JP4982693B2 - Method for cleaning metal nanoparticles - Google Patents
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- JP4982693B2 JP4982693B2 JP2006343794A JP2006343794A JP4982693B2 JP 4982693 B2 JP4982693 B2 JP 4982693B2 JP 2006343794 A JP2006343794 A JP 2006343794A JP 2006343794 A JP2006343794 A JP 2006343794A JP 4982693 B2 JP4982693 B2 JP 4982693B2
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- 239000002082 metal nanoparticle Substances 0.000 title claims description 39
- 238000000034 method Methods 0.000 title claims description 21
- 238000004140 cleaning Methods 0.000 title claims description 13
- 239000000758 substrate Substances 0.000 claims description 59
- 229910052594 sapphire Inorganic materials 0.000 claims description 22
- 239000010980 sapphire Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 7
- 230000002093 peripheral effect Effects 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 50
- 229910052697 platinum Inorganic materials 0.000 description 25
- 239000002105 nanoparticle Substances 0.000 description 21
- 238000007740 vapor deposition Methods 0.000 description 15
- 229910003481 amorphous carbon Inorganic materials 0.000 description 12
- 238000005566 electron beam evaporation Methods 0.000 description 12
- 238000010894 electron beam technology Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000000089 atomic force micrograph Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000313 electron-beam-induced deposition Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- -1 HOPG Chemical compound 0.000 description 1
- 241001534066 Smithatris supraneanae Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
本発明は、金属ナノ粒子のクリーニング方法、例えば燃料電池等の金属触媒ナノ粒子形成後や、カーボンナノチューブの下地膜としての金属触媒ナノ粒子形成後等に、この金属ナノ粒子をクリーニングする方法に関する。本発明において金属ナノ粒子といった場合のナノオーダは、３０ｎｍ程度以下で、かつ１ｎｍ程度以上をいうものとする。 The present invention relates to a method for cleaning metal nanoparticles, for example, a method for cleaning metal nanoparticles after formation of metal catalyst nanoparticles such as a fuel cell or after formation of metal catalyst nanoparticles as an underlayer of carbon nanotubes. In the present invention, the nano-order in the case of the metal nanoparticles is about 30 nm or less and about 1 nm or more.
従来、ドライプロセスによりナノオーダの金属粒子(このナノオーダとは、上記したような範囲内である)を作製する場合には、電子ビーム蒸着法や抵抗加熱蒸着法等により、グラファイト又はアモルファスカーボン等からなる基板を２００〜５００℃に加熱しながら、その基板上に金属粒子を数ｎｍ蒸着し、凝集させて作製している。 Conventionally, when producing nano-order metal particles by dry process (this nano-order is in the above range), it is made of graphite or amorphous carbon by electron beam vapor deposition or resistance heating vapor deposition. While the substrate is heated to 200 to 500 ° C., several nanometers of metal particles are vapor-deposited and aggregated on the substrate.
上記電子ビーム蒸着法の場合、例えば、図１に模式的に示す電子ビーム蒸着装置を用いて金属ナノ粒子を作製している。 In the case of the electron beam evaporation method, for example, metal nanoparticles are produced using an electron beam evaporation apparatus schematically shown in FIG.
