JP2016153519A - Metal composite particle and method for producing the same - Google Patents
Metal composite particle and method for producing the same Download PDFInfo
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Abstract
Description
本発明は、局在表面プラズモン共鳴効果及び磁性を兼ね備える金属複合体粒子及びその製造方法に関する。 The present invention relates to a metal composite particle having both localized surface plasmon resonance effect and magnetism, and a method for producing the same.
磁性ナノ粒子は、直径が１ｎｍ〜１００ｎｍ程度の大きさの磁性粒子である。ナノ粒子に特有の、比表面積が大きい、物性が粒径に依存する、といった性質から、様々な用途の検討がされている。用途の例としては、高密度磁気記録媒体、磁性流体としての特性を活かしたスピーカー及びシール材料、磁気ハイパーサーミア（磁気温熱療法）、ＭＲＩ造影剤、磁気ドラッグデリバリーシステム、特定の物質（医薬品、抗原、抗体、レセプター、ハプテン、酵素、タンパク質、ペプチド、糖、核酸、ホルモン、病原体、毒素等）の選択的分離及び捕集、イムノクロマトグラフィー等の免疫測定、細胞の操作、血液の浄化（病原体の除去）などが挙げられる。 Magnetic nanoparticles are magnetic particles having a diameter of about 1 nm to 100 nm. Various uses have been studied because of the properties specific to nanoparticles, such as a large specific surface area and physical properties depending on the particle size. Examples of applications include high-density magnetic recording media, speakers and seal materials that take advantage of their properties as magnetic fluids, magnetic hyperthermia (magnetic hyperthermia), MRI contrast agents, magnetic drug delivery systems, specific substances (pharmaceuticals, antigens, Selective separation and collection of antibodies, receptors, haptens, enzymes, proteins, peptides, sugars, nucleic acids, hormones, pathogens, toxins, etc., immunoassay such as immunochromatography, cell manipulation, blood purification (pathogen removal) Etc.
また、上記磁性ナノ粒子に、局在表面プラズモン共鳴（Ｌｏｃａｌｉｚｅｄ Ｓｕｒｆａｃｅ Ｐｌａｓｍｏｎ Ｒｅｓｏｎａｎｃｅ：ＬＳＰＲ）を生じる金属を複合化（以下、「磁性−ＬＳＰＲ複合体ナノ粒子」という。）する検討も行われている（特許文献１〜３等）。ＬＳＰＲは、数ｎｍ〜１００ｎｍ程度のサイズの金属ナノ粒子において、電子が特定の波長の電磁波と相互作用を生じて共鳴する現象である。このＬＳＰＲは、金属ナノ粒子の周辺媒質の誘電率εｍ（λ）（＝（ｎｍ（λ））２）（ｎｍはその屈折率）の変化に敏感である為、「金属ナノ粒子の周辺媒質の誘電率（屈折率）の変化に応じて共鳴する波長が変化する」、という特徴を持っており、この特徴を活かして、結露センサー、湿度センサー、バイオセンサー、ケミカルセンサーなどのセンシング分野に応用する検討が盛んにおこなわれている。 In addition, studies are also underway to combine a metal that generates localized surface plasmon resonance (LSPR) with the magnetic nanoparticles (hereinafter referred to as “magnetic-LSPR composite nanoparticles”) (hereinafter referred to as “magnetic-LSPR composite nanoparticles”). Patent documents 1 to 3). LSPR is a phenomenon in which electrons interact with an electromagnetic wave having a specific wavelength and resonate in metal nanoparticles having a size of several nm to 100 nm. Since this LSPR is sensitive to changes in the dielectric constant ε m (λ) (= (n m (λ)) 2 ) (n m is its refractive index) of the surrounding medium of the metal nanoparticles, The resonance wavelength changes according to the change in the dielectric constant (refractive index) of the surrounding medium. Taking advantage of this feature, sensing fields such as condensation sensors, humidity sensors, biosensors, chemical sensors, etc. There are a lot of studies on the application of this technology.
前記磁性−ＬＳＰＲ複合体ナノ粒子のメリットは、磁気光学効果が期待できる点（特許文献１）、免疫測定や特定の分子を分離及び収集する場合において、当該特定の分子と結合した時にＬＳＰＲが変化することから、いわゆるプローブまたはセンサーになる点（特許文献２及び３）、前記磁性ナノ粒子の用途において、前記磁性ナノ粒子を、生体内を初め各材料内に投入した際に、動態をイメージングするためのマーカーとして機能する点（特許文献２）等が挙げられる。一般には、前記マーカーとしては有機蛍光色素分子を使用する。前記有機蛍光色素分子を検出する際にレーザー等の励起光を照射する必要があるが、耐光性が十分でなく、使用中に蛍光強度が低下する傾向にあった。つまり、マーカーとして有機蛍光色素分子を使用する場合は、耐久性が低い。これに対し、前記ＬＳＰＲを生じる金属であれば、無機の結晶であり、蛍光ではなくプラズモン散乱光を検出することになるため、耐光性・耐久性に優れる。 Advantages of the magnetic-LSPR composite nanoparticles are that a magneto-optical effect can be expected (Patent Document 1), and in the case of immunoassay or separation and collection of a specific molecule, LSPR changes when bound to the specific molecule. Therefore, in the application of the magnetic nanoparticles, the dynamics are imaged when the magnetic nanoparticles are first introduced into each material in the living body in the use of the so-called probe or sensor (Patent Documents 2 and 3). (Patent document 2) etc. which function as a marker for this. In general, an organic fluorescent dye molecule is used as the marker. When detecting the organic fluorescent dye molecules, it is necessary to irradiate excitation light such as a laser, but the light resistance is not sufficient and the fluorescence intensity tends to decrease during use. That is, when organic fluorescent dye molecules are used as markers, the durability is low. On the other hand, if the metal produces LSPR, it is an inorganic crystal, and it detects plasmon scattered light instead of fluorescence, so it has excellent light resistance and durability.
前記磁性−ＬＳＰＲ複合体ナノ粒子を構成する磁性ナノ粒子は、当然ながらその磁性は強い方が望ましい。前記磁性ナノ粒子の各用途において、感度、分離能力、操作性等の諸機能が向上するからである。この他に、従来品よりも磁性ナノ粒子のサイズを小さくしても同等の機能が発現するという利点もある。 Naturally, it is desirable that the magnetic nanoparticles constituting the magnetic-LSPR composite nanoparticles have stronger magnetism. This is because various functions such as sensitivity, separation ability, and operability are improved in each application of the magnetic nanoparticles. In addition, there is an advantage that an equivalent function is exhibited even if the size of the magnetic nanoparticles is made smaller than that of the conventional product.
このような理由から、従来磁性ナノ粒子として使用されてきた、γ−Ｆｅ２Ｏ３、Ｆｅ３Ｏ４、Ｆｅ−Ｐｔ合金といった強磁性体と比較して、軟磁性材料の中でも飽和磁束密度が極めて高い軟磁性材料であるＦｅ−Ｃｏ合金（パーメンジュールとも呼ばれる。以下、「ＦｅＣｏ」という。）が注目され、検討が行われている。例えば、ＦｅＣｏ粒子に銀粒子をＰｕｌｓｅｄ ｌａｓｅｒ ｄｅｗｅｔｔｉｎｇ法により結合させた例が開示されている（非特許文献１）。また、特許文献４では、磁性ナノロッドコア、接着層及びそれらを完全に被覆するプラズモン金属からなる磁性ナノ物質が開示され、前記磁性ナノロッドコアとしてＦｅＣｏが適用可能であると示唆されている。しかし、実際にはＦｅＣｏを磁性ナノロッドコアとして適用した具体例は開示されていない。 For this reason, compared with ferromagnetic materials such as γ-Fe 2 O 3 , Fe 3 O 4 , and Fe—Pt alloys that have been used as conventional magnetic nanoparticles, the saturation magnetic flux density among soft magnetic materials is low. Fe—Co alloys (also called permendurs, hereinafter referred to as “FeCo”), which are extremely high soft magnetic materials, have attracted attention and are being studied. For example, an example in which silver particles are bonded to FeCo particles by a pulsed laser dewetting method is disclosed (Non-Patent Document 1). Patent Document 4 discloses a magnetic nanorod core, an adhesive layer, and a magnetic nanomaterial made of plasmon metal that completely covers them, and suggests that FeCo can be applied as the magnetic nanorod core. However, a specific example in which FeCo is actually applied as a magnetic nanorod core is not disclosed.
少なくとも、非特許文献１及び特許文献４に開示された発明を用いても、前記磁性ナノ粒子の各用途に適用できるＦｅＣｏ−ＬＳＰＲ複合体ナノ粒子を作製することは困難であると考えられる。なぜなら、ＦｅＣｏは容易に酸化されて磁性が低下することから、ＦｅＣｏの表面を、ＬＳＰＲを生じる金属等のシェルによって十分被覆し、ＦｅＣｏの酸化を抑制する必要があるが、非特許文献１及び特許文献４に開示された方法では、ＦｅＣｏの酸化抑制が難しいと考えられるからである。 Even if at least the inventions disclosed in Non-Patent Document 1 and Patent Document 4 are used, it is considered difficult to produce FeCo-LSPR composite nanoparticles applicable to each application of the magnetic nanoparticles. Because FeCo is easily oxidized and its magnetism is lowered, it is necessary to sufficiently coat the surface of FeCo with a shell such as a metal that generates LSPR to suppress oxidation of FeCo. This is because it is considered difficult to suppress the oxidation of FeCo by the method disclosed in Document 4.
本発明の目的は、上記磁性ナノ粒子の各用途に適用可能な、磁性、ＬＳＰＲ特性及び耐久性に優れた金属複合体粒子を提供することにある。 The objective of this invention is providing the metal composite particle excellent in magnetism, LSPR characteristic, and durability applicable to each use of the said magnetic nanoparticle.
