JP2002363127A - Three-dimensional super crystal composite metal ultrafine particle, method and apparatus for producing the same - Google Patents
Three-dimensional super crystal composite metal ultrafine particle, method and apparatus for producing the sameInfo
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- JP2002363127A JP2002363127A JP2001168701A JP2001168701A JP2002363127A JP 2002363127 A JP2002363127 A JP 2002363127A JP 2001168701 A JP2001168701 A JP 2001168701A JP 2001168701 A JP2001168701 A JP 2001168701A JP 2002363127 A JP2002363127 A JP 2002363127A
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- ultrafine
- composite metal
- solvent
- dimensional
- particles
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、複合金属超微粒子
三次元超結晶及びその製造方法、並びに製造装置に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite metal ultrafine particle three-dimensional supercrystal, a method for producing the same, and a production apparatus.
【０００２】[0002]
【従来の技術】三次元超結晶とは、例えば直径１０ｎｍ
程度の超微粒子を構成要素として、あたかも原子を構成
要素とする結晶と同様な格子構造を持つ構成物を指す。
三次元超結晶は、一般に知られている原子同士が原子間
力で結合した原子結晶（例えば、鉄）、イオンが電気的
な相互作用で結合したイオン結晶（例えば、ＮａＣ
ｌ）、分子が分子間力で結合した分子結晶（例えばグラ
ニュー糖）の各結晶とは異なり、粒子と粒子の間の弱い
相互作用により結合され、そのため特異な特性を示すと
思われるが、現時点ではどの様な特性を持つかは明らか
にされていない。2. Description of the Related Art A three-dimensional supercrystal is, for example, 10 nm in diameter.
It refers to a composition having a lattice structure similar to that of a crystal having atoms as its constituent elements, as if it were composed of ultra-fine particles.
The three-dimensional supercrystal is generally known as an atomic crystal in which atoms are bonded to each other by interatomic force (for example, iron), and an ionic crystal in which ions are bonded by electrical interaction (for example, NaC
l) Unlike molecules of molecular crystals (eg, granulated sugar) in which molecules are bonded by an intermolecular force, they are bonded by weak interaction between particles, and thus may exhibit unique characteristics. It is not clear what characteristics it has.
【０００３】これまでに一般に三次元超結晶としては、
炭素フラーレンからなる超結晶やシリカゲルから構成さ
れる超結晶等がある。これらは何れも炭素やシリカなど
単一成分からなる超粒子から構成された超結晶である。[0003] Until now, three-dimensional supercrystals have generally been:
There are supercrystals composed of carbon fullerenes and supercrystals composed of silica gel. These are all supercrystals composed of superparticles composed of a single component such as carbon and silica.
【０００４】これに対し、粒子径の揃った有機化合物か
らなる殻と金属からなる核から形成された複合金属超微
粒子を基本構成要素として構成された超構造は、これま
で二次元配列構造膜、及びそれを数層重ねた構造が知ら
れている。しかしながら、真の立体結晶は知られておら
ず、特に、二次元構造では形成されない体心立方格子構
造は知られていない。On the other hand, a superstructure composed of a composite metal ultrafine particle formed from a shell made of an organic compound having a uniform particle diameter and a nucleus made of a metal as a basic constituent element has heretofore been a two-dimensional array structure film, Further, a structure in which several layers are stacked is known. However, no true three-dimensional crystal is known, and in particular, no body-centered cubic lattice structure that is not formed in a two-dimensional structure is known.
【０００５】[0005]
【発明が解決しようとする課題】三次元超結晶は、ナノ
サイズ構造物の基本技術の一つとして、電子デバイスや
光デバイスなどへの応用素材として有望である。特に、
有機化合物からなる殻と金属からなる核から形成された
複合金属超微粒子を基本構成要素として構成された超構
造は、その殻を構成する有機層が金属からなる核を一定
の距離で離す構造であるため、結果として超格子構造物
を形作る。これにより、これまで製作が困難であった、
Ｘ線などの波長域電磁波に対する反射材、屈折材及びフ
ィルター素材として極めて有望な素材である。また、格
子間を形成する有機層構造を工夫することにより、特定
の粒子間に回路を形成することが可能になり、ナノサイ
ズデバイスを形成することが容易になる。このように、
複合金属超微粒子から構成される三次元超結晶は、各種
のデバイスを形成するのに必要であり、更に新たな技術
が切望されている。[0003] Three-dimensional supercrystals are promising as one of the basic technologies for nano-sized structures as a material applied to electronic devices and optical devices. In particular,
An ultrastructure composed of ultrafine composite metal particles formed from a shell made of an organic compound and a nucleus made of a metal has a structure in which the organic layer that forms the shell separates the nucleus made of a metal by a certain distance. As a result, they form superlattice structures. Due to this, it was difficult to manufacture until now,
It is a very promising material as a reflection material, a refraction material and a filter material for electromagnetic waves in the wavelength range such as X-rays. In addition, by devising the structure of the organic layer that forms the lattice, a circuit can be formed between specific particles, and a nano-sized device can be easily formed. in this way,
Three-dimensional supercrystals composed of composite metal ultrafine particles are necessary for forming various devices, and further new technologies are eagerly desired.
【０００６】本発明は上記事情に鑑みて為されたもの
で、複合金属超微粒子から構成される三次元超結晶、及
びこの種の三次元超結晶を工業的規模で安定に製造でき
るようにした製造方法並びに製造装置を提供することを
目的とする。The present invention has been made in view of the above circumstances, and has made it possible to stably produce a three-dimensional supercrystal composed of ultrafine composite metal particles and this type of three-dimensional supercrystal on an industrial scale. It is an object to provide a manufacturing method and a manufacturing apparatus.