図１に示すように、電子ビーム蒸着装置は、円筒形状の真空チャンバ１からなる。この真空チャンバ１内には、その下部の底フランジに取り付けられた電子ビーム蒸着源１２が設けられ、電子ビーム蒸着源１２には蒸着材料１３を収納するための空間(ルツボ)が設けられ、そして電子ビーム蒸着源１２に対向して基板ステージ１４が設けられている。この基板ステージ１４は、その電子ビーム蒸着源１２側に、金属ナノ粒子を蒸着するための基板Ｓが取り付けられるようになっている。基板ステージ１４の電子ビーム蒸着源側と反対の側には、その中心に、基板マニピュレータ１５が真空チャンバ１上部壁面を貫通して取り付けられ、基板Ｓが基板ステージ１４と共に、基板マニピュレータ１５により回転できるように構成されている。そして、基板Ｓを取り付ける基板ステージ１４の面と反対側の面にはヒータ等の加熱手段１６が取り付けられ、基板ステージ１４、ひいては基板Ｓを加熱できるように構成されている。 As shown in FIG. 1, the electron beam evaporation apparatus includes a cylindrical vacuum chamber 1. In this vacuum chamber 1, an electron beam evaporation source 12 attached to the bottom flange of the lower part is provided, the electron beam evaporation source 12 is provided with a space (crucible) for storing the evaporation material 13, and A substrate stage 14 is provided facing the electron beam evaporation source 12. The substrate stage 14 is configured such that a substrate S for depositing metal nanoparticles is attached to the electron beam evaporation source 12 side. On the opposite side of the substrate stage 14 from the electron beam evaporation source side, a substrate manipulator 15 is attached through the upper wall surface of the vacuum chamber 1 at the center, and the substrate S can be rotated together with the substrate stage 14 by the substrate manipulator 15. It is configured as follows. A heating means 16 such as a heater is attached to the surface opposite to the surface of the substrate stage 14 to which the substrate S is attached, so that the substrate stage 14 and, in turn, the substrate S can be heated.
基板Ｓの近傍には膜厚測定子１７が取り付けられて、基板に付着する金属ナノ粒子の厚みを測定できるように構成されている。 A film thickness gauge 17 is attached in the vicinity of the substrate S so that the thickness of the metal nanoparticles adhering to the substrate can be measured.
真空チャンバ１には、その壁面に真空排気系１８がターボ分子ポンプ１８−１、バルブ１８−２及びロータリポンプ１８−３の順序で設けられ、ターボ分子ポンプ１８−１からロータリポンプ１８−３まで金属製の真空配管１８−４で接続され、真空チャンバ１内の真空排気を行うことができるように構成されている。真空チャンバ１内は、この真空排気系により１０−５Ｐａ以下に保つことができるようになっている。 The vacuum chamber 1 is provided with an evacuation system 18 on its wall surface in the order of a turbo molecular pump 18-1, a valve 18-2, and a rotary pump 18-3, from the turbo molecular pump 18-1 to the rotary pump 18-3. It is connected by a metal vacuum pipe 18-4 so that the vacuum chamber 1 can be evacuated. The inside of the vacuum chamber 1 can be maintained at 10 −5 Pa or less by this vacuum exhaust system.
図１に示す電子ビーム蒸着装置を用いて金属ナノ粒子を作製するプロセスの一例について以下説明する。例えば、基板Ｓとして高配向耐熱グラファイト(High Orientated Pyretic Graphite、以下、ＨＯＰＧと称す)基板を用い、このＨＯＰＧ基板を基板ステージ１４上に載置し、加熱手段１６により６００℃まで加熱する。蒸着材料１３としての白金を電子ビーム蒸着源１２のルツボ内へ充填し、電子ビーム蒸着源を稼働させて電子ビームをルツボに投入し、白金を溶融、蒸発させてＨＯＰＧ基板上に所定の厚みの白金を蒸着する。蒸着粒子の厚みは、膜厚測定子１７に付着した重量から、その同じ量がＨＯＰＧ基板に均一に付着したものとして、その重量を基板面積と蒸着材料の比重とから計算して算出する。蒸着した金属粒子の大きさは、ＡＦＭ(原子間力顕微鏡)を用いて粒子の高さを測定し、粒子の高さが粒子の直径と比例すると仮定して算出する。 An example of a process for producing metal nanoparticles using the electron beam evaporation apparatus shown in FIG. 1 will be described below. For example, a highly oriented heat resistant graphite (hereinafter referred to as HOPG) substrate is used as the substrate S, and this HOPG substrate is placed on the substrate stage 14 and heated to 600 ° C. by the heating means 16. The crucible of the electron beam vapor deposition source 12 is filled with platinum as the vapor deposition material 13, the electron beam vapor deposition source is operated, the electron beam is injected into the crucible, and the platinum is melted and evaporated to have a predetermined thickness on the HOPG substrate. Deposit platinum. The thickness of the vapor deposition particles is calculated from the weight adhering to the film thickness gauge 17 by calculating the weight from the substrate area and the specific gravity of the vapor deposition material, assuming that the same amount is uniformly adhering to the HOPG substrate. The size of the deposited metal particles is calculated by measuring the height of the particles using an AFM (Atomic Force Microscope) and assuming that the height of the particles is proportional to the diameter of the particles.