すなわち、本発明は、
金属コア；
前記金属コアを被覆する第１シェル；
前記第１シェルを被覆する第２シェル；
を有する、金属複合体粒子であって、以下のａ〜ｃの構成：
ａ）前記金属コアが、前記第１シェルの構成材料よりもイオン化傾向が小さい金属である；
ｂ）前記第１シェルの構成材料が、磁性材料である；
ｃ）前記金属コアおよび／または前記第２シェルが、可視光領域に局在表面プラズモン共鳴を持つ元素からなる；
を備えた金属複合体粒子に関する。
That is, the present invention
Metal core;
A first shell covering the metal core;
A second shell covering the first shell;
A metal composite particle having the following constitutions a to c:
a) the metal core is a metal having a smaller ionization tendency than the constituent material of the first shell;
b) the constituent material of the first shell is a magnetic material;
c) the metal core and / or the second shell is made of an element having localized surface plasmon resonance in the visible light region;
The present invention relates to a metal composite particle comprising:
また、本発明の金属複合体粒子は、前記第１シェルに対する、前記第２シェルが、前記第１シェルの全面を実質的に被覆しているものであってもよい。 In the metal composite particle of the present invention, the second shell may substantially cover the entire surface of the first shell with respect to the first shell.
また、本発明の金属複合体粒子は、好ましくは、前記第１シェルが、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、マンガン（Ｍｎ）、Ｆｅ２Ｏ３、Ｆｅ３Ｏ４、ＡＦｅ２Ｏ４（ここで、ＡはＭｎ、Ｃｏ、Ｎｉ、ＣｕまたはＺｎを意味する）、ＦｅＰｔ、ＣｏＰｔ、ＦｅＮｉ、またはＦｅＣｏであってもよい。 In the metal composite particles of the present invention, preferably, the first shell has iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), Fe 2 O 3 , Fe 3 O 4 , AFe 2 O 4 (where A means Mn, Co, Ni, Cu or Zn), FePt, CoPt, FeNi, or FeCo.
また、本発明の金属複合体粒子は、好ましくは、前記第２シェルが、金（Ａｕ）、銀（Ａｇ）、銅（Ｃｕ）、パラジウム（Ｐｄ）、白金（Ｐｔ）、錫（Ｓｎ）、ロジウム（Ｒｈ）、イリジウム（Ｉｒ）、またはこれらの金属種の合金であってもよい。 In the metal composite particles of the present invention, preferably, the second shell is made of gold (Au), silver (Ag), copper (Cu), palladium (Pd), platinum (Pt), tin (Sn), Rhodium (Rh), iridium (Ir), or an alloy of these metal species may be used.
また、本発明の金属複合体粒子は、好ましくは、前記金属コアが、金（Ａｕ）、銀（Ａｇ）、銅（Ｃｕ）、パラジウム（Ｐｄ）、白金（Ｐｔ）、錫（Ｓｎ）、ロジウム（Ｒｈ）、イリジウム（Ｉｒ）、またはこれらの金属種の合金であってもよい。 In the metal composite particles of the present invention, preferably, the metal core has gold (Au), silver (Ag), copper (Cu), palladium (Pd), platinum (Pt), tin (Sn), rhodium. (Rh), iridium (Ir), or an alloy of these metal species may be used.
また、本発明の金属複合体粒子の製造方法は、上記いずれかの金属複合体粒子を製造する方法であって、
以下の工程Ｉ及び工程II：
I）金属コア及び前記金属コアを被覆する第１シェルを備えた金属複合体粒子前駆体を合成する工程；
II）前記金属複合体粒子前駆体の分散液に、第２シェルの前駆体溶液を加えて、前記第２シェルの前駆体を還元することで、金属複合体粒子を合成する工程；
を備えている。
Further, the method for producing metal composite particles of the present invention is a method for producing any one of the above metal composite particles,
The following step I and step II:
I) synthesizing a metal composite particle precursor comprising a metal core and a first shell covering the metal core;
II) A step of synthesizing metal composite particles by adding a precursor solution of a second shell to the dispersion of the metal composite particle precursors and reducing the precursor of the second shell;
It has.
また、本発明の金属複合体粒子の製造方法は、前記工程Iにおいて、前記第１シェルを構成する一部の金属種の前駆体溶液に、前記金属コアの前駆体及び前記第１シェルを構成する他の金属種の前駆体の混合溶液を加えて、加熱し、前記金属コアの前駆体ならびに前記第１シェルを構成する一部の、及び他の金属種の前駆体を還元することで、前記金属複合体粒子前駆体を合成してもよい。 Further, in the method for producing metal composite particles of the present invention, in the step I, the precursor of the metal core and the first shell are formed in the precursor solution of a part of the metal species constituting the first shell. Adding a mixed solution of precursors of other metal species to be heated and reducing the precursor of the metal core and a part of the first shell and the precursor of other metal species, The metal composite particle precursor may be synthesized.
また、本発明の金属複合体粒子の製造方法は、前記工程Iにおいて、前記金属コアの前駆体及び前記第１シェルを構成する金属の前駆体の混合溶液を、加熱し、前記金属コアの前駆体及び前記第１シェルを構成する金属の前駆体を還元することで、前記金属複合体粒子前駆体を合成してもよい。 In the method for producing metal composite particles of the present invention, in the step I, the mixed solution of the metal core precursor and the metal precursor constituting the first shell is heated, and the metal core precursor is heated. The metal composite particle precursor may be synthesized by reducing a metal precursor constituting the body and the first shell.
また、本発明の金属複合体粒子の製造方法は、前記工程Iにおいて、前記金属コアの前駆体溶液に、前記第１シェルを構成する金属の前駆体溶液を加えて、加熱し、前記金属コアの前駆体及び前記第１シェルを構成する金属の前駆体を還元することで、前記金属複合体粒子前駆体を合成してもよい。 Further, in the method for producing metal composite particles of the present invention, in the step I, the precursor solution of the metal constituting the first shell is added to the precursor solution of the metal core and heated, and the metal core is heated. The metal composite particle precursor may be synthesized by reducing the precursor of the metal and the precursor of the metal constituting the first shell.
本発明の金属複合体粒子は、特定の金属コア、前記金属コアを被覆する特定の第１シェル及び前記第１シェルを被覆する特定の第２シェルを備えるため、例えばＦｅＣｏのような酸化されやすい磁性ナノ粒子を第１シェルに用いても、耐酸化性等の耐久性に優れる。従って、本発明の金属複合体粒子は、例えば、磁性、ＬＳＰＲ特性、表面増強ラマン散乱（ＳＥＲＳ）特性、耐酸化性や耐光性等の耐久性に優れた、磁性−ＬＳＰＲ複合体ナノ粒子として利用できる。さらに、本発明の金属複合体粒子は、粒径を小さくしても前記機能を発現する。従って、本発明によれば、磁性−ＬＳＰＲ複合体ナノ粒子の前記特徴を活かして、従来のものよりも優れた、高密度磁気記録材料、磁性流体としての特性を活かしたスピーカー及びシール材料、磁気ハイパーサーミア（磁気温熱療法）、ＭＲＩの造影剤、ドラッグデリバリーシステム、特定の物質（医薬品、抗原、抗体、レセプター、ハプテン、酵素、タンパク質、ペプチド、糖、核酸、ホルモン、病原体、毒素等）の選択的分離及び捕集、イムノクロマトグラフィー等の免疫測定、細胞の操作、血液の浄化（病原体の除去）などを提供できると考えられる。 Since the metal composite particle of the present invention includes a specific metal core, a specific first shell covering the metal core, and a specific second shell covering the first shell, the metal composite particle is easily oxidized, for example, FeCo. Even when magnetic nanoparticles are used in the first shell, the durability such as oxidation resistance is excellent. Therefore, the metal composite particles of the present invention are used as magnetic-LSPR composite nanoparticles having excellent durability such as magnetism, LSPR characteristics, surface enhanced Raman scattering (SERS) characteristics, oxidation resistance and light resistance, for example. it can. Furthermore, the metal composite particles of the present invention exhibit the above functions even when the particle size is reduced. Therefore, according to the present invention, taking advantage of the above-mentioned characteristics of the magnetic-LSPR composite nanoparticles, the high density magnetic recording material superior to the conventional one, the speaker and seal material utilizing the characteristics as a magnetic fluid, the magnetic Selective hyperthermia (magnetic hyperthermia), MRI contrast media, drug delivery systems, specific substances (pharmaceuticals, antigens, antibodies, receptors, haptens, enzymes, proteins, peptides, sugars, nucleic acids, hormones, pathogens, toxins, etc.) It is considered that separation and collection, immunoassay such as immunochromatography, cell manipulation, blood purification (pathogen removal), and the like can be provided.
本発明の実施の形態について、以下に説明する。
本実施の形態の金属複合体粒子は、
金属コア；
前記金属コアを被覆する第１シェル；
前記第１シェルを被覆する第２シェル；
を有する、金属複合体粒子であって、以下のａ〜ｃの構成：
ａ）前記金属コアが、前記第１シェルの構成材料よりもイオン化傾向が小さい金属である；
ｂ）前記第１シェルの構成材料が、磁性材料である；
ｃ）前記金属コアおよび／または第２シェルが、可視光領域に局在表面プラズモン共鳴を持つ元素からなる；
ことを特徴とする。
Embodiments of the present invention will be described below.
The metal composite particles of the present embodiment are
Metal core;
A first shell covering the metal core;
A second shell covering the first shell;
A metal composite particle having the following constitutions a to c:
a) the metal core is a metal having a smaller ionization tendency than the constituent material of the first shell;
b) the constituent material of the first shell is a magnetic material;
c) the metal core and / or the second shell is made of an element having localized surface plasmon resonance in the visible light region;
It is characterized by that.