【０００７】[0007]
【課題を解決するための手段】請求項１に記載の発明
は、有機化合物からなる殻と金属からなる核から形成さ
れた粒子径の揃った複合金属超微粒子を基本構成要素と
して構成され、たとえば六方最密構造、面心立方最密構
造または体心立方構造をもつ複合金属超微粒子三次元超
結晶である。この三次元超結晶は、例えば、１０層以上
の立体構造をもつ複合金属超微粒子からなる。Means for Solving the Problems According to the first aspect of the present invention, ultrafine composite metal particles having a uniform particle diameter formed from a shell made of an organic compound and a nucleus made of a metal are used as basic constituent elements. It is a composite metal ultrafine particle three-dimensional supercrystal having a hexagonal close-packed structure, a face-centered cubic close-packed structure, or a body-centered cubic structure. The three-dimensional supercrystal is composed of, for example, composite metal ultrafine particles having a three-dimensional structure or more.
【０００８】請求項２に記載の発明は、金属成分が、Ｃ
ｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｇａ、Ｉｎ、Ｓｉ、Ｇ
ｅ、Ｓｎ、Ｐｄ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐ
ｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｖ、Ｃｒ、Ｍｎ、Ｙ、Ｚｒ、Ｎ
ｂ、Ｍｏ、Ｃａ、Ｓｒ、Ｂａ、Ｓｂ及びＢｉの少なくと
も１種であることを特徴とする請求項１記載の複合金属
超微粒子三次元超結晶である。この金属成分は、金属一
種、混合物、或いはこれらの金属の合金等のあらゆる状
態を包含する。[0008] In the invention according to claim 2, the metal component is C
u, Ag, Au, Zn, Cd, Ga, In, Si, G
e, Sn, Pd, Fe, Co, Ni, Ru, Rh, P
d, Os, Ir, Pt, V, Cr, Mn, Y, Zr, N
The composite metal ultrafine particle three-dimensional supercrystal according to claim 1, which is at least one of b, Mo, Ca, Sr, Ba, Sb and Bi. The metal component includes any state such as a single metal, a mixture, or an alloy of these metals.
【０００９】請求項３に記載の発明は、有機化合物から
なる殻と金属からなる核から形成された粒子径の揃った
複合金属超微粒子を溶媒中に分散させ、この溶媒の温度
を徐々に低下させて複合金属超微粒子の結晶を成長させ
ることを特徴とする複合金属超微粒子三次元超結晶の製
造方法である。これにより、複合金属超微粒子の温度差
による溶媒中への溶解度類似の分散度差を利用して複合
金属超微粒子の結晶を成長させることができる。According to a third aspect of the present invention, a composite metal ultrafine particle having a uniform particle diameter formed from a shell made of an organic compound and a nucleus made of a metal is dispersed in a solvent, and the temperature of the solvent is gradually lowered. A method for producing a three-dimensional supercrystal of composite metal ultrafine particles, characterized by growing crystals of ultrafine composite metal particles. Thereby, the crystals of the ultrafine composite metal particles can be grown by utilizing the difference in the degree of dispersion similar to the solubility in the solvent due to the temperature difference of the ultrafine composite metal particles.
【００１０】請求項４に記載の発明は、有機化合物から
なる殻と金属からなる核から形成された粒子径の揃った
複合金属超微粒子を溶媒中に分散させ、この溶媒を徐々
に乾燥させて複合金属超微粒子の結晶を成長させること
を特徴とする複合金属超微粒子三次元超結晶の製造方法
である。これにより、複合金属超微粒子を分散した溶媒
の乾燥による複合金属超微粒子の析出現象を利用して複
合金属超微粒子の結晶を成長させることができる。According to a fourth aspect of the present invention, a composite metal ultrafine particle having a uniform particle size formed from a shell made of an organic compound and a nucleus made of a metal is dispersed in a solvent, and the solvent is gradually dried. A method for producing a three-dimensional supercrystal of ultrafine composite metal particles, which comprises growing crystals of the ultrafine composite metal particles. Thereby, the crystals of the ultrafine composite metal particles can be grown by utilizing the precipitation phenomenon of the ultrafine composite metal particles by drying the solvent in which the ultrafine composite metal particles are dispersed.
【００１１】請求項５に記載の発明は、有機化合物から
なる殻と金属からなる核から形成された粒子径の揃った
複合金属超微粒子を分散させた溶媒を保持する溶媒タン
クと、前記複合金属超微粒子の結晶が成長するように、
前記溶媒タンク内の溶媒の温度を制御する温度制御装
置、または溶媒の乾燥を制御する乾燥制御装置の少なく
とも一方を有することを特徴とする複合金属超微粒子三
次元超結晶の製造装置である。A fifth aspect of the present invention provides a solvent tank for holding a solvent in which ultrafine composite metal particles having a uniform particle size and formed from a shell made of an organic compound and a core made of a metal are dispersed. As ultrafine crystals grow,
A three-dimensional supercrystal of composite metal ultrafine particles, comprising at least one of a temperature controller for controlling the temperature of the solvent in the solvent tank and a drying controller for controlling the drying of the solvent.
