TWI568666B - Method of fabricating nano wire and nano wire complex - Google Patents
Method of fabricating nano wire and nano wire complex Download PDFInfo
- Publication number
- TWI568666B TWI568666B TW101122680A TW101122680A TWI568666B TW I568666 B TWI568666 B TW I568666B TW 101122680 A TW101122680 A TW 101122680A TW 101122680 A TW101122680 A TW 101122680A TW I568666 B TWI568666 B TW I568666B
- Authority
- TW
- Taiwan
- Prior art keywords
- ion
- nanowire
- metal
- solvent
- metal compound
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0547—Nanofibres or nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
Description
本發明係主張關於2011年06月23日申請之韓國專利案號No.10-2011-0061028之優先權。藉以引用的方式併入本文用作參考。 The present invention claims priority to Korean Patent No. 10-2011-0061028 filed on Jun. 23, 2011. This is incorporated herein by reference.
本發明係關於一種奈米線製造方法以及一種奈米線複合物。 The present invention relates to a method of manufacturing a nanowire and a nanowire composite.
包含有透明材料之一透明電極係被應用於各種電子產品中，例如一顯示裝置、一太陽能電池、以及一可攜式行動裝置。有關以一奈米線(奈米尺寸線形結構)用作為透明電極之透明導電材料之研究係廣泛的進行。 A transparent electrode comprising a transparent material is used in various electronic products such as a display device, a solar cell, and a portable mobile device. Research on transparent conductive materials using a nanowire (nano size linear structure) as a transparent electrode has been extensively carried out.
因奈米線具有絕佳之電傳導性質、彈性、與穿透率，故透明電極可表現出優秀的特性。然而，在反應過程中，奈米線很容易會結塊聚合，形成奈米粒子。因此，奈米線的製造並不簡單。這會造成奈米線的生產良率(product yield)顯著降低約10%，所以奈米線的實際應用會受到限制，變得困難。又，用以加速形成奈米線之反應的材料，如催化劑(catalysts)，會殘留在奈米線之表面上；這可能會導致奈米線表面的氧化或腐蝕，亦可能減弱其導電性。 Since the nanowire has excellent electrical conductivity, elasticity, and transmittance, the transparent electrode can exhibit excellent characteristics. However, during the reaction, the nanowires are prone to agglomerate polymerization to form nanoparticles. Therefore, the manufacture of the nanowire is not simple. This causes a significant reduction in the product yield of the nanowire by about 10%, so the practical application of the nanowire is limited and becomes difficult. Further, materials for accelerating the reaction of forming the nanowires, such as catalysts, may remain on the surface of the nanowire; this may cause oxidation or corrosion of the surface of the nanowire, and may also weaken its conductivity.
本發明實施例係提供一種長且細的線。 Embodiments of the present invention provide a long and thin line.
根據本發明實施例，一種奈米線製造方法係包括：藉由使一第一離子與一第二離子在一溶劑中反應，來形成複數個晶種粒子(seed particles)；以及藉由添加、加熱一金屬化合物(metallic compound)於該溶劑中，來形成一金屬奈米線。 According to an embodiment of the invention, a nanowire manufacturing method includes: forming a plurality of seed particles by reacting a first ion with a second ion in a solvent; and adding, by A metallic compound is heated in the solvent to form a metal nanowire.
根據本發明實施例，該第一離子可為一金屬離子(metallic ion)；而該第二離子可為一鹵素離子(halogen ion)。 According to an embodiment of the invention, the first ion may be a metallic ion; and the second ion may be a halogen ion.
根據本發明實施例，該晶種粒子可包括一金屬，該金屬係與構成該金屬化合物之一金屬相同。 According to an embodiment of the present invention, the seed particles may include a metal which is the same as a metal constituting one of the metal compounds.
根據本發明實施例，該晶種粒子與該金屬化合物可包括銀(silver)。 According to an embodiment of the invention, the seed particles and the metal compound may comprise silver.
根據本發明實施例，該晶種粒子可包括氯化銀(silver chloride)。 According to an embodiment of the invention, the seed particles may comprise silver chloride.
根據本發明實施例，一奈米線複合物係包括：一金屬奈米線；以及一晶種粒子，與該金屬奈米線相接合。該晶種粒子係具有一粒徑落在5nm至100nm之範圍內。 According to an embodiment of the invention, a nanowire composite system comprises: a metal nanowire; and a seed crystal particle bonded to the metal nanowire. The seed crystal particles have a particle size falling within the range of 5 nm to 100 nm.
根據本發明實施例，該晶種粒子係被提供於該金屬奈米線中，或該金屬奈米線之一端。 According to an embodiment of the invention, the seed particle system is provided in the metal nanowire or at one end of the metal nanowire.