上記したようにして基板Ｓの表面に蒸着された白金ナノ粒子のＡＦＭ像写真を図２に示し、また、蒸着された白金ナノ粒子の断面ＴＥＭ像写真を図３に示す。これらの図面から、所定の粒径(８〜１０ｎｍ)の白金ナノ粒子が得られており、この白金ナノ粒子の表面がアモルファスカーボンで被覆されていることが分かる(基板温度が６００℃なので、白金が基板上で動いて基板由来のカーボンで被覆される)。白金ナノ粒子が、アモルファスカーボンにより被覆されているために、図２に示すように、その粒子自体が不鮮明に観察される。 An AFM image photograph of the platinum nanoparticles deposited on the surface of the substrate S as described above is shown in FIG. 2, and a cross-sectional TEM image photograph of the deposited platinum nanoparticles is shown in FIG. From these drawings, it is understood that platinum nanoparticles having a predetermined particle size (8 to 10 nm) are obtained, and the surface of the platinum nanoparticles is coated with amorphous carbon (since the substrate temperature is 600 ° C., Moves on the substrate and is coated with carbon from the substrate). Since the platinum nanoparticles are covered with amorphous carbon, the particles themselves are observed unclearly as shown in FIG.
従来は、上記したようにして得られたアモルファスカーボン被覆白金ナノ粒子を酸素プラズマ中に曝すことにより、表面のアモルファスカーボンを燃焼させて除去している。しかし、白金ナノ粒子を酸素プラズマ中で曝露すると、結晶化した白金ナノ粒子にイオンエネルギによるダメージが入って、結晶性が壊れたり、また、酸素が白金ナノ粒子に触れることにより、白金ナノ粒子の表面が酸化して酸化白金が生じるので、触媒活性が死活又は劣化するという問題が生じており、より簡便かつ有用なアモルファスカーボン等の不純物の除去方法の開発が求められている。 Conventionally, the amorphous carbon-coated platinum nanoparticles obtained as described above are exposed to oxygen plasma to burn and remove the amorphous carbon on the surface. However, when platinum nanoparticles are exposed in oxygen plasma, the crystallized platinum nanoparticles are damaged by ion energy, the crystallinity is broken, and oxygen touches the platinum nanoparticles. Since the surface is oxidized to produce platinum oxide, there is a problem that the catalytic activity is life-threatening or deteriorating, and there is a demand for the development of a simpler and more useful method for removing impurities such as amorphous carbon.
本発明の課題は、上述の従来技術の問題点を解決することにあり、極めて簡便な方法で金属ナノ粒子表面をクリーニングする方法を提供することにある。 An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a method for cleaning the surface of metal nanoparticles by a very simple method.
本発明の金属ナノ粒子のクリーニング方法は、粒径１〜１００ｎｍの金属ナノ粒子が付着している基板に対してサファイア板を押し付けて重ね合わせた後に、このサファイア板を剥がすことにより、基板上に付着した金属ナノ粒子の表面及びその周辺部に存在する不純物を取り除き、金属ナノ粒子の表面及びその周辺部を清浄化せしめることを特徴とする。
The cleaning method of the metal nanoparticles of the present invention, after the superposed against the sapphire plate to the substrate to the metal nanoparticle particle size 1～100N m is attached, by peeling the sapphire plate, substrate The present invention is characterized in that impurities existing on the surface of the metal nanoparticles and its peripheral part attached to the surface are removed, and the surface of the metal nanoparticles and its peripheral part are cleaned .