【００１２】[0012]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。本発明の複合金属超微粒子三次元超結晶は、複合
金属超微粒子を基本構成要素として構成され、六方最密
構造、面心立方最密構造または体心立方構造などの結晶
構造をもつ。図１にこれらの結晶構造を示す。たとえ
ば、六方最密構造をもつ複合金属超微粒子三次元超結晶
は、図１（ａ）に示すように、六角柱の各頂点と六角面
の中心の各７カ所、及びこれらに挟まれた位置の３箇所
の計１７カ所に基本構成要素としての複合金属超微粒子
１０が配置されている。また、面心立方最密構造をもつ
複合金属超微粒子三次元超結晶は、図１（ｂ）に示すよ
うに、立方体の各頂点と各面の中心の計１４カ所に基本
構成要素としての複合金属超微粒子１０が配置されてい
る。更に、体心立方構造をもつ複合金属超微粒子三次元
超結晶は、図１（ｃ）に示すように、立方体の各頂点と
立方体の中心の計９カ所に基本構成要素としての複合金
属超微粒子１０が配置されている。Embodiments of the present invention will be described below. The composite metal ultrafine particle three-dimensional supercrystal of the present invention is composed of composite metal ultrafine particles as a basic component and has a crystal structure such as a hexagonal close-packed structure, a face-centered cubic close-packed structure, or a body-centered cubic structure. FIG. 1 shows these crystal structures. For example, as shown in FIG. 1A, the three-dimensional supercrystal of a composite metal ultrafine particle having a hexagonal close-packed structure has seven vertices of a hexagonal prism and seven locations at the center of a hexagonal plane, and positions sandwiched therebetween. The composite metal ultrafine particles 10 as basic constituent elements are arranged in a total of 17 places of the three. Further, as shown in FIG. 1 (b), the composite metal ultrafine particle three-dimensional supercrystal having a face-centered cubic close-packed structure has a composite as a basic component at a total of 14 vertices of the cube and the center of each surface. Metal ultrafine particles 10 are arranged. Further, as shown in FIG. 1 (c), the composite metal ultrafine particles having a body-centered cubic structure are composed of the composite metal ultrafine particles as basic constituents at a total of 9 points at each vertex of the cube and at the center of the cube. 10 are arranged.
【００１３】基本構成要素としての複合金属超微粒子１
０は、図２に示すように、有機化合物からなる殻１２と
その中に単結晶若しくは多結晶体金属が析出した核（コ
ア）１４とから形成された核構造を持つもので、この核
１４の粒子径Ｄの平均は、通常１〜１０ｎｍ程度であ
る。この粒子径Ｄの平均は、最終製品の用途等により変
更することができる。Ultrafine composite metal particles 1 as basic constituent elements
Numeral 0 has a nuclear structure formed from a shell 12 made of an organic compound and a nucleus (core) 14 in which a single crystal or polycrystalline metal is deposited, as shown in FIG. Is usually about 1 to 10 nm. The average of the particle diameter D can be changed depending on the use of the final product.
【００１４】前記殻１２を形成する有機化合物として
は、ステアリン酸、オレイン酸、パルミチン酸、ラウリ
ン酸、ミリスチン酸、デカン酸、ラウレン酸、吉草酸な
どの脂肪酸、ステアリルアルコール、オレイルアルコー
ル、パルミチルアルコール、ラウリルアルコール、ミリ
スチルアルコールあるいは炭素数２〜１８のアルカンチ
オール、メルカプトコハク酸などが挙げられる。この有
機化合物としては、何らかの形で核１４を形成する金属
と結合できるものが使用でき、各種界面活性剤のよう
に、何らかの形で核１４の表面に付着するものであって
もよい。つまり、核１４を形成する金属を保護し安定に
孤立させ得るものであればよい。Examples of the organic compound forming the shell 12 include fatty acids such as stearic acid, oleic acid, palmitic acid, lauric acid, myristic acid, decanoic acid, laurenic acid and valeric acid, stearyl alcohol, oleyl alcohol, palmityl alcohol. , Lauryl alcohol, myristyl alcohol, alkanethiols having 2 to 18 carbon atoms, mercaptosuccinic acid, and the like. As the organic compound, a compound that can bind to the metal forming the nucleus 14 in some form can be used, and a compound that adheres to the surface of the nucleus 14 in some form, such as various surfactants, may be used. That is, any material can be used as long as it can protect the metal forming the nucleus 14 and stably isolate it.
【００１５】金属成分は、上記金属有機化合物に由来す
るものであれば特に制限されないが、Ｃｕ、Ａｇ、Ａ
ｕ、Ｚｎ、Ｃｄ、Ｇａ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐ
ｄ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉ
ｒ、Ｐｔ、Ａｕ、Ｖ、Ｃｒ、Ｍｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍ
ｏ、Ｃａ、Ｓｒ、Ｂａ、Ｓｂ及びＢｉの少なくとも１種
であることが好ましい。金属成分としては、これらの金
属一種、混合物、或いはこれらの金属の合金等のあらゆ
る状態を包含する。複合金属超微粒子１０における金属
成分の比率は、適宜設定できるが、通常は５０〜９０重
量％程度である。The metal component is not particularly limited as long as it is derived from the above-mentioned metal organic compound. Cu, Ag, A
u, Zn, Cd, Ga, In, Si, Ge, Sn, P
d, Fe, Co, Ni, Ru, Rh, Pd, Os, I
r, Pt, Au, V, Cr, Mn, Y, Zr, Nb, M
It is preferably at least one of o, Ca, Sr, Ba, Sb and Bi. The metal component includes all kinds of states such as one kind of these metals, a mixture thereof, and an alloy of these metals. The ratio of the metal component in the composite ultrafine metal particles 10 can be appropriately set, but is usually about 50 to 90% by weight.