如上所述，根據本發明實施例之奈米線製造方法，在由溶劑形成晶種粒子之步驟後，使用該晶種粒子，來形成金屬奈米線。在此情況下，根據本發明實施例之奈米線製造方法，該晶種粒子之粒徑可被適當調整。舉例而言，該晶種粒子可具有一非常小的粒徑落在約5nm至約100nm之範圍內。 As described above, according to the nanowire manufacturing method of the embodiment of the present invention, after the step of forming seed particles from a solvent, the seed crystal particles are used to form a metal nanowire. In this case, according to the method for producing a nanowire according to an embodiment of the present invention, the particle diameter of the seed particles can be appropriately adjusted. For example, the seed particles can have a very small particle size falling within the range of from about 5 nm to about 100 nm.
在此情況下，金屬奈米線可由該晶種粒子長成。因該晶種粒子係具有非常小的粒徑，故該金屬奈米線可具有非常細的直徑。 In this case, the metal nanowire can be grown from the seed particles. Since the seed crystal particles have a very small particle size, the metal nanowires can have a very fine diameter.
根據本發明實施例，一種奈米線製造方法係包括下列步驟：藉由使一第一離子與一第二離子在一溶劑中反應，來形成複數個晶種粒子；以及藉由添加一金屬化合物於該溶劑中，並加熱添加了該金屬化合物之該溶劑，來形成一金屬奈米線。 According to an embodiment of the present invention, a nanowire manufacturing method includes the steps of: forming a plurality of seed particles by reacting a first ion with a second ion in a solvent; and adding a metal compound The solvent in which the metal compound is added is heated in the solvent to form a metal nanowire.
此外，該第一離子可為金屬離子；而該第二離子可為鹵素離子。 Additionally, the first ion can be a metal ion; and the second ion can be a halogen ion.
此外，該些晶種粒子與該金屬化合物可包括相同之金屬。 Furthermore, the seed particles and the metal compound may comprise the same metal.
此外，該些晶種粒子與該金屬化合物可包括銀(Ag)。 Further, the seed particles and the metal compound may include silver (Ag).
此外，該些晶種粒子可包括氯化銀(AgCl)。 Further, the seed particles may include silver chloride (AgCl).
此外，各晶種粒子可具有一粒徑落在約5nm至約100nm之範圍內。 Further, each seed particle may have a particle size falling within the range of from about 5 nm to about 100 nm.
以下將配合圖式，進一步詳述本發明揭示之內容。 The disclosure of the present invention will be further described in detail below with reference to the drawings.
圖1係根據本發明實施例，繪示有奈米線製造方法之一流程圖。 1 is a flow chart showing a method of manufacturing a nanowire according to an embodiment of the invention.
參閱圖1，根據本發明實施例之一種奈米線製造方法係可包括下列步驟：加熱一溶劑(步驟ST10)；添加一覆蓋劑(capping agent)於該溶劑之中(步驟ST20)；形成複數個晶種粒子於該溶劑之中(步驟ST30)；添加一第四金屬化合物於該溶劑之中(步驟ST40)；添加一室溫溶劑於該溶劑之中(步驟ST50)；以及精煉出一奈米線(步驟ST60)。這些步驟並非必要不可少的步驟，而是可根據製造方法來取捨各步驟的執行與否，且可以改變該些步驟的順序。在下文中，將更詳細的說明各步驟。 Referring to FIG. 1, a nanowire manufacturing method according to an embodiment of the present invention may include the steps of: heating a solvent (step ST10); adding a capping agent to the solvent (step ST20); forming a plurality a seed crystal particle in the solvent (step ST30); adding a fourth metal compound to the solvent (step ST40); adding a room temperature solvent to the solvent (step ST50); and refining one Rice noodles (step ST60). These steps are not indispensable steps, but the execution of each step can be made according to the manufacturing method, and the order of the steps can be changed. In the following, the steps will be explained in more detail.
在加熱一溶劑(步驟ST10)之該步驟中，該溶劑係被加熱至足夠形成該金屬奈米線之反應溫度(reaction temperature)。 In this step of heating a solvent (step ST10), the solvent is heated to a reaction temperature sufficient to form the metal nanowire.
該溶劑可包括多元醇(polyol)。該多元醇係被用作為一溫和的還原劑(reducing agent)，同時作為混合不同材料之一溶劑；所以，該多元醇係協助該金屬奈米線之形成。舉例而言，該多元醇可包括乙二醇(ethylene glycol，EG)、丙二醇(propylene glycol，PG)、甘油(glycerine)、丙三醇(glycerol)、或葡萄糖(glucose)。另，可考慮該溶劑及該金屬化合物之類型及特性，來調整該反應溫度。 The solvent can include a polyol. The polyol is used as a mild reducing agent and as a solvent for mixing different materials; therefore, the polyol assists in the formation of the metal nanowire. For example, the polyol may include ethylene glycol (EG), propylene glycol (PG), glycerine, glycerol, or glucose. Further, the reaction temperature can be adjusted in consideration of the solvent and the type and characteristics of the metal compound.
