201213618 六、發明說明： 【發明所屬之技術領域】 本發明係與一種奈米銀有關， 銀之方法。 【先前技術】 特別是指一種以電化學法成長奈米201213618 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a silver silver-related method. [Prior Art] In particular, it refers to an electrochemical growth of nano
隨著人口急 自然資源耗竭、 籲求’因此使材料具備新的功能與結構為可能的方法，其中在結構上特 別是奈米結構的發展值得關注。現今奈米科技現已發展成為全球性的 科學研究賴’並且獅:至各種科學紅程躺，使得材制製造過 程、基本性質與功能性等各方面，在學術界與產業界帶來不小的遠景。 1986年Yasu j i Sawada 4人提出’在硫化辞溶液中利用電化學法 在基板上’儿積樹狀結構的金屬鋅，並利用改變電解液濃度與操作電壓 來控制金>1鋅的結構職。在特定賴作條件巾可以·製備出雛 1999年’ A. Datta等人利用硝酸銀與二氧化矽不同的比例濃度，得 到銀粒子直&可由銀離子濃度與電化學的操作電壓控制，2_年 JixmngFang f人提出電化學法製備樹狀結構的金屬銀，文獻中探討 了反應時間與錄結構尺寸關係。With the rapid population of natural resources depleted and appealed, it is therefore possible to make materials with new functions and structures, of which the development of structures, especially nanostructures, deserves attention. Nowadays, nanotechnology has developed into a global scientific research and lion: to various scientific red lie, making the manufacturing process, basic nature and functionality of the material industry bring a lot of academic and industrial circles. The vision. In 1986, Yasu ji Sawada proposed to use 'electrochemical method on the substrate' to form a metal-like zinc structure on the substrate, and to control the structure of gold >1 zinc by changing the electrolyte concentration and operating voltage. . In the specific conditions of the towel can be prepared to prepare the younger in 1999 'A. Datta et al. using different ratios of silver nitrate and cerium oxide to obtain silver particles straight & can be controlled by silver ion concentration and electrochemical operating voltage, 2_ In the year, JixmngFang f proposed electrochemical preparation of metallic silver in a dendritic structure. The relationship between reaction time and recorded structure size was discussed in the literature.
結構金屬♦，但其製程方式*同。 清同時參閱+華民隨書號數I3G41〇m專糖，該案件係揭露一 201213618 ，金屬ά奸之kn 枝置陽極金Structure metal ♦, but its process method is the same. At the same time, see + Huamin with the book number I3G41〇m special sugar, the case is revealed a 201213618, metal traitor kn branch anode gold
屬電極及陰極金屬電極，並在财_盛裝具有界面潍劑之成長溶 液與具機基之溶液’當陽、陰極金屬電極間通以電流後，於陽極金屬 _析出之金雜子為界祕_所包覆㈣彡齡屬奈綠子，再藉 由具有曝之溶肢變界祕_之軟性微賊板的雜，而成功合 成出筆曲的棒狀金屬奈米粒子;前述之具有·之溶液係於異丙醇、甲 醇、丙醇、氯乙醇、乙二醇、正丁醇、二丙酮醇中選擇其一者。 之 ^該案雖亦可形成金屬奈米結構，但其所形成之方法及製程所需 私兄皆與本案不烟，故與本案雜大的差異。 【發明内容】 ' =發明主要目的在提供—種以電化學法成長奈健之方法 可沉積形成可控制外形之奈米銀。 便具 本發明以電化學法成長奈米銀之方法，其係包含有： 將一導電基板及—導置於—容財，且該容器中係容 含量;=x:G:M擰=及—溶劑’而該醋酸銀與該檸檬酸兩者濃度 相連接’而該電子源係具有—陽極及—陰極，其中，該導電== 該導Ϊ體則與該陽極相連接’又，該電子“提^ 形成太鴻—沉積時間進行沉積，而使該導電基板上可沉積 少ί = 彳_壓係至少要2伏特，時間係至 此’可過上财法並改㈣電基板及導狀相對位置 以精確控制奈米銀的外形。 置 【實施方式】 201213618 首先，請參閱第-圖所示，為本發明第一實施例之示意圖，其步 驟如下： 係將導電基板10 /X:泡於異丙醇（Is〇_pr〇卿〇1)中並使用超 音波震盪儀震黯洗數分鐘，完錢將該導電基板1Q取出，再將其浸 泡於丙_ (AeetGiie)巾，亦朗超音波震舰震黯洗數分鐘；再取 出該導電基板1G，並浸泡於錄子水帽盪清絲分鐘，而完成該導 電基板10之清洗動作’其中’於本發明實施例中該導電基板1〇係可 #為銦錫氧化物（lndium Tin 0xide，IT〇)玻璃基板或銀基板。 更進-步再將該導電基板1〇與一電子源2〇相連接，該電子源職 為直流電源供應器，且該電子源2〇係具有一陽極及一陰極，並可提供 -㈣電壓’該猶電壓係至少要2伏特，且該賴係為2伏特至 1〇伏特之間，又，該導電基板1G係與該陰極相連接，於本發明實施例 中該電子獅係具有二鍍銀朗，且其—係與料電基板1()相連接， 同時’該鍍銀線21係透過-導電固定件3〇而固定於該導電基板ι〇之表 #面，且該導電固定件30係可為銅膠帶或導電夾（圖未示），而該轉帶 係可只黏職導電基板1〇之-侧，或_於該導電基板版四周當 忒導電基板10四周皆黏貼該銅膠帶時，其可提升該導電基板1〇整體的 電流密度’另，該電子源20之_則係透過另一鑛銀線21連接一導電 體40，而於本發明實施例中該導電體4〇係為白金⑽材質之柱體。 