JP5765727B2 - Nanoparticle production method and nanoparticle dispersion - Google Patents
Nanoparticle production method and nanoparticle dispersion Download PDFInfo
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- JP5765727B2 JP5765727B2 JP2010266456A JP2010266456A JP5765727B2 JP 5765727 B2 JP5765727 B2 JP 5765727B2 JP 2010266456 A JP2010266456 A JP 2010266456A JP 2010266456 A JP2010266456 A JP 2010266456A JP 5765727 B2 JP5765727 B2 JP 5765727B2
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- 239000002105 nanoparticle Substances 0.000 title claims description 84
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000006185 dispersion Substances 0.000 title claims description 5
- 239000002608 ionic liquid Substances 0.000 claims description 100
- 229910052751 metal Inorganic materials 0.000 claims description 67
- 239000002184 metal Substances 0.000 claims description 67
- 238000004544 sputter deposition Methods 0.000 claims description 31
- 239000011258 core-shell material Substances 0.000 claims description 29
- 238000007740 vapor deposition Methods 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 11
- 239000002082 metal nanoparticle Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 67
- 239000010931 gold Substances 0.000 description 44
- 238000000034 method Methods 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 21
- 239000013077 target material Substances 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 238000003917 TEM image Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 239000011521 glass Substances 0.000 description 13
- -1 tetrafluoroborate Chemical compound 0.000 description 13
- 229910052738 indium Inorganic materials 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910003437 indium oxide Inorganic materials 0.000 description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 5
- 238000005240 physical vapour deposition Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
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- AMKUSFIBHAUBIJ-UHFFFAOYSA-N 1-hexylpyridin-1-ium Chemical class CCCCCC[N+]1=CC=CC=C1 AMKUSFIBHAUBIJ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
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- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
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- OIDIRWZVUWCCCO-UHFFFAOYSA-N 1-ethylpyridin-1-ium Chemical class CC[N+]1=CC=CC=C1 OIDIRWZVUWCCCO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910014203 BMI-BF4 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- TYOCDPIZUIQUSO-UHFFFAOYSA-N 1-butyl-2,3-dimethyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1C TYOCDPIZUIQUSO-UHFFFAOYSA-N 0.000 description 1
- KSOGGGZFEJTGPZ-UHFFFAOYSA-M 1-butyl-2,3-dimethylimidazol-3-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+]=1C=CN(C)C=1C KSOGGGZFEJTGPZ-UHFFFAOYSA-M 0.000 description 1
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- KVBQNFMTEUEOCD-UHFFFAOYSA-M 1-butylpyridin-1-ium;bromide Chemical compound [Br-].CCCC[N+]1=CC=CC=C1 KVBQNFMTEUEOCD-UHFFFAOYSA-M 0.000 description 1
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 1
- BEFWDPZVLOCGRP-UHFFFAOYSA-M 1-butylpyridin-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+]1=CC=CC=C1 BEFWDPZVLOCGRP-UHFFFAOYSA-M 0.000 description 1
- HTZVLLVRJHAJJF-UHFFFAOYSA-M 1-decyl-3-methylimidazolium chloride Chemical compound [Cl-].CCCCCCCCCCN1C=C[N+](C)=C1 HTZVLLVRJHAJJF-UHFFFAOYSA-M 0.000 description 1
- OPXNHKQUEXEWAM-UHFFFAOYSA-M 1-dodecyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCN1C=C[N+](C)=C1 OPXNHKQUEXEWAM-UHFFFAOYSA-M 0.000 description 1
- GITMVCYKHULLDM-UHFFFAOYSA-M 1-ethyl-2,3-dimethylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1C GITMVCYKHULLDM-UHFFFAOYSA-M 0.000 description 1
- NUJYCYLTUXYHQU-UHFFFAOYSA-M 1-ethyl-2,3-dimethylimidazol-3-ium;chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1C NUJYCYLTUXYHQU-UHFFFAOYSA-M 0.000 description 1
- GWQYPLXGJIXMMV-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1 GWQYPLXGJIXMMV-UHFFFAOYSA-M 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 1
- ABFDKXBSQCTIKH-UHFFFAOYSA-M 1-ethylpyridin-1-ium;bromide Chemical compound [Br-].CC[N+]1=CC=CC=C1 ABFDKXBSQCTIKH-UHFFFAOYSA-M 0.000 description 1
- AMFMJCAPWCXUEI-UHFFFAOYSA-M 1-ethylpyridin-1-ium;chloride Chemical compound [Cl-].CC[N+]1=CC=CC=C1 AMFMJCAPWCXUEI-UHFFFAOYSA-M 0.000 description 1
- ZCPPLZJPPBIWRU-UHFFFAOYSA-M 1-hexadecyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCN1C=C[N+](C)=C1 ZCPPLZJPPBIWRU-UHFFFAOYSA-M 0.000 description 1
- KTUDCAXDKIVTNY-UHFFFAOYSA-M 1-hexyl-2,3-dimethylimidazol-3-ium;bromide Chemical compound [Br-].CCCCCCN1C=C[N+](C)=C1C KTUDCAXDKIVTNY-UHFFFAOYSA-M 0.000 description 1
- NCTQEXWJEPRHLV-UHFFFAOYSA-M 1-hexyl-2,3-dimethylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCCCN1C=C[N+](C)=C1C NCTQEXWJEPRHLV-UHFFFAOYSA-M 0.000 description 1
- WWTKHYARIDYUKG-UHFFFAOYSA-N 1-hexyl-2,3-dimethylimidazol-3-ium;trifluoroborane Chemical compound FB(F)F.CCCCCCN1C=C[N+](C)=C1C WWTKHYARIDYUKG-UHFFFAOYSA-N 0.000 description 1
- BQBJIBLQQWXKBH-UHFFFAOYSA-M 1-hexyl-2,3-dimethylimidazol-3-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCCCC[N+]=1C=CN(C)C=1C BQBJIBLQQWXKBH-UHFFFAOYSA-M 0.000 description 1
- BGSUDDILQRFOKZ-UHFFFAOYSA-M 1-hexyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCCCN1C=C[N+](C)=C1 BGSUDDILQRFOKZ-UHFFFAOYSA-M 0.000 description 1
- RABFGPMWVQNDHI-UHFFFAOYSA-M 1-hexyl-3-methylimidazol-3-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCCCC[N+]=1C=CN(C)C=1 RABFGPMWVQNDHI-UHFFFAOYSA-M 0.000 description 1
- NKRASMXHSQKLHA-UHFFFAOYSA-M 1-hexyl-3-methylimidazolium chloride Chemical compound [Cl-].CCCCCCN1C=C[N+](C)=C1 NKRASMXHSQKLHA-UHFFFAOYSA-M 0.000 description 1
- SZRSEFNUSHACPD-UHFFFAOYSA-M 1-hexylpyridin-1-ium;bromide Chemical compound [Br-].CCCCCC[N+]1=CC=CC=C1 SZRSEFNUSHACPD-UHFFFAOYSA-M 0.000 description 1
- JEOSMYVMLZTQOH-UHFFFAOYSA-M 1-hexylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCC[N+]1=CC=CC=C1 JEOSMYVMLZTQOH-UHFFFAOYSA-M 0.000 description 1
- QFAUKQKOJVLHEL-UHFFFAOYSA-M 1-hexylpyridin-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCCCC[N+]1=CC=CC=C1 QFAUKQKOJVLHEL-UHFFFAOYSA-M 0.000 description 1
- OGLIVJFAKNJZRE-UHFFFAOYSA-N 1-methyl-1-propylpiperidin-1-ium Chemical compound CCC[N+]1(C)CCCCC1 OGLIVJFAKNJZRE-UHFFFAOYSA-N 0.000 description 1
- LCXGSWXECDJESI-UHFFFAOYSA-M 1-methyl-3-octadecylimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCN1C=C[N+](C)=C1 LCXGSWXECDJESI-UHFFFAOYSA-M 0.000 description 1
- SDXDXENAFAXVMX-UHFFFAOYSA-M 1-methyl-3-tetradecylimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCN1C=C[N+](C)=C1 SDXDXENAFAXVMX-UHFFFAOYSA-M 0.000 description 1
- OXFBEEDAZHXDHB-UHFFFAOYSA-M 3-methyl-1-octylimidazolium chloride Chemical compound [Cl-].CCCCCCCCN1C=C[N+](C)=C1 OXFBEEDAZHXDHB-UHFFFAOYSA-M 0.000 description 1
- WSGXZBGUVSEGIN-UHFFFAOYSA-M FC(S(=O)(=O)[O-])(F)F.[Li+].C(CCC)N1CN(C=C1)C Chemical compound FC(S(=O)(=O)[O-])(F)F.[Li+].C(CCC)N1CN(C=C1)C WSGXZBGUVSEGIN-UHFFFAOYSA-M 0.000 description 1
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- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WUFQNPMBKMKEHN-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;diethyl-(2-methoxyethyl)-methylazanium Chemical compound CC[N+](C)(CC)CCOC.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F WUFQNPMBKMKEHN-UHFFFAOYSA-N 0.000 description 1
- NFLGAVZONHCOQE-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;trimethyl(propyl)azanium Chemical compound CCC[N+](C)(C)C.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F NFLGAVZONHCOQE-UHFFFAOYSA-N 0.000 description 1
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- BXHHZLMBMOBPEH-UHFFFAOYSA-N diethyl-(2-methoxyethyl)-methylazanium Chemical compound CC[N+](C)(CC)CCOC BXHHZLMBMOBPEH-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
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- 238000007733 ion plating Methods 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- RVKZDIDATLDTNR-UHFFFAOYSA-N sulfanylideneeuropium Chemical compound [Eu]=S RVKZDIDATLDTNR-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Description
本発明は、ナノ粒子の製造方法及びナノ粒子分散液に関し、詳しくはコアシェル構造を持つナノ粒子の製造方法及びそのナノ粒子分散液に関する。 The present invention relates to a method for producing nanoparticles and a nanoparticle dispersion, and more particularly to a method for producing nanoparticles having a core-shell structure and the nanoparticle dispersion.