ここで、前記金属コアは、前記第１シェルの構成材料よりもイオン化傾向が小さい金属であれば、任意の金属を使用することができる。なお、ここでいう金属は、合金も含む。なぜなら、このような金属であれば、ガルバニ交換反応により前記第１シェルを構成する金属が前記第２シェルに溶出することを防ぐことができる。その結果、第１シェルの酸化を防ぐことができる。好ましくは、可視光領域に局在表面プラズモン共鳴を持つ金属であり、金、銀、銅、パラジウム、白金、錫、ロジウム、イリジウム、またはこれらの金属種の合金である。より好ましくは、化学安定性の観点から、金または銀である。なお、前記金属コアまたは第２シェルが、金属複合体粒子において局在表面プラズモン共鳴を発現する源であることから、前記金属コア及び第２シェルのうち、少なくとも一方が、可視光領域に局在表面プラズモン共鳴を持つ金属からなる必要がある。 Here, any metal can be used for the metal core as long as the metal core has a smaller ionization tendency than the constituent material of the first shell. Here, the metal includes an alloy. This is because such a metal can prevent the metal constituting the first shell from eluting into the second shell by the galvanic exchange reaction. As a result, the oxidation of the first shell can be prevented. Preferably, it is a metal having localized surface plasmon resonance in the visible light region, and is gold, silver, copper, palladium, platinum, tin, rhodium, iridium, or an alloy of these metal species. More preferred is gold or silver from the viewpoint of chemical stability. In addition, since the metal core or the second shell is a source that expresses localized surface plasmon resonance in the metal composite particle, at least one of the metal core and the second shell is localized in the visible light region. It must be made of a metal with surface plasmon resonance.
また、前記第１シェルは、磁性材料であれば、任意の材料を使用することができる。前記第１シェルは、金属複合体粒子において磁性を発現する源であることから、磁性、つまり飽和磁束密度が高い磁性材料を用いることが好ましく、この場合、硬磁性体でも軟磁性体でも良い。好ましくは、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅ２Ｏ３、Ｆｅ３Ｏ４、ＡＦｅ２Ｏ４（ここで、ＡはＭｎ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ等を意味する）、ＦｅＰｔ、ＣｏＰｔ、ＦｅＮｉ、またはＦｅＣｏである。より好ましくは、前記のとおり軟磁性材料の中でも飽和磁束密度が極めて高い軟磁性材料であるＦｅＣｏである。 The first shell can be made of any material as long as it is a magnetic material. Since the first shell is a source that develops magnetism in the metal composite particles, it is preferable to use a magnetic material having a high magnetic flux, that is, a saturation magnetic flux density. In this case, a hard magnetic material or a soft magnetic material may be used. Preferably, Fe, Co, Ni, Mn, Fe 2 O 3 , Fe 3 O 4 , AFe 2 O 4 (where A means Mn, Co, Ni, Cu, Zn, etc.), FePt, CoPt, FeNi or FeCo. More preferably, it is FeCo which is a soft magnetic material having a very high saturation magnetic flux density among the soft magnetic materials as described above.
また、前記金属コアが、可視光領域に局在表面プラズモン共鳴を持つ金属からなる場合、前記第２シェルは、任意の金属を使用することができる。一方、前記金属コアが、可視光領域に局在表面プラズモン共鳴を持たない金属からなる場合、前記第２シェルは、可視光領域に局在表面プラズモン共鳴を持つ金属である必要がある。なお、ここでいう金属は、合金も含む。好ましくは、前記第２シェルが可視光領域に局在表面プラズモン共鳴を持つ金属からなることが、局在表面プラズモン共鳴の強度が高いため好ましい。より好ましくは、前記第２シェルが、金、銀、銅、パラジウム、白金、錫、ロジウム、イリジウム、またはこれらの金属種の合金である。さらに好ましくは、化学安定性の観点から、金または銀である。 Further, when the metal core is made of a metal having localized surface plasmon resonance in the visible light region, any metal can be used for the second shell. On the other hand, when the metal core is made of a metal having no localized surface plasmon resonance in the visible light region, the second shell needs to be a metal having a localized surface plasmon resonance in the visible light region. Here, the metal includes an alloy. Preferably, the second shell is made of a metal having localized surface plasmon resonance in the visible light region because the intensity of localized surface plasmon resonance is high. More preferably, the second shell is gold, silver, copper, palladium, platinum, tin, rhodium, iridium, or an alloy of these metal species. More preferred is gold or silver from the viewpoint of chemical stability.
本実施の形態に係る金属複合体粒子の構成材料の組み合わせとして、前記ガルバニ交換反応を抑制し、金属複合体粒子に十分な磁性及び化学的安定性を付与することが可能であり、さらに、可視光領域での局在表面プラズモン共鳴の強度が高いことから、金属コアの構成材料が銀であり、第１シェルの構成材料がＦｅＣｏであり、第２シェルの構成材料が銀である組み合わせが最も好ましい。ここで、ＦｅＣｏとして、Ｆｅ：Ｃｏ＝５０ａｔｏｍ％：５０ａｔｏｍ％の比率である場合は、この組成で飽和磁束密度が最も高くなるため、さらに好ましい。 As a combination of constituent materials of the metal composite particles according to the present embodiment, the galvanic exchange reaction can be suppressed, and sufficient magnetic and chemical stability can be imparted to the metal composite particles. Since the intensity of localized surface plasmon resonance in the optical region is high, the combination in which the constituent material of the metal core is silver, the constituent material of the first shell is FeCo, and the constituent material of the second shell is silver is the most. preferable. Here, when FeCo is a ratio of Fe: Co = 50 atom%: 50 atom%, the saturation magnetic flux density is the highest with this composition, which is more preferable.
図１は、金属複合体粒子の模式的な断面図である。図１に例示するように、本実施の形態の金属複合体粒子１００は、金属コア１０と第１シェル２０と第２シェル３０を有しており、第１シェル２０が金属コア１０を被覆し、第２シェルが第１シェル２０を被覆する、３層のコア−シェル構造である。ここで、金属コア１０に対する第１シェル２０の被覆状態は、金属コア１０の全表面積に対し、例えば３０％以上の被覆率であれば、第１シェル２０−第２シェル３０間のガルバニ交換反応を抑制できるので、本発明の効果を発現できる。第１シェル２０が、金属コア１０の全表面積に対し、９０％以上の被覆率であれば、前記抑制の効果がより高いので好ましく、より好ましくは、第１シェル２０が、金属コア１０の全面を実質的に被覆している構造である。 FIG. 1 is a schematic cross-sectional view of metal composite particles. As illustrated in FIG. 1, the metal composite particle 100 of the present embodiment includes a metal core 10, a first shell 20, and a second shell 30, and the first shell 20 covers the metal core 10. , A three-layer core-shell structure in which the second shell covers the first shell 20. Here, if the covering state of the first shell 20 with respect to the metal core 10 is, for example, a coverage of 30% or more with respect to the total surface area of the metal core 10, the galvanic exchange reaction between the first shell 20 and the second shell 30 is performed. Therefore, the effect of the present invention can be expressed. If the first shell 20 has a coverage of 90% or more with respect to the total surface area of the metal core 10, it is preferable because the suppression effect is higher, and more preferably, the first shell 20 is the entire surface of the metal core 10. It is the structure which has coat | covered substantially.
また、第１シェル２０に対する第２シェル３０の被覆状態は、第１シェル２０の全表面積に対し、例えば３０％以上の被覆率であれば、第１シェル２０の酸化を抑制する効果はあるので、本発明の効果を発現できる。第２シェル３０が第１シェル２０の全表面積に対し、９０％以上の被覆率であれば、前記抑制の効果がより高いので好ましく、より好ましくは、第２シェル３０が、第１シェル２０の全面を実質的に被覆している構造である。 Further, if the covering state of the second shell 30 with respect to the first shell 20 is, for example, a covering rate of 30% or more with respect to the total surface area of the first shell 20, there is an effect of suppressing oxidation of the first shell 20. The effect of the present invention can be expressed. If the covering ratio of the second shell 30 is 90% or more with respect to the total surface area of the first shell 20, it is preferable because the suppression effect is higher, and more preferably, the second shell 30 is the first shell 20. It is a structure that substantially covers the entire surface.
また、金属複合体粒子１００の粒径は、その用途により任意に選択できる。好ましくは、可視光領域に局在表面プラズモン共鳴を生じ、かつ磁性ナノ粒子としての効果を発現するため、平均粒子径が１ｎｍ以上３００ｎｍ未満である。より好ましくは、前記の効果が強まるため、平均粒子径が３ｎｍ以上１００ｎｍ未満である。さらに好ましくは、上記用途において、より小さい物質を、分離、捕集または検出できたり、適用する材料を軽量化することができたりすることから、平均粒子径が５ｎｍ以上５０ｎｍ未満であり、さらに好ましくは、５ｎｍ以上３０ｎｍ未満である。 Moreover, the particle size of the metal composite particle 100 can be arbitrarily selected according to its use. Preferably, the average particle diameter is 1 nm or more and less than 300 nm in order to cause localized surface plasmon resonance in the visible light region and to exhibit the effect as a magnetic nanoparticle. More preferably, the average particle diameter is 3 nm or more and less than 100 nm because the above effect is enhanced. More preferably, in the above-mentioned use, a smaller substance can be separated, collected or detected, and the applied material can be reduced in weight, so that the average particle diameter is 5 nm or more and less than 50 nm, and more preferably. Is 5 nm or more and less than 30 nm.