再準備-容器50，該容器50内係容置有一容液5卜該容液51係具 有-醋酸銀、-檸檬酸及一溶劑，而該溶劑係可為去離子水⑽加㈣ Water)或蒸鶴水，並將該醋酸銀及該檸檬酸與該溶劑進行擾掉，其中， 201213618 該醋酸銀與該檸檬酸之莫耳比係由1:1至5:1，該醋酸銀與該擰檬酸兩 者濃度含量皆大於2x1〇—4M ;待攪拌後，則可將該導電基板10及該導電 體40間隔放置於該容器5〇内，進行通電沉積，而於本發明第一實施例 中該導電基板10與該導電體4〇兩者係大體垂直於該容器5〇底部，且兩 者係大體平行相對設置；而在該電子源2〇對該導電基板1〇及該導電體 40通電後，並經過一沉積時間進行沉積後，該容器5〇内之銀離子即會 /儿積至》亥導電基板1〇之表面上，並形成奈米銀，其中，該沉積時間 係至少要10秒，該沉積時間係為10秒至秒之間；而當該操作電壓為 2伏特，該沉積時間為10秒，且該導電固定件3〇僅黏貼於該導電基板1〇 之一側（圖未示），同時，依本發明第一實施例該導電基板10及該導電 體40之擺财式’稱絲議上射絲靖狀結構之奈米銀6〇， 而此樹狀結構之奈米銀60係大體以6〇度角進行不斷自我模仿重複生長 成碎形結構(如第二圖所示⑷至第二圖⑹），此外，絲容腳内之 _容液51已達飽和狀態，由於飽和已無法再溶解更多之醋酸銀及捧樣 酸’故在該容的底部沉積許多無法被溶解的醋酸銀及檸檬酸，當 /合液51靜置進行電化學反應時，在該溶液以頂部的濃度較低，在該溶 液51底部的漢度馳高’故該導電基板1〇於最接近該導電固定件之 知表面上所"u積形成之奈米銀，其因該溶液51頂部濃度較低，所 以在同-沉積時間及同一操作電壓下，其緻密度較低(如第二圖⑷）， ^該導電基板脏所沉積形成之奈米綱會隨著越靠近該容液邮 邛’而使其沉積緻密度越高，而第二圖⑹係顯示最靠近該容液Μ底部 201213618 ::參_三_)及第三_)卿，分顺本發㈣一實施 乎_嶋細，蝴_所形成之奈 祕，於本實施财雜作龍_定為2伏特，細關沉積時間進 订讀’其中，第三_之沉積時嶋3G秒，而第三_則觸 秒’由柳鳴_，咖_日細增加，奈細的緻密 度隨之增加。 再請參閱細_)至細圖⑻所示，為本發明第-實施例之夺 米銀之_，簡示導電基板於高電流密度時卿成之奈米銀；於本 實施例中雜作電壓縣2伏特，且觀積咖係_秒，並將該導電 固定件30黏貼於該導電基板10一側四周（如第一圖所示），而使該導電 基板10整體之紐密度增加，_财可清楚看出於高微密度時， 該第四圖(A)至細圖⑹所形成之奈米賴結構緻密度較第二圖⑷ 至第二圖（C)高’另’若_料賴定個(銅膠帶)將該導電基板1〇 外周側整_狀_(圖未示），其可使料絲删之電餘度更為 增加且均自，且亦可使料f基板職輯形权奈練⑼之均句度 更為一致。 另’請同時參閱第五圖及第六圖⑴至⑹圖所示，分別為本發明 第二實施例之示意圖及奈絲之s職；於本發明第二實_中該導電 基板10係平放於該容㈣底部，而該導電體侧健纽置於該容器 5〇内，且料電基板10及該導電體4〇兩者大體係呈垂直設£，同時， 該操作電壓係為2伏特，該沉積時間係為6〇秒，而若依第二實施例中該 導電基板10與該導電體40所擺設之方式進行沉積時，於較靠近該導電 201213618 體40所沉積形成之奈米銀6〇係呈平整的顆粒狀球體(如第六圖（a))，且 隨著該導電基板10之表面與該導電體4〇距離增加，該導電基板1〇與該 導電體侧f場方向的改變，造成該溶液51巾絲子槪速度改變， 其所沉積形成之奈麵赚面雜嫌之變化，該奈米麵大體係呈 顆粒狀球體’且其表面漸有凸起物，不再是平整的表面（如第六圖 (B) )，而於該導電基板1〇最遠離該導電體4〇位置處，該奈米銀之表 面形態已轉變為顆粒狀球體上有著U形狀凸起物（如第六圖 (C) );因此，由上述可知該導電體4〇與該導電基板1〇的相對位置會決 定銀離子在該溶親巾到達該導電基板屬速度與方向並形成形狀 不-的外型’所峻由改變該導電基錢及該導電體撕目對位置可精 確控制奈米銀60的形貌。 兹’再將本發明之及其可達成之翻功效陳述如下： f發明㈣化學法成長奈米銀之方法，其可透過上述方法並改變 a板及導電體間之相對位置，以制精確控制奈綠的外形。 上所述，本發明在_產品中實有其極佳之進步實雌，同時 的構= 構之技術資料，文獻中亦未發現有相同或近似 申請"Γ〖在先’是以，本發明實已具備發明專利要件，爰依法提出 用本t月發明之較佳可行實施例而已，故舉凡應 發明之專1=她_之雜結觀化，理應包含在本 201213618 【圖式簡單說明】 第一圖為本發明第—實施例之示意圖。 第工圖⑴為本發明第一實施例之奈米銀之娜圖。 第二圖⑻為本發明第一實施例之奈米銀之鯽圖。 第=圖（c)為本發明第一實施例之奈米銀之SEM圖。 第三圖（A)為本發明第一實施例之奈米銀之珊圖 2V 4冗積咖為30秒所形狀絲銀。 如操作電髮 第二圖（B)為本發明第一實施例之奈米銀之SM圖 • 2V，沉積時間為60秒所形成之奈米銀。 如操作電壓 第四圖(A)為本發明第一實施例之奈米銀之SM圖， 高電流密度時所形成之奈米銀。 如導電基板於 第四圖（B)為本發明第一實施例之奈米銀之腿圖，以顯 高電流密度時所形成之奈米銀。 ’、電基板於 第四圖（c)為本發明第一實施例之奈米銀之SEM圖，以 高電流密度時所形成之奈米銀。 導電基板於 第五圖為本發明第二實施例之示意圖。 •第六圖為本發明第二實施例之奈米銀之SEM圖。 第六圖（B)為本發明第二實施例之奈米銀之SEM圖。 第六圖（c)為本發明第二實施例之奈米銀之SEM圖。 【主要元件符號說明】 10 導電基板 20 電子源 21 鍍銀線 30 導電固定件 40 導電體 50 容器 51 容液 60 奈米銀It belongs to the electrode and the cathode metal electrode, and in the financial solution, the growth solution with the interface agent and the solution with the machine base, the current between the anode and the cathode metal electrode, the gold metal in the anode metal is the boundary. _ covered (4) 彡 属 belongs to the green nectar, and then by the exposed soft thief board of the dissolved limbs, the rod-shaped metal nanoparticles are successfully synthesized; The solution is selected from the group consisting of isopropanol, methanol, propanol, chlorohydrin, ethylene glycol, n-butanol, and diacetone alcohol. Although the case can also form a metal nanostructure, the methods and processes required for the formation of the case are not related to the case, so it is different from the case. SUMMARY OF THE INVENTION 'The main purpose of the invention is to provide a method for electrochemical growth of Naijian which can be deposited to form a nano silver with a controllable shape. The method for electrochemically growing nano silver according to the present invention comprises: placing a conductive substrate and a conductive material in a container, and the content of the content in the container; = x: G: M screw = a solvent 'and the silver acetate is linked to the concentration of the citric acid' and the electron source has an anode and a cathode, wherein the conductivity == the conductor is connected to the anode - and the electron “Improve the formation of Taihong—deposition time for deposition, so that the conductive substrate can be deposited less than ί = 彳 _ pressure system is