TW201422339A - Method of preparing nanoparticles having core-shell structure and nanoparticles prepared by the same - Google Patents
Method of preparing nanoparticles having core-shell structure and nanoparticles prepared by the same Download PDFInfo
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Abstract
Description
本發明係有關於一種核殼結構(core-shell structure)奈米粒子(nanoparticle)製備方法及其所製備出的奈米粒子。 The present invention relates to a core-shell structure nanoparticle preparation method and nanoparticle prepared therefrom.
由於透明導電電極在於觸控面板、平板顯示器、和其他光電元件上之應用，透明導電電極之重要性係日益增加。目前為止，在有機太陽能電池的領域中，銦錫氧化物(Indium-Tin Oxide,ITO)為最為廣泛使用之透明電極材料。然而，由於銦錫氧化物為塑膠材料，製程需在高溫下進行，銦錫氧化物容易受到外部物理震擊(physical shock)而損壞，且易於彎曲和變形。再者，當在聚合物基板上塗佈銦錫氧化物時，若基板彎曲，銦錫氧化物膜便會損壞。最重要的是，由於銦的匱乏，使得銦錫氧化物之價格持續增加，因此銦錫氧化物之供給成為一大問題。 Since transparent conductive electrodes are used in touch panels, flat panel displays, and other optoelectronic components, the importance of transparent conductive electrodes is increasing. In the past, in the field of organic solar cells, Indium-Tin Oxide (ITO) is the most widely used transparent electrode material. However, since indium tin oxide is a plastic material, the process needs to be performed at a high temperature, and indium tin oxide is easily damaged by an external physical shock and is easily bent and deformed. Further, when the indium tin oxide is coated on the polymer substrate, if the substrate is bent, the indium tin oxide film is damaged. Most importantly, the supply of indium tin oxide continues to increase due to the lack of indium, so the supply of indium tin oxide has become a major problem.
近日，作為解決此類銦錫氧化物之問題的解決方 案，導電性聚合物、碳奈米管(carbon nanotubes)、石墨烯(grapheme)、與金屬奈米線(metal nanowire)和奈米粒子(nanoparticles)已引起關注，其可作為可撓性透明電極之材料，並且可取代銦錫氧化物。 Recently, as a solution to the problem of such indium tin oxide Cases, conductive polymers, carbon nanotubes, grapheme, metal nanowires, and nanoparticles have attracted attention as flexible transparent electrodes. Material, and can replace indium tin oxide.
然而，碳奈米管或石墨烯具有低導電性且只稍微地改善透光度。再者，以銀奈米線為代表的金屬奈米線價格昂貴，因此若只使用銀奈米線製備透明電極，透明電極變為昂貴，且透明電極之表面變為粗糙，使得層疊(laminate)與印刷後續材料以成為如薄膜電晶體(Thin-Film Transistor,TFT)之元件係非常困難。再者，由於在金屬奈米線之上執行噴墨印刷製程係為困難，且金屬奈米線之製程不能在高溫下進行，故金屬奈米線具有製程上的應用限制。並且，當金屬奈米線延伸，其導電性會減低。 However, carbon nanotubes or graphene have low conductivity and only slightly improve light transmittance. Furthermore, the metal nanowire represented by the silver nanowire is expensive, so if only the silver nanowire is used to prepare the transparent electrode, the transparent electrode becomes expensive, and the surface of the transparent electrode becomes rough, so that the laminate is laminated. It is very difficult to print subsequent materials to become a component system such as a thin film transistor (TFT). Furthermore, since it is difficult to perform an inkjet printing process on a metal nanowire, and the process of the metal nanowire cannot be performed at a high temperature, the metal nanowire has application limitations in the process. Also, when the metal nanowire is extended, its conductivity is reduced.
同時，金屬奈米粒子以導電性墨水(conductive ink)之形式製備，並且用於藉由噴墨製程(inkjet process)或其他相似方法來製備電極。此類金屬奈米粒子可包括金、銀、鉑、銅、鎳、鐵、鈷、鋅、鉻、錳等等之奈米粒子。特別地，銅、鎳、鐵、鈷、鋅、鉻、錳之奈米粒子可以低價製備，但比起貴金屬之奈米粒子而言具有較低的氧化穩定性。 Meanwhile, the metal nanoparticle is prepared in the form of a conductive ink, and is used to prepare an electrode by an inkjet process or the like. Such metal nanoparticles may include nanoparticles of gold, silver, platinum, copper, nickel, iron, cobalt, zinc, chromium, manganese, and the like. In particular, copper, nickel, iron, cobalt, zinc, chromium, manganese nanoparticles can be prepared at low cost, but have lower oxidation stability than noble metal nanoparticles.
