was 5 minutes: 112% between 0.2V-1.2V; 10 minutes: 1340%; 20 minutes: 2930%; 25 minutes: 2930%; 30 minutes: 1940%.
本発明によれば、ダイヤモンド電極の表面積の増大とＢドープ，Ｎドープにより高速に導電性のダイヤモンド電極を容易に達成し得て、燃料電池用酸素還元電極やガスセンサの検出電極などに有利に活用されこの種産業に貢献すること多大なものがある。 According to the present invention, a diamond electrode that is electrically conductive can be easily achieved at a high speed by increasing the surface area of the diamond electrode and by B-doping or N-doping, and it can be advantageously used for an oxygen reduction electrode for a fuel cell or a detection electrode for a gas sensor. There is a great deal to contribute to this kind of industry.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014130477A JP6415133B2 (en) | 2014-06-25 | 2014-06-25 | Method for producing conductive diamond electrode |
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| CN105688971A (en) * | 2016-02-29 | 2016-06-22 | 大连理工大学 | Electrochemical reduction CO2 catalyst based on boron and nitrogen co-doped nano-diamond and preparation method and application of catalyst |
| CN113125536A (en) * | 2021-03-31 | 2021-07-16 | 吉林大学 | Preparation method of electrochemical sensor electrode material for detecting aniline |
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| JP6415133B2 (en) | 2018-10-31 |
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