at least 2 volts, the time is so close to the financial method and change (four) electrical substrate and guide relative The position is to precisely control the shape of the nano silver. [Embodiment] 201213618 First, please refer to the first figure, which is a schematic view of the first embodiment of the present invention, and the steps are as follows: The conductive substrate 10 /X: is bubbled Isopropanol (Is〇_pr〇卿〇1) was shaken for several minutes using an ultrasonic oscillator, and the conductive substrate 1Q was taken out and then immersed in a _ (AeetGiie) towel, also The sonic shock ship is shocked and washed for a few minutes; then the conductive substrate 1G is taken out and immersed in the recording water cap In the embodiment of the present invention, the conductive substrate 1 is an indium tin oxide (ITO) glass substrate or a silver substrate. Further, the conductive substrate 1 is connected to an electron source 2A, the electron source is a DC power supply, and the electron source 2 has an anode and a cathode, and can provide a - (four) voltage The U.S. voltage system is at least 2 volts, and the Lai system is between 2 volts and 1 volt. Further, the conductive substrate 1G is connected to the cathode. In the embodiment of the invention, the electronic lion system has two silver plating. Lang, and it is connected to the material substrate 1 (), and the silver plated wire 21 is fixed to the surface of the conductive substrate by the conductive member 3, and the conductive member 30 The tape can be a copper tape or a conductive clip (not shown), and the tape can be adhered only to the side of the conductive substrate, or the copper tape can be adhered around the conductive substrate 10 around the conductive substrate. When it can increase the current density of the entire conductive substrate 1 ', the electron source 20 _ is connected to a conductor 40 through another mineral silver wire 21, and in the embodiment of the invention, the conductor 4 is a cylinder of platinum (10) material. Re-preparation - container 50, the container 50 is housed There is a liquid 5, the liquid 51 has - silver acetate, - citric acid and a solvent, and the solvent can be deionized water (10) plus (four) Water) or steamed crane water, and the silver acetate and the citric acid and The solvent is disturbed, wherein, 201213618, the molar ratio of the silver acetate to the citric acid is from 1:1 to 5:1, and the concentration of both the silver acetate and the citric acid is greater than 2x1〇-4M; After being stirred, the conductive substrate 10 and the conductive body 40 are placed in the container 5〇 to be electrically deposited, and in the first embodiment of the present invention, the conductive substrate 10 and the conductive body 4 are both The container is substantially perpendicular to the bottom of the container 5, and the two are disposed substantially in parallel; and after the electron source 2 is electrically connected to the conductive substrate 1 and the conductor 40, and after deposition for a deposition time, the container The silver ions in the 5th layer will accumulate on the surface of the conductive substrate 1 and form Rice silver, wherein the deposition time is at least 10 seconds, and the deposition time is between 10 seconds and seconds; and when the operating voltage is 2 volts, the deposition time is 10 seconds, and the conductive fixing member 3 is only Adhering to one side of the conductive substrate 1 (not shown), and at the same time, according to the first embodiment of the present invention, the conductive