【００１６】複合金属超微粒子１０は、例えば金属有機
化合物を、空気を遮断した不活性ガス雰囲気下におい
て、その金属有機化合物の分解開始温度以上、かつ、完
全分解温度未満の温度範囲内で加熱することによって作
製することができる。この金属有機化合物としては、特
にその種類は制限されず、前記で挙げたものを使用する
ことができる。これらの中でも、特にオレイン酸塩、パ
ラトルイル酸塩、ステアリン酸塩、ｎ−ドデカン酸塩、
金属エトキシド、金属アセチルアセトネート等が好まし
い。金属有機化合物の金属成分については、その用途等
に応じて適宜選択すれば良い。The ultrafine composite metal particles 10 heat a metal organic compound, for example, in an inert gas atmosphere with air shut off within a temperature range not lower than the decomposition start temperature of the metal organic compound and lower than the complete decomposition temperature. It can be manufactured by the following. The type of the metal organic compound is not particularly limited, and the above-mentioned compounds can be used. Among these, oleate, paratoluate, stearate, n-dodecanoate,
Metal ethoxide, metal acetylacetonate and the like are preferred. The metal component of the metal organic compound may be appropriately selected depending on its use and the like.
【００１７】複合金属超微粒子１０は、水溶液中で金属
イオンを水素化ホウ素ナトリウム等の還元剤を用いて還
元し、その際にメルカプトコハク酸を用いて複合化して
作製しても良い。更に、ヘリウムガス中で金属蒸気を蒸
発させて作製する、いわゆるガス中蒸発法で作製しても
良い。以上のように、複合金属超微粒子１０は、上記の
何れの方法で作製しても良いが、粒径分布が１５％以下
の範囲で揃っていて、溶媒中に安定に分散するものであ
る必要がある。The ultrafine composite metal particles 10 may be produced by reducing metal ions in an aqueous solution using a reducing agent such as sodium borohydride, and then compounding them using mercaptosuccinic acid. Further, it may be manufactured by a so-called gas evaporation method, which is manufactured by evaporating metal vapor in helium gas. As described above, the composite metal ultrafine particles 10 may be produced by any of the methods described above, but it is necessary that the ultrafine composite metal particles 10 have a uniform particle size distribution of 15% or less and are stably dispersed in a solvent. There is.
【００１８】図３に、前述の複合金属超微粒子１０を使
用した三次元超結晶の製造例を示す。先ず、複合超微粒
子、例えば金属として銀を用いた複合銀超微粒子を、所
定の温度の溶媒、例えば６５℃のｎ−ドデカン中に所定
の濃度で分散させる。そして、この溶媒（ｎ−ドデカ
ン）の温度を、例えば５℃／ｈの割合で徐々に低下さ
せ、溶媒の温度を最終的に、例えば３０℃まで低下させ
る。これにより、三次元超結晶を発生させ成長させるこ
とができる。FIG. 3 shows an example of the production of a three-dimensional supercrystal using the composite metal ultrafine particles 10 described above. First, composite ultrafine particles, for example, composite silver ultrafine particles using silver as a metal, are dispersed at a predetermined concentration in a solvent at a predetermined temperature, for example, n-dodecane at 65 ° C. Then, the temperature of the solvent (n-dodecane) is gradually lowered at a rate of, for example, 5 ° C./h, and the temperature of the solvent is finally lowered to, for example, 30 ° C. Thereby, a three-dimensional supercrystal can be generated and grown.
【００１９】複合金属超微粒子は、いわゆる溶解度と同
じように溶媒に対する溶解度ほど明確ではないが、安定
分散度が認められる場合がある。例えば、ステアリン酸
で被覆された平均粒径５ｎｍの銀複合超微粒子の場合、
６０℃のトルエン１００ｍｌ中に約２０ｇ安定して分散
する。この場合、温度が３０℃に下がると、１０ｇ程度
しか安定して分散しない。従って、温度を上げた溶剤中
に安定に分散できるだけの複合超微粒子を分散させてお
いて、溶媒の温度を緩やかに低下させることにより、温
度差による溶媒中への溶解度類似の分散度差を利用して
複合金属超微粒子三次元超結晶の作製することができ
る。この際、針状の構造物に種となる超結晶を付けてお
くことで、大きな超結晶を得ることもできる。The ultrafine composite metal particles are not as clear as the solubility in a solvent, as in the case of the so-called solubility, but may exhibit a stable degree of dispersion. For example, in the case of silver composite ultrafine particles having an average particle size of 5 nm coated with stearic acid,
About 20 g is stably dispersed in 100 ml of toluene at 60 ° C. In this case, when the temperature drops to 30 ° C., only about 10 g is stably dispersed. Therefore, by dispersing the composite ultrafine particles that can be stably dispersed in the solvent at the increased temperature, and gradually lowering the temperature of the solvent, a difference in the degree of dispersion similar to the solubility in the solvent due to the temperature difference is used. Thus, a three-dimensional supercrystal of composite metal ultrafine particles can be produced. At this time, a large supercrystal can be obtained by attaching a supercrystal serving as a seed to the needle-shaped structure.
【００２０】図４は、三次元超結晶の他の製造例を示す
もので、これは、複合超微粒子、例えば金属として銀を
用いた複合銀超微粒子を、所定の温度の溶媒、例えば６
５℃のトルエン中に所定の濃度で分散させ、この溶媒
（トルエン）を、例えば５％／ｈの割合で徐々に乾燥さ
せ、溶媒の量を最終的に、例えば３０％まで低下させ、
これにより、三次元超結晶を発生させ成長させるように
している。FIG. 4 shows another example of the production of a three-dimensional supercrystal, in which composite ultrafine particles, for example, composite silver ultrafine particles using silver as a metal, are mixed with a solvent at a predetermined temperature, for example, 6 μm.