更特別地，銅的價格便宜且具有絕佳的導電性。然而，若銅係為奈米粒子之形式，其表面很容易氧化且導電性大幅地降低。為此，不可利用銅作為導電性墨水。又，為了防止表面氧化而使用抗氧化劑可能亦會造成導電性之下降。再者，目前導 電性墨水主要係以銀作為奈米粒子，價格相當昂貴，並且近幾年來銀之價格更劇烈地增加。因此，極度地需要相對低價且具有高導電性的替代性金屬。 More specifically, copper is inexpensive and has excellent electrical conductivity. However, if the copper is in the form of nanoparticles, the surface thereof is easily oxidized and the conductivity is largely lowered. For this reason, copper cannot be used as the conductive ink. Moreover, the use of an antioxidant in order to prevent surface oxidation may also cause a decrease in conductivity. Furthermore, the current guide Electrolytic inks are mainly made of silver as nano particles, which are quite expensive, and the price of silver has increased more sharply in recent years. Therefore, an alternative metal that is relatively low in cost and has high conductivity is extremely required.
一種建議是用核殼結構奈米粒子預防組成核部分的金屬粒子之氧化，並改善粒子之導電性。作為代表性範例，由銀所形成之殼層(shell layer)結構係形成於由銅所形成的核奈米粒子(core nanoparticles)之表面上。在具有此種結構之奈米粒子中，由銀所形成的殼層可防止核部分的銅之氧化，且可以增強整個粒子的導電性。 One suggestion is to use core-shell nanoparticles to prevent oxidation of metal particles that make up the core portion and to improve the conductivity of the particles. As a representative example, a shell layer structure formed of silver is formed on the surface of core nanoparticles formed of copper. In the nanoparticle having such a structure, the shell layer formed of silver can prevent oxidation of copper in the core portion and can enhance the conductivity of the entire particle.
根據傳統之方法，為了製備核殼結構奈米粒子，核粒子之前驅物係在單一相(single phase)中，也就是在單一種溶劑之中，由還原劑還原，以製備核奈米粒子。接著，將用來在粒子上形成殼層之材料緩慢地加入其中，而進行還原反應以在粒子之表面上形成殼層。 According to a conventional method, in order to prepare core-shell structured nanoparticles, the nuclear particle precursors are reduced in a single phase, that is, in a single solvent, by a reducing agent to prepare core nanoparticles. Next, a material for forming a shell layer on the particles is slowly added thereto, and a reduction reaction is carried out to form a shell layer on the surface of the particles.
上述傳統方法之問題為，若在單一相進行還原反應以製備核奈米粒子，所製備的核奈米粒子之尺寸將不容易控制，且不容易將其分離。又，當藉由添加稀釋過的銀鹽溶液合成核殼結構，不容易調整溶液的給進速率(feeding rate)，因此還原的銀並不會在奈米粒子的表面上形成，而是通常會聚集(aggregate)成塊(clump)。再者，要調整所形成的殼層之厚度並不容易。 A problem with the above conventional method is that if a single phase is subjected to a reduction reaction to prepare core nanoparticles, the size of the prepared core nanoparticles will not be easily controlled and it is not easy to separate them. Moreover, when the core-shell structure is synthesized by adding the diluted silver salt solution, it is not easy to adjust the feeding rate of the solution, so the reduced silver does not form on the surface of the nanoparticle, but usually Aggregate clumps. Furthermore, it is not easy to adjust the thickness of the formed shell layer.
本發明係關於製備核殼結構奈米粒子之方法，藉此，可輕易地調整粒子尺寸、可輕易地分離粒子、且可在室溫下製備均勻的粒子。 The present invention relates to a method for producing core-shell structured nanoparticles, whereby the particle size can be easily adjusted, particles can be easily separated, and uniform particles can be prepared at room temperature.
又，本發明亦關於形成殼層之方法，藉此，可調整殼層之厚度，且可防止殼層形成材料之聚集。 Further, the present invention is also directed to a method of forming a shell layer whereby the thickness of the shell layer can be adjusted and the aggregation of the shell layer forming material can be prevented.
再者，本發明之一個目的係提供抗氧化的奈米粒子，其具有高導電性以及經濟效益。 Furthermore, it is an object of the present invention to provide antioxidant nanoparticles which are highly conductive and economical.