また、金属複合体粒子１００における各層（金属コア１０、第１シェル２０及び第２シェル３０）の層厚は、その用途により任意に選択できる。ここで「層厚」とは、金属コア層１０については直径（図１における層厚Ｄ１０）を意味し、第１シェル２０及び第２シェル３０については、金属複合体粒子１００の半径方向における厚み（図１における層厚Ｄ２０および層厚Ｄ３０）を意味する。好ましくは、金属コア１０及び第２シェル３０の少なくとも一方において、可視光領域に局在表面プラズモン共鳴を生じ、かつ第１シェル２０において、磁性ナノ粒子としての効果を発現するため、各層とも１００ｎｍ未満である。より好ましくは、前記の効果が強まるため、金属コア１０の層厚Ｄ１０が５０ｎｍ未満であり、第１シェル２０の層厚Ｄ２０が２０ｎｍ未満であり、第２シェル３０の層厚Ｄ３０が２０ｎｍ未満である。さらに好ましくは、上記用途において、より小さい物質を、分離、捕集または検出できたり、適用する材料を軽量化することができたりすることから、金属コア１０の層厚Ｄ１０が３０ｎｍ未満であり、第１シェル２０の層厚Ｄ２０が１０ｎｍ未満であり、第２シェル３０の層厚Ｄ３０が５ｎｍ未満である。 The layer thickness of each layer (metal core 10, first shell 20, and second shell 30) in metal composite particle 100 can be arbitrarily selected depending on its application. Here, “layer thickness” means the diameter (layer thickness D10 in FIG. 1) for the metal core layer 10, and the radial thickness of the metal composite particle 100 for the first shell 20 and the second shell 30. (Layer thickness D20 and layer thickness D30 in FIG. 1). Preferably, at least one of the metal core 10 and the second shell 30 causes localized surface plasmon resonance in the visible light region, and the first shell 20 exhibits an effect as a magnetic nanoparticle. It is. More preferably, since the above effect is enhanced, the layer thickness D10 of the metal core 10 is less than 50 nm, the layer thickness D20 of the first shell 20 is less than 20 nm, and the layer thickness D30 of the second shell 30 is less than 20 nm. is there. More preferably, the layer thickness D10 of the metal core 10 is less than 30 nm because, in the above application, a smaller substance can be separated, collected or detected, or the applied material can be reduced in weight. The layer thickness D20 of the first shell 20 is less than 10 nm, and the layer thickness D30 of the second shell 30 is less than 5 nm.
金属複合体粒子１００の形状は、例えば球体、長球体、立方体、切頭四面体、双角錐、正八面体、正十面体、正二十面体等の種々の形状であってよいが、局在表面プラズモン共鳴よる吸収スペクトルがシャープになる球形が最も好ましい。ここで、金属複合体粒子１００の形状は、透過型電子顕微鏡（ＴＥＭ）により観察することにより確認できる。また、金属複合体粒子１００の平均粒子径は、ＴＥＭ観察により任意１００粒の金属複合体粒子１００を測定したときの面積平均径とする。また、金属コア１０の粒子径は、ＴＥＭ観察により無作為に抽出した１００個以上の粒子について、面積平均径を求めることによって見積もることができる。第１シェル２０の層厚Ｄ２０及び第２シェル３０の層厚Ｄ３０は、これらのシェルを形成する前後の粒子について、上記と同様にＴＥＭ観察により無作為に抽出した１００個以上の粒子の面積平均径を求め、シェルを形成する前後の粒子の平均粒子径の変化量から見積もることができる。また、球体の金属複合体粒子１００とは、形状が球体及び球体に近い金属微粒子で、平均長径と平均短径の比が１又は１に近いもの(好ましくは０．８以上)をいう。さらに、それぞれの金属複合体粒子１００における長径と短径との関係が、好ましくは長径＜短径×１．３５の範囲内、より好ましくは長径≦短径×１．２５の範囲内がよい。なお、金属複合体粒子１００が球体でない場合(例えば正八面体など)は、その金属複合体粒子１００におけるエッジ長さが最大となる長さを金属複合体粒子１００の長径とし、エッジ長さが最小となる長さを金属複合体粒子１００の短径として、さらに前記長径をその金属複合体粒子１００の粒子径とみなすこととする。 The shape of the metal composite particle 100 may be various shapes such as a sphere, a long sphere, a cube, a truncated tetrahedron, a digonal pyramid, an octahedron, an icosahedron, and an icosahedron. A spherical shape with a sharp absorption spectrum due to plasmon resonance is most preferable. Here, the shape of the metal composite particles 100 can be confirmed by observing with a transmission electron microscope (TEM). Moreover, let the average particle diameter of the metal composite particle 100 be an area average diameter when 100 arbitrary metal composite particles 100 are measured by TEM observation. Moreover, the particle diameter of the metal core 10 can be estimated by calculating | requiring an area average diameter about 100 or more particles randomly extracted by TEM observation. The layer thickness D20 of the first shell 20 and the layer thickness D30 of the second shell 30 are the area averages of 100 or more particles randomly extracted by TEM observation in the same manner as described above for the particles before and after forming these shells. The diameter can be obtained and estimated from the amount of change in the average particle diameter of the particles before and after forming the shell. The spherical metal composite particles 100 are spheres and metal fine particles close to a sphere, and the ratio of the average major axis to the average minor axis is close to 1 or 1 (preferably 0.8 or more). Furthermore, the relationship between the major axis and the minor axis in each metal composite particle 100 is preferably in the range of major axis <minor axis × 1.35, more preferably in the range of major axis ≦ minor axis × 1.25. When the metal composite particle 100 is not a sphere (for example, a regular octahedron), the length at which the edge length in the metal composite particle 100 is the maximum is the major axis of the metal composite particle 100, and the edge length is the minimum. And the major axis is regarded as the particle diameter of the metal composite particle 100.
（金属複合体粒子の製造方法）
本発明の金属複合体粒子の製造方法は、以下のI〜IIの製造工程：
I）金属コア及び前記金属コアを被覆する第１シェルを備えた金属複合体粒子前駆体を合成する工程；
II）前記金属複合体粒子前駆体の分散液に、第２シェルの前駆体溶液を加えて、前記第２シェルの前駆体を還元することで、前記金属複合体粒子を合成する工程；
を含むことができる。ここでは、本発明の金属複合体粒子の製造方法の例について、金属コア及び第２シェルの構成材料を銀、第１シェルの構成材料をＦｅＣｏとした、Ａｇ／ＦｅＣｏ／Ａｇ粒子を代表例として、以下に詳細に説明する。
(Method for producing metal composite particles)
The method for producing metal composite particles of the present invention includes the following production steps I to II:
I) synthesizing a metal composite particle precursor comprising a metal core and a first shell covering the metal core;
II) A step of adding the second shell precursor solution to the dispersion of the metal composite particle precursor to synthesize the metal composite particles by reducing the second shell precursor;
Can be included. Here, as an example of the method for producing the metal composite particles of the present invention, Ag / FeCo / Ag particles, in which the constituent material of the metal core and the second shell is silver and the constituent material of the first shell is FeCo, are used as representative examples. This will be described in detail below.
（第１の製造方法）
第１の製造方法は、以下のIa〜IIの製造工程：
Ia）前記第１シェルを構成する一部の金属の前駆体溶液に、前記金属コアの前駆体及び前記第１シェルを構成する他の金属の前駆体の混合溶液を加えて、加熱し、前記金属コアの前駆体ならびに前記第１シェルを構成する一部の及び他の前駆体を還元することで、金属コア及び前記金属コアを被覆する第１シェルを備えた金属複合体粒子前駆体を合成する工程；
II）前記金属複合体粒子前駆体の分散液に、第２シェルの前駆体溶液を加えて、前記第２シェルの前駆体を還元することで、前記金属複合体粒子を合成する工程；
を備えることが好ましい。
(First manufacturing method)
The first production method comprises the following production steps Ia to II:
Ia) A mixed solution of a precursor of the metal core and a precursor of another metal constituting the first shell is added to a precursor solution of a part of the metal constituting the first shell, and heated, A metal composite particle precursor having a metal core and a first shell covering the metal core is synthesized by reducing a metal core precursor and a part of and other precursors constituting the first shell. The step of:
II) A step of adding the second shell precursor solution to the dispersion of the metal composite particle precursor to synthesize the metal composite particles by reducing the second shell precursor;
It is preferable to provide.
前記金属コアの前駆体として、例えばＡｇＮＯ３を使用し、オレイルアミンを加えて、必要に応じて超音波を印加しながら、または加熱しながら溶解する。これに前記第１シェルを構成する一部の金属前駆体として、例えばＦｅ（ａｃａｃ）３を加えて溶解する。この溶液を、原料溶液１Ａとする。なお、ＡｇＮＯ３の代わりに、例えばＡｇ（ａｃａｃ）を用いても良い。また、Ｆｅ（ａｃａｃ）３の代わりに、例えばＦｅ（ａｃａｃ）２を用いても良い。また、オレイルアミンは、還元剤兼表面保護剤の役割を有する。オレイルアミンの代わりに、例えば脂肪酸やアルカンチオールを用いても良い。 As a precursor of the metal core, for example, AgNO 3 is used, oleylamine is added, and dissolved while applying ultrasonic waves or heating as necessary. For example, Fe (acac) 3 is added and dissolved as a part of the metal precursor constituting the first shell. This solution is referred to as a raw material solution 1A. For example, Ag (acac) may be used instead of AgNO 3 . Further, instead of Fe (acac) 3 , for example, Fe (acac) 2 may be used. In addition, oleylamine has the role of a reducing agent and a surface protecting agent. Instead of oleylamine, for example, fatty acid or alkanethiol may be used.