舉例而言，若一銀奈米線係由使用具有絕佳還原力之丙二醇作為溶劑來形成，則該反應溫度可落在約80℃至140℃之範圍內。若該反應溫度小於80℃，則該反應速率變慢，造成反應無法平順地進行，進而增加製程所需的時間。若該反應溫度大於140℃，則因聚合現象(aggregation phenomenon)的影響，該銀奈米線可能無法形成，進而導致生產良率的降低。 For example, if a silver nanowire system is formed by using propylene glycol having an excellent reducing power as a solvent, the reaction temperature may fall within a range of about 80 ° C to 140 ° C. If the reaction temperature is less than 80 ° C, the reaction rate becomes slow, causing the reaction to proceed unsmoothly, thereby increasing the time required for the process. If the reaction temperature is more than 140 ° C, the silver nanowire may not be formed due to an aggregation phenomenon, which may result in a decrease in production yield.
如上所述，根據本實施例，該銀奈米線可在一低於習知技藝(使用具有絕佳還原力之丙二醇作為溶劑)中之該反應溫度(例如160℃)之一反應溫度下製造。根據習知技藝，因高反應溫度之故，銀奈米線係具有較短的長度(例如小於5 μm)；這會在形成一網絡結構時造成不利的影響。另外，銀奈米線之生產良率亦會被降低。相反的，根據本實施例，一銀奈米線係具有20 μm或以上之長度，降低反應溫度，其製造可具有較高之生產良率。 As described above, according to the present embodiment, the silver nanowire can be produced at a reaction temperature lower than the reaction temperature (for example, 160 ° C) in a conventional technique (using a propylene glycol having an excellent reducing power as a solvent). . According to conventional techniques, the silver nanowire has a shorter length (e.g., less than 5 μm) due to high reaction temperatures; this can adversely affect the formation of a network structure. In addition, the production yield of silver nanowires will also be reduced. In contrast, according to the present embodiment, a silver nanowire system having a length of 20 μm or more lowers the reaction temperature, and its production can have a higher production yield.
接著，在添加一覆蓋劑於該溶劑之中(步驟ST20)之步驟中，促進該奈米線形成之覆蓋劑係被添加入溶劑之中。若形成該奈米線之還原反應係迅速地進行，則該金屬係會集合在一起，使得該奈米線的形成變得困難。據此，該覆蓋劑係可藉由將包含於該溶劑中之材料適當地散佈開來，以避免該金屬集結聚合。 Next, in the step of adding a covering agent to the solvent (step ST20), a coating agent for promoting the formation of the nanowire is added to the solvent. If the reduction reaction for forming the nanowire is rapidly performed, the metal systems are brought together, making formation of the nanowire difficult. Accordingly, the covering agent can be suitably dispersed by dispersing the material contained in the solvent to avoid aggregation polymerization of the metal.
該覆蓋劑係可包括各種材料。舉例而言，該覆蓋劑係可包括選自由：聚乙烯吡咯烷酮(polyvinylpyrrolidone，PVP)、聚乙烯 醇(polyvinyl alcohol，PVA)、十六烷基三甲基溴化銨(cetyl trimethyl ammonium bromide，CTAB)、十六烷基三甲基氯化銨(cetyl trimethyl ammonium chloride，CTAC)、及聚丙烯醯胺(polyacrylamide，PAA)所組成之群組之材料。 The covering agent can include a variety of materials. For example, the covering agent may comprise selected from the group consisting of: polyvinylpyrrolidone (PVP), polyethylene Polyvinyl alcohol (PVA), cetyl trimethyl ammonium bromide (CTAB), cetyl trimethyl ammonium chloride (CTAC), and polypropylene A group of materials consisting of polyacrylamide (PAA).
然後，在形成複數個晶種粒子於該溶劑之中(步驟ST30)之步驟中，一第一金屬化合物及一第二金屬化合物係被添加於該溶劑之中。據此，包含於該第一金屬化合物內之該第一離子可與包含於該第二金屬化合物內之該第二離子反應，進而形成該些晶種粒子。在此情況下，該第一離子可與該第二離子反應，形成一第三金屬化合物，而該些晶種粒子可包含有該第三金屬化合物。 Then, in the step of forming a plurality of seed crystal particles in the solvent (step ST30), a first metal compound and a second metal compound are added to the solvent. Accordingly, the first ions contained in the first metal compound can react with the second ions contained in the second metal compound to form the seed particles. In this case, the first ion may react with the second ion to form a third metal compound, and the seed particles may comprise the third metal compound.
該第一離子可包括金屬離子。更詳細而言，該第一離子可包括金離子(gold ions)、銀離子(silver ions)、鉑離子(platinum ions)、或鈀離子(palladium ions)。 The first ion can include a metal ion. In more detail, the first ions may include gold ions, silver ions, platinum ions, or palladium ions.
該第二離子可包括鹵素離子。更詳細而言，該第二離子可包括氯離子(chlorine ions)、溴離子(bromide ions)、或碘離子(iodide ions)。 The second ion can include a halide ion. In more detail, the second ion may include chlorine ions, bromide ions, or iodide ions.
換句話說，包含於該些晶種粒子中之該第三金屬化合物可表現如下述化學式1：化學式1 MX In other words, the third metal compound contained in the seed particles can exhibit the following chemical formula 1: Chemical Formula 1 MX
在此情況下，X代表氯(Cl)、溴(Br)、或碘(I)，而M代表金(Au)、銀(Ag)、鉑(Pt)、或鈀(Pd)。 In this case, X represents chlorine (Cl), bromine (Br), or iodine (I), and M represents gold (Au), silver (Ag), platinum (Pt), or palladium (Pd).