本發明係提供核殼結構奈米粒子，包括一殼層，此殼層係由如以下化學式1所示的一前驅物在核金屬粒子(core metal particle)之表面上形成：
在化學式1中，X代表氫、具有1至6個碳原子之烷基(alkyl group)、或鹵素(halogen)，且n係為0至23的整數。 In Chemical Formula 1, X represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a halogen, and n is an integer of 0 to 23.
較佳地，核金屬粒子可以是銅、鎳、鐵、鈷、鋅、鉻、或錳的粒子。 Preferably, the core metal particles may be particles of copper, nickel, iron, cobalt, zinc, chromium, or manganese.
較佳地，核金屬粒子可由如以下化學式2所示之前驅物所製備：[化學式2]M-Rm Preferably, the core metal particles can be prepared from a precursor as shown in the following Chemical Formula 2: [Chemical Formula 2] MR m
在化學式2中，M代表銅、鎳、鐵、鈷、鋅、鉻、 或錳，m係為1至5，R代表，且多於一個的R可 彼此相同或不同。 In Chemical Formula 2, M represents copper, nickel, iron, cobalt, zinc, chromium, or manganese, and m is 1 to 5, and R represents And more than one R may be the same or different from each other.
(在此，X代表氫、具有1至6個碳原子之烷基、或鹵素，且n係為0至23的整數。) (here, X represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a halogen, and n is an integer of 0 to 23.)
較佳地，核金屬粒子可由金屬己酸鹽(metal hexanoate)所製備。 Preferably, the core metal particles are prepared from metal hexanoate.
本發明提供一種核殼結構奈米粒子之方法，此製備方法包括還原如以下化學式1所示之一前驅物，在複數個核金屬粒子之表面上形成一殼層：
在化學式1中，X代表氫、具有1至6個碳原子之烷基、或鹵素，且n係為0至23的整數。 In Chemical Formula 1, X represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a halogen, and n is an integer of 0 to 23.
較佳地，核金屬粒子之製備可藉由以一水相還原劑還原有機相之金屬己酸鹽。 Preferably, the core metal particles are prepared by reducing the metal hexanoate of the organic phase with an aqueous phase reducing agent.
較佳地，前驅物可以一包括有機相溶劑之溶液的形式滴加至核金屬粒子。 Preferably, the precursor may be added dropwise to the core metal particles in the form of a solution comprising an organic phase solvent.
較佳地，溶液之給進速率(feeding rate)可在1毫升/分鐘至30毫升/分鐘之範圍之中。 Preferably, the feeding rate of the solution may range from 1 ml/min to 30 ml/min.
較佳地，溶液係可包括包含具有4至18個碳原子的烷基的胺類。 Preferably, the solution may include an amine comprising an alkyl group having 4 to 18 carbon atoms.
較佳地，相對於核金屬粒子，前驅物可使用100至200重量份(parts by weight)的量。 Preferably, the precursor may be used in an amount of from 100 to 200 parts by weight relative to the core metal particles.
藉由以下配合附圖對於本發明範例性的實施例所進行的詳細說明，本發明之上述及其他目標、特徵與優點，對於本領域中具有通常知識者而言將變得更為明確。 The above and other objects, features and advantages of the present invention will become more apparent to those skilled in the <
第1圖繪示根據本發明之一製備方法來製備核粒子並形成殼層之製程示意圖。 FIG. 1 is a schematic view showing a process for preparing nuclear particles and forming a shell layer according to a preparation method of the present invention.
第2圖顯示在一範例中所製備的銅奈米粒子與銅銀(Cu@Ag)粒子之掃描式電子顯微鏡(SEM)照片。 Figure 2 shows a scanning electron microscope (SEM) photograph of copper nanoparticles and copper silver (Cu@Ag) particles prepared in one example.
第3圖顯示在一比較例中所製備的粒子之描式電子顯微鏡照片。 Fig. 3 shows a scanning electron micrograph of the particles prepared in a comparative example.
第4圖顯示由在一範例中所製備的含有銅銀粒子之墨水(ink)所形成的塗佈膜之掃描式電子顯微鏡照片。 Fig. 4 shows a scanning electron micrograph of a coating film formed of an ink containing copper silver particles prepared in an example.
以下將參照附圖，詳細地對於本發明範例性的實施例進行描述。雖然本發明以其實施例進行揭露與描述，本發明所屬技術領域中具有通常知識者將能夠清楚的了解到，在不脫離本發明之精神和範圍內，可作各種之更動與潤飾。 Exemplary embodiments of the present invention will be described in detail below with reference to the accompanying drawings. While the invention has been shown and described with reference to the embodiments of the embodiments of the present invention, it will be understood that various modifications and changes can be made without departing from the spirit and scope of the invention.