substrate 10 and the conductive body 40 are arranged in a neat manner. The rice silver is 6〇, and the nanostructured silver 60 system of the tree structure is continuously self-imitation and repeated into a fractal structure at a 6-degree angle (as shown in the second figure (4) to the second figure (6)). _Liquor 51 in the foot has reached saturation, because it can no longer dissolve more silver acetate and holding acid because of saturation, so many silver acetate and citric acid which cannot be dissolved are deposited at the bottom of the volume. When the liquid 51 is allowed to stand for electrochemical reaction, the concentration of the solution at the top is lower, and the height of the bottom of the solution 51 is higher. Therefore, the conductive substrate 1 is on the surface closest to the conductive member. The formation of nano silver, which is due to the lower concentration of the top of the solution 51, so in the same - At the same time and at the same operating voltage, the density is low (as shown in the second figure (4)), and the nano-frame formed by the deposition of the conductive substrate is deposited closer to the liquid carrier. The higher, the second figure (6) shows the closest to the bottom of the liquid Μ 2012 201213618 :: _ _ three _) and the third _) Qing, the shun this hair (four) one implementation _ 嶋 fine, the butterfly _ formed Secret, in this implementation of the financial miscellaneous dragon _ set to 2 volts, fine deposition time into the reading 'where, the third _ deposition time 嶋 3G seconds, and the third _ then touch the seconds' by Liu Ming _, coffee _ As the daily fine increases, the density of the fineness increases. Referring to the detail _) to the detailed view (8), the smear of the silver in the first embodiment of the present invention is a simplified representation of the nano-silver of the conductive substrate at a high current density; The voltage is 2 volts, and the conductive device is _ sec, and the conductive fixing member 30 is adhered to the side of the conductive substrate 10 (as shown in the first figure), so that the overall density of the conductive substrate 10 is increased. It can be clearly seen that at high microdensity, the density of the nano-structure formed by the fourth (A) to (6) is higher than that of the second (4) to the second (C). The substrate (the copper tape) is formed on the outer peripheral side of the conductive substrate 1 (not shown), which can increase the electrical margin of the filament and increase the self-recovery, and can also make the material f substrate The average sentence of the job title right (9) is more consistent. In addition, please refer to the fifth figure and the sixth figure (1) to (6), which are respectively a schematic view of the second embodiment of the present invention and the position of the nanowire; in the second embodiment of the present invention, the conductive substrate 10 is flat. Placed on the bottom of the capacitor (4), and the conductor side is placed in the container 5, and the power substrate 10 and the conductor 4 are vertically disposed, and the operating voltage is 2 In the volt, the deposition time is 6 sec., and if the conductive substrate 10 and the conductor 40 are deposited in the second embodiment, the nano-formed nano-deposited near the conductive body 201213618 The silver 6 lanthanum is a flat granular sphere (as shown in FIG. 6( a )), and the conductive substrate 1 〇 and the conductor side f field increase as the distance between the surface of the conductive substrate 10 and the conductor 