該第三金屬化合物對於該溶劑可具有極低的可溶性。因此，該第三金屬化合物係脫離該溶劑，而形成該些晶種粒子。 The third metal compound can have very low solubility for the solvent. Therefore, the third metal compound is detached from the solvent to form the seed particles.
該些晶種粒子可具有很小的粒徑。該些晶種粒子之粒徑可落在約1nm至約1 μm之範圍內。更詳細而言，該些晶種粒子之粒徑可落在約5nm至約100nm之範圍內。上述之晶種粒子可均勻地散佈於該溶劑中。 The seed particles may have a small particle size. The particle size of the seed particles may fall within the range of from about 1 nm to about 1 μm. In more detail, the particle size of the seed particles may fall within the range of from about 5 nm to about 100 nm. The above seed particles can be uniformly dispersed in the solvent.
該第二金屬化合物與該第一金屬化合物之莫耳比(molar ratio)係為約1：1。此外，該第一金屬化合物可以約0.0001wt%至約0.3wt%之含量被添加於該溶劑中。又，該第二金屬化合物可以約0.0001wt%至約0.3wt%之含量被添加於該溶劑中。 The molar ratio of the second metal compound to the first metal compound is about 1:1. Further, the first metal compound may be added to the solvent in an amount of from about 0.0001% by weight to about 0.3% by weight. Also, the second metal compound may be added to the solvent in an amount of from about 0.0001% by weight to about 0.3% by weight.
該第一金屬化合物可包括包含有該第一離子之鹽(salts)。此外，該第一金屬化合物可包括硝酸鹽(nitrates)。更詳細而言，該第一金屬化合物可包括硝酸銀(silver nitrate)。 The first metal compound may include a salt containing the first ion. Further, the first metal compound may include nitrates. In more detail, the first metal compound may include silver nitrate.
該第二金屬化合物可包括包含有該第二離子之鹽(salts)。此外，該第二金屬化合物可包括鈉鹽(sodium salts)。更詳細而言，該第二金屬化合物可包括氯化鈉(sodium chloride)。 The second metal compound may include a salt containing the second ion. Further, the second metal compound may include sodium salts. In more detail, the second metal compound may include sodium chloride.
隨後，在添加一第四金屬化合物於該溶劑之中(步驟ST40)之步驟中，製備一反應溶液(reaction solution)，係藉由將該第 四金屬化合物添加於該溶劑之中。 Subsequently, in the step of adding a fourth metal compound in the solvent (step ST40), a reaction solution is prepared by using the A tetrametallic compound is added to the solvent.
在此情況下，在一額外溶劑中熔化之該第四金屬化合物係可被添加入一溶劑中(該溶劑中係加有覆蓋劑，且有晶種粒子提供於其中)。該額外溶劑所包含之材料，可與構成初始溶劑(initial solvent)之材料為相同或不同者。此外，該第四金屬化合物可在該些晶種粒子形成後一段預設時間間隔以後再行添加。因此，溫度可穩定保持在一適當的反應溫度。 In this case, the fourth metal compound which is melted in an additional solvent may be added to a solvent in which a covering agent is added and in which seed particles are provided. The additional solvent may comprise the same or different materials as the materials constituting the initial solvent. Further, the fourth metal compound may be added after a predetermined time interval after the seed particles are formed. Therefore, the temperature can be stably maintained at a suitable reaction temperature.
在此情況下，可製造該第四金屬化合物，其係包括用以形成一金屬奈米線之金屬。為形成銀奈米線，該金屬化合物可包括硝酸銀(AgNO3)或銀氰化鉀(KAg(CN)2)。 In this case, the fourth metal compound can be produced, which includes a metal for forming a metal nanowire. To form the silver nanowire, the metal compound may include silver nitrate (AgNO 3 ) or silver potassium cyanide (KAg(CN) 2 ).
如上所述，若該第四金屬化合物係被添加於一溶劑中(該溶劑中係包括覆蓋劑及晶種粒子)，反應會發生，進而可開始金屬奈米線之製造流程。在此情況下，該金屬奈米線可自晶種粒子生長成。也就是說，還原該第四金屬化合物所脫出之金屬係會自晶種粒子生長，以形成該金屬奈米線。 As described above, when the fourth metal compound is added to a solvent (including a coating agent and seed crystal particles in the solvent), a reaction occurs, and the production process of the metal nanowire can be started. In this case, the metal nanowire can be grown from seed particles. That is, the metal which is removed by the reduction of the fourth metal compound is grown from the seed particles to form the metal nanowire.
在此情況下，因該些晶種粒子係具有一非常小的粒徑，故該金屬奈米線係可長成具有一很小的直徑。 In this case, since the seed crystal particles have a very small particle diameter, the metal nanowire system can be grown to have a small diameter.