Dispersing the solvent (toluene) at a predetermined concentration in toluene at 5 ° C., and gradually drying the solvent (toluene) at a rate of, for example, 5% / h, finally reducing the amount of the solvent to, for example, 30%;
Thereby, a three-dimensional supercrystal is generated and grown.
【００２１】このように、複合金属超微粒子を、目的に
応じた溶媒中に濃厚に分散しておき、溶媒を徐々に乾燥
させ過飽和状態を現出させることにより、超結晶を成長
させることもできる。As described above, the supercrystals can be grown by dispersing the ultrafine composite metal particles in a solvent suitable for the purpose and then gradually drying the solvent to reveal a supersaturated state. .
【００２２】図５は、この三次元結晶の製造装置の一例
を示す。これは、溶媒を保持する溶媒タンク１６と、こ
の溶媒タンク１６内に保持した溶媒の温度を精密に制御
する温度制御装置１８と、溶媒タンク１６内の圧力を制
御して溶媒の乾燥を制御する乾燥制御装置としての減圧
装置２０とを備えている。そして、溶媒タンク１６内に
保持した溶媒の液面付近まで達する針２２が備えられ、
この針２２の先端（下端）に複合超微粒子三次元超結晶
からなる種結晶２４を取付けることで、この種結晶２４
に三次元超結晶を成長させるようになっている。FIG. 5 shows an example of an apparatus for producing this three-dimensional crystal. This includes a solvent tank 16 for holding the solvent, a temperature controller 18 for precisely controlling the temperature of the solvent held in the solvent tank 16, and controlling the pressure in the solvent tank 16 to control the drying of the solvent. A decompression device 20 as a drying control device is provided. And, a needle 22 is provided to reach near the liquid level of the solvent held in the solvent tank 16,
By attaching a seed crystal 24 made of a composite ultrafine particle three-dimensional supercrystal to the tip (lower end) of the needle 22, the seed crystal 24
3D supercrystals are grown.
【００２３】この例によれば、溶媒タンク１６内に複合
金属超微粒子を分散させた溶剤を保持し、針２２の先端
（下端）に複合超微粒子三次元超結晶からなる種結晶２
４を取付けた状態で、前述のように、溶媒の温度を徐々
に低下させるか、または溶媒を徐々に乾燥させること
で、三次元超結晶を成長させることができる。According to this example, the solvent in which the composite metal ultrafine particles are dispersed is held in the solvent tank 16, and the seed crystal 2 composed of the composite ultrafine particle three-dimensional supercrystal is placed at the tip (lower end) of the needle 22.
As described above, the three-dimensional supercrystal can be grown by gradually lowering the temperature of the solvent or gradually drying the solvent in the state where the substrate 4 is attached.
【００２４】（実施例１）ミリスチン酸銀を用いて作製
した複合銀超微粒子を用いて体心立方格子構造をもつ複
合銀超微粒子三次元超結晶を作製した。先ず、原料とし
てミリスチン酸を用い、水酸化ナトリウムによりケン化
後、硝酸銀と反応させてミリスチン酸銀を作製し、析出
したミリスチン酸銀を吸引濾過器で濾別した後、乾燥機
を用いて乾燥した。Example 1 Three-dimensional supercrystals of composite silver ultrafine particles having a body-centered cubic lattice structure were prepared using composite silver ultrafine particles prepared using silver myristate. First, using myristic acid as a raw material, after saponification with sodium hydroxide, reacted with silver nitrate to produce silver myristate, and the precipitated silver myristate was filtered off with a suction filter, and then dried using a dryer. did.
【００２５】このようにして得られたミリスチン酸銀１
００ｇを秤量し、これを容量５００ｍｌのナス型フラス
コに投入し窒素気流下（流量１００ｍｌ／ｍｉｎ）でマ
ントルヒーターを用いて加熱した。加熱温度は２５０℃
とし、この温度で４時間保持した。加熱に伴って白色の
ミリスチン酸銀は、はじめに溶融し、その後加熱分解し
て変性し、徐々に変色して最終的には紫色になった。得
られた試料を精製して複合金属超微粒子粉末を得た。こ
の複合金属超微粒子粉末４０ｇを、図５に示す溶媒タン
ク１６内に保持した６５℃に暖めたｎ−ドデカン中に分
散させた。The thus obtained silver myristate 1
00 g was weighed, put into a 500 ml eggplant type flask, and heated using a mantle heater under a nitrogen stream (flow rate 100 ml / min). Heating temperature is 250 ° C
And kept at this temperature for 4 hours. Upon heating, the white silver myristate first melted, then thermally decomposed and denatured, gradually discolored and finally turned purple. The obtained sample was purified to obtain ultrafine composite metal powder. 40 g of this composite metal ultrafine particle powder was dispersed in n-dodecane heated to 65 ° C. held in a solvent tank 16 shown in FIG.