本発明者らは、ナノ粒子の製造方法として、スライドガラス上にイオン液体を載せ、これを蒸着装置内に静置し、イオン液体に対向する位置にターゲット材として所定の金属（例えば金）を装着し、そのスパッタリングを行うことにより、所定の金属のナノ粒子がイオン液体に分散した分散液を得る方法を開示している（特許文献１）。この方法によれば、ターゲット材からナノ粒子を直接製造するため、煩雑な操作を必要とせずにナノ粒子を得ることができるし、副生成物もないという利点がある。同様の方法は、特許文献２にも開示されている。一方、コアシェル構造を持つナノ粒子も知られている。例えば、ケミカルデポジションの手法を用いて、金をコアとしパラジウムをシェルとするコアシェル構造のナノ粒子を得る例が報告されている（非特許文献１）。この非特許文献１では、化学還元法で金属イオンを還元することによって金をコアとしパラジウムをシェルとするコアシェル構造のナノ粒子を作製している。 As a method for producing nanoparticles, the present inventors put an ionic liquid on a slide glass, place it in a vapor deposition apparatus, and place a predetermined metal (for example, gold) as a target material at a position facing the ionic liquid. A method for obtaining a dispersion liquid in which nanoparticles of a predetermined metal are dispersed in an ionic liquid by mounting and performing sputtering is disclosed (Patent Document 1). According to this method, since the nanoparticles are directly produced from the target material, there is an advantage that the nanoparticles can be obtained without requiring a complicated operation and there are no by-products. A similar method is also disclosed in Patent Document 2. On the other hand, nanoparticles having a core-shell structure are also known. For example, there has been reported an example in which nanoparticles having a core-shell structure with gold as a core and palladium as a shell are obtained using a chemical deposition technique (Non-patent Document 1). In Non-Patent Document 1, core-shell nanoparticles with gold as a core and palladium as a shell are produced by reducing metal ions by a chemical reduction method.
しかしながら、非特許文献１に記載された製造方法では、酸化還元電位の違いを利用しているため、金属の種類が限定され、汎用性が低いという問題があった。また、還元反応を順次実施するため、製造手順が煩雑になるという問題があった。 However, since the manufacturing method described in Non-Patent Document 1 uses the difference in redox potential, there are problems that the types of metals are limited and the versatility is low. In addition, since the reduction reaction is sequentially performed, there is a problem that the manufacturing procedure becomes complicated.
本発明はこのような課題を解決するためになされたものであり、金属の種類を限定することなく簡単な操作によりコアシェル構造のナノ粒子を製造することを主目的とする。 The present invention has been made to solve such problems, and has as its main object to produce core-shell structured nanoparticles by a simple operation without limiting the type of metal.
本発明者らは、コアシェル構造を持つナノ粒子を製造するにあたり、イオン液体に金属のスパッタリングを行う手法を適用できないかを種々検討した結果、まずイオン液体に金をスパッタリングしたあと、引き続きそのイオン液体にインジウムをスパッタリングすると、金をコアとしインジウム酸化物をシェルとするコアシェル構造のナノ粒子が得られることを見いだし、本発明を完成するに至った。 As a result of various studies on whether or not a technique of sputtering metal to an ionic liquid can be applied to the production of nanoparticles having a core-shell structure, the present inventors first sputtered gold into the ionic liquid, and then continued to the ionic liquid. When indium was sputtered on, it was found that core-shell nanoparticles having gold as a core and indium oxide as a shell were obtained, and the present invention was completed.
すなわち、本発明のナノ粒子の製造方法は、イオン液体に第１金属を蒸着することにより前記第１金属のナノ粒子が分散されたイオン液体を得たあと、引き続き前記第１金属のナノ粒子の表面が酸化されていない状態で前記イオン液体に第２金属を蒸着することにより前記第１金属をコアとし前記第２金属及び／又はその酸化物をシェルとするコアシェル構造のナノ粒子を得るものである。 That is, in the method for producing nanoparticles of the present invention, after obtaining the ionic liquid in which the first metal nanoparticles are dispersed by depositing the first metal on the ionic liquid, By depositing a second metal on the ionic liquid in a state where the surface is not oxidized, a core-shell nanoparticle having the first metal as a core and the second metal and / or its oxide as a shell is obtained. is there.
本発明のナノ粒子の製造方法によれば、イオン液体に第１金属と第２金属のスパッタリングを連続して行うという簡単な操作により、コアシェル構造を持つナノ粒子を得ることができる。また、化学還元法などを利用するものではないため、第１金属と第２金属とは組み合わせも制限されず、汎用性が高い。このコアシェル構造を持つナノ粒子が凝集したとしても、シェルが存在していることからコアをなす第１金属同士が凝集することはない。このため、例えばコアをなす第１金属が触媒機能を有し、シェルが多孔性を有する場合、このナノ粒子が凝集したとしても、反応基質が多孔性のシェルを通じて効率よくコアと接触することができるため、第１金属の触媒機能を十分発揮することができる。 According to the method for producing nanoparticles of the present invention, nanoparticles having a core-shell structure can be obtained by a simple operation of continuously performing sputtering of a first metal and a second metal on an ionic liquid. Moreover, since a chemical reduction method or the like is not used, the combination of the first metal and the second metal is not limited, and versatility is high. Even if the nanoparticles having the core-shell structure are aggregated, the first metal forming the core does not aggregate because the shell exists. For this reason, for example, when the first metal forming the core has a catalytic function and the shell has porosity, even if the nanoparticles are aggregated, the reaction substrate can efficiently contact the core through the porous shell. Therefore, the catalytic function of the first metal can be sufficiently exhibited.
本発明のナノ粒子の製造方法は、イオン液体に第１金属を蒸着することにより前記第１金属のナノ粒子が分散されたイオン液体を得たあと、引き続き前記第１金属のナノ粒子の表面が酸化されていない状態で前記イオン液体に第２金属を蒸着することにより前記第１金属をコアとし前記第２金属及び／又はその酸化物をシェルとするコアシェル構造のナノ粒子を得るものである。 In the method for producing nanoparticles according to the present invention, after obtaining the ionic liquid in which the first metal nanoparticles are dispersed by depositing the first metal on the ionic liquid, the surface of the first metal nanoparticles is continuously applied. By depositing a second metal on the ionic liquid in an unoxidized state, a core-shell nanoparticle having the first metal as a core and the second metal and / or its oxide as a shell is obtained.