在該金屬奈米線完全長成後，該些晶種粒子可由下列流程(例如一精煉流程(refining process))來去除之。亦即，在下述流程中，可將該些晶種粒子與該金屬奈米線分離，並去除之。 After the metal nanowires are fully grown, the seed particles can be removed by the following process (e.g., a refining process). That is, in the following scheme, the seed crystal particles may be separated from the metal nanowire and removed.
然而，可能會殘留一部份的晶種粒子。因此，一部份的第三金屬化合物可於根據本實施例之該金屬奈米線中被檢測出。 However, a portion of the seed particles may remain. Therefore, a part of the third metal compound can be detected in the metal nanowire according to the embodiment.
亦即，該些晶種粒子可與該金屬奈米線結合，進而形成一奈米線複合物。 That is, the seed particles can be combined with the metal nanowire to form a nanowire composite.
圖2係根據本發明實施例，繪示有一奈米線複合物之圖式；圖3係繪示有另一奈米線複合物之圖式。 2 is a diagram showing a nanowire composite according to an embodiment of the present invention; and FIG. 3 is a diagram showing another nanowire composite.
如圖2、3所示，部分金屬奈米線可具有一奈米線複合物10或11之形式。該些晶種粒子100係與該金屬奈米線200相結合。表現出該奈米線複合物10或11之形式之該金屬奈米線所佔之比例可為約0.1%至約0.001%。 As shown in Figures 2 and 3, a portion of the metal nanowire may have the form of a nanowire composite 10 or 11. The seed particles 100 are combined with the metal nanowire 200. The proportion of the metal nanowires in the form of the nanowire composite 10 or 11 may range from about 0.1% to about 0.001%.
特別是，如圖2所示，該些晶種粒子100可被提供於該金屬奈米線200之一端。另，如圖3所示，多個晶種粒子110可被提供於金屬奈米線200之中。 In particular, as shown in FIG. 2, the seed particles 100 may be provided at one end of the metal nanowire 200. In addition, as shown in FIG. 3, a plurality of seed particles 110 may be provided in the metal nanowire 200.
在此情況下，該些晶種粒子100、110之該粒徑可落在約1nm至約1 μm之範圍內；更詳細而言，落在約5nm至約100nm之範圍內。更詳細而言，該些晶種粒子100、110之該粒徑可落在約10nm至約50nm之範圍內。如上所述，當具有很小粒徑的該些晶種粒子100、110被檢測到時，可經由根據本發明實施例之製造方法來形成具有很小直徑之該金屬奈米線。 In this case, the particle size of the seed particles 100, 110 may fall within the range of from about 1 nm to about 1 μm; more specifically, fall within the range of from about 5 nm to about 100 nm. In more detail, the particle size of the seed particles 100, 110 may fall within the range of from about 10 nm to about 50 nm. As described above, when the seed particles 100, 110 having a small particle diameter are detected, the metal nanowire having a small diameter can be formed via a manufacturing method according to an embodiment of the present invention.
根據本發明實施例，可基於100重量份(weight part)的該金 屬化合物(如硝酸銀AgNO3或銀氰化鉀KAg(CN)2)，來添加60重量份至330重量份的該覆蓋劑。若添加的該覆蓋劑小於60重量份，則可充分避免凝聚現象的出現。若添加的該覆蓋劑大於330重量份，則可形成球狀或立方狀的該金屬奈米粒子，且該覆蓋劑會留在製造出的該金屬奈米線中，故會減弱該金屬奈米線之導電力。 According to an embodiment of the present invention, 60 parts by weight to 330 parts by weight of the covering agent may be added based on 100 parts by weight of the metal compound such as silver nitrate AgNO 3 or silver potassium cyanide KAg (CN) 2 . If the amount of the coating agent added is less than 60 parts by weight, the occurrence of agglomeration can be sufficiently avoided. If the coating agent is added in an amount of more than 330 parts by weight, the spherical or cubic metal nanoparticles may be formed, and the covering agent may remain in the manufactured metal nanowire, thereby weakening the metal nanoparticle. The electrical conductivity of the line.
又，該第一及該第二金屬化合物之含量，相對於100重量份的第四金屬化合物，可落在0.00001重量份至0.5重量份之範圍內。若添加的該第一及該第二金屬化合物之含量小於0.00001重量份，則可能無法充分加速促進反應。另，若添加的該第一及該第二金屬化合物之含量大於0.5重量份，則銀會被迅速的還原，使得多個銀奈米粒子產生，或者該奈米線可能具有一較厚的直徑以及一較短的長度。此外，一催化劑係留在該金屬奈米線中，這可能會減弱導電性。 Further, the content of the first and second metal compounds may fall within the range of 0.00001 part by weight to 0.5 part by weight with respect to 100 parts by weight of the fourth metal compound. If the content of the first and second metal compounds to be added is less than 0.00001 parts by weight, the accelerated reaction may not be sufficiently accelerated. In addition, if the content of the first and second metal compounds added is more than 0.5 parts by weight, the silver may be rapidly reduced, so that a plurality of silver nanoparticles may be produced, or the nanowire may have a thicker diameter. And a shorter length. In addition, a catalyst system remains in the metal nanowire, which may weaken the conductivity.