【００２６】３０分間安定に保持した後、予め作製して
おいた種結晶（体心立方格子構造超微粒子）２４を針２
２の先に付けて溶媒の液面近くに配置し、毎時５℃の条
件で３０℃まで温度を低下させた。これにより、体心立
方構造をもつ複合銀超微粒子三次元超結晶が形成され、
容器の底部の一部には六方最密構造と面心立方最密構造
をもつ複合銀超微粒子三次元超結晶も形成された。After holding stably for 30 minutes, a seed crystal (body-centered cubic lattice structure ultrafine particles) 24 prepared in advance is
2 and placed near the liquid surface of the solvent, and the temperature was lowered to 30 ° C. at 5 ° C./hour. Thereby, a composite silver ultrafine particle three-dimensional supercrystal having a body-centered cubic structure is formed,
At a part of the bottom of the container, a three-dimensional supercrystal of composite silver ultrafine particles having a hexagonal close-packed structure and a face-centered cubic close-packed structure was also formed.
【００２７】この時に得られた凝集物をシリコン基板上
にサンプリングし、ＨＲＳＥＭ（日立製作所製、ＳＥＭ
Ｓ−５０００）で観察した。図６（ａ）及び（ｂ）
は、このＨＲＳＥＭ写真のコピーである。この写真から
観察される結果からみて、これらの塊は１〜３μｍ程度
の大きさの島状構造をしている。The aggregate obtained at this time is sampled on a silicon substrate and subjected to HRSEM (SEM, manufactured by Hitachi, Ltd.).
S-5000). FIGS. 6A and 6B
Is a copy of this HRSEM photograph. From the results observed in this photograph, these lumps have an island-like structure with a size of about 1 to 3 μm.
【００２８】これらの島状構造を拡大して綿密に観察す
ると、数ナノの粒子の規則配列が認められる。更に高分
解で見ると、図７に示すように、領域Ａに示される超微
粒子が４回対称配列しているところと、領域Ｂ及びＢ’
のように、３回対称の最稠密構造をとって配列している
様子が確認できる。When these island-like structures are enlarged and closely observed, an ordered arrangement of several nano particles is recognized. When viewed at a higher resolution, as shown in FIG. 7, the ultrafine particles shown in the region A are four-fold symmetrically arranged, and the regions B and B '
It can be seen that they are arranged in a three-fold symmetrical close-packed structure as shown in FIG.
【００２９】また、領域ＢとＢ’の境目には、同じ３回
対称の最稠密構造ではあるが、階段状に見えるステップ
が認められ、三次元積層構造になっていることが判る。
従って、粒径５ｎｍの銀超微粒子の配列積層構造は、実
施の凝集物が１〜３μｍ程度の島状構造であることか
ら、数１０層以上の三次元的大きさを持った、いわゆる
超構造であることが推定される。Further, at the boundary between the regions B and B ', although the structure is the same dense structure having the same three-fold symmetry, steps which look like a step are recognized, indicating that the structure has a three-dimensional laminated structure.
Accordingly, the arrayed laminated structure of silver ultrafine particles having a particle diameter of 5 nm has a three-dimensional size of several tens of layers or more, since the actual aggregate has an island-like structure of about 1 to 3 μm. Is estimated.
【００３０】（実施例２）ガス中蒸発法を用いて作製し
た複合金超微粒子を用いて六方最密構造をもつ複合金超
微粒子三次元超結晶を作製した。先ず、２×１０３パス
カルのアルゴンガス中で電子ビームを用いて金を蒸発さ
せ、この金蒸気をターピネオール蒸気と共にトラップに
導き非イオン界面活性剤を用いて安定化させて界面活性
剤安定化複合金超微粒子を作製した。Example 2 Three-dimensional supercrystals of composite gold ultrafine particles having a hexagonal close-packed structure were prepared using composite gold ultrafine particles produced by the in-gas evaporation method. First, gold is evaporated using an electron beam in 2 × 10 3 Pascal argon gas, and this gold vapor is introduced into a trap together with terpineol vapor and stabilized using a nonionic surfactant to form a surfactant-stabilized composite. Ultrafine gold particles were produced.
【００３１】この、複合金超微粒子粉末４０ｇを、図５
に示す溶媒タンク１６で保持した６５℃に暖めたトルエ
ン中に分散させた。３０分間安定に保持した後、毎時５
℃の条件で３０℃まで温度を低下させたところ、容器の
底部に六方最密構造をもつ複合金超微粒子三次元超結晶
が形成された。なおこの一部には面心立方最密構造およ
び体心立方格子構造をもつ複合金超微粒子三次元超結晶
も形成された。5 g of the ultrafine composite gold powder was
Was dispersed in toluene heated to 65 ° C. held in a solvent tank 16 shown in FIG. After keeping it stable for 30 minutes,
When the temperature was lowered to 30 ° C. under the condition of 30 ° C., a three-dimensional supercrystal of composite gold ultrafine particles having a hexagonal close-packed structure was formed at the bottom of the container. Incidentally, a three-dimensional supercrystal of composite ultrafine gold particles having a face-centered cubic close-packed structure and a body-centered cubic lattice structure was also formed on a part of this.
【００３２】（実施例３）アルカンチオールを用いて安
定化させた複合金超微粒子を用いて体心立方格子構造を
もつ複合金属超微粒子三次元超結晶を作製した。先ず、
塩化金酸にクエン酸を加え加熱還元し、得られた金超微
粒子にＣ１８のアルカンチオールを加え安定化させた複
合金超微粒子を作製した。この複合金超微粒子をアセト
ンに分散させ、緩やかに乾燥させた。乾燥した後、反応
容器の底部に六方最密構造、面心立方最密構造および体
心立方構造からなる複合金超微粒子三次元超結晶の多結
晶体が形成された。Example 3 Three-dimensional supercrystals of composite metal ultrafine particles having a body-centered cubic lattice structure were prepared using composite gold ultrafine particles stabilized using alkanethiol. First,
Citric acid was added to chloroauric acid and reduced by heating to obtain composite ultrafine gold particles which were stabilized by adding C18 alkanethiol to the obtained ultrafine gold particles. The ultrafine composite gold particles were dispersed in acetone and gently dried. After drying, a polycrystalline three-dimensional supercrystalline composite gold ultrafine particle having a hexagonal close-packed structure, a face-centered cubic close-packed structure, and a body-centered cubic structure was formed at the bottom of the reaction vessel.