當由高氧化性之金屬製備奈米粒子時，為了改善氧
化穩定性並增強奈米粒子之導電性，本發明提供包含有殼層結構之核殼結構奈米粒子，殼層結構係由如以下化學式1所示之前驅物在核金屬奈米粒子之表面上形成：
在化學式1中，X代表氫、具有1至6個碳原子之烷基、或鹵素，且n係為0至23的整數。 In Chemical Formula 1, X represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a halogen, and n is an integer of 0 to 23.
可利用具有特別低的氧化穩定性之銅、鎳、鐵、鈷、鋅、鉻、或錳作為組成核粒子之金屬。為了由這些金屬製備核金屬粒子，可使用如以下化學式2所示的金屬前驅物：[化學式2]M-Rm Copper, nickel, iron, cobalt, zinc, chromium, or manganese having particularly low oxidative stability can be utilized as the metal constituting the core particles. In order to prepare nuclear metal particles from these metals, a metal precursor such as the following Chemical Formula 2 can be used: [Chemical Formula 2] MR m
在化學式2中，M代表銅、鎳、鐵、鈷、鋅、鉻、 或錳，m係為1至5，R代表，且多於一個的R可 彼此相同或不同。 In Chemical Formula 2, M represents copper, nickel, iron, cobalt, zinc, chromium, or manganese, and m is 1 to 5, and R represents And more than one R may be the same or different from each other.
(此處，X代表氫、具有1至6個碳原子之烷基、或鹵素，且n係為0至23的整數。) (Here, X represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a halogen, and n is an integer of 0 to 23.)
此前驅物在非極性溶劑中具有高溶解度。因此，用於製備核金屬奈米粒子之反應溶液係易於製備。 Previously, the drive had high solubility in a non-polar solvent. Therefore, the reaction solution for preparing the core metal nanoparticles is easy to prepare.
在本發明之一範例中，藉由在溶劑與包覆劑(capping agent)中溶解金屬己酸鹽(metal hexanoate)來製備反應溶液。包覆劑係參與到金屬己酸鹽的還原反應之中，且包覆於所製備的奈米粒子之周圍以便於穩定粒子。又，包覆劑係防止所製備的金屬奈米粒子氧化。再者，包覆劑調整所製備之粒子的粒子尺寸。因此，較佳地，包覆劑可具有適當的鏈長(chain length)。 In one example of the present invention, a reaction solution is prepared by dissolving metal hexanoate in a solvent and a capping agent. The coating agent participates in the reduction reaction of the metal hexanoate and is coated around the prepared nanoparticles to stabilize the particles. Further, the coating agent prevents oxidation of the prepared metal nanoparticles. Further, the coating agent adjusts the particle size of the prepared particles. Therefore, preferably, the coating agent may have an appropriate chain length.
在本發明中，例如可使用胺類(amine)作為包覆劑。較佳地，此胺類可包含具有4至18個碳原子的烷基。在本發明中，較佳地，可使用丁基胺(butyl amine)、辛胺(octylamine)、十二烷胺(dodecylamine)、油胺(oleylamine)作為包覆劑。更佳地，可使用油胺作為包覆劑。油胺係為油酸(oleic acid)之胺類，油酸為一種脂肪酸，且油胺具有相對高之分子量。因此，油胺可與金屬奈米粒子結合且可在粒子表面上形成一個層。所以，可以防止外部氣體擴散至金屬奈米粒子之核裡，如此可增加金屬奈米粒子之氧化穩定性。再者，與金屬奈米粒子結合的油胺可使得奈米粒子易於在溶劑中分散。 In the present invention, for example, an amine can be used as a coating agent. Preferably, the amine may comprise an alkyl group having from 4 to 18 carbon atoms. In the present invention, preferably, a butyl amine, an octylamine, a dodecylamine, or an oleylamine can be used as a coating agent. More preferably, oleylamine can be used as a coating agent. The oleylamine is an amine of oleic acid, the oleic acid is a fatty acid, and the oleylamine has a relatively high molecular weight. Thus, oleylamine can be combined with metallic nanoparticles and can form a layer on the surface of the particles. Therefore, it is possible to prevent the external gas from diffusing into the core of the metal nanoparticle, which can increase the oxidation stability of the metal nanoparticle. Further, the oleylamine combined with the metal nanoparticles can make the nanoparticles easily dispersed in a solvent.