この原料溶液１Ａとは別に、以下の方法で原料溶液２Ａを調製する。前記第２シェルの前駆体として、例えばＡｇＮＯ３を使用し、オレイルアミンを加えて、必要に応じて超音波を印加しながら、または加熱しながら溶解する。これにトルエンを加えて溶解する。なお、トルエンの代わりに、例えばアルカンやクロロホルムを用いても良い。 Separately from this raw material solution 1A, a raw material solution 2A is prepared by the following method. For example, AgNO 3 is used as the precursor of the second shell, and oleylamine is added and dissolved while applying ultrasonic waves or heating as necessary. Toluene is added to this and dissolved. For example, alkane or chloroform may be used instead of toluene.
更に原料溶液１Ａ及び２Ａとは別に、以下の方法で原料溶液３Ａを調製する。前記第１シェルを構成する一部の金属前駆体として、例えばＣｏ（ａｃａｃ）２を使用し、これに１,２−ｈｅｘａｄｅｃａｎｅｄｉｏｌ、オレイルアミン、オレイン酸、テトラエチレングリコールを加える。なお、Ｃｏ（ａｃａｃ）２の代わりに、例えばＣｏ（ａｃａｃ）３を使用しても良い。また、１,２−ｈｅｘａｄｅｃａｎｅｄｉｏｌは、還元補助剤の役割を有する。オレイルアミンの役割は、前記原料溶液１Ａの場合と同じである。オレイン酸は、表面保護剤の役割を有する。テトラエチレングリコールは、溶媒及び還元剤の役割を有する。オレイン酸の代わりに、例えばステアリン酸を用いても良く、テトラエチレングリコールの代わりに、例えばエチレングリコールを用いても良い。 Further, separately from the raw material solutions 1A and 2A, a raw material solution 3A is prepared by the following method. For example, Co (acac) 2 is used as a part of the metal precursor constituting the first shell, and 1,2-hexadecandiol, oleylamine, oleic acid, and tetraethylene glycol are added thereto. For example, Co (acac) 3 may be used instead of Co (acac) 2 . 1,2-hexadecandiol has the role of a reducing aid. The role of oleylamine is the same as that of the raw material solution 1A. Oleic acid has a role of a surface protecting agent. Tetraethylene glycol has a role of a solvent and a reducing agent. For example, stearic acid may be used instead of oleic acid, and ethylene glycol may be used instead of tetraethylene glycol.
ここで、原料溶液１Ａ中のＡｇＮＯ３及びＦｅ（ａｃａｃ）３、原料溶液２Ａ中のＡｇＮＯ３ならびに原料溶液３Ａ中のＣｏ（ａｃａｃ）２の仕込み比は、目的とする金属複合体粒子の層構成に応じて、適宜調整できる。特にＦｅ（ａｃａｃ）３及びＣｏ（ａｃａｃ）２の仕込み比は、目的とする第１シェル（ＦｅＣｏ）の組成に応じて適宜調整する。第１シェルにおいて、Ｃｏが２０ａｔｏｍ％以上８０ａｔｏｍ％以下であることが、飽和磁束密度が高いため好ましい。Ｆｅ、Ｃｏともに５０ａｔｏｍ％であるものが、特に飽和磁束密度が高いので、より好ましい。なお、この組成は、パーメンジュールともいう。このＦｅＣｏに、更に１ｗｔ％以上、５ｗｔ％以下のバナジウムを添加しても良い。バナジウムの添加により加工性が向上するので好ましい。 Here, the raw material solution 1A in AgNO 3 and Fe (acac) 3 of, AgNO 3 and Co (acac) 2 in feed ratio in the feed solution 3A in the feed solution. 2A, the layer structure of the metal composite particles of interest Can be adjusted as appropriate. In particular, the charging ratio of Fe (acac) 3 and Co (acac) 2 is appropriately adjusted according to the composition of the target first shell (FeCo). In the first shell, it is preferable that Co is 20 atom% or more and 80 atom% or less because the saturation magnetic flux density is high. It is more preferable that both Fe and Co are 50 atom% because the saturation magnetic flux density is particularly high. This composition is also called permendur. Further, 1 wt% or more and 5 wt% or less of vanadium may be added to this FeCo. Addition of vanadium is preferable because processability is improved.
次に、前記原料溶液３Ａを加熱し、水等の揮発成分を除去する。加熱条件は、前記除去の目的が達成でき、他の組成物が分解または反応しない範囲で適宜選択できる。例えば１００℃で１０分間撹拌する。撹拌後、さらに加熱し、原料溶液１Ａを加え、１次反応液とする。加熱条件（温度、昇温速度等）は、使用する材料により適宜選択するが、例えば１６０℃以上１８０℃以下の範囲が好ましい。
次に、１次反応液をさらに昇温し、原料溶液２Ａを加え、２次反応液とする。加熱条件（温度、昇温速度等）は、使用する材料により適宜選択するが、例えば２３０℃以上２７０℃以下の範囲が好ましい。前記原料溶液２Ａを加えた後、例えば２１０℃以上２４０℃以下の範囲でさらに撹拌しても良い。
次に、２次反応液を室温まで冷却し、アセトンを加えて沈殿物を析出させる。更に濾過、遠心分離等の方法により、上澄みと沈殿物を分離する。アセトンの代わりに例えばメタノールを使用しても良い。更に分離した沈殿物に大過剰のヘキサンを加えて再分散させた後、再度アセトンを加えて沈殿物を析出させる。ヘキサンの代わりに例えばトルエンを使用しても良い。そして、再び沈殿物を分離し、これを真空乾燥機等の適宜の方法で乾燥させる。必要に応じて、さらにヘキサンによる再分散−アセトンによる沈殿物の析出を繰り返してもよい。
Next, the raw material solution 3A is heated to remove volatile components such as water. The heating conditions can be appropriately selected as long as the purpose of the removal can be achieved and other compositions do not decompose or react. For example, stirring is performed at 100 ° C. for 10 minutes. After stirring, the mixture is further heated and the raw material solution 1A is added to obtain a primary reaction solution. The heating conditions (temperature, temperature increase rate, etc.) are appropriately selected depending on the materials used, but for example, a range of 160 ° C. or higher and 180 ° C. or lower is preferable.
Next, the temperature of the primary reaction liquid is further increased, and the raw material solution 2A is added to obtain a secondary reaction liquid. The heating conditions (temperature, temperature increase rate, etc.) are appropriately selected depending on the materials used, but for example, a range of 230 ° C. or higher and 270 ° C. or lower is preferable. After adding the raw material solution 2A, for example, stirring may be performed in a range of 210 ° C. or higher and 240 ° C. or lower.
Next, the secondary reaction solution is cooled to room temperature, and acetone is added to precipitate a precipitate. Further, the supernatant and the precipitate are separated by a method such as filtration or centrifugation. For example, methanol may be used instead of acetone. Further, a large excess of hexane is added to the separated precipitate for redispersion, and then acetone is added again to precipitate the precipitate. For example, toluene may be used instead of hexane. And a deposit is isolate | separated again and this is dried by appropriate methods, such as a vacuum dryer. If necessary, re-dispersion with hexane-precipitation of a precipitate with acetone may be repeated.
以上の作業により、金属コア層としてＡｇ、第１シェル層としてＦｅＣｏ（Ｆｅ：Ｃｏ＝５０ａｔｏｍ％：５０ａｔｏｍ％）、第２シェル層としてＡｇとする、金属複合体粒子が生成する。 Through the above operations, metal composite particles are produced in which Ag is used as the metal core layer, FeCo is used as the first shell layer (Fe: Co = 50 atom%: 50 atom%), and Ag is used as the second shell layer.
（第２の製造方法）
第２の製造方法は、以下のIb〜IIの製造工程：
Ib）前記金属コアの前駆体及び前記第１シェルを構成する金属の前駆体の混合溶液を、加熱し、前記金属コアの前駆体及び前記第１シェルを構成する金属の前駆体を還元することで、前記金属コア及び前記金属コアを被覆する前記第１シェルを備えた金属複合体粒子前駆体を合成する工程；
II）前記金属複合体粒子前駆体の分散液に、第２シェルの前駆体溶液を加えて、前記第２シェルの前駆体を還元することで、前記金属複合体粒子を合成する工程；
を備えることが好ましい。
(Second manufacturing method)
The second production method comprises the following production steps Ib to II:
Ib) Heating a mixed solution of the metal core precursor and the metal precursor constituting the first shell to reduce the metal core precursor and the metal precursor constituting the first shell. A step of synthesizing a metal composite particle precursor including the metal core and the first shell covering the metal core;
II) A step of adding the second shell precursor solution to the dispersion of the metal composite particle precursor to synthesize the metal composite particles by reducing the second shell precursor;
It is preferable to provide.
前記第１の製造方法との違いは、原料溶液１Ａ、２Ａ及び３Ａを調製する代わりに、原料溶液１Ｂ、２Ａ及び３Ｂを調製する点である。前記第１の製造方法及び第２の製造方法における原料溶液２Ａは共通する。また、使用する原料とその役割及び組成は、前記第１の製造方法と共通する。以下に説明する。 The difference from the first manufacturing method is that instead of preparing the raw material solutions 1A, 2A and 3A, the raw material solutions 1B, 2A and 3B are prepared. The raw material solution 2A in the first manufacturing method and the second manufacturing method is common. Moreover, the raw material to be used, its role and composition are common to the first manufacturing method. This will be described below.