【００３３】（実施例４）ミリスチルアルコールを用い
て作製した複合銀超微粒子を用いて体心立方格子構造を
もつ複合銀超微粒子三次元超結晶を作製した。先ず、酢
酸銀５０ｇとミリスチルアルコール１００ｇを容量５０
０ｍｌのナス型フラスコに投入し窒素気流下（流量１０
０ｍｌ／ｍｉｎ）でマントルヒーターを用いて加熱し
た。加熱温度は２００℃とし、この温度で１時間保持し
た。加熱に伴って白色のミリスチルアルコールが溶融
し、急激に酢酸銀と反応し変色して最終的には紫色にな
った。得られた試料を精製して複合銀超微粒子粉末を得
た。Example 4 Three-dimensional ultrafine silver composite particles having a body-centered cubic lattice structure were produced using ultrafine silver composite particles prepared using myristyl alcohol. First, a volume of 50 g of silver acetate and 100 g of myristyl alcohol were added.
Into a 0 ml eggplant-shaped flask under a nitrogen stream (flow rate 10
(0 ml / min) using a mantle heater. The heating temperature was 200 ° C., and this temperature was maintained for 1 hour. With heating, the white myristyl alcohol melted and rapidly reacted with silver acetate to change color and finally turned purple. The obtained sample was purified to obtain composite silver ultrafine particle powder.
【００３４】この、複合銀超微粒子粉末４０ｇを、図５
に示す溶媒タンク１６で保持した６５℃に暖めたトルエ
ン中に分散させた。３０分間安定に保持した後、予め作
製しておいた種結晶（六方最密構造超微粒子）２４を針
２２の先に付けて、溶媒の液面近くに配置し、温度を保
ったまま、５％／ｈの割合で徐々に乾燥させ、溶媒を３
０％まで低下させた。大きさ５ｍｍ角程度の大きな複合
銀超微粒子三次元超結晶が形成された。5 g of the composite ultrafine silver powder was
Was dispersed in toluene heated to 65 ° C. held in a solvent tank 16 shown in FIG. After holding stably for 30 minutes, a seed crystal (hexagonal close-packed structure ultrafine particles) 24 prepared in advance is attached to the tip of the needle 22 and placed near the liquid surface of the solvent. % / H, the solvent was gradually dried.
Reduced to 0%. A large composite silver ultrafine particle three-dimensional supercrystal having a size of about 5 mm square was formed.
【００３５】[0035]
【発明の効果】以上説明したように、本発明によれば、
少なくとも１０層以上の立体構造を持つ複合金属超微粒
子からなる六方最密構造、面心立方最密構造または体心
立方構造などの複合金属超微粒子三次元超結晶を工業的
に安定して得ることができる。As described above, according to the present invention,
To obtain industrially stable three-dimensional supercrystals of composite metal ultrafine particles such as a hexagonal close-packed structure, a face-centered cubic close-packed structure, or a body-centered cubic structure composed of ultrafine composite metal particles having a three-dimensional structure of at least 10 layers. Can be.
【図１】本発明の複合超微粒子三次元超結晶の結晶構造
を示す図である。FIG. 1 is a view showing a crystal structure of a composite ultrafine particle three-dimensional supercrystal of the present invention.
【図２】本発明に使用される複合金属超微粒子の構造を
模式的に示す図である。FIG. 2 is a diagram schematically showing a structure of a composite metal ultrafine particle used in the present invention.
【図３】本発明の実施の形態の超結晶の製造例を示すブ
ロック図である。FIG. 3 is a block diagram illustrating an example of manufacturing a supercrystal according to an embodiment of the present invention.
【図４】本発明の実施の形態の超結晶の他の製造例を示
すブロック図である。FIG. 4 is a block diagram showing another example of manufacturing the supercrystal according to the embodiment of the present invention.
【図５】本発明の実施の形態の超結晶の製造装置の概略
を示す図である。FIG. 5 is a diagram schematically showing an apparatus for manufacturing a supercrystal according to an embodiment of the present invention.
【図６】実施例１で得られた複合銀超微粒子三次元超結
晶のＳＥＭ写真のコピーである。FIG. 6 is a copy of an SEM photograph of the composite silver ultrafine particle three-dimensional supercrystal obtained in Example 1.
【図７】実施例１で得られた複合銀超微粒子三次元超結
晶の更に高分解したＳＥＭ写真のコピーである。FIG. 7 is a copy of a further-resolved SEM photograph of the composite silver ultrafine particle three-dimensional supercrystal obtained in Example 1.