然後，在添加該室溫溶劑於該溶劑之中(步驟ST50)之步驟中，該室溫溶劑係被添加於有反應開始進行之該溶劑中。該室溫溶劑所包括之材料可與使用於反應初始階段之材料相同或不同者。舉例而言，該室溫溶劑可包括多元醇(polyol)如乙二醇(ethylene glycol，EG)及丙二醇(propylene glycol，PG)。 Then, in the step of adding the room temperature solvent to the solvent (step ST50), the room temperature solvent is added to the solvent in which the reaction starts. The room temperature solvent may comprise the same or different materials as used in the initial stage of the reaction. For example, the room temperature solvent may include a polyol such as ethylene glycol (EG) and propylene glycol (PG).
作為反應開始進行之處之該溶劑，其係持續地被加熱，以維持一恆定的反應溫度；該溫度可在反應進行過程中提升。如上所 述，可藉由以添加該室溫溶劑於反應進行之該溶劑中，暫時降低該溶劑之溫度，來將該反應溫度控制得更恆定。 The solvent, which is where the reaction begins, is continuously heated to maintain a constant reaction temperature; this temperature can be elevated during the progress of the reaction. As above As described above, the reaction temperature can be controlled to be more constant by temporarily reducing the temperature of the solvent by adding the room temperature solvent to the solvent in the reaction.
添加該室溫溶劑於該溶劑之中(步驟ST50)之步驟可進行一次或多次，依該反應時間、該反應溶液之溫度之考量而定。 The step of adding the room temperature solvent to the solvent (step ST50) may be carried out one or more times depending on the reaction time and the temperature of the reaction solution.
隨後，在精煉出該奈米線(步驟ST60)之步驟中，該金屬奈米線係被精煉並收集於該反應溶液中。 Subsequently, in the step of refining the nanowire (step ST60), the metal nanowire is refined and collected in the reaction solution.
更詳細來說，若被用作為一非極性溶劑(non-polar solvent)之丙酮(acetone)係取代水，而被添加於該反應溶液中，則因覆蓋劑殘留於該金屬奈米線之表面的緣故，該金屬奈米線會沉積於該溶液之下部分。這是因為儘管該覆蓋劑充分的溶於該溶劑裡，但其並不溶於丙酮中，所以仍會聚結、況積。之後，當該溶液之上部分被排去時，一部份的覆蓋劑及奈米粒子也會隨之被去除。 More specifically, if acetone is used as a non-polar solvent instead of water and added to the reaction solution, the covering agent remains on the surface of the metal nanowire. For this reason, the metal nanowire will deposit on the lower portion of the solution. This is because although the covering agent is sufficiently soluble in the solvent, it is not soluble in acetone, so it still coalesces and accumulates. Thereafter, when the upper portion of the solution is discharged, a portion of the covering agent and the nanoparticles are also removed.
若蒸餾水(distilled water)係被添加於剩餘的溶液中，金屬奈米線與金屬奈米粒子係會散佈開來。此外，若添加更多丙酮，則該金屬奈米線係沉積，該金屬奈米粒子係散佈於該溶液之上部分。接著，若該溶液之上部分被排去，則一部份的覆蓋劑及該聚結的奈米粒子也會隨之被去除。在藉由重複進行上述流程來收集該金屬奈米線以後，該金屬奈米線係被儲放於該蒸餾水之中。將該金屬奈米線儲放於該蒸餾水之中可以避免該金屬奈米線重再聚合。 If distilled water is added to the remaining solution, the metal nanowires and the metal nanoparticle system are dispersed. Further, if more acetone is added, the metal nanowire is deposited, and the metal nanoparticle is dispersed on the upper portion of the solution. Then, if the upper portion of the solution is removed, a portion of the covering agent and the coalesced nanoparticles are also removed. After the metal nanowire is collected by repeating the above procedure, the metal nanowire is stored in the distilled water. The metal nanowire is stored in the distilled water to avoid heavy repolymerization of the metal nanowire.
如上所述，根據本發明實施例之金屬奈米線製造方法，該金屬奈米線係使用具有極小粒徑之晶種粒子來長成。由此，可形成具有很小直徑的該金屬奈米線。 As described above, according to the method for producing a metal nanowire according to an embodiment of the present invention, the metal nanowire is grown using seed particles having a very small particle diameter. Thereby, the metal nanowire having a small diameter can be formed.
200 ml的丙二醇係被加熱至126℃，且6.7 g的聚乙烯吡咯烷酮與0.1 g的溴化鉀係被添加、熔化。接著，添加0.35mmol的鈉鹽和0.35mmol的硝酸銀，以形成晶種粒子。經過約十分鐘的等待時間後，2.3 g的硝酸銀係熔化於100 ml的丙二醇之中，並被加入包含有聚乙烯吡咯烷酮及晶種粒子之溶液裡。之後，此反應係繼續進行約兩小時，以完成銀奈米線之製造。 200 ml of propylene glycol was heated to 126 ° C, and 6.7 g of polyvinylpyrrolidone and 0.1 g of potassium bromide were added and melted. Next, 0.35 mmol of a sodium salt and 0.35 mmol of silver nitrate were added to form seed particles. After a waiting time of about ten minutes, 2.3 g of silver nitrate was melted into 100 ml of propylene glycol and added to a solution containing polyvinylpyrrolidone and seed particles. Thereafter, the reaction was continued for about two hours to complete the manufacture of the silver nanowire.