オレイルアミンとトルエンを混合し、原料溶液１Ｂを調製する。また、これとは別に、ＡｇＮＯ３、Ｆｅ（ａｃａｃ）３、Ｃｏ（ａｃａｃ）２、１，２−ｈｅｘａｄｅｃａｎｅｄｉｏｌ、オレイルアミン、オレイン酸、テトラエチレングリコールを混合し、原料溶液３Ｂを調製する。以後は、原料溶液３Ａの代わりに原料溶液３Ｂを用い、原料溶液１Ａの代わりに原料溶液１Ｂを用いた他は、前記第１の製造方法と同様の方法で、金属複合体粒子を得る。 Oleylamine and toluene are mixed to prepare a raw material solution 1B. Separately, AgNO 3 , Fe (acac) 3 , Co (acac) 2 , 1,2-hexadecandiol, oleylamine, oleic acid, and tetraethylene glycol are mixed to prepare a raw material solution 3B. Thereafter, metal composite particles are obtained by the same method as in the first manufacturing method, except that the raw material solution 3B is used instead of the raw material solution 3A and the raw material solution 1B is used instead of the raw material solution 1A.
（第３の製造方法）
第３の製造方法は、以下のIc〜IIの製造工程：
Ic）前記金属コアの前駆体溶液に、前記第１シェルを構成する金属の前駆体溶液を加えて、加熱し、前記金属コアの前駆体及び前記第１シェルを構成する金属の前駆体を還元することで、前記金属コア及び前記金属コアを被覆する第１シェルを備えた金属複合体粒子前駆体を合成する工程；
II）前記金属複合体粒子前駆体の分散液に、第２シェルの前駆体溶液を加えて、前記第２シェルの前駆体を還元することで、金属複合体粒子を合成する工程；
を備えることが好ましい。
(Third production method)
The third production method comprises the following production steps Ic to II:
Ic) The precursor solution of the metal constituting the first shell is added to the precursor solution of the metal core and heated to reduce the precursor of the metal core and the precursor of the metal constituting the first shell. A step of synthesizing the metal composite particle precursor including the metal core and the first shell covering the metal core;
II) A step of synthesizing metal composite particles by adding a precursor solution of a second shell to the dispersion of the metal composite particle precursors and reducing the precursor of the second shell;
It is preferable to provide.
前記第１の製造方法との違いは、原料溶液１Ａ、２Ａ及び３Ａを調製する代わりに、原料溶液１Ｃ、２Ａ及び３Ｃを調製する点である。前記第１の製造方法及び第３の製造方法における原料溶液２Ａは共通する。また、使用する原料とその役割及び組成は、前記第１の製造方法と共通する。以下に説明する。 The difference from the first manufacturing method is that instead of preparing the raw material solutions 1A, 2A and 3A, the raw material solutions 1C, 2A and 3C are prepared. The raw material solution 2A in the first manufacturing method and the third manufacturing method is common. Moreover, the raw material to be used, its role and composition are common to the first manufacturing method. This will be described below.
ＡｇＮＯ３にオレイルアミンを加えて、必要に応じ超音波を印加しながら、または加熱しながら溶解する。これにＦｅ（ａｃａｃ）３及びＣｏ（ａｃａｃ）２を加えて溶解する。この溶液を、原料溶液１Ｃとする。また、これとは別に、１，２−ｈｅｘａｄｅｃａｎｅｄｉｏｌ、オレイルアミン、オレイン酸、テトラエチレングリコールを混合し、原料溶液３Ｃを調製する。以後は、原料溶液３Ａの代わりに原料溶液３Ｃを用い、原料溶液１Ａの代わりに原料溶液１Ｃを用いた他は、前記第１の製造方法と同様の方法で、金属複合体粒子を得る。 Add oleylamine to AgNO 3 and dissolve while applying ultrasonic waves or heating as necessary. To this, Fe (acac) 3 and Co (acac) 2 are added and dissolved. This solution is referred to as a raw material solution 1C. Separately, 1,2-hexadecandiol, oleylamine, oleic acid, and tetraethylene glycol are mixed to prepare a raw material solution 3C. Thereafter, metal composite particles are obtained in the same manner as in the first manufacturing method, except that the raw material solution 3C is used instead of the raw material solution 3A and the raw material solution 1C is used instead of the raw material solution 1A.
（第４の製造方法）
第４の製造方法は、以下のId〜IIの製造工程：
Id）前記金属コアの前駆体溶液に、前記第１シェルを構成する金属の前駆体及び前記第２シェルを構成する金属の前駆体の混合溶液を加えて加熱し、前記金属コアの前駆体、前記第１シェルを構成する金属の前駆体及び前記第２シェルを構成する金属の前駆体を還元することで、前記金属コア及び前記金属コアを被覆する第１シェルを備えた金属複合体粒子前駆体を合成する工程；
II）前記金属複合体粒子前駆体の分散液に、第２シェルの前駆体溶液を加えて、前記第２シェルの前駆体を還元することで、金属複合体粒子を合成する工程；
を備えることが好ましい。
(Fourth manufacturing method)
The fourth production method is a production process of the following Id to II:
Id) A mixed solution of the metal precursor composing the first shell and the metal precursor composing the second shell is added to the metal core precursor solution and heated, and the metal core precursor is heated. A metal composite particle precursor including a metal core and a first shell covering the metal core by reducing a metal precursor constituting the first shell and a metal precursor constituting the second shell. Synthesizing the body;
II) A step of synthesizing metal composite particles by adding a precursor solution of a second shell to the dispersion of the metal composite particle precursors and reducing the precursor of the second shell;
It is preferable to provide.
前記第１の製造方法との違いは、原料溶液１Ａ、２Ａ及び３Ａを調製する代わりに、原料溶液１Ｄ、２Ａ及び３Ｄを調製する点である。前記第１の製造方法及び第４の製造方法における原料溶液２Ａは共通する。また、使用する原料とその役割及び組成は、前記第１の製造方法と共通する。以下に説明する。 The difference from the first manufacturing method is that instead of preparing the raw material solutions 1A, 2A and 3A, the raw material solutions 1D, 2A and 3D are prepared. The raw material solution 2A in the first manufacturing method and the fourth manufacturing method is common. Moreover, the raw material to be used, its role, and composition are common with the said 1st manufacturing method. This will be described below.
オレイルアミン、トルエン、Ｆｅ（ａｃａｃ）３及びＣｏ（ａｃａｃ）２を混合し、溶解する。この溶液を、原料溶液１Ｄとする。また、これとは別に、ＡｇＮＯ３、１，２−ｈｅｘａｄｅｃａｎｅｄｉｏｌ、オレイルアミン、オレイン酸、テトラエチレングリコールを混合し、原料溶液３Ｄを調製する。以後は、原料溶液３Ａの代わりに原料溶液３Ｄを用い、原料溶液１Ａの代わりに原料溶液１Ｄを用いた他は、前記第１の製造方法と同様の方法で、金属複合体粒子を得る。 Oleylamine, toluene, Fe (acac) 3 and Co (acac) 2 are mixed and dissolved. This solution is referred to as a raw material solution 1D. Separately, AgNO 3 , 1,2-hexadecandiol, oleylamine, oleic acid, and tetraethylene glycol are mixed to prepare a raw material solution 3D. Thereafter, metal composite particles are obtained in the same manner as in the first manufacturing method, except that the raw material solution 3D is used instead of the raw material solution 3A and the raw material solution 1D is used instead of the raw material solution 1A.
以上の製造方法により得られる金属複合体粒子は、その表面に、公知の化学物質を吸着または被覆しても良い。前記化学物質の構造及び吸着量は、金属複合体粒子の用途に応じ、適宜選択できる。具体的には、適当な化学物質の吸着または被覆により、特定の物質との選択的な相互作用、分散性、粒径制御、表面状態（親水性、疎水性）、生体適合性に関する機能を付与することができる。
［実施例］
The metal composite particles obtained by the above production method may adsorb or coat a known chemical substance on the surface. The structure and adsorption amount of the chemical substance can be appropriately selected according to the use of the metal composite particles. Specifically, functions such as selective interaction with specific substances, dispersibility, particle size control, surface condition (hydrophilicity, hydrophobicity), and biocompatibility are provided by adsorption or coating of appropriate chemical substances. can do.
[Example]
以下、本発明を実施例によって具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
（実施例１）
＜原料溶液１Ａの合成＞
ＡｇＮＯ３（０．１ｍｍｏｌ）をオレイルアミン（１ｍＬ）に超音波を印加しながら溶解した。白濁したところでトルエン（２ｍＬ）を加え、超音波を印加し完全に溶解した。これに、Ｆｅ（ａｃａｃ）３（０．２ｍｍｏｌ）を加え、溶解した。
Example 1
<Synthesis of raw material solution 1A>
AgNO 3 (0.1 mmol) was dissolved in oleylamine (1 mL) while applying ultrasonic waves. When it became cloudy, toluene (2 mL) was added, and ultrasonic waves were applied to dissolve completely. To this, Fe (acac) 3 (0.2 mmol) was added and dissolved.
＜原料溶液２Ａの合成＞
ＡｇＮＯ３（０．１ｍｍｏｌ）をオレイルアミン（１ｍＬ）に超音波を印加しながら溶解した。白濁したところでトルエン（２ｍＬ）を加え、超音波を印加し完全に溶解した。
<Synthesis of raw material solution 2A>
AgNO 3 (0.1 mmol) was dissolved in oleylamine (1 mL) while applying ultrasonic waves. When it became cloudy, toluene (2 mL) was added, and ultrasonic waves were applied to dissolve completely.
＜原料溶液３Ａの合成＞
５０ｍＬの三口フラスコにＣｏ（ａｃａｃ）２（０．２ｍｍｏｌ）、１,２−ｈｅｘａｄｅｃａｎｅｄｉｏｌ（１．０ ｍｍｏｌ）、オレイルアミン（１０ｍｍｏｌ）、オレイン酸（８ｍｍｏｌ）、テトラエチレングリコール（１０ ｍＬ）を入れた。
<Synthesis of raw material solution 3A>
Co (acac) 2 (0.2 mmol), 1,2-hexadecandiol (1.0 mmol), oleylamine (10 mmol), oleic acid (8 mmol), and tetraethylene glycol (10 mL) were placed in a 50 mL three-necked flask.