本発明のナノ粒子の製造方法において、第１金属のナノ粒子が分散されたイオン液体に第２金属を蒸着する際には、第１金属のナノ粒子の表面が酸化されていないことが必要である。第１金属のナノ粒子の表面が酸化されている場合には、第２金属が第１金属を包み込むことができず、イオン液体中に第１金属のナノ粒子と第２金属のナノ粒子が混合分散した状態となってしまう。このため、第１金属は第２金属に比べて酸化されにくいものを用いることが好ましく、貴金属を用いることがより好ましい。第１金属が第２金属に比べて酸化されやすいものを用いると、第１金属と第２金属とを順次イオン液体に蒸着したとしても、コアシェル構造のナノ粒子は得られないことがある。この場合、おそらく、酸化しやすい第１金属のナノ粒子が生成したあと、第２金属の蒸着の準備中に第１金属のナノ粒子が空気と接触して表面が酸化されてしまったことが原因だと思われる。なお、貴金属とは、Ａｕ，Ａｇ，Ｐｔ，Ｐｄ，Ｒｈ，Ｉｒ，Ｒｕ，Ｏｓの８つの元素をいう。 In the method for producing nanoparticles according to the present invention, when the second metal is deposited on the ionic liquid in which the first metal nanoparticles are dispersed, it is necessary that the surface of the first metal nanoparticles is not oxidized. is there. When the surface of the first metal nanoparticles is oxidized, the second metal cannot encapsulate the first metal, and the first metal nanoparticles and the second metal nanoparticles are mixed in the ionic liquid. It will be in a distributed state. For this reason, it is preferable to use the first metal that is less likely to be oxidized than the second metal, and it is more preferable to use a noble metal. If the first metal is more easily oxidized than the second metal, even if the first metal and the second metal are sequentially deposited on the ionic liquid, the core-shell structure nanoparticles may not be obtained. In this case, the first metal nanoparticles that are likely to oxidize are generated, and then the surface of the first metal nanoparticles contacted with air during the preparation for vapor deposition of the second metal and the surface was oxidized. I think. The noble metal refers to eight elements of Au, Ag, Pt, Pd, Rh, Ir, Ru, and Os.
イオン液体とは、陽イオンと陰イオンのみから構成される塩であるにもかかわらず常温で液体である一連の化合物をいう。イオン液体は、高温でも安定であり液体温度範囲が広い、蒸気圧が略ゼロ、イオン性でありながら低粘性、高い酸化・還元耐性などの特性を有している。本発明に適用可能なイオン液体は、親水性であっても疎水性であってもよく、またその種類は特に限定されるものではないが、例えば脂肪族系イオン液体、イミダゾリウム系イオン液体、ピリジニウム系イオン液体などが挙げられる。脂肪族系イオン液体としては、Ｎ，Ｎ，Ｎ−トリメチル−Ｎ−プロピルアンモニウムビス（トリフルオロメタンスルホニル）アミド（以下、ＴＭＰＡ−ＴＦＳＡという）やＮ−メチル−Ｎ−プロピルピペリジニウムビス（トリフルオロメタンスルホニル）アミド、Ｎ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−（２−メトキシエチル）アンモニウムビス（トリフルオロメタンスルホニル）アミド、Ｎ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−（２−メトキシエチル）アンモニウムテトラフルオロホウ酸塩などを挙げることができる。イミダゾリウム系イオン液体としては、１，３−ジアルキルイミダゾリウム塩、１，２，３−トリアルキルイミダゾリウム塩などが挙げられる。具体的には、１，３−ジアルキルイミダゾリウム塩としては、１−エチル−３−メチルイミダゾリウムブロマイドや１−エチル−３−メチル−イミダゾリウムクロライド、１−エチル−３−メチルイミダゾリウム（Ｌ）−乳酸塩、１−エチル−３−メチルイミダゾリウムヘキサフルオロリン酸塩、１−エチル−３−メチルイミダゾリウムテトラフルオロホウ酸塩（以下、ＥＭＩ−ＢＦ４という）、１−ブチル−３−メチルイミダゾリウムクロライド、１−ブチル−３−メチルイミダゾリウムヘキサフルオロリン酸塩、１−ブチル−３−メチルイミダゾリウムテトラフルオロホウ酸塩（以下、ＢＭＩ−ＢＦ４という）、１−ブチル−３−メチルイミダゾリウムトリフルオロメタンスルホン酸塩、１−ブチル−３−メチルイミダゾリウム（Ｌ）−乳酸塩、１−ヘキシル−３−メチルイミダゾリウムブロマイド、１−ヘキシル−３−メチルイミダゾリウムクロライド、１−ヘキシル−３−メチルイミダゾリウムヘキサフルオロリン酸塩、１−ヘキシル−３−メチルイミダゾリウムテトラフルオロホウ酸塩、１−ヘキシル−３−メチルイミダゾリウムトリフルオロメタンスルホン酸塩、１−オクチル−３−メチルイミダゾリウムクロライド、１−オクチル−３−メチルイミダゾリウムヘキサフルオロリン酸塩、１−デシル−３−メチルイミダゾリウムクロライド、１−ドデシル−３−メチルイミダゾリウムクロライド、１−テトラデシル−３−メチルイミダゾリウムクロライド、１−ヘキサデシル−３−メチルイミダゾリウムクロライド、１−オクタデシル−３−メチルイミダゾリウムクロライドなどが挙げられる。１，２，３−トリアルキルイミダゾリウム塩としては、１−エチル−２，３−ジメチルイミダゾリウムブロマイドや１−エチル−２，３−ジメチルイミダゾリウムクロライド、１−ブチル−２，３−ジメチルイミダゾリウムブロマイド、１−ブチル−２，３−ジメチルイミダゾリウムクロライド、１−ブチル−２，３−ジメチルイミダゾリウムテトラフルオロホウ酸塩、１−ブチル−２，３−ジメチルイミダゾリウムトリフルオロメタンスルホン酸塩、１−ヘキシル−２，３−ジメチルイミダゾリウムブロマイド、１−ヘキシル−２，３−ジメチルイミダゾリウムクロライド、１−ヘキシル−２，３−ジメチルイミダゾリウムトラフルオロホウ酸塩、１−ヘキシル−２，３−ジメチルイミダゾリウムトリフルオロメタンスルホン酸塩などが挙げられる。また、ピリジニウム系イオン液体としては、エチルピリジニウム塩やブチルピリジニウム塩、ヘキシルピリジニウム塩などが挙げられる。具体的には、エチルピリジニウム塩としては、１−エチルピリジニウムブロマイドや１−エチルピリジニウムクロライドが挙げられ、ブチルピリジニウム塩としては、１−ブチルピリジニウムブロマイドや１−ブチルピリジニウムクロライド、１−ブチルピリジニウムヘキサフルオロリン酸塩、１−ブチルピリジニウムテトラフルオロホウ酸塩、１−ブチルピリジニウムトリフルオロメタンスルホン酸塩などが挙げられ、ヘキシルピリジニウム塩としては、１−ヘキシルピリジニウムブロマイドや１−ヘキシルピリジニウムクロライド、１−ヘキシルピリジニウムヘキサフルオロリン酸塩、１−ヘキシルピリジニウムテトラフルオロホウ酸塩、１−ヘキシルピリジニウムトリフルオロメタンスルホン酸塩などが挙げられる。 An ionic liquid refers to a series of compounds that are liquid at room temperature despite being a salt composed only of cations and anions. The ionic liquid is stable even at high temperatures, has a wide liquid temperature range, has a vapor pressure of substantially zero, has ionic properties, low viscosity, and high oxidation / reduction resistance. The ionic liquid applicable to the present invention may be hydrophilic or hydrophobic, and the type thereof is not particularly limited. For example, aliphatic ionic liquid, imidazolium ionic liquid, Examples include pyridinium-based ionic liquids. Examples of aliphatic ionic liquids include N, N, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) amide (hereinafter referred to as TMPA-TFSA) and N-methyl-N-propylpiperidinium bis (trifluoromethane). Sulfonyl) amide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) amide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium Examples thereof include tetrafluoroborate. Examples of the imidazolium-based ionic liquid include 1,3-dialkylimidazolium salts and 1,2,3-trialkylimidazolium salts. Specifically, 1,3-dialkylimidazolium salts include 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methyl-imidazolium chloride, 1-ethyl-3-methylimidazolium (L ) -Lactate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate (hereinafter referred to as EMI-BF4), 1-butyl-3-methyl Imidazolium chloride, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate (hereinafter referred to as BMI-BF4), 1-butyl-3-methylimidazole Lithium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium (L)- Acid salt, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium tetra Fluoroborate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-decyl- 3-methylimidazolium chloride, 1-dodecyl-3-methylimidazolium chloride, 1-tetradecyl-3-methylimidazolium chloride, 1-hexadecyl-3-methylimidazolium chloride, 1-octadecyl-3-methylimidazolium chloride Ido and the like. Examples of 1,2,3-trialkylimidazolium salts include 1-ethyl-2,3-dimethylimidazolium bromide, 1-ethyl-2,3-dimethylimidazolium