作為從金屬己酸鹽製備金屬奈米之製程範例，如第1圖之第①部分所示，以水相還原劑還原有機相金屬己酸鹽。金屬己酸鹽係由有機相與水相之間的分配平衡(partition equilibrium)所移動，並以水相中的還原劑還原，且接著分布並存在於水相與有機相之中，如第②部分所示。根據此製程，能夠防止可能因快速反應而造成的粒子之聚集。再者，可防止製程當中可能發生的 金屬氧化。因此，根據此製程，在相對低溫下(較佳地，為室溫至60℃)，可輕易地由所使用的包覆劑之種類來調整粒子尺寸，且可得到具有均勻形狀的奈米粒子。 As an example of a process for preparing metal nanoparticles from a metal hexanoate, as shown in the first part of Fig. 1, the organic phase metal hexanoate is reduced with an aqueous phase reducing agent. The metal hexanoate is moved by a partition equilibrium between the organic phase and the aqueous phase, and is reduced by a reducing agent in the aqueous phase, and then distributed and present in the aqueous phase and the organic phase, such as the second Part of it. According to this process, aggregation of particles which may be caused by rapid reaction can be prevented. Furthermore, it can prevent possible occurrences in the process. Metal oxidation. Therefore, according to this process, at a relatively low temperature (preferably, room temperature to 60 ° C), the particle size can be easily adjusted by the kind of the coating agent to be used, and a nanoparticle having a uniform shape can be obtained. .
可藉由還原如以下化學式1所示之前驅物，在如上所述之核金屬奈米粒子之表面上形成殼層：
在化學式1中，X代表氫、具有1至6個碳原子之烷基、或鹵素，且n係為0至23的整數。 In Chemical Formula 1, X represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a halogen, and n is an integer of 0 to 23.
前驅物在非極性溶劑中具有高溶解度，且在非極性溶劑與極性溶劑之間具有分配平衡，據此可防止聚集之問題，此為在聚合物之表面上使用其他前驅物形成殼層時的傳統問題。亦即，以本發明之前驅物，藉由調整非極性溶劑與極性溶劑之間的分配平衡，可調整氧化還原反應速率，以防止聚集。因此，根據本發明，施加於金屬粒子之表面上的前驅物並不會聚集，而只會吸收於粒子之表面以形成殼層。因此，本發明可提供殼核結構，此殼核結構之表面上有均勻的殼層形成。 The precursor has a high solubility in a non-polar solvent and has a distribution balance between the non-polar solvent and the polar solvent, thereby preventing the problem of aggregation, which is when a shell is formed using other precursors on the surface of the polymer. Traditional issues. That is, with the precursor of the present invention, the redox reaction rate can be adjusted to prevent aggregation by adjusting the distribution balance between the nonpolar solvent and the polar solvent. Therefore, according to the present invention, the precursor applied to the surface of the metal particles does not aggregate, but only absorbs on the surface of the particles to form a shell. Accordingly, the present invention can provide a core-shell structure having a uniform shell layer formed on the surface of the core-shell structure.
再者，當殼層形成時，藉由調整反應溫度與前驅物之濃度，可形成具有所需厚度之殼層。因此，在本發明之核殼結構奈米粒子中，可由反應溫度與前驅物之濃度調整殼層厚度。較 佳地，反應溫度可在室溫至40℃的範圍之中，且可使用相對於核金屬粒子之100至200重量份之前驅物。在低溫時，核粒子之表面活性係大幅地減少，且並不會進行反應。相對地，若反應溫度比上述之溫度範圍更高，反應速率係大幅地增加，造成聚集，因而無法形成均勻的殼層結構。又，若前驅物的用量係相對於核粒子之小於100重量份，前驅物以自由分子(free molecule)的狀態存在並因而不與核粒子之表面反應，或者殼層並未形成為足夠增加導電性之厚度。若前驅物之用量大，大於200重量份，前驅物溶液之黏度(viscosity)係增加，且殼層無法均勻地形成於核粒子的整個表面上，且亦可能會發生局部地聚集。 Further, when the shell layer is formed, a shell layer having a desired thickness can be formed by adjusting the reaction temperature and the concentration of the precursor. Therefore, in the core-shell structured nanoparticle of the present invention, the thickness of the shell layer can be adjusted by the reaction temperature and the concentration of the precursor. More Preferably, the reaction temperature may be in the range of room temperature to 40 ° C, and 100 to 200 parts by weight of the precursor relative to the core metal particles may be used. At low temperatures, the surface activity of the core particles is greatly reduced and does not react. In contrast, if the reaction temperature is higher than the above temperature range, the reaction rate is greatly increased to cause aggregation, and thus a uniform shell structure cannot be formed. Further, if the amount of the precursor is less than 100 parts by weight relative to the core particles, the precursor exists in a free molecule state and thus does not react with the surface of the core particle, or the shell layer is not formed to sufficiently increase the conductivity The thickness of sex. If the amount of the precursor is large, more than 200 parts by weight, the viscosity of the precursor solution is increased, and the shell layer cannot be uniformly formed on the entire surface of the core particle, and local aggregation may occur.