＜金属複合体粒子Ａの合成＞
原料溶液３Ａを１００℃で１０分間撹拌することで、揮発成分（水など）を系外へ除去した。その後２５０℃まで昇温した。昇温過程で、原料溶液１Ａを注入した。続いて、原料溶液２Ａを注入し、１０分間反応させた。冷却後、上澄み溶液と沈殿物に分けた。アセトンを加えて遠心分離した後、上澄みを捨て、大過剰のヘキサンを沈殿物に加え再分散させた。再度アセトンで生成物を再沈殿させた後、上澄みを捨て、真空乾燥機で乾燥させた。
<Synthesis of Metal Composite Particle A>
The raw material solution 3A was stirred at 100 ° C. for 10 minutes to remove volatile components (such as water) out of the system. Thereafter, the temperature was raised to 250 ° C. In the temperature raising process, the raw material solution 1A was injected. Subsequently, the raw material solution 2A was injected and allowed to react for 10 minutes. After cooling, it was divided into a supernatant solution and a precipitate. After adding acetone and centrifuging, the supernatant was discarded, and a large excess of hexane was added to the precipitate for redispersion. After reprecipitation of the product with acetone again, the supernatant was discarded and dried with a vacuum dryer.
以上の処理の結果、金属複合体粒子Ａ（褐色の粉末、５０ｍｇ）が得られた。Ｘ線回折（ＸＲＤ、リガク製、ＭｉｎｉＦｌｅｘ６００、Ｘ線源：ＣｕＫα）、走査透過電子顕微鏡（ＳＴＥＭ、日本電子製、ＪＥＭ−ＡＲＭ２００Ｆ、加速電圧：２００ｋＶ）、エネルギー分散型Ｘ線分析装置（ＥＤＳ、日本電子製、ＪＥＤ−２３００Ｔ）及び高周波誘導結合プラズマ発光分光分析（ＩＣＰ−ＯＥＳ、島津製作所製、ＩＣＰ−７０００）によって構造および組成を解析したところ、コアから外殻に向かって、銀−ＦｅＣｏ−銀の三層構造であり、コアの銀は直径が１４ｎｍであり、ＦｅＣｏ層の層厚は１ｎｍであり、最外殻の銀層の層厚は、１ｎｍ以下であり、ＦｅＣｏ層はコアの銀の全面を被覆し、かつ最外殻の銀層はＦｅＣｏ層の全面を被覆していた。また、金属複合体粒子Ａ中に酸素は検出されなかったことから、ＦｅＣｏ層は酸化されていないことが分かった。 As a result of the above treatment, metal composite particles A (brown powder, 50 mg) were obtained. X-ray diffraction (XRD, Rigaku, MiniFlex600, X-ray source: CuKα), scanning transmission electron microscope (STEM, JEOL Ltd., JEM-ARM200F, acceleration voltage: 200 kV), energy dispersive X-ray analyzer (EDS, Japan) The structure and composition were analyzed by JE-2300T (Electronics, ICP-OES, manufactured by Shimadzu Corporation, ICP-7000) and high-frequency inductively coupled plasma optical emission spectrometry. From the core toward the outer shell, silver-FeCo-silver The core silver has a diameter of 14 nm, the thickness of the FeCo layer is 1 nm, the thickness of the outermost silver layer is 1 nm or less, and the FeCo layer is made of the core silver. The entire surface was covered, and the outermost silver layer covered the entire surface of the FeCo layer. Moreover, since oxygen was not detected in the metal composite particles A, it was found that the FeCo layer was not oxidized.
また、超伝導量子干渉磁束計（ＳＱＵＩＤ、Ｑｕａｎｔｕｍ Ｄｅｓｉｇｎ製、ＭＰＭＳ）を用いて、磁化曲線を測定したところ、超常磁性体であることが分かった。さらに、紫外−可視分光法（Ｐｅｒｋｉｎ Ｅｌｍｅｒ製）を用いて吸収スペクトルを測定したところ、局在表面プラズモン共鳴に基づく吸収（極大吸収波長＝４０７ｎｍ）が発現した。 Moreover, when a magnetization curve was measured using a superconducting quantum interference magnetometer (SQUID, manufactured by Quantum Design, MPMS), it was found to be a superparamagnetic material. Furthermore, when an absorption spectrum was measured using ultraviolet-visible spectroscopy (manufactured by Perkin Elmer), absorption based on localized surface plasmon resonance (maximum absorption wavelength = 407 nm) was expressed.
（実施例２）
＜原料溶液１Ｂの合成＞
オレイルアミン（１ｍＬ）とトルエン（２ｍＬ）を混合した。
(Example 2)
<Synthesis of raw material solution 1B>
Oleylamine (1 mL) and toluene (2 mL) were mixed.
＜原料溶液３Ｂの合成＞
５０ｍＬの三口フラスコにＡｇＮＯ３（０．１ｍｍｏｌ）、Ｆｅ（ａｃａｃ）３（０．２ ｍｍｏｌ）、Ｃｏ（ａｃａｃ）２（０．２ｍｍｏｌ）、１，２−ｈｅｘａｄｅｃａｎｅｄｉｏｌ（１．０ｍｍｏｌ）、オレイルアミン（１０ｍｍｏｌ）、オレイン酸（８ｍｍｏｌ）、テトラエチレングリコール（１０ｍＬ）を入れた。
<Synthesis of raw material solution 3B>
In a 50 mL three-necked flask, AgNO 3 (0.1 mmol), Fe (acac) 3 (0.2 mmol), Co (acac) 2 (0.2 mmol), 1,2-hexadecandiol (1.0 mmol), oleylamine (10 mmol) ), Oleic acid (8 mmol), and tetraethylene glycol (10 mL).
＜金属複合体粒子Ｂの合成＞
原料溶液３Ａの代わりに原料溶液３Ｂを用い、原料溶液１Ａの代わりに原料溶液１Ｂを用いた他は、実施例１と同様の方法で、金属複合体粒子Ｂ（褐色の粉末、５０ｍｇ）が得られた。Ｘ線回折（ＸＲＤ、リガク製、ＭｉｎｉＦｌｅｘ６００、Ｘ線源：ＣｕＫα）、走査透過電子顕微鏡（ＳＴＥＭ、日本電子製、ＪＥＭ−ＡＲＭ２００Ｆ、加速電圧：２００ｋＶ）及びエネルギー分散型Ｘ線分析装置（ＥＤＳ、日本電子製、ＪＥＤ−２３００Ｔ）によって構造および組成を解析したところ、コアから外殻に向かって、銀−ＦｅＣｏ−銀の三層構造であり、コアの銀は直径が１３ｎｍであり、ＦｅＣｏ層の層厚は３ｎｍであり、最外殻の銀層の層厚は、１ｎｍ以下であり、ＦｅＣｏ層はコアの銀の全面を被覆し、かつ最外殻の銀層はＦｅＣｏ層の全面を被覆していた。また、金属複合体粒子Ｂ中に酸素は検出されなかったことから、ＦｅＣｏ層は酸化されていないことが分かった。
<Synthesis of Metal Composite Particle B>
Metal composite particles B (brown powder, 50 mg) were obtained in the same manner as in Example 1 except that the raw material solution 3B was used instead of the raw material solution 3A and the raw material solution 1B was used instead of the raw material solution 1A. It was. X-ray diffraction (XRD, Rigaku, MiniFlex600, X-ray source: CuKα), scanning transmission electron microscope (STEM, JEOL, JEM-ARM200F, acceleration voltage: 200 kV) and energy dispersive X-ray analyzer (EDS, Japan) When the structure and composition were analyzed by JED-2300T manufactured by Denki, it was a three-layer structure of silver-FeCo-silver from the core toward the outer shell, the core silver had a diameter of 13 nm, and the layer of the FeCo layer The thickness is 3 nm, the thickness of the outermost silver layer is 1 nm or less, the FeCo layer covers the entire surface of the core silver, and the outermost silver layer covers the entire surface of the FeCo layer. It was. Moreover, since oxygen was not detected in the metal composite particle B, it was found that the FeCo layer was not oxidized.
（実施例３）
＜原料溶液１Ｃの合成＞
ＡｇＮＯ３（０．１ｍｍｏｌ）をオレイルアミン（１ｍＬ）に超音波を印加しながら溶解した。白濁したところでトルエン（２ｍＬ）を加え、超音波を印加し完全に溶解した。これに、Ｆｅ（ａｃａｃ）３（０．２ ｍｍｏｌ）、Ｃｏ（ａｃａｃ）２（０．２ｍｍｏｌ）を加え、溶解した。
(Example 3)
<Synthesis of raw material solution 1C>
AgNO 3 (0.1 mmol) was dissolved in oleylamine (1 mL) while applying ultrasonic waves. When it became cloudy, toluene (2 mL) was added, and ultrasonic waves were applied to dissolve completely. To this, Fe (acac) 3 (0.2 mmol) and Co (acac) 2 (0.2 mmol) were added and dissolved.
＜原料溶液３Ｃの合成＞
５０ｍＬの三口フラスコに１，２−ｈｅｘａｄｅｃａｎｅｄｉｏｌ（１．０ｍｍｏｌ）、オレイルアミン（１０ｍｍｏｌ）、オレイン酸（８ｍｍｏｌ）、テトラエチレングリコール（１０ｍＬ）を入れた。
<Synthesis of raw material solution 3C>
1,2-hexadecandiol (1.0 mmol), oleylamine (10 mmol), oleic acid (8 mmol), and tetraethylene glycol (10 mL) were placed in a 50 mL three-necked flask.