chloride, and 1-butyl-2,3-dimethylimidazole. Lithium bromide, 1-butyl-2,3-dimethylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-hexyl-2,3-dimethylimidazolium bromide, 1-hexyl-2,3-dimethylimidazolium chloride, 1-hexyl-2,3-dimethylimidazolium trifluoroborate, 1-hexyl-2,3 -Dimethylimidazolium trifluoromethanesulfonate It is. Examples of pyridinium-based ionic liquids include ethyl pyridinium salts, butyl pyridinium salts, and hexyl pyridinium salts. Specifically, examples of the ethylpyridinium salt include 1-ethylpyridinium bromide and 1-ethylpyridinium chloride, and examples of the butylpyridinium salt include 1-butylpyridinium bromide, 1-butylpyridinium chloride and 1-butylpyridinium hexafluoro. Examples thereof include phosphate, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium trifluoromethanesulfonate, etc. Examples of hexylpyridinium salts include 1-hexylpyridinium bromide, 1-hexylpyridinium chloride, and 1-hexylpyridinium. Examples include hexafluorophosphate, 1-hexylpyridinium tetrafluoroborate, 1-hexylpyridinium trifluoromethanesulfonate, and the like.
これらのイオン液体のうち、例えば、親水性の高いイミダゾリウム系化合物としてＥＭＩ−ＢＦ４やＢＭＩ−ＢＦ４を本発明に用いたり、疎水性の高い脂肪族系化合物としてＴＭＰＡ−ＴＦＳＡなどを本発明に用いたりすることができる。 Of these ionic liquids, for example, EMI-BF4 or BMI-BF4 is used in the present invention as a highly hydrophilic imidazolium compound, or TMPA-TFSA is used in the present invention as a highly hydrophobic aliphatic compound. Can be.
本発明のナノ粒子の製造方法において、蒸着は、周知の化学蒸着法（ＣＶＤ法）や物理蒸着法（ＰＶＤ法）などの乾式成膜法により基板上にナノ粒子を析出させるのと同様の装置・手順で実施可能であるが、このうち、固体状態の金属から金属原子を蒸発させるか又は叩き出すことにより成膜する物理蒸着法（例えば、真空蒸着法やイオンプレーティング法、スパッタリング法など）が好ましい。物理蒸着法によれば、バルク材料からナノ粒子を比較的簡単な系で直接製造することができる。また、物理蒸着法のうちスパッタリング法がより好ましい。スパッタリング法では、金属の蒸発を行う際にるつぼを必要としないため、純度の高いナノ粒子を製造することができる。なお、蒸発原理としては、真空蒸着法の場合には、例えば抵抗加熱方式や遠赤外線加熱方式、電子ビーム加熱方式、アーク加熱方式、高周波誘導加熱方式などを用いることができ、イオンプレーティング法の場合には、例えば高周波励起方式やイオンビーム方式、クラスタ方式などを用いることができ、スパッタリング法の場合には、例えばＤＣスパッタ方式、マグネトロンスパッタ方式、高周波スパッタ方式、イオンビームスパッタ方式などを用いることができる。 In the method for producing nanoparticles according to the present invention, the vapor deposition is the same as that for depositing nanoparticles on a substrate by a dry film forming method such as a well-known chemical vapor deposition method (CVD method) or physical vapor deposition method (PVD method). -Although it is possible to carry out according to the procedure, among these, physical vapor deposition method (for example, vacuum deposition method, ion plating method, sputtering method, etc.) that forms a film by evaporating or knocking out metal atoms from a solid state metal Is preferred. According to the physical vapor deposition method, nanoparticles can be directly produced from a bulk material in a relatively simple system. Of the physical vapor deposition methods, the sputtering method is more preferable. The sputtering method does not require a crucible when performing metal evaporation, so that highly pure nanoparticles can be produced. As the evaporation principle, in the case of the vacuum deposition method, for example, a resistance heating method, a far infrared heating method, an electron beam heating method, an arc heating method, a high frequency induction heating method, etc. can be used. In this case, for example, a high frequency excitation method, an ion beam method, a cluster method, or the like can be used. In the case of a sputtering method, for example, a DC sputtering method, a magnetron sputtering method, a high frequency sputtering method, an ion beam sputtering method, or the like is used. Can do.
本発明のナノ粒子の製造方法において、シェルは多孔性であることが好ましい。コアシェル構造を持つナノ粒子が凝集したとしても、シェルが存在していることからコアをなす第１金属同士が凝集することはない。このため、例えばコアをなす第１金属が触媒機能を有し、シェルが多孔性を有する場合、このナノ粒子が凝集したとしても、反応基質が多孔性のシェルを通じて効率よくコアと接触することができるため、第１金属の触媒機能を十分発揮することができる。 In the method for producing nanoparticles of the present invention, the shell is preferably porous. Even if the nanoparticles having the core-shell structure are aggregated, the first metals forming the core are not aggregated because the shell is present. For this reason, for example, when the first metal forming the core has a catalytic function and the shell has porosity, even if the nanoparticles are aggregated, the reaction substrate can efficiently contact the core through the porous shell. Therefore, the catalytic function of the first metal can be sufficiently exhibited.
本発明のナノ粒子の製造方法においては、第１金属や第２金属をイオン液体に蒸着させる際、減圧下で行うのが好ましい。減圧下で行えば、純度の高いナノ粒子を短時間で生成することができる。ここで、「減圧下」とは、気圧が大気よりも低い状態であればよく、好ましくは２０Ｐａ以下である。 In the method for producing nanoparticles of the present invention, the first metal or the second metal is preferably deposited under reduced pressure when vapor-deposited on the ionic liquid. If performed under reduced pressure, highly pure nanoparticles can be produced in a short time. Here, “under reduced pressure” may be any pressure as long as the atmospheric pressure is lower than the atmosphere, and is preferably 20 Pa or less.
蒸着法としてスパッタリング法を採用する場合、ガス雰囲気下で行うとしてもよい。ガスを送り込む場合、使用するガスは希ガスが好ましく、アルゴンガスがより好ましい。このときのアルゴンガスの圧力は、２０Ｐａ以下が好ましい。蒸着電流の大きさは、原料や蒸着装置に応じて適宜設定すればよい。また、反応時間も反応温度やイオン液体の量などによって好ましい範囲が変わるが、数十秒〜数時間の範囲で設定するのが好ましく、３０秒〜２０分の範囲で設定するのがより好ましい。 When the sputtering method is employed as the vapor deposition method, it may be performed in a gas atmosphere. When the gas is fed, the gas used is preferably a rare gas, more preferably argon gas. The pressure of the argon gas at this time is preferably 20 Pa or less. What is necessary is just to set the magnitude | size of vapor deposition current suitably according to a raw material or a vapor deposition apparatus. The preferred range of the reaction time varies depending on the reaction temperature, the amount of ionic liquid, etc., but it is preferably set in the range of several tens of seconds to several hours, more preferably in the range of 30 seconds to 20 minutes.