前記サファイア板は、アニール処理して表面を清浄化したものが好ましい。 The sapphire plate preferably has a surface cleaned by annealing.
本発明によれば、基板上に付着されている金属ナノ粒子に対して、その上からサファイア板を押し付けて重ね合わせた後、このサファイア板を剥がすことにより、金属ナノ粒子の表面及びその周辺部に付着している不純物を、金属ナノ粒子の結晶性を劣化させずに、かつ表面酸化も起こさせずに、簡単に剥離することができるので、金属ナノ粒子表面を清浄化し得るというクリーニング効果を奏する。 According to the present invention, the surface of the metal nanoparticles and the peripheral portion thereof are removed by peeling off the sapphire plate after pressing the sapphire plate on the metal nanoparticle attached on the substrate and superimposing it. Impurities attached to the metal nanoparticles can be easily removed without degrading the crystallinity of the metal nanoparticles and without causing surface oxidation. Play.
以下、本発明に係る金属ナノ粒子のクリーニング方法の一実施の形態として、電子ビーム蒸着法により基板上に蒸着せしめた金属ナノ粒子に対するクリーニング方法について説明するが、この金属ナノ粒子は、電子ビーム蒸着法や抵抗加熱蒸着法等で基板上に蒸着したものでも、また、その他の方法(例えば、スパッタ法、アーク蒸着法)で基板上に付着せしめたものでも良い。 Hereinafter, as an embodiment of the cleaning method for metal nanoparticles according to the present invention, a cleaning method for metal nanoparticles deposited on a substrate by an electron beam evaporation method will be described. It may be deposited on the substrate by a method such as resistance heating deposition or the like, or may be deposited on the substrate by other methods (for example, sputtering or arc deposition).
本発明に係るクリーニング方法の一実施の形態によれば、電子ビーム蒸着法により、公知のプロセス条件で粒径１〜１００ｎｍ程度の金属ナノ粒子を基板上に蒸着させ、この金属ナノ粒子が基板上に付着している状態の基板を用いてクリーニングを行う。 According to an embodiment of the cleaning method of the present invention, metal nanoparticles having a particle size of about 1 to 100 nm are deposited on a substrate under a known process condition by an electron beam deposition method, and the metal nanoparticles are deposited on the substrate. Cleaning is performed using the substrate attached to the substrate.
上記基板上の金属ナノ粒子に対しサファイア板を押し付けて、金属ナノ粒子が付着した基板とサファイア板とを重ね合わせ、所定の時間、例えば１時間程度放置した後にサファイア板を剥がすことにより、基板上に付着した金属ナノ粒子の表面及びその周辺部に存在している不純物膜が除去され、金属ナノ粒子表面及びその周辺部が清浄化される。このように、金属ナノ粒子及びその周辺部が清浄化されるのは、アモルファスカーボン等のような不純物からなる膜が金属ナノ粒子表面及びその周辺部から剥がれ、サファイア板に密着して除去されるからである。 The sapphire plate is pressed against the metal nanoparticles on the substrate, the substrate to which the metal nanoparticles are adhered and the sapphire plate are overlapped, and left for a predetermined time, for example, about 1 hour, and then peeled off the sapphire plate. The impurity film existing on the surface of the metal nanoparticles and the periphery thereof attached to the surface is removed, and the surface of the metal nanoparticles and the periphery thereof are cleaned. As described above, the metal nanoparticles and the peripheral portion thereof are cleaned because the film made of impurities such as amorphous carbon is peeled off from the surface of the metal nanoparticle and the peripheral portion thereof and adhered to the sapphire plate. Because.