在使用500 ml的丙酮來稀釋該溶液以後，600 ml的丙酮係被加入該稀釋溶液中。然後，包含丙二醇之該溶液之上部分，以及散佈其中之銀奈米粒子，係被去除。在重複進行上述流程三次以後，將所得到的結果儲存於10 ml的蒸餾水中。 After diluting the solution with 500 ml of acetone, 600 ml of acetone was added to the diluted solution. Then, the upper portion of the solution containing propylene glycol, and the silver nanoparticles dispersed therein are removed. After repeating the above procedure three times, the obtained results were stored in 10 ml of distilled water.
與實驗例不同，在此處使用平均粒徑約2.5 μm之氯化銀粒子，加入溶劑中，取代以鈉鹽和硝酸銀間反應來形成晶種粒子之製程。其餘的製程步驟均以與實驗例相同方式進行之。 Unlike the experimental examples, silver chloride particles having an average particle diameter of about 2.5 μm were used here, and added to a solvent to replace the process of forming a seed particle by reacting a sodium salt with silver nitrate. The rest of the process steps were carried out in the same manner as in the experimental examples.
如表1所示，一較細、較長的銀奈米線係形成於實驗例中。 As shown in Table 1, a finer, longer silver nanowire system was formed in the experimental example.
在本說明書中所提到的“一實施例”、“實施例”、“範例實施例”等任何的引用，代表本發明之至少一實施例中包括關於該實施例的一特定特徵、結構或特性。此類用語出現在文中多處但不盡然要參考相同的實施例。此外，在特定特徵、結構或特性的描述關係到任何實施例中，皆認為在熟習此技藝者之智識範圍內其利用如此的其他特徵、結構或特徵來實現其它實施例。 Any reference to "an embodiment", "an embodiment", "an example embodiment" or the like in this specification means that a particular feature, structure or structure of the embodiment is included in at least one embodiment of the invention. characteristic. Such terms appear in many places in the text but do not necessarily refer to the same embodiment. In addition, in the description of a particular feature, structure, or characteristic, it is contemplated that such other features, structures, or characteristics may be utilized to implement other embodiments within the scope of those skilled in the art.
雖然參考實施例之許多說明性實施例來描述實施例，但應理解，熟習此項技藝者可想出將落入本發明之原理的精神及範疇內的眾多其他修改及實施例。更特定言之，在本發明、圖式及所附申請專利範圍之範疇內，所主張組合配置之零部件及/或配置的各種變化及修改為可能的。對於熟悉此項技術者而言，除了零部件 及/或配置之變化及修改外，替代用途亦將顯而易見。 While the invention has been described with respect to the embodiments of the embodiments of the present invention More particularly, various variations and modifications are possible in the component parts and/or arrangements of the claimed combinations. For those familiar with this technology, except for parts Alternatives and modifications, as well as alternatives, will also be apparent.
ST10~ST60‧‧‧步驟 ST10~ST60‧‧‧Steps
10、11‧‧‧奈米線複合物 10, 11‧‧‧ nanowire compound
100、110‧‧‧晶種粒子 100, 110‧‧‧ seed particles
200‧‧‧金屬奈米線 200‧‧‧Metal nanowire
圖1係根據本發明實施例，繪示有一奈米線製造方法之一方塊流程圖；圖2係根據本發明實施例，繪示有一奈米線複合物之圖式；以及圖3係繪示有另一奈米線複合物之圖式。 1 is a block diagram showing a method for fabricating a nanowire according to an embodiment of the present invention; FIG. 2 is a diagram showing a nanowire composite according to an embodiment of the present invention; and FIG. There is another pattern of nanowire complexes.