4 增加 increases. The change of direction causes the speed of the solution 51 to change, and the sediment formed by the formation of the surface is mischievous. The large surface of the nano-surface is a granular sphere and its surface is gradually convex. Is a flat surface (such as the sixth figure (B)), and the conductive substrate 1 is farthest from the conductive At the position of 4 〇, the surface morphology of the nano silver has been converted into a U-shaped protrusion on the granular sphere (as shown in FIG. 6(C)); therefore, the conductor 4〇 and the conductive substrate 1 are known from the above. The relative position of the crucible determines the speed at which the silver ion reaches the speed and direction of the conductive substrate and forms a shape that does not have a shape. The conductivity of the conductive base and the position of the conductive body can be precisely controlled. The shape of the silver 60. The invention and its achievable reversal effect are as follows: f invention (4) a method of chemically growing nano silver, which can be controlled by the above method and changing the relative position between the a plate and the electric conductor for precise control Nai green shape. As described above, the present invention has an excellent progress in the product, and the technical data of the structure and structure are not found in the literature. The same or similar application is not found in the literature. The invention has already possessed the requirements of the invention patent, and has proposed the preferred and feasible embodiment of the invention in this month. Therefore, it should be included in this 201213618. The first figure is a schematic view of a first embodiment of the present invention. The first working diagram (1) is a nano silver diagram of the first embodiment of the present invention. The second figure (8) is a diagram of the nano silver of the first embodiment of the present invention. Fig. (c) is an SEM image of the nano silver of the first embodiment of the present invention. The third figure (A) is the nano silver of the first embodiment of the present invention. The 2V 4 redundant coffee is 30 seconds in shape of silver. For example, the operation of the second embodiment (B) is the silver diagram of the nano silver of the first embodiment of the present invention. 2V, the nano silver formed by the deposition time of 60 seconds. For example, the operating voltage is shown in Fig. 4(A) as the SM diagram of the nano silver of the first embodiment of the present invention, and the nano silver formed at a high current density. For example, the conductive substrate is in the fourth diagram (B) of the nano silver of the first embodiment of the present invention, and the nano silver formed at a high current density is used. The fourth substrate (c) is an SEM image of the nano silver of the first embodiment of the present invention, which is formed of nano silver at a high current density. The fifth embodiment of the conductive substrate is a schematic view of a second embodiment of the present invention. • The sixth figure is an SEM image of the nano silver of the second embodiment of the present invention. Fig. 6(B) is an SEM image of the nano silver of the second embodiment of the present invention. Figure 6 (c) is an SEM image of the nano silver of the second embodiment of the present invention. [Main component symbol description] 10 Conductive substrate 20 Electron source 21 Silver plated wire 30 Conductive fixing member 40 Conductor 50 Container 51 Capacitor 60 Nano silver