例如，在形成殼層之製程中，如第1圖所示，藉由非極性溶劑與極性溶劑之間的分配平衡所合成之核粒子，係分布於極性相與非極性相之中。在非極性溶劑相中之前驅物溶液係緩慢地滴加其中，以便促進還原反應。在此例中，較佳地，前驅物溶液之給進速率可在1毫升/分鐘至30毫升/分鐘的範圍之中。這是因為若給進速率低於1毫升/分鐘，反應可能進行得太慢，而若給進速率高於30毫升/分鐘，還原反應可能在高速率之下進行，且可能發生聚集。 For example, in the process of forming the shell layer, as shown in Fig. 1, the core particles synthesized by the distribution balance between the non-polar solvent and the polar solvent are distributed in the polar phase and the non-polar phase. The precursor solution is slowly added dropwise in the non-polar solvent phase to promote the reduction reaction. In this case, preferably, the feed rate of the precursor solution may be in the range of 1 ml/min to 30 ml/min. This is because if the feed rate is less than 1 ml/min, the reaction may proceed too slowly, and if the feed rate is higher than 30 ml/min, the reduction reaction may proceed at a high rate and aggregation may occur.
同時，在殼層形成反應期間，核金屬聚合物作為前驅物之還原劑。也就是說，即使沒有另外的還原劑，金屬粒子係直接地還原前驅物，且殼層係於金屬粒子的表面上形成。因此，相較於藉由利用另外的還原劑之還原反應來形成殼層之範例，在 本發明之殼層形成反應中，可輕易地調整反應速率，且核與殼層之間的結合變得穩固(solid)。 At the same time, the core metal polymer acts as a reducing agent for the precursor during the shell formation reaction. That is, even without an additional reducing agent, the metal particles directly reduce the precursor, and the shell layer is formed on the surface of the metal particles. Therefore, compared to the example of forming a shell by a reduction reaction using another reducing agent, In the shell formation reaction of the present invention, the reaction rate can be easily adjusted, and the bond between the core and the shell becomes solid.
較佳地，前驅物溶液可包括包含有4至18個碳原子的烷基的胺類。作為胺類，例如可使用三乙胺(triethylamine)、丁胺(butylamine)、辛胺(octylamine)、十二烷胺(dodecylamine)及油胺(oleylamine)。 Preferably, the precursor solution may comprise an amine comprising an alkyl group having from 4 to 18 carbon atoms. As the amine, for example, triethylamine, butylamine, octylamine, dodecylamine, and oleylamine can be used.
胺類藉由反應平衡(reaction equilibrium)調整前驅物之離子化，如下所示：
又，處於離子態之前驅物藉由以下所示之氧化還原反應在金屬離子之表面上形成殼層。在此例中，胺類作為陰離子摻雜物(dopant)，如下所示。因此，胺類促使由前驅物形成殼層。 Further, the precursor forms a shell layer on the surface of the metal ion by the redox reaction shown below before the ion state. In this case, an amine is used as an anionic dopant as shown below. Thus, the amine promotes the formation of a shell from the precursor.
2Ag++Cuo→2Ago+Cu2+ 2Ag + +Cu o →2Ag o +Cu 2+
因此，調整胺類之濃度係為調整殼層形成反應速率與殼層之厚度的一種方法。在本發明中，較佳地，前驅物溶液包含有濃度大於0重量百分比(wt%)並且小於10重量百分比的胺類。 Therefore, adjusting the concentration of the amine is one method of adjusting the reaction rate of the shell formation reaction and the thickness of the shell layer. In the present invention, preferably, the precursor solution contains amines having a concentration greater than 0 weight percent (wt%) and less than 10 weight percent.