１０ 複合金属超微粒子 １２ 殻 １４ 核 １６ 溶媒タンク １８ 温度制御装置 ２０ 減圧装置（乾燥制御装置） ２２ 針 ２４ 種結晶 DESCRIPTION OF SYMBOLS 10 Ultrafine composite metal 12 Shell 14 Nucleus 16 Solvent tank 18 Temperature control device 20 Decompression device (drying control device) 22 Needle 24 Seed crystal
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０７Ｃ 53/126 Ｃ０７Ｃ 53/126 59/265 59/265 Ｃ３０Ｂ 29/66 Ｃ３０Ｂ 29/66 Ｆターム(参考） 4G077 AA10 BA01 BF10 CB06 EC01 4H006 AA02 AC47 AD15 BN10 BS10 BS70 4K018 BA01 BA02 BA03 BA04 BA09 BA13 BA20 BB05 BC09 BC15 BC29 KA32 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (Reference) C07C 53/126 C07C 53/126 59/265 59/265 C30B 29/66 C30B 29/66 F term (reference) 4G077 AA10 BA01 BF10 CB06 EC01 4H006 AA02 AC47 AD15 BN10 BS10 BS70 4K018 BA01 BA02 BA03 BA04 BA09 BA13 BA20 BB05 BC09 BC15 BC29 KA32
Claims (5)
から形成された粒子径の揃った複合金属超微粒子を基本
構成要素として構成された複合金属超微粒子三次元超結
晶。1. A composite metal ultrafine particle three-dimensional supercrystal comprising, as basic components, composite metal ultrafine particles having a uniform particle diameter formed from a shell made of an organic compound and a nucleus made of a metal.
Ｃｄ、Ｇａ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｄ、Ｆｅ、Ｃ
ｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｖ、
Ｃｒ、Ｍｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｃａ、Ｓｒ、Ｂ
ａ、Ｓｂ及びＢｉの少なくとも１種であることを特徴と
する請求項１記載の複合金属超微粒子三次元超結晶。2. The method according to claim 1, wherein the metal component is Cu, Ag, Au, Zn,
Cd, Ga, In, Si, Ge, Sn, Pd, Fe, C
o, Ni, Ru, Rh, Pd, Os, Ir, Pt, V,
Cr, Mn, Y, Zr, Nb, Mo, Ca, Sr, B
2. The composite metal ultrafine particle three-dimensional supercrystal according to claim 1, which is at least one of a, Sb, and Bi.
から形成された粒子径の揃った複合金属超微粒子を溶媒
中に分散させ、 この溶媒の温度を徐々に低下させて前記複合金属超微粒
子の結晶を成長させることを特徴とする複合金属超微粒
子三次元超結晶の製造方法。3. A composite metal ultrafine particle having a uniform particle diameter formed from a shell made of an organic compound and a nucleus made of a metal is dispersed in a solvent, and the temperature of the solvent is gradually lowered to produce the composite metal ultrafine particle. A method for producing a three-dimensional supercrystal of composite metal ultrafine particles, characterized by growing a crystal of (i).
から形成された粒子径の揃った複合金属超微粒子を溶媒
中に分散させ、 この溶媒を徐々に乾燥させて前記複合金属超微粒子の結
晶を成長させることを特徴とする複合金属超微粒子三次
元超結晶の製造方法。4. Ultrafine composite metal particles formed from a shell made of an organic compound and a nucleus made of a metal and having a uniform particle size are dispersed in a solvent, and the solvent is gradually dried to crystallize the ultrafine composite metal particles. A method for producing three-dimensional supercrystals of composite metal ultrafine particles, characterized by growing a crystal.
から形成された粒子径の揃った複合金属超微粒子を分散
させた溶媒を保持する溶媒タンクと、 前記複合金属超微粒子の結晶が成長するように、前記溶
媒タンク内の溶媒の温度を制御する温度制御装置、また
は溶媒の乾燥を制御する乾燥制御装置の少なくとも一方
を有することを特徴とする複合金属超微粒子三次元超結
晶の製造装置。5. A solvent tank for holding a solvent in which ultrafine composite metal particles of uniform particle size formed from a shell made of an organic compound and a nucleus made of metal are dispersed, and crystals of the ultrafine composite metal particles grow. As described above, an apparatus for producing a three-dimensional supercrystal of composite metal ultrafine particles, comprising at least one of a temperature controller for controlling the temperature of the solvent in the solvent tank and a drying controller for controlling the drying of the solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001168701A JP2002363127A (en) | 2001-06-04 | 2001-06-04 | Three-dimensional super crystal composite metal ultrafine particle, method and apparatus for producing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6743395B2 (en) * | 2000-03-22 | 2004-06-01 | Ebara Corporation | Composite metallic ultrafine particles and process for producing the same |
| JP2015034347A (en) * | 2009-04-24 | 2015-02-19 | 独立行政法人科学技術振興機構 | Solid solution type alloy fine particles, and method for manufacturing the same |
| CN109020807A (en) * | 2017-06-09 | 2018-12-18 | 鲁南制药集团股份有限公司 | A kind of myristic acid sodium crystal and preparation method thereof |
-
2001
- 2001-06-04 JP JP2001168701A patent/JP2002363127A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6743395B2 (en) * | 2000-03-22 | 2004-06-01 | Ebara Corporation | Composite metallic ultrafine particles and process for producing the same |
| US6871773B2 (en) | 2000-03-22 | 2005-03-29 | Ebara Corp. | Composite metallic ultrafine particles and process for producing the same |
| JP2015034347A (en) * | 2009-04-24 | 2015-02-19 | 独立行政法人科学技術振興機構 | Solid solution type alloy fine particles, and method for manufacturing the same |
| CN109020807A (en) * | 2017-06-09 | 2018-12-18 | 鲁南制药集团股份有限公司 | A kind of myristic acid sodium crystal and preparation method thereof |
| CN109020807B (en) * | 2017-06-09 | 2022-06-24 | 鲁南制药集团股份有限公司 | Sodium myristate crystal form and preparation method thereof |
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