本実施の形態で用いる金属ナノ粒子を蒸着せしめた基板を作製する電子ビーム蒸着装置としては、図１に示す装置を用い、また、その蒸着プロセスは上記したプロセスと同様にして行う。 As an electron beam evaporation apparatus for producing a substrate on which metal nanoparticles are evaporated used in this embodiment, the apparatus shown in FIG. 1 is used, and the evaporation process is performed in the same manner as described above.
本発明によれば、金属ナノ粒子を付着せしめるための基板としては、例えばＨＯＰＧのようなグラファイト、シリコン、アモルファスカーボン、シリカ等からなる基板を挙げることができる。 According to the present invention, examples of the substrate on which the metal nanoparticles are attached include a substrate made of graphite such as HOPG, silicon, amorphous carbon, silica, or the like.
また、付着せしめる金属ナノ粒子の金属材料としては、例えば白金、コバルト、鉄、ニッケル、クロム等を挙げることができる。 Moreover, as a metal material of the metal nanoparticle to adhere, platinum, cobalt, iron, nickel, chromium etc. can be mentioned, for example.
サファイア板は、例えば所定の温度(例えば、１３００℃等)でアニール処理して表面を清浄化したものが好ましく、アニール処理により表面にステップ構造が形成されたもの等でも良い。 The sapphire plate preferably has a surface that has been cleaned by annealing at a predetermined temperature (eg, 1300 ° C., for example), and may have a step structure formed on the surface by annealing.
金属ナノ粒子が付着した基板とサファイア板とを重ね合わせて放置する時間は、特に制限はないが、例えば１〜４時間程度で良い。また、その重ね合わせる力は、金属ナノ粒子が圧壊されない程度であれば良く、例えばサファイア板の自重であっても、１ｋｇ程度までのおもりを載せても良い。 There is no particular limitation on the time for which the metal nanoparticle-attached substrate and the sapphire plate are left to stand, but may be, for example, about 1 to 4 hours. Further, the superimposing force is sufficient as long as the metal nanoparticles are not crushed. For example, the weight of the sapphire plate may be the weight of the sapphire plate or a weight of up to about 1 kg may be placed.
図１に示す電子ビーム蒸着装置を用いて、１ｃｍ×１ｃｍ角のＨＯＰＧ基板Ｓ上に白金ナノ粒子を蒸着せしめた。 Platinum nanoparticles were deposited on a 1 cm × 1 cm HOPG substrate S using the electron beam deposition apparatus shown in FIG.
まず、このＨＯＰＧ基板Ｓを基板ステージ１４上に載置し、加熱手段１６により５００℃まで加熱した。蒸着材料としての白金を電子ビーム蒸着源１２のルツボ内へ充填し、電子ビーム蒸着源を稼働させて電子ビームをルツボに投入し、白金を溶融、蒸発させてＨＯＰＧ基板Ｓ上に所定の厚みの白金ナノ粒子を蒸着せしめた。蒸着粒子の大きさは、膜厚測定子１７に付着した重量から、その同じ量がＨＯＰＧ基板Ｓに均一に付着したものとして、その重量を基板面積と蒸着材料の比重とから計算して算出したところ、粒径８〜１０ｎｍであった。ＨＯＰＧ基板Ｓ上に蒸着された白金ナノ粒子のＡＦＭ像は図２に示したものと同様であり、粒子表面及びその周辺部に基板由来のアモルファスカーボンが存在していることが、ＡＭＦ像が不鮮明なことにより確認された。 First, the HOPG substrate S was placed on the substrate stage 14 and heated to 500 ° C. by the heating means 16. The crucible of the electron beam vapor deposition source 12 is filled with platinum as a vapor deposition material, the electron beam vapor deposition source is operated, the electron beam is injected into the crucible, and the platinum is melted and evaporated to a predetermined thickness on the HOPG substrate S. Platinum nanoparticles were deposited. The size of the vapor deposition particles was calculated by calculating the weight based on the substrate area and the specific gravity of the vapor deposition material, assuming that the same amount adhered uniformly to the HOPG substrate S from the weight adhering to the film thickness gauge 17. However, the particle size was 8 to 10 nm. The AFM image of the platinum nanoparticles deposited on the HOPG substrate S is the same as that shown in FIG. 2, and the presence of amorphous carbon derived from the substrate on the particle surface and its peripheral part is unclear. That was confirmed.