根據本發明，藉由使用化學式1所示的前驅物，以及調整前驅物溶液之濃度、反應溫度、給進速率、與胺類的量，可在核粒子之表面上形成所需厚度之殼層。 According to the present invention, a shell having a desired thickness can be formed on the surface of the core particle by using the precursor shown in Chemical Formula 1, and adjusting the concentration of the precursor solution, the reaction temperature, the feed rate, and the amount of the amine. .
在下文中，本發明將參照以下範例進行詳細地解說。然而，提供下述範例係用以理解本發明，並非用以限定本發明。 Hereinafter, the present invention will be explained in detail with reference to the following examples. However, the following examples are provided to understand the invention and are not intended to limit the invention.
範例example
(1)銅奈米粒子之製備 (1) Preparation of copper nanoparticles
將1.1克之異辛酸銅(Cu(II)2-ethylhexanoate)、0.7克之丁胺、與30毫升之二甲苯(xylene)放入100毫升之圓底燒瓶中，並於其中溶解。在溶液加熱至60℃之後，將其中具有0.2克之聯胺(hydrazine)(使用具有80%純度之試劑)作為還原劑之溶液溶解於含有12毫升乙醇的混合溶液之中，且快速地將18毫升的水加入溶液中。然後，將反應溶液維持在60℃之下靜置4小時。因此，形成銅奈米粒子。 1.1 g of copper (Cu(II) 2-ethylhexanoate), 0.7 g of butylamine, and 30 ml of xylene were placed in a 100 ml round bottom flask and dissolved therein. After the solution was heated to 60 ° C, a solution having 0.2 g of hydrazine (using a reagent having an 80% purity) as a reducing agent was dissolved in a mixed solution containing 12 ml of ethanol, and 18 ml was quickly added. Water is added to the solution. Then, the reaction solution was allowed to stand at 60 ° C for 4 hours. Therefore, copper nanoparticles are formed.
(2)殼層之形成 (2) Formation of shell
將含有銅奈米粒子之溶液冷卻至室溫。然後，將0.6克之乙醛(acetaldehyde)(使用具有85%純度之試劑)加入其中，以便於淬熄(quench)還原劑之還原反應。此後，將含有銅奈米粒子之溶液放入設定在25℃的恆溫槽之中。接著，將2-庚酸甲酯銀 (Ag 2-methyl heptanoate)以相對於奈米粒子150重量份的量，以及將三乙胺(triethylamine)以相對於奈米粒子0.1重量份的量，在30毫升之二甲苯中溶解而得之溶液，以10毫升/分鐘之給進速率緩慢地滴加入其中。此後，將所得溶液於室溫下靜置1小時。因而，形成殼層。 The solution containing the copper nanoparticles was cooled to room temperature. Then, 0.6 g of acetaldehyde (using an agent having 85% purity) was added thereto to facilitate quenching the reduction reaction of the reducing agent. Thereafter, the solution containing the copper nanoparticles was placed in a thermostat set at 25 °C. Next, methyl 2-heptanoate silver (Ag 2-methyl heptanoate) is obtained by dissolving in an amount of 150 parts by weight relative to the nanoparticles and triethylamine in an amount of 0.1 part by weight relative to the nanoparticles to 30 ml of xylene. The solution was slowly added dropwise thereto at a feed rate of 10 ml/min. Thereafter, the resulting solution was allowed to stand at room temperature for 1 hour. Thus, a shell layer is formed.
比較例Comparative example
對於上述在範例中的(2)殼層之形成，使用0.6克之硝酸銀(AgNO3)替代2-庚酸甲酯銀。然而，硝酸銀並未順利溶解，且將此種狀態下的硝酸銀放入含有銅奈米粒子的溶液中。因此，會觀察到硝酸銀與水層分離。 For the formation of the (2) shell layer in the above example, 0.6 g of silver nitrate (AgNO 3 ) was used instead of 2-methyl methyl heptanoate. However, silver nitrate was not dissolved smoothly, and silver nitrate in this state was placed in a solution containing copper nanoparticles. Therefore, separation of silver nitrate from the aqueous layer is observed.
評估範例Evaluation example
1.粒子之辨認 Identification of particles
為了辨認分別在範例與比較例中製備的銅奈米粒子與銅銀粒子(Cu@Ag particles)，以掃描式電子顯微鏡拍攝這些粒子的影像。結果分別顯示於第2圖與第3圖中。 In order to identify copper nanoparticles and copper silver particles (Cu@Ag particles) prepared in the examples and comparative examples, images of these particles were taken by a scanning electron microscope. The results are shown in Figures 2 and 3, respectively.