蒸着法としてスパッタリング法を採用する場合、例えば以下のようにして行うとしてもよい。図１（ａ）に示すように、蒸着装置１０として、真空にすることが可能な蒸着チャンバー１２と、蒸着チャンバー１２の上面に設置されターゲット材１８を装着可能な陰極１４と、陰極１４に対向する位置に設置された陽極１６とを備えたものを使用する場合には、まず、第１金属からなるターゲット材１８を陰極１４に装着し、イオン液体２２を載せたガラス基板２０を陽極１６上に配置する。そして、蒸着チャンバー１２内を真空又はガス雰囲気下（例えばアルゴンガスなど）にした状態で陰極１４に高電圧を印加する。すると、蒸着チャンバー１２内にグロー放電が発生し、グロー放電によって生じたガスイオンがターゲット材１８に衝突することにより、ターゲット材１８を構成している第１金属の原子がスパッタ蒸発される。そして、ターゲット材１８からたたき出された第１金属の原子が対面するイオン液体２２に入り込み、第１金属の原子から構成されるナノ粒子がイオン液体２２に分散する。続いて、図１（ｂ）に示すように、陰極１４に第２金属からなるターゲット材２４を装着し、第２金属の原子をスパッタ蒸発させる。すると、ターゲット材２４からたたき出された第２金属の原子が対面するイオン液体２２に入り込む。このとき、イオン液体２２に分散している第１の金属が酸化されていなければ、第２金属の原子は第１の金属の原子から構成されるナノ粒子の周りを取り囲む。その結果、イオン液体２２には、第１の金属からなるコアと第２の金属及び／又はその酸化物からなるシェルとを備えたナノ粒子が分散した状態となる。そして、図１（ｃ）に示すように、こうしたコアシェル構造を持つナノ粒子が分散したイオン液体２２をガラス基板２０から試験管２６に回収する。 When the sputtering method is employed as the vapor deposition method, for example, it may be performed as follows. As shown in FIG. 1A, as a vapor deposition apparatus 10, a vapor deposition chamber 12 that can be evacuated, a cathode 14 that is installed on the upper surface of the vapor deposition chamber 12 and can be fitted with a target material 18, and faces the cathode 14. In the case of using the one provided with the anode 16 installed at the position to be used, first, the target material 18 made of the first metal is mounted on the cathode 14, and the glass substrate 20 on which the ionic liquid 22 is placed is placed on the anode 16. To place. Then, a high voltage is applied to the cathode 14 in a state where the inside of the vapor deposition chamber 12 is in a vacuum or a gas atmosphere (for example, argon gas). Then, glow discharge is generated in the vapor deposition chamber 12, and gas ions generated by the glow discharge collide with the target material 18, so that atoms of the first metal constituting the target material 18 are sputter evaporated. Then, atoms of the first metal knocked out from the target material 18 enter the ionic liquid 22 facing each other, and nanoparticles composed of the atoms of the first metal are dispersed in the ionic liquid 22. Subsequently, as shown in FIG. 1B, a target material 24 made of a second metal is mounted on the cathode 14, and atoms of the second metal are sputter evaporated. Then, the atoms of the second metal knocked out from the target material 24 enter the ionic liquid 22 facing each other. At this time, if the first metal dispersed in the ionic liquid 22 is not oxidized, the atoms of the second metal surround the nanoparticles composed of the atoms of the first metal. As a result, in the ionic liquid 22, nanoparticles having a core made of the first metal and a shell made of the second metal and / or an oxide thereof are dispersed. And as shown in FIG.1 (c), the ionic liquid 22 in which the nanoparticle which has such a core-shell structure was disperse | distributed is collect | recovered from the glass substrate 20 to the test tube 26. FIG.
このようにして得られるコアシェル構造を持つナノ粒子のサイズは、特に限定するものではないが、例えばコアの直径は１〜１０ｎｍ程度、シェルの厚さは０．５〜２ｎｍ程度である。コアの直径やシェルの厚みは、用いるイオン液体の性質（例えば親水性、疎水性など）や反応時間の長短などによって変化すると考えられる。 The size of the nanoparticles having the core-shell structure thus obtained is not particularly limited. For example, the diameter of the core is about 1 to 10 nm and the thickness of the shell is about 0.5 to 2 nm. The diameter of the core and the thickness of the shell are considered to vary depending on the properties of the ionic liquid used (for example, hydrophilicity, hydrophobicity, etc.) and the length of the reaction time.
本発明のナノ粒子の製造方法によって得られるコアシェル構造を持つナノ粒子は、シェルが多孔性を有していると考えられる。この点は、以下の実験事実によって支持される。すなわち、図１（ａ）の蒸着装置１０において、インジウムからなるターゲット材１８を陰極１４に装着し、イオン液体２２にインジウムナノ粒子を分散させたところ、コア部分にインジウム、シェル部分にアモルファスの酸化インジウムが存在する中実ナノ粒子が得られた。この中実ナノ粒子を分散させたイオン液体を空気中で２５０℃、１時間加熱したところ、中が空洞の中空ナノ粒子が得られた。この中空ナノ粒子は、酸化インジウムから構成されているものであった。この実験事実から、反応メカニズムは、コア部分がインジウム、シェル部分が酸化インジウムの中実ナノ粒子を空気中で加熱すると、シェル部分の微小隙間を通じて空気中の酸素とコア部分のインジウムとが反応して酸化インジウムが生成し、それと共にコア部分に空洞が生じたと考えられる。なお、もしシェル部分が緻密であれば、空気中で加熱したとしてもコア部分のインジウムと空気中の酸素とは反応せず、中実ナノ粒子のまま変化しないと考えられる。 The nanoparticles having a core-shell structure obtained by the method for producing nanoparticles of the present invention are considered to have a porous shell. This point is supported by the following experimental facts. That is, in the vapor deposition apparatus 10 of FIG. 1A, when the target material 18 made of indium is mounted on the cathode 14 and indium nanoparticles are dispersed in the ionic liquid 22, indium is formed in the core portion and amorphous oxidation is formed in the shell portion. Solid nanoparticles with indium present were obtained. When the ionic liquid in which the solid nanoparticles were dispersed was heated in air at 250 ° C. for 1 hour, hollow nanoparticles having a hollow inside were obtained. The hollow nanoparticles were composed of indium oxide. From this experimental fact, the reaction mechanism is as follows. When solid nanoparticles of indium oxide in the core part and indium oxide in the shell part are heated in air, oxygen in the air reacts with indium in the core part through a minute gap in the shell part. It is considered that indium oxide was generated and a cavity was formed at the same time. If the shell part is dense, even if heated in the air, the indium in the core part and oxygen in the air do not react and remain solid nanoparticles.
本発明のナノ粒子の製造方法により製造されたナノ粒子をイオン液体から回収するには、用いたイオン液体に該イオン液体と親和性の高い溶媒を添加することにより行うことができる。すなわち、イオン液体と親和性の高い溶媒を該イオン液体に添加することにより、イオン液体中のナノ粒子が沈降する。このように、煩雑な操作を必要とすることなくイオン液体からナノ粒子を回収することができる。ここで、イオン液体と親和性の高い溶媒とは、例えばイオン液体として親水性のものを用いた場合には水、メタノール、エタノール、アセトンなどを挙げることができ、疎水性のものを用いた場合にはエーテル、ヘプタン、クロロホルム、塩化メチレンなどが挙げられる。 The nanoparticles produced by the method for producing nanoparticles of the present invention can be recovered from the ionic liquid by adding a solvent having a high affinity for the ionic liquid to the used ionic liquid. That is, by adding a solvent having a high affinity for the ionic liquid to the ionic liquid, the nanoparticles in the ionic liquid are precipitated. Thus, nanoparticles can be recovered from the ionic liquid without requiring complicated operations. Here, the solvent having a high affinity with the ionic liquid can be exemplified by water, methanol, ethanol, acetone, etc. when a hydrophilic one is used as the ionic liquid, and when a hydrophobic one is used. Includes ether, heptane, chloroform, methylene chloride and the like.