＜金属複合体粒子Ｃの合成＞
原料溶液３Ａの代わりに原料溶液３Ｃを用い、原料溶液１Ａの代わりに原料溶液１Ｃを用いた他は、実施例１と同様の方法で、金属複合体粒子Ｃ（褐色の粉末、５０ｍｇ）が得られた。Ｘ線回折（ＸＲＤ、リガク製、ＭｉｎｉＦｌｅｘ６００、Ｘ線源：ＣｕＫα）、走査透過電子顕微鏡（ＳＴＥＭ、日本電子製、ＪＥＭ−ＡＲＭ２００Ｆ、加速電圧：２００ｋＶ）及びエネルギー分散型Ｘ線分析装置（ＥＤＳ、日本電子製、ＪＥＤ−２３００Ｔ）によって構造および組成を解析したところ、コアから外殻に向かって、銀−ＦｅＣｏ−銀の三層構造であり、コアの銀は直径が１３ｎｍであり、ＦｅＣｏ層の層厚は４ｎｍであり、最外殻の銀層の層厚は、１ｎｍ以下であり、ＦｅＣｏ層はコアの銀の全面を被覆し、かつ最外殻の銀層はＦｅＣｏ層の全面を被覆していた。また、金属複合体粒子Ｃ中に酸素は検出されなかったことから、ＦｅＣｏ層は酸化されていないことが分かった。
<Synthesis of Metal Composite Particle C>
Metal composite particles C (brown powder, 50 mg) were obtained in the same manner as in Example 1 except that the raw material solution 3C was used instead of the raw material solution 3A and the raw material solution 1C was used instead of the raw material solution 1A. It was. X-ray diffraction (XRD, Rigaku, MiniFlex600, X-ray source: CuKα), scanning transmission electron microscope (STEM, JEOL, JEM-ARM200F, acceleration voltage: 200 kV) and energy dispersive X-ray analyzer (EDS, Japan) When the structure and composition were analyzed by JED-2300T manufactured by Denki, it was a three-layer structure of silver-FeCo-silver from the core toward the outer shell, the core silver had a diameter of 13 nm, and the layer of the FeCo layer The thickness is 4 nm, the thickness of the outermost silver layer is 1 nm or less, the FeCo layer covers the entire surface of the core silver, and the outermost silver layer covers the entire surface of the FeCo layer. It was. Further, since oxygen was not detected in the metal composite particles C, it was found that the FeCo layer was not oxidized.
（実施例４）
＜原料溶液１Ｄの合成＞
オレイルアミン（１ ｍＬ）とトルエン（２ ｍＬ）を混合した。これに、Ｆｅ（ａｃａｃ）３（０．２ｍｍｏｌ）とＣｏ（ａｃａｃ）２（０．２ｍｍｏｌ）を加え、溶解した。
Example 4
<Synthesis of raw material solution 1D>
Oleylamine (1 mL) and toluene (2 mL) were mixed. To this, Fe (acac) 3 (0.2 mmol) and Co (acac) 2 (0.2 mmol) were added and dissolved.
＜原料溶液３Ｄの合成＞
５０ｍＬの三口フラスコにＡｇＮＯ３（０．１ｍｍｏｌ）、１,２−ｈｅｘａｄｅｃａｎｅｄｉｏｌ（１．０ｍｍｏｌ）、オレイルアミン（１０ｍｍｏｌ）、オレイン酸（８ｍｍｏｌ）、テトラエチレングリコール（１０ｍＬ）を入れた。
<Synthesis of raw material solution 3D>
AgNO 3 (0.1 mmol), 1,2-hexadecandiol (1.0 mmol), oleylamine (10 mmol), oleic acid (8 mmol), and tetraethylene glycol (10 mL) were placed in a 50 mL three-necked flask.
＜金属複合体粒子Ｄの合成＞
原料溶液３Ａの代わりに原料溶液３Ｄを用い、原料溶液１Ａの代わりに原料溶液１Ｄを用いた他は、実施例１と同様の方法で、金属複合体粒子Ｄ（褐色の粉末、５０ｍｇ）が得られた。Ｘ線回折（ＸＲＤ、リガク製、ＭｉｎｉＦｌｅｘ６００、Ｘ線源：ＣｕＫα）、走査透過電子顕微鏡（ＳＴＥＭ、日本電子製、ＪＥＭ−ＡＲＭ２００Ｆ、加速電圧：２００ｋＶ）、エネルギー分散型Ｘ線分析装置（ＥＤＳ、日本電子製、ＪＥＤ−２３００Ｔ）、Ｘ線光電子分光装置（ＸＰＳ、島津Ｋｒａｔｏｓ製、ＡＸＩＳ−ＵＬＴＲＡ ＤＬＤ）及び高周波誘導結合プラズマ発光分光分析（ＩＣＰ−ＯＥＳ、島津製作所製、ＩＣＰ−７０００）によって構造および組成を解析したところ、コアから外殻に向かって、銀−ＦｅＣｏ−銀の三層構造であり、コアの銀は直径が８ｎｍであり、ＦｅＣｏ層の層厚は３ｎｍであり、最外殻の銀層の層厚は、１ｎｍ以下であり、ＦｅＣｏ層はコアの銀の全面を被覆し、かつ最外殻の銀層はＦｅＣｏ層の全面を被覆していた。また、金属複合体粒子Ｄ中に酸素は検出されなかったことから、ＦｅＣｏ層は酸化されていないことが分かった。
<Synthesis of Metal Composite Particle D>
Metal composite particles D (brown powder, 50 mg) were obtained in the same manner as in Example 1 except that the raw material solution 3D was used instead of the raw material solution 3A, and the raw material solution 1D was used instead of the raw material solution 1A. It was. X-ray diffraction (XRD, Rigaku, MiniFlex600, X-ray source: CuKα), scanning transmission electron microscope (STEM, JEOL Ltd., JEM-ARM200F, acceleration voltage: 200 kV), energy dispersive X-ray analyzer (EDS, Japan) Structure and composition by electron, JED-2300T), X-ray photoelectron spectrometer (XPS, Shimadzu Kratos, AXIS-ULTRA DLD) and high frequency inductively coupled plasma emission spectroscopy (ICP-OES, Shimadzu, ICP-7000) As a result of analysis, the three-layer structure of silver-FeCo-silver from the core toward the outer shell, the core silver has a diameter of 8 nm, the layer thickness of the FeCo layer is 3 nm, and the outermost silver The layer thickness is 1 nm or less, the FeCo layer covers the entire surface of the core silver, and the outermost silver layer is the entire FeCo layer. It was not cover. Moreover, since oxygen was not detected in the metal composite particle D, it was found that the FeCo layer was not oxidized.
また、超伝導量子干渉磁束計（ＳＱＵＩＤ、Ｑｕａｎｔｕｍ Ｄｅｓｉｇｎ製、ＭＰＭＳ）を用いて、磁化曲線を測定したところ、超常磁性体であることが分かった。さらに、紫外−可視分光法（Ｐｅｒｋｉｎ Ｅｌｍｅｒ製）を用いて吸収スペクトルを測定したところ、局在表面プラズモン共鳴に基づく吸収（極大吸収波長＝４０７ｎｍ）が発現した。 Moreover, when a magnetization curve was measured using a superconducting quantum interference magnetometer (SQUID, manufactured by Quantum Design, MPMS), it was found to be a superparamagnetic material. Furthermore, when an absorption spectrum was measured using ultraviolet-visible spectroscopy (manufactured by Perkin Elmer), absorption based on localized surface plasmon resonance (maximum absorption wavelength = 407 nm) was expressed.
以上、本発明の実施の形態を例示の目的で詳細に説明したが、本発明は上記実施の形態に制約されることはなく、種々の変形が可能である。 As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment, A various deformation | transformation is possible.
１０…金属コア、２０…第１シェル、３０…第２シェル、１００…金属複合体粒子 DESCRIPTION OF SYMBOLS 10 ... Metal core, 20 ... 1st shell, 30 ... 2nd shell, 100 ... Metal composite particle
Claims (9)
前記金属コアを被覆する第１シェル；
前記第１シェルを被覆する第２シェル；
を有する、金属複合体粒子であって、以下のａ〜ｃの構成：
ａ）前記金属コアが、前記第１シェルの構成材料よりもイオン化傾向が小さい金属である；
ｂ）前記第１シェルの構成材料が、磁性材料である；
ｃ）前記金属コアおよび／または前記第２シェルが、可視光領域に局在表面プラズモン共鳴を持つ元素からなる；
を備えた金属複合体粒子。 Metal core;
A first shell covering the metal core;
A second shell covering the first shell;
A metal composite particle having the following constitutions a to c:
a) the metal core is a metal having a smaller ionization tendency than the constituent material of the first shell;
b) the constituent material of the first shell is a magnetic material;
c) the metal core and / or the second shell is made of an element having localized surface plasmon resonance in the visible light region;
Metal composite particles comprising
以下の工程Ｉ及び工程II：
I）金属コア及び前記金属コアを被覆する第１シェルを備えた金属複合体粒子前駆体を合成する工程；
II）前記金属複合体粒子前駆体の分散液に、第２シェルの前駆体溶液を加えて、前記第２シェルの前駆体を還元することで、金属複合体粒子を合成する工程；
を備えた金属複合体粒子の製造方法。 A method for producing the metal composite particles according to claim 1,
The following step I and step II:
I) synthesizing a metal composite particle precursor comprising a metal core and a first shell covering the metal core;
II) A step of synthesizing metal composite particles by adding a precursor solution of a second shell to the dispersion of the metal composite particle precursors and reducing the precursor of the second shell;
A method for producing metal composite particles comprising:
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