請參照第2圖，會觀察到根據本發明所製備的銅奈米粒子具有平均100奈米之粒子直徑，且具有均勻的球形。又，由於銀殼形成於銅奈米粒子之上，粒子之大小係增加。 Referring to Figure 2, it will be observed that the copper nanoparticles prepared according to the present invention have an average particle diameter of 100 nm and have a uniform spherical shape. Further, since the silver shell is formed on the copper nanoparticles, the size of the particles increases.
同時，如第3圖所示，從在比較例中所製備之粒子的表面，觀察到在殼層形成製程期間所產生的聚集。 Meanwhile, as shown in Fig. 3, the aggregation generated during the shell formation process was observed from the surface of the particles prepared in the comparative examples.
2.膜之形成與觀察 2. Formation and observation of film
製備相對於所合成的銅銀奈米粒子含有25重量百分比之無水辛烷的墨水，在製備墨水之後，在玻璃基材上將墨水以2000每分鐘轉速(rpm)之下旋塗(spin-coated)達30秒，且接著在惰性氣體(氫氣(5%)+氬氣(95%))之氣氛之中進行300℃之熱處理達15分鐘。 An ink containing 25 weight percent of anhydrous octane relative to the synthesized copper silver nanoparticles was prepared, and after the ink was prepared, the ink was spin-coated at 2000 revolutions per minute (rpm) on a glass substrate. ) for 30 seconds, and then heat-treated at 300 ° C for 15 minutes in an atmosphere of an inert gas (hydrogen (5%) + argon (95%)).
膜表面之影像係以掃描式電子顯微鏡拍攝。可從第4圖中觀察到，當銀在核粒子之上融化時，形成塗膜(coating film)。因此，可見到在範例中所製備的核粒子之上，殼層形成得很好，並且熱處理將殼層之一部分組成融化以形成塗膜。在核粒子上之殼層所形成的銀塗膜，可防止核粒子之氧化，並具有優異的導電性。 The image of the film surface was taken with a scanning electron microscope. It can be observed from Fig. 4 that when silver is melted over the core particles, a coating film is formed. Therefore, it can be seen that on the core particles prepared in the examples, the shell layer is formed well, and the heat treatment melts a part of the shell layer to form a coating film. The silver coating film formed on the shell layer on the core particles can prevent oxidation of the core particles and has excellent conductivity.
根據本發明，由於可藉由有機相(非極性溶劑)與水相(極性溶劑)之間的分配平衡來調整還原反應，而可合成尺寸可調整且外形均勻的核奈米粒子。又，由於殼層形成前驅物具有高溶解度，且能夠藉由所使用的分配平衡調整氧化還原反應速率，而可藉由調整反應溫度與濃度來調整殼層之厚度。 According to the present invention, since the reduction reaction can be adjusted by the distribution balance between the organic phase (non-polar solvent) and the aqueous phase (polar solvent), core nanoparticles having an adjustable size and uniform shape can be synthesized. Further, since the shell layer forming precursor has high solubility, and the redox reaction rate can be adjusted by the distribution balance used, the thickness of the shell layer can be adjusted by adjusting the reaction temperature and concentration.
又，根據本發明，在所製備的核殼結構奈米粒子當中，易於氧化之核粒子係由不易氧化且具有高導電性之材料所包覆(encapsulate)。因此，可防止氧化並改善粒子之導電性。 Further, according to the present invention, among the prepared core-shell structured nanoparticles, the core particles which are easily oxidized are encapsulated by a material which is not easily oxidized and has high conductivity. Therefore, oxidation can be prevented and the conductivity of the particles can be improved.
再者，根據本發明，由於高價金屬只存在於殼層當 中，本發明相較於整個粒子由高價金屬所製成的情況而言，極具經濟效益。 Furthermore, according to the present invention, since high-priced metals are present only in the shell layer, The present invention is extremely economical in comparison to the case where the entire particle is made of a high-priced metal.
很明顯地，對於本發明所屬技術領域中具有通常知識者而言，顯然可在不脫離本發明之精神和範圍內，對前述的本發明範例性實施例作各種之更動與潤飾。因此，當此類更動與潤飾落在本發明申請專利範圍及其等價範圍內時，本發明涵蓋所有此類更動與潤飾。 It will be apparent to those skilled in the art that the present invention may be modified and modified in various embodiments of the present invention without departing from the spirit and scope of the invention. Accordingly, the present invention covers all such modifications and refinements when such modifications and refinements fall within the scope of the invention and its equivalents.
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