次いで、サファイア板として、１３００℃でアニール処理した１２ｍｍ×１２ｍｍ角のサファイア板を用い、このサファイア板を、上記白金ナノ粒子の蒸着されたＨＯＰＧ基板Ｓに対して、大気中、室温で載せて重ね合わせ、１００ｇ重の圧力をかけた状態で１時間放置した。 Next, a 12 mm × 12 mm square sapphire plate annealed at 1300 ° C. is used as the sapphire plate, and this sapphire plate is placed on the HOPG substrate S on which the platinum nanoparticles are deposited at room temperature in the air. They were combined and allowed to stand for 1 hour under a pressure of 100 g.
その後、サファイア板を剥がし、ＨＯＰＧ基板Ｓの表面をＡＦＭ観察した。このＡＦＭ像を図４に示す。図４から明らかなように、ＡＦＭ像で示される白金ナノ粒子の像が図２で示される白金ナノ粒子の像よりも鮮明になっていた。これは、アモルファスカーボンとサファイア板との密着性が白金とアモルファスカーボンとの密着性より強いため、白金ナノ粒子の最表面及び粒子周辺部に付着していたアモルファスカーボンが剥離してサファイア板へと移行したためである。 Thereafter, the sapphire plate was peeled off, and the surface of the HOPG substrate S was observed with AFM. This AFM image is shown in FIG. As is clear from FIG. 4, the platinum nanoparticle image shown in the AFM image was clearer than the platinum nanoparticle image shown in FIG. This is because the adhesion between the amorphous carbon and the sapphire plate is stronger than the adhesion between the platinum and the amorphous carbon, so the amorphous carbon adhering to the outermost surface of the platinum nanoparticle and the periphery of the particle is peeled off to the sapphire plate. This is because of the transition.
本発明によれば、基板上に付着した金属ナノ粒子の表面及びその周辺部を被覆していた不純物膜を、金属ナノ粒子の結晶性を劣化させずに、かつ表面酸化も起こさせずに、簡単に剥離して、金属ナノ粒子表面を清浄化することができるので、本発明は、燃料電池の触媒粒子形成技術の分野や、半導体分野における配線形成技術の分野や、カーボンナノチューブの下地膜としての触媒層形成技術の分野等において利用可能である。 According to the present invention, without impairing the crystallinity of the metal nanoparticles and causing the surface oxidation, the impurity film covering the surface of the metal nanoparticles attached on the substrate and the periphery thereof is not caused. Since the surface of the metal nanoparticles can be easily peeled off, the present invention is applied to the field of catalyst particle formation technology for fuel cells, the field of wiring formation technology in the semiconductor field, and the underlayer of carbon nanotubes. It can be used in the field of the catalyst layer forming technology.
１ 真空チャンバ １２ 電子ビーム蒸着源
１３ 蒸着材料 １４ 基板ステージ
１５ 基板マニピュレータ １６ 加熱手段
１７ 膜厚測定子 １８ 真空排気系
１８−１ ターボ分子ポンプ １８−２ バルブ
１８−３ ロータリポンプ １８−４ 真空配管
Ｓ 基板
DESCRIPTION OF SYMBOLS 1 Vacuum chamber 12 Electron beam evaporation source 13 Vapor deposition material 14 Substrate stage 15 Substrate manipulator 16 Heating means 17 Film thickness gauge 18 Vacuum exhaust system 18-1 Turbo molecular pump 18-2 Valve 18-3 Rotary pump 18-4 Vacuum piping S substrate
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