以下、本発明の好適な実施例を詳しく説明する。下記の実施例及び比較例はいずれも図１の蒸着装置１０を用いて行った。実施例１は、第１金属としてＡｕ、第２金属としてＩｎを用いてコアシェル構造のナノ粒子が分散したイオン液体を製造した例であり、比較例１は、第１金属としてＩｎ、第２金属としてＡｕを用いてＩｎナノ粒子とＡｕナノ粒子とが混合分散したイオン液体を製造した例である。実施例２は、第１金属としてＡｕ、第２金属としてＳｎを用いてコアシェル構造のナノ粒子が分散したイオン液体を製造した例である。 Hereinafter, preferred embodiments of the present invention will be described in detail. The following examples and comparative examples were both performed using the vapor deposition apparatus 10 of FIG. Example 1 is an example of producing an ionic liquid in which nanoparticles of a core-shell structure are dispersed using Au as the first metal and In as the second metal, and Comparative Example 1 is In and the second metal. In this example, Au is used to produce an ionic liquid in which In nanoparticles and Au nanoparticles are mixed and dispersed. Example 2 is an example of manufacturing an ionic liquid in which nanoparticles of a core-shell structure are dispersed using Au as the first metal and Sn as the second metal.
［実施例１］
１２０℃で３時間減圧加熱を行ったイオン液体（ＥＭＩ−ＢＦ４）０．６０ｃｍ3をスライドガラス上に広げ、Ａｕをターゲット材としてイオン液体に向かってスパッタ蒸着を行った。具体的には、チャンバー内はアルゴンガスで置換し、圧力２．０Ｐａ、スパッタ電流１０ｍＡ、スパッタ時間５分とした。このイオン液体を「実施例１Ａ」と称する。次に、スライドガラス上のイオン液体はそのままとし、Ｉｎをターゲット材として、イオン液体に向かってスパッタ蒸着を行った。具体的には、チャンバー内はアルゴンガスで置換し、圧力２．０Ｐａ、スパッタ電流１０ｍＡ、スパッタ時間３０分とした。その後、スライドガラス上のイオン液体０．１０ｃｍ3を試験管に回収した。このイオン液体を「実施例１Ｂ」と称する。そして、回収したイオン液体を大気圧下、２５０℃で１時間、ホットスターラーで加熱した。このイオン液体を「実施例１Ｃ」と称する。
[Example 1]
An ionic liquid (EMI-BF4) 0.60 cm 3 heated under reduced pressure at 120 ° C. for 3 hours was spread on a slide glass, and sputtering deposition was performed toward the ionic liquid using Au as a target material. Specifically, the inside of the chamber was replaced with argon gas, and the pressure was 2.0 Pa, the sputtering current was 10 mA, and the sputtering time was 5 minutes. This ionic liquid is referred to as “Example 1A”. Next, the ionic liquid on the slide glass was left as it was, and sputter deposition was performed toward the ionic liquid using In as a target material. Specifically, the inside of the chamber was replaced with argon gas, and the pressure was 2.0 Pa, the sputtering current was 10 mA, and the sputtering time was 30 minutes. Thereafter, 0.10 cm 3 of the ionic liquid on the slide glass was collected in a test tube. This ionic liquid is referred to as “Example 1B”. And the collect | recovered ionic liquid was heated with the hot stirrer at 250 degreeC under atmospheric pressure for 1 hour. This ionic liquid is referred to as “Example 1C”.
図２は、実施例１Ｂ、実施例１Ｃの吸収スペクトルのグラフである。図２には、比較のために実施例１Ａ（Ａｕのみ）、Ｉｎのみの吸収スペクトルも併せて示す。実施例１Ｂでは、３００ｎｍ付近のＩｎ由来とみられるピークが観察されたが、５００ｎｍ付近のＡｕ由来とみられるピークは観察されなかった。このことから、実施例１Ｂのイオン液体に分散しているナノ粒子は、蒸着したＩｎあるいはその酸化物によってＡｕ粒子が被覆され、Ａｕ粒子の未修飾表面が露出していないと考えられる。一方、実施例１Ｃでは、Ｉｎ由来とみられるピークもＡｕ由来とみられるピークも観察された。このことから、実施例１Ｂのイオン液体に分散しているナノ粒子は、ＩｎだけでなくＡｕも表面に現れていると考えられ、加熱処理によって表面組成が変化したと考えられる。 FIG. 2 is a graph of the absorption spectra of Example 1B and Example 1C. FIG. 2 also shows the absorption spectra of Example 1A (Au only) and In only for comparison. In Example 1B, a peak considered to be derived from In near 300 nm was observed, but a peak considered to be derived from Au near 500 nm was not observed. From this, it is considered that the nanoparticles dispersed in the ionic liquid of Example 1B are covered with the Au particles by the deposited In or its oxide, and the unmodified surface of the Au particles is not exposed. On the other hand, in Example 1C, a peak that appears to be derived from In and a peak that appears to be derived from Au were also observed. From this, it is considered that the nanoparticles dispersed in the ionic liquid of Example 1B appeared not only with In but also Au on the surface, and the surface composition was changed by the heat treatment.
図３は、実施例１Ａのイオン液体中の粒子のＴＥＭ像の写真（図３（ａ））及び粒径のヒストグラム（図３（ｂ））である。図３に示すように、実施例１Ａには、平均粒径が２．８±０．５ｎｍのＡｕ粒子が分散していることが確認された。また、粒子の形状は球形で、大きな凝集体も観察されなかった。 FIG. 3 is a photograph (FIG. 3A) of a TEM image of particles in the ionic liquid of Example 1A and a histogram of particle diameter (FIG. 3B). As shown in FIG. 3, it was confirmed that Au particles having an average particle diameter of 2.8 ± 0.5 nm were dispersed in Example 1A. Moreover, the shape of the particles was spherical, and no large aggregates were observed.
図４は、実施例１Ｂのイオン液体中の粒子のＴＥＭ像の写真である。図４のＴＥＭ像のコントラスト強度比から、コアシェル構造を持つナノ粒子が観察された。図４のＴＥＭ像からこのナノ粒子の粒径、コア径、シェル厚を計測したところ、それぞれ５．５±０．８ｎｍ，２．８±０．４ｎｍ，１．４±０．３ｎｍであった。コア径の値は、図３に示したＡｕ粒子の粒径と一致することから、コアシェル構造を持つナノ粒子はコア部分がＡｕであり、シェル部分がＩｎ又はその酸化物であると考えられた。その確認のために、このナノ粒子のＸＰＳ及びＨＲＴＥＭ測定を行った。 FIG. 4 is a photograph of a TEM image of particles in the ionic liquid of Example 1B. From the contrast intensity ratio of the TEM image in FIG. 4, nanoparticles having a core-shell structure were observed. When the particle size, core diameter, and shell thickness of the nanoparticles were measured from the TEM image of FIG. 4, they were 5.5 ± 0.8 nm, 2.8 ± 0.4 nm, and 1.4 ± 0.3 nm, respectively. . Since the value of the core diameter coincided with the particle diameter of the Au particles shown in FIG. 3, it was considered that the core part of the nanoparticles having the core-shell structure was Au in the core part and In or its oxide in the shell part. . For confirmation, XPS and HRTEM measurements were performed on the nanoparticles.
実施例１Ｂのイオン液体中に生成した粒子のＸＰＳスペクトルを、図５に示す。図５のＸＰＳスペクトルでは、Ｉｎの３ｄ5/2と３ｄ3/2のダブレットピークが観察された。これらピークを成分分離したところ、各々のピークが２成分のピークからなることがわかった。Ｉｎ ３ｄ5/2においては、４４６．８ｅＶのＩｎ2Ｏ3に帰属される大きなピークと４４４．１ｅＶのＩｎ金属に帰属される小さなピークとが存在することがわかった。Ｉｎ ３ｄ3/2においては、４５４．３ｅＶのＩｎ2Ｏ3の大きなピークと４５１．６ｅＶのＩｎ金属の小さなピークに分離できた。このことから、コアシェル粒子のシェルの大部分がＩｎ2Ｏ3から形成されることが示唆される。この粒子のＨＲＴＥＭ像を図６及び図７に示す。図６及び図７のＨＲＴＥＭ像では、明確な格子像を持つ粒子が観察された。格子面間隔を計測したところ、コア部分の格子面間隔は０．２４ｎｍでＡｕの｛１１１｝面に一致し、シェル部分の格子面間隔は０．２７ｎｍで菱面体型Ｉｎ2Ｏ3の｛１１０｝面に一致した（ＪＣＰＤＳデータファイル：Ｎｏ．２２−０３３６）。このことから、実施例１Ｂのイオン液体中に分散したナノ粒子は、コア部分がＡｕ、シェル部分がＩｎ2Ｏ3であることがわかった。 The XPS spectrum of the particles produced in the ionic liquid of Example 1B is shown in FIG. In the XPS spectrum of FIG. 5, Ind doublet peaks of 3d 5/2 and 3d 3/2 were observed. When these peaks were separated into components, it was found that each peak consists of two component peaks. In In 3d 5/2 , it was found that there was a large peak attributed to 446.8 eV In 2 O 3 and a small peak attributed to 444.1 eV In metal. In In 3d 3/2 , a large peak of 454.3 eV In 2 O 3 and a small peak of 451.6 eV In metal could be separated. This suggests that most of the shell of the core-shell particle is formed from In 2 O 3 . HRTEM images of these particles are shown in FIGS. In the HRTEM images of FIGS. 6 and 7, particles having a clear lattice image were observed. When the lattice spacing was measured, the lattice spacing of the core portion was 0.24 nm and coincided with the {111} plane of Au, and the lattice spacing of the shell portion was 0.27 nm and the rhombohedral In 2 O 3 {110 } Surface (JCPDS data file: No. 22-0336). From this, it was found that the nanoparticles dispersed in the ionic liquid of Example 1B had a core portion of Au and a shell portion of In 2 O 3 .
図８は、実施例１Ｃのイオン液体中の粒子のＴＥＭ像の写真、図９は、図８の部分拡大写真である。実施例１Ｃつまり加熱処理後の粒子は、実施例１Ｂつまり加熱処理前の粒子とほとんど粒径が変わらず、凝集もほとんどみられなかった。これは、実施例１Ｂのナノ粒子がコアシェル構造を持つため、加熱処理中における粒子の成長や凝集が妨げられたと考えられる。 8 is a photograph of a TEM image of particles in the ionic liquid of Example 1C, and FIG. 9 is a partially enlarged photograph of FIG. The particle diameter of Example 1C, that is, the heat-treated particle was almost the same as that of Example 1B, that is, the particle before the heat-treatment, and almost no aggregation was observed. This is probably because the nanoparticles of Example 1B had a core-shell structure, which prevented the growth and aggregation of the particles during the heat treatment.
図１０は、実施例１Ｂ、実施例１Ｃの各粒子のＸＲＤパターンのグラフである。図１０には、比較のためにＡｕ、Ｉｎ、Ｉｎ2Ｏ3のＸＲＤパターンも併せて示す。図１０から、実施例１Ｂ、実施例１Ｃのどちらの粒子も、Ａｕの｛１１１｝面に由来するピークが観察されたが、ＩｎやＩｎ2Ｏ3に由来するピークははっきりと観察されなかった。これは、各ナノ粒子のシェルの厚さが２ｎｍ以下と薄いため、測定上はピークとして現れなかったものと考えられる。 FIG. 10 is a graph of the XRD pattern of each particle of Example 1B and Example 1C. FIG. 10 also shows XRD patterns of Au, In, and In 2 O 3 for comparison. From FIG. 10, in both the particles of Example 1B and Example 1C, peaks derived from the {111} plane of Au were observed, but peaks derived from In and In 2 O 3 were not clearly observed. . It is considered that this was not shown as a peak in the measurement because the thickness of the shell of each nanoparticle was as thin as 2 nm or less.
［比較例１］
１２０℃で３時間減圧加熱を行ったイオン液体（ＥＭＩ−ＢＦ４）０．６０ｃｍ3をスライドガラス上に広げ、Ｉｎをターゲット材としてイオン液体に向かってスパッタ蒸着を行った。具体的には、チャンバー内はアルゴンガスで置換し、圧力２．０Ｐａ、スパッタ電流１０ｍＡ、スパッタ時間３０分とした。このときのイオン液体を「比較例１Ａ」と称する。次に、スライドガラス上のイオン液体はそのままとし、Ａｕをターゲット材として、イオン液体に向かってスパッタ蒸着を行った。具体的には、チャンバー内はアルゴンガスで置換し、圧力２．０Ｐａ、スパッタ電流１０ｍＡ、スパッタ時間５分とした。その後、スライドガラス上のイオン液体０．１０ｃｍ3を試験管に回収した。このときのイオン液体を「比較例１Ｂ」と称する。そして、回収したイオン液体を大気圧下、２５０℃で１時間、ホットスターラーで加熱した。このときのイオン液体を「比較例１Ｃ」と称する。
[Comparative Example 1]
An ionic liquid (EMI-BF4) 0.60 cm 3 heated under reduced pressure at 120 ° C. for 3 hours was spread on a slide glass, and sputter deposition was performed toward the ionic liquid using In as a target material. Specifically, the inside of the chamber was replaced with argon gas, and the pressure was 2.0 Pa, the sputtering current was 10 mA, and the sputtering time was 30 minutes. The ionic liquid at this time is referred to as “Comparative Example 1A”. Next, the ionic liquid on the slide glass was left as it was, and sputtering was performed toward the ionic liquid using Au as a target material. Specifically, the inside of the chamber was replaced with argon gas, and the pressure was 2.0 Pa, the sputtering current was 10 mA, and the sputtering time was 5 minutes. Thereafter, 0.10 cm 3 of the ionic liquid on the slide glass was collected in a test tube. The ionic liquid at this time is referred to as “Comparative Example 1B”. And the collect | recovered ionic liquid was heated with the hot stirrer at 250 degreeC under atmospheric pressure for 1 hour. The ionic liquid at this time is referred to as “Comparative Example 1C”.
図１１は、比較例１Ｂ、比較例１Ｃの吸収スペクトルのグラフである。図１１には、実施例１Ｂの吸収スペクトルも併せて示す。比較例１Ｂでは、３００ｎｍ付近のＩｎ由来とみられる大きなピークが観察されたが、５００ｎｍ付近のＡｕ由来とみられるピークは観察されなかった。一方、比較例１Ｃでは、５００ｎｍ付近にＡｕ由来のピークが現れ、３００ｎｍ付近のＩｎ由来とみられるピークは減少した。 FIG. 11 is a graph of absorption spectra of Comparative Example 1B and Comparative Example 1C. FIG. 11 also shows the absorption spectrum of Example 1B. In Comparative Example 1B, a large peak considered to be derived from In near 300 nm was observed, but a peak considered to be derived from Au near 500 nm was not observed. On the other hand, in Comparative Example 1C, a peak derived from Au appeared in the vicinity of 500 nm, and a peak considered to be derived from In in the vicinity of 300 nm decreased.
図１２は、比較例１Ｂのイオン液体中の粒子のＴＥＭ像の写真、図１３は、比較例１Ｃのイオン液体中の粒子のＴＥＭ像の写真である。図１２に示す加熱処理前の比較例１ＢのＴＥＭ像では、直径１４±３．７ｎｍの大きな粒子と、直径２．３±０．４６ｎｍの小さな粒子とが確認された。大きな粒子は、Ｉｎのみをスパッタした場合のＩｎ粒子の粒径とほぼ一致した。また、小さな粒子は、Ａｕのみをスパッタした場合のＡｕ粒子の粒径とほぼ一致した。このことから、比較例１Ｂのイオン液体には、Ｉｎ粒子とＡｕ粒子とが個々に生成し、混在していると考えられる。また、図１３に示す加熱処理後の比較例１ＣのＴＥＭ像では、中空粒子やコントラストの強い粒子など、複数の種類の粒子が観察された。これは、加熱処理によりＩｎ粒子は中空化し、Ａｕ粒子は成長して粒径が増大したものと考えられる。以上のことから、最初にＩｎ、次にＡｕという順番でスパッタすると、コアシェル構造を持つナノ粒子が得られず、Ｉｎ粒子とＡｕ粒子とが個別に生成すると考えられる。その原因は、おそらくターゲット材をＩｎからＡｕに切り替える際、イオン液体中のＩｎ粒子が空気中の酸素と接触し、粒子表面が酸化してＩｎ2Ｏ3となり、このＩｎ2Ｏ3の存在がＩｎ粒子の周りにＡｕのシェルが生成するのを阻止したと考えられる。これに対して、実施例１では、ターゲット材をＡｕからＩｎに切り替える際、イオン液体中のＡｕ粒子が空気中の酸素と接触したが、Ａｕは非常に酸化されにくいため、粒子表面が酸化されず、その結果Ａｕ粒子の周りにＩｎのシェルが生成したと考えられる。 FIG. 12 is a photograph of a TEM image of particles in the ionic liquid of Comparative Example 1B, and FIG. 13 is a photograph of a TEM image of particles in the ionic liquid of Comparative Example 1C. In the TEM image of Comparative Example 1B before the heat treatment shown in FIG. 12, large particles having a diameter of 14 ± 3.7 nm and small particles having a diameter of 2.3 ± 0.46 nm were confirmed. The large particles almost coincided with the particle size of In particles when only In was sputtered. The small particles almost coincided with the particle size of Au particles when only Au was sputtered. From this, it is considered that In particles and Au particles are individually generated and mixed in the ionic liquid of Comparative Example 1B. Further, in the TEM image of Comparative Example 1C after the heat treatment shown in FIG. 13, a plurality of types of particles such as hollow particles and particles with strong contrast were observed. This is presumably because the In particles were hollowed out by the heat treatment, and the Au particles grew and the particle size increased. From the above, it is considered that when particles are sputtered first in the order of In and then Au, nanoparticles having a core-shell structure cannot be obtained, and In particles and Au particles are generated individually. This is probably because when the target material is switched from In to Au, the In particles in the ionic liquid come into contact with oxygen in the air, the surface of the particles is oxidized to In 2 O 3 , and this In 2 O 3 is present. It is thought that the formation of Au shells around the In particles was prevented. On the other hand, in Example 1, when the target material was switched from Au to In, Au particles in the ionic liquid contacted oxygen in the air. However, since Au is very difficult to oxidize, the particle surface is oxidized. As a result, it is considered that an In shell was generated around the Au particles.
［実施例２］
１２０℃で３時間減圧加熱を行ったイオン液体（ＥＭＩ−ＢＦ４）０．６０ｃｍ3をスライドガラス上に広げ、Ａｕをターゲット材としてイオン液体に向かってスパッタ蒸着を行った。具体的には、チャンバー内はアルゴンガスで置換し、圧力２．０Ｐａ、スパッタ電流１０ｍＡ、スパッタ時間５分とした。次に、スライドガラス上のイオン液体はそのままとし、Ｓｎをターゲット材として、イオン液体に向かってスパッタ蒸着を行った。具体的には、チャンバー内はアルゴンガスで置換し、圧力２．０Ｐａ、スパッタ電流２０ｍＡ、スパッタ時間２０分とした。その後、スライドガラス上のイオン液体を試験管に回収した。
[Example 2]
An ionic liquid (EMI-BF4) 0.60 cm 3 heated under reduced pressure at 120 ° C. for 3 hours was spread on a slide glass, and sputtering deposition was performed toward the ionic liquid using Au as a target material. Specifically, the inside of the chamber was replaced with argon gas, and the pressure was 2.0 Pa, the sputtering current was 10 mA, and the sputtering time was 5 minutes. Next, the ionic liquid on the slide glass was left as it was, and sputter deposition was performed toward the ionic liquid using Sn as a target material. Specifically, the inside of the chamber was replaced with argon gas, and the pressure was set to 2.0 Pa, the sputtering current was 20 mA, and the sputtering time was 20 minutes. Thereafter, the ionic liquid on the slide glass was collected in a test tube.
図１４は、実施例２で回収したイオン液体中の粒子のＴＥＭ像の写真、図１５は、図１４の部分拡大写真である。これらの写真におけるコントラスト強度比から、Ａｕ粒子のまわりにＳｎＯxシェルが形成され、コアシェル構造を持つナノ粒子が生成したことが示唆される。このナノ粒子は、粒径が実施例１Ｂ，１Ｃと比べると非常に小さく、約４ｎｍ程度であった。また、シェルの厚みが非常に薄いことが確認できた。このことから、ターゲット材の金属種を変えると、粒子生成・成長の挙動が変化して粒径やシェルの厚さに影響が現れると考えられる。 14 is a photograph of a TEM image of particles in the ionic liquid recovered in Example 2, and FIG. 15 is a partially enlarged photograph of FIG. The contrast intensity ratios in these photographs suggest that SnO x shells were formed around the Au particles and nanoparticles with a core-shell structure were generated. These nanoparticles had a particle size that was very small compared to Examples 1B and 1C, and was about 4 nm. It was also confirmed that the shell was very thin. From this, it is considered that changing the metal species of the target material changes the behavior of particle generation / growth and affects the particle size and shell thickness.
以上の実施例１，２では、Ａｕをコア、ＩｎＯxをシェルとするコアシェル構造のナノ粒子やＡｕをコア、ＳｎＯxをシェルとするコアシェル構造のナノ粒子が得られた。一方、比較例１では、Ｉｎをコア、Ａｕをシェルとするコアシェル構造のナノ粒子は得られなかった。このことから、他の金属の組み合わせであっても、比較例１のように最初のナノ粒子が酸化されてしまうような場合を除けば、同様にしてコアシェル構造のナノ粒子が得られることが期待される。また、イオン液体はその構造に依存した特性を持つため、イオン液体種によって粒子の構造が制御できると考えられる。また、スパッタ条件によって粒子の粒径や金属濃度を変化させることも可能と考えられる。 In Examples 1 and 2 described above, core-shell structure nanoparticles with Au as the core and InO x as the shell, and core-shell structure nanoparticles with Au as the core and SnO x as the shell, were obtained. On the other hand, in Comparative Example 1, nanoparticles having a core-shell structure with In as the core and Au as the shell were not obtained. From this, it is expected that core-shell nanoparticles can be obtained in the same manner except for the case where the first nanoparticles are oxidized as in Comparative Example 1 even when other metal combinations are used. Is done. In addition, since the ionic liquid has characteristics depending on its structure, it is considered that the particle structure can be controlled by the ionic liquid species. It is also considered possible to change the particle size and metal concentration of the particles depending on the sputtering conditions.
本発明のナノ粒子の製造方法によって得られたナノ粒子は、例えば触媒金属からなるコアと多孔性の金属からなるシェルとを備えている場合には、触媒化学の分野に利用可能である。また、種々のデバイスや太陽電池などの分野にも応用可能であると考えられる。 The nanoparticles obtained by the method for producing nanoparticles according to the present invention can be used in the field of catalytic chemistry, for example, when a core made of a catalytic metal and a shell made of a porous metal are provided. Moreover, it is thought that it is applicable also to field | areas, such as various devices and a solar cell.
１０ 蒸着装置、１２ 蒸着チャンバー、１４ 陰極、１６ 陽極、１８ ターゲット材、２０ ガラス基板、２２ イオン液体、２４ ターゲット材、２６ 試験管 DESCRIPTION OF SYMBOLS 10 Deposition apparatus, 12 Deposition chamber, 14 Cathode, 16 Anode, 18 Target material, 20 Glass substrate, 22 Ionic liquid, 24 Target material, 26 Test tube
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