ST10~ST60‧‧‧步驟 ST10~ST60‧‧‧Steps
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110061028A KR20130000504A (en) | 2011-06-23 | 2011-06-23 | Method of fabricating nano wire and nano wire complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201307190A TW201307190A (en) | 2013-02-16 |
| TWI568666B true TWI568666B (en) | 2017-02-01 |
Family
ID=47423115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW101122680A TWI568666B (en) | 2011-06-23 | 2012-06-25 | Method of fabricating nano wire and nano wire complex |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20140220341A1 (en) |
| KR (1) | KR20130000504A (en) |
| CN (1) | CN103635418B (en) |
| TW (1) | TWI568666B (en) |
| WO (1) | WO2012177093A2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104797363B (en) | 2012-09-27 | 2018-09-07 | 罗地亚经营管理公司 | It manufactures silver nanostructured method and can be used for the copolymer of the method |
| CN103498197A (en) * | 2013-09-09 | 2014-01-08 | 东莞市明源钟表科技有限公司 | Nanowire |
| WO2019065379A1 (en) * | 2017-09-27 | 2019-04-04 | Ｄｏｗａエレクトロニクス株式会社 | Silver powder mixture, method for producing same, and conductive paste |
| CN109211991B (en) * | 2018-09-25 | 2021-06-22 | 红河学院 | Construction and application of nitrogen and sulfur co-doped graphene loaded alloy nanowire composite material-based electrochemical sensor |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7173525B2 (en) * | 2004-07-23 | 2007-02-06 | Innovalarm Corporation | Enhanced fire, safety, security and health monitoring and alarm response method, system and device |
| CN100342064C (en) * | 2005-09-23 | 2007-10-10 | 浙江大学 | Silver nanometer wire synthesizing process |
| US20090045720A1 (en) * | 2005-11-10 | 2009-02-19 | Eun Kyung Lee | Method for producing nanowires using porous glass template, and multi-probe, field emission tip and devices employing the nanowires |
| WO2008072479A1 (en) * | 2006-12-13 | 2008-06-19 | Panasonic Corporation | Nanowire, device comprising nanowire, and their production methods |
| US7922787B2 (en) * | 2008-02-02 | 2011-04-12 | Seashell Technology, Llc | Methods for the production of silver nanowires |
| JP5249147B2 (en) * | 2009-07-07 | 2013-07-31 | 本田技研工業株式会社 | Curling method |
| US8512438B2 (en) * | 2009-08-25 | 2013-08-20 | Cambrios Technologies Corporation | Methods for controlling metal nanostructures morphology |
| US8274138B2 (en) * | 2009-09-30 | 2012-09-25 | Eastman Kodak Company | II-VI semiconductor nanowires |
| US20130192423A1 (en) * | 2012-01-27 | 2013-08-01 | Blue Nano Inc. | Method of producing silver nanowires |
-
2011
- 2011-06-23 KR KR1020110061028A patent/KR20130000504A/en not_active Application Discontinuation
-
2012
- 2012-06-25 WO PCT/KR2012/004977 patent/WO2012177093A2/en active Application Filing
- 2012-06-25 US US14/128,791 patent/US20140220341A1/en not_active Abandoned
- 2012-06-25 TW TW101122680A patent/TWI568666B/en not_active IP Right Cessation
- 2012-06-25 CN CN201280030925.XA patent/CN103635418B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Linfeng Gou et. al, "Convenient, rapid synthesis of Ag nanowires", Chem. Mater., Vol. 19, 2007, pp. 1755-1760. * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012177093A3 (en) | 2013-04-04 |
| WO2012177093A2 (en) | 2012-12-27 |
| CN103635418B (en) | 2016-08-31 |
| TW201307190A (en) | 2013-02-16 |
| KR20130000504A (en) | 2013-01-03 |
| CN103635418A (en) | 2014-03-12 |
| US20140220341A1 (en) | 2014-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2632850B1 (en) | Nano wire and method for manufacturing the same | |
| CN108372313B (en) | Nano silver wire dispersion liquid with small wire diameter distribution and preparation method of conductive ink thereof | |
| Caswell et al. | Seedless, surfactantless wet chemical synthesis of silver nanowires | |
| JP5611220B2 (en) | Method for producing metal nanowire using ionic liquid | |
| TWI568666B (en) | Method of fabricating nano wire and nano wire complex | |
| EP2688701B1 (en) | Method for producing silver nanofilaments | |
| KR101478076B1 (en) | Metal NANOWIRE AND METHOD FOR MANUFACTURING THE SAME | |
| KR101842763B1 (en) | preparation method of copper nano-structures | |
| TWI429598B (en) | Silver nanowires and preparation method thereof | |
| CN104923803A (en) | Method for synthesizing copper nanowire ink with high stability and high conductivity by one-step method | |
| KR101360688B1 (en) | Nanowire and method for manufacturing the same | |
| KR101305892B1 (en) | Nanowire and method for manufacturing the same by using low temperature polyol process | |
| KR101536633B1 (en) | Process for preparing silver nanowire | |
| KR101326952B1 (en) | Nanowire and method for manufacturing the same | |
| KR101307973B1 (en) | Mass Production Method of Ag NanoWire | |
| KR102513899B1 (en) | Metal nanowire and Method of manufacturing thereof | |
| CN113649558B (en) | Nano silver wire and preparation method thereof | |
| Zhang et al. | Simple fabrication of morphology-tunable Ag2S and Ag architectures assisted by denatured bovine serum albumin | |
| KR20130014279A (en) | Nanowire and method for manufacturing the same | |
| US9956616B2 (en) | Nano-wire and method for manufacturing the same | |
| KR20150036902A (en) | Nano solution and manufacturing apparatus of nanowire | |
| KR20130014277A (en) | Nanowire and method for manufacturing the same | |
| JP2008031518A (en) | Nanorod, and method for producing nanorod | |
| KR102152632B1 (en) | Nanowire ink | |
| KR101295621B1 (en) | Preparation method of silver solution for thin film deposition and fabrication method of transparent silver electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |