201029536 ' 六、發明說明： 【發明所屬之技術領域】 本發明涉及一種墨水以及採用該墨水製備導電線路的方法， 特別涉及一種基於奈米碳管的墨水以及採用該墨水製備導電線路 的方法。 【先前技術】 近年來，資訊、通訊、以及消費性電子已經逐漸成為全世界 ❹ 工業中發展最快的產業。而在資訊、通訊以及消費性電子產σ的 產業中’印刷線路板（Printed circuit board，PCB)係其不可缺/Ν 的重要組件。印刷線路板係電子元件的支樓體及電子元器件線路 - 連接的提供者。由於它係採用電子印刷技術製作的，故被稱為“印 . 刷線路板。 傳統的印刷線路板多採用絲網印刷的方法製造，一般製造印 刷線路板的過程包括將金屬_壓於基板表面，再用旋轉塗佈的 參方法在金屬薄膜表面形成一光阻層，而後再加以光罩曝光、顯影、 刻姓’進而再加以鑽孔、壓合與電鍍等多項步驟，最後還需多項 測試及修補後才能完成整個流程，過程相當繁雜、能耗高、對環 境有污染。 隨著數位喷墨印表機技術的發展，先前麟已有糊喷墨印 表機製造印觀路板的方法。嘴墨印表鋪糾刷祕板可採用 抗敍油墨、阻焊油墨和字元油墨’时墨的方法直射在覆銅板 上再、，，工過固化得到製品。更簡單的方法，還可將導電墨水直接 4 201029536 =印,絕緣，表面’經過進—步的處理在絕緣基板表面形成電 ，從而獲传_祕板。她于傳闕__法 機製造印觀路板的流錄短，对墨印表機製造的線路較 小因此喷墨技術將會給印刷線路製造業帶來更快的速度和更低 的成本，以及更高的佈線密度。 ❸ ❹ “技術中已_用直射印金屬奈米粒子溶液（n咖 M)的方法來製備導電線路的技術。Cab〇t c〇rp_〇n公司的201029536 ' VI. EMBODIMENT OF THE INVENTION: TECHNICAL FIELD The present invention relates to an ink and a method of preparing a conductive line using the same, and more particularly to a carbon nanotube-based ink and a method of preparing a conductive line using the ink. [Prior Art] In recent years, information, communication, and consumer electronics have gradually become the fastest growing industries in the world. In the industries of information, communication and consumer electronics, 'Printed circuit board (PCB) is an important component that is indispensable. Printed circuit boards are the building blocks of electronic components and the wiring of electronic components - the provider of the connection. Because it is made by electronic printing technology, it is called "printing. Brush circuit board. Traditional printed circuit boards are mostly manufactured by screen printing. Generally, the process of manufacturing printed circuit boards includes pressing metal to the surface of the substrate. Then, a photoresist layer is formed on the surface of the metal film by spin coating, and then the mask is exposed, developed, engraved, and then drilled, pressed and plated, and multiple tests are required. After the repair, the whole process can be completed, the process is quite complicated, the energy consumption is high, and the environment is polluted. With the development of the digital inkjet printer technology, the method of manufacturing the printed road board by the past ink paste inkjet printer The nozzle ink printing table can be used to prevent the ink, the solder resist ink and the character ink's method of direct ink on the copper clad plate, and then the product is cured to obtain the product. The simpler method can also Directly conductive ink 4 201029536 = printed, insulated, surface 'processed through the step-by-step process to form electricity on the surface of the insulating substrate, so that the _ secret board. She in the Chuan __ legal machine to manufacture the printed circuit board record Short, the line of inkjet printer manufacturing is smaller, so inkjet technology will bring faster speed and lower cost to the printed circuit manufacturing industry, as well as higher wiring density. ❸ ❹ “Technology has been used A technique of directly printing a metal nanoparticle solution (n coffee M) to prepare a conductive line. Cab〇t c〇rp_〇n company
Vanheusden於2〇〇5年丄月14日申請，2〇〇6年8月％日八 開的公開縣職)_1891讓的美國專财請揭示了一種^ 屬奈米粒子溶液及制該金屬奈練子製料電線路的方 法。藉由將包括金屬奈綠子及適㈣分散継__金屬奈 米粒子减噴印在—基底上形成線路，騎該祕進行高温乾燥 處理’使得所述金屬奈練顿接在—起，從而在基底上形成導 電線路。__賴金屬奈練子驗製備導躲路的方法需 要對基底進行高溫處理，從祕制了基錢料的種類。 為解決上述問題，2006年6月15日公開的公開號為 US2〇〇6/〇l；3〇7〇〇Al的美國專利申請’提出了一種含銀的噴墨墨水 及種使用該含銀的喷墨墨水在基板形成圖形的方法，其藉由嘴 墨印表機將上述含銀鹽的墨水喷印在基板上，形成圖案或圖形； 然後，使用帶有還原劑的墨水噴印在所述銀鹽組成的圖案或圖形 上，從而在基板表面形成金屬銀組成的圖形或圖案。然而，所述 方法具有以下缺點··第一，該方法需要使用帶有還原劑的墨水將 5 201029536 ' 銀鹽中的銀離子藉由化學反應還原成銀鹽。使得該製備方法工藝 複雜’且成本較高。第二，採用該方法製備的線路由銀離子還原 後形成的銀顆粒相互連接構成，而銀離子還原成的銀顆粒分佈不 夠均勻’因此形成的導電線路厚度不夠均勻，其導電性較差。 為解決上述問題，先前技術提供一種形成含有奈米碳管與金 屬複合物的電鍍互連導線的方法，其包括以下步驟：準備一奈米 碳官的分散液，其包含一有機溶劑及分散於該有機溶劑的奈米礙 ❿管；將該奈米碳管的分散液印刷於一基材的一表面，及從該表面 揮發移除該有機溶劑，而形成一導電基線；及於一含有金屬離子 的電鑛浴中對該表面進行電鑛，從而在該導電基線上形成奈来礙 管與金屬複合材料的電鍍互連導線。Vanheusden applied for the 14th of the next month on the 14th of the 2nd, 5th, 6th, and 8th of August, and opened the county office in the 8th and 8th of the year. _1891 let the US special wealth disclose a kind of nanoparticle solution and the metal The method of sub-material electrical circuit. By using a metal neon green and a suitable (four) dispersed 継__ metal nanoparticle to be printed on the substrate to form a line, riding the secret to perform a high-temperature drying process, so that the metal is tuned to A conductive line is formed on the substrate. The method of preparing the road to avoid the road requires high-temperature treatment of the substrate, and the type of the base material is secreted. In order to solve the above problem, U.S. Patent Application Serial No. US 2 〇〇 6/ 〇l; 3 〇 7 〇〇 Al, issued on June 15, 2006, proposes a silver-containing inkjet ink and uses the silver-containing ink. a method of forming a pattern on a substrate by inkjet ink, which prints the silver salt-containing ink onto a substrate by a nozzle ink printer to form a pattern or a pattern; and then, printing ink using a reducing agent A pattern or pattern composed of a silver salt is formed to form a pattern or pattern of metallic silver on the surface of the substrate. However, the method has the following disadvantages. First, the method requires the use of an ink with a reducing agent to reduce the silver ions in the silver salt of the 5 201029536 ' silver salt to a silver salt by a chemical reaction. This makes the preparation process complicated and costly. Second, the silver particles formed by the reduction of silver ions are connected to each other by the method, and the silver particles reduced by the silver ions are not uniformly distributed. Thus, the thickness of the conductive lines formed is not uniform enough, and the conductivity is poor. In order to solve the above problems, the prior art provides a method of forming an electroplated interconnecting wire comprising a carbon nanotube and a metal composite, comprising the steps of: preparing a nano carbon carrier dispersion comprising an organic solvent and dispersed in a nanotube of the organic solvent; printing the dispersion of the carbon nanotube on a surface of a substrate, and volatilizing the organic solvent from the surface to form a conductive baseline; and forming a conductive metal The surface is electromineralized in an ionized electric bath to form a plated interconnect wire of the inner tube and the metal composite on the conductive baseline.
所述方法由於採用電鑛的方法在奈米碳管形成的導電基線表 面進行電H，因而财法制的墨水中的奈米碳管必須為金屬性 的奈米碳管，而且若要使奈米碳管形朗導·鱗電，該墨水 中的絲碳管的含量紐高，·就需要大量的分散_該奈米 兔管分散在墨树。而所述分散财絲去，導致奈米碳管形成 的導電基線中存在大量分㈣，從而使得該導電基_導電性不 =，使得在電鑛過程帽述導電綠上各處紐獲得的金屬層 孚度不均勻’從轉致藉由該方轉得料線導電性較差。 該墨水製備厚度均勻 有鑒於此，提供一種墨水及一種採用 導電性強的導電線路的方法實為必要。 6 201029536 一種墨水，其包括：溶劑及分散於該溶劑中的複數個奈米碳 官’其中’該墨水進-步包括貴金屬離子及連接劑、該貴金屬離 子藉由所述連接劑附著于奈米碳管表面。 一種製備導電線路的方法，其包括以下步驟：提供一墨水， 該墨水包括：溶劑及均勻分散於溶劑中的奈米碳管，貴金屬離子 及連接劑，所述責金屬離子藉由連接劑附著在奈米碳管表面；在 一基底表面形成包含奈米碳管及貴金屬離子的導電線路預製體； 碜將所述導電線路預製體中的貴金屬離子還原為貴金屬顆粒；以及 對包含貴金屬顆粒及奈米碳管的導電線路預製體進行金屬化處 理。 與先前技術相比較’所述墨水及採用該墨水製造導電線路的 方法具有以下優點：其一，所述墨水採用奈米碳管作為導電體以 及載體’貴金屬離子藉由連接劑均勻附著在奈米碳管的表面，從 而使得奈来碳管表面附著有大量的貴金屬離子，增強了該墨水的 ® 導電性。其二’所述製備導電線路的方法藉由先喷印含有奈米碳 管及貴金屬離子的導電線路預製體，將該貴金屬離子還原為貴金 屬後’再對線路進行金屬化處理’由於該線路包含貴金屬增強了 線路的導電性。貴金屬可作金屬化處理時的催化還原中心，使得 金屬將奈米碳管及貴金屬均勻包裹，從而可獲得厚度均勻的含有 貴金屬及奈米碳管的導電線路。 【實施方式】 下面將結合附圖及具體實施例’對本發明提供的墨水及採用 7 201029536 該墨水製備導電線路的方法作進一步詳細說明。The method uses electric ore method to conduct electricity H on the conductive baseline surface formed by the carbon nanotubes, so the carbon nanotubes in the chemical ink must be metallic carbon nanotubes, and if the nanometer carbon nanotubes are to be Carbon tube shape and scale electricity, the content of the carbon tube in the ink is high, and a large amount of dispersion is required. The nano rabbit tube is dispersed in the ink tree. And the dispersing of the filaments causes a large amount of sub-fraction (4) in the conductive baseline formed by the carbon nanotubes, so that the conductivity-conductivity is not =, so that the metal obtained in the electroplating process is electrically conductive. The layer has a non-uniformity of viscosity. From the transfer, the wire is less conductive by the party. The ink preparation is uniform in thickness. In view of the above, it is necessary to provide an ink and a method using a conductive line having high conductivity. 6 201029536 An ink comprising: a solvent and a plurality of nanocarbons dispersed in the solvent, wherein the ink further comprises a noble metal ion and a linking agent, and the noble metal ion is attached to the nanometer by the connecting agent Carbon tube surface. A method of preparing a conductive circuit, comprising the steps of: providing an ink comprising: a solvent and a carbon nanotube uniformly dispersed in a solvent, a noble metal ion and a linking agent, wherein the metal ion is attached by a bonding agent a surface of a carbon nanotube; a conductive line preform comprising a carbon nanotube and a noble metal ion formed on a surface of the substrate; 碜 reducing precious metal ions in the conductive line preform to precious metal particles; and containing noble metal particles and nanoparticles The conductive line preform of the carbon tube is metallized. Compared with the prior art, the ink and the method for manufacturing the conductive circuit using the ink have the following advantages: First, the ink uses a carbon nanotube as an electric conductor and the carrier 'a noble metal ion is uniformly attached to the nanometer by a connecting agent. The surface of the carbon tube, which allows a large amount of precious metal ions to adhere to the surface of the carbon nanotubes, enhancing the conductivity of the ink. The method of preparing the conductive line by first printing a conductive line preform containing a carbon nanotube and a noble metal ion, and then reducing the noble metal ion to a noble metal and then [metallizing the line] because the line includes Precious metals enhance the electrical conductivity of the line. The noble metal can be used as a catalytic reduction center in the metallization treatment, so that the metal uniformly wraps the carbon nanotubes and the noble metal, thereby obtaining a conductive line containing a precious metal and a carbon nanotube having a uniform thickness. [Embodiment] Hereinafter, an ink provided by the present invention and a method of preparing a conductive line using the ink of 7 201029536 will be further described in detail with reference to the accompanying drawings and specific embodiments.
• 本發背關提供H卜其成分包括：責金屬離子’ I . 米石反官’溶劑’黏度調節劑’表面活性劑以及連接劑。其中，戶斤 述貴金屬離子的質量百分含量為1%〜S5%，所述奈轉管的質責 百分含量為0.2〜5%，所述溶劑的質量百分含量為5〇〜8〇%，所述 黏度調節劑的質量百分含量為αι〜3〇%，所述表面活性劑的質責 百分含量為0.1〜5%，所述連接劑的質量百分含量為〇1〜娜。進 ⑩-步，該墨水中還可以加人—定量的保關，所述保濕劑質量畜 分含量為0.1〜40%。 所述貝金屬離子可以為金離子、銀離子、把離子或始離子。 本發明實關巾’ f金麟子為雜子，可將硝酸銀直接溶于水 中’獲得具有銀離子的溶液。 所述連接劑為一水溶性聚合物，其包括聚乙烯吼咯烷酮 (PW)、聚乙稀醇（pVA)以及聚維酮等中的一種或多種。本發 明實施例中，連接劑為聚乙烯吡咯烷酮。連接劑可以和墨水中的 貴金屬離子（如Au+、Ag+、Pt+或Pd+)生成絡合物，該絡合物可 以纏繞在奈米碳管的表面，從而使得貴金屬離子均勻附著在奈米 碳管表面。加入連接劑還可以提高墨水的黏合性。在將墨水列印 到基底上之後，隨著黏度調節劑以及表面活性劑等其他成分的揮 發，奈米碳管很容易脫落。而該連接劑可以將表面附著有責金屬 離子的奈米碳管固定於基底表面。 墨水中奈米碳管的質量百分含量不能過高，否則會由於奈米 8 201029536 ==，從而將印表機的喷頭堵塞;墨水中 1主今;i S百刀含I不能過低，因為實際應财需要盡可处 在奈米碳管麵，使得形成的導電線路^ 貴金屬：=較水製備獲得的導電線路由“ 一斤述不米碳&包括單壁奈米碳管 '雙壁奈米碳管及多壁奈 碳管巾的—種或多種。該奈米碳管可崎由電弧放電法、雷^蒸 發法或者化學氣相沉積法製備獲得。所述奈米碳管的直徑小於5,〇 奈米’長度小於2微米。—方面’奈米碳管的直徑越小，長度越 大，其比表面積越大，對貴金屬離子的吸附能力就越強。另一方 面’奈米&管的長度越大，就越齡散，從*容轉致該墨水在 使用時容祕印表__堵塞。本發财施射，_直徑小 於50奈米，長度為5〇〜200奈米的奈米碳管製備墨水，既可以使 奈米碳管均勻分散，使用時也不會將印表機的喷頭堵塞，又可以 參使知該含有奈米碳管的墨水具有一定的吸附性，以利於其應用於 導電線路製備中。 進一步，所述奈米碳管可為經過功能化處理的奈米碳管。該 奈米碳管表面帶有親水性功能團，該功能團包括缓基(_c〇〇印、羥 Hon)' 氨基(_nh2)等中的一種或多種。該功能 團形成于奈米碳管管壁上或端部。可以理解，借助於該功能團， 奈米碳管均勻分散於墨水中。本發明實施例中，奈米碳管表面帶 有複數個羧基(-COOH)與羥基(-OH)。 201029536 所述黏度調即劑為有機溶劑或水溶性聚合物，用以調節墨水 的黏合性。所錢度調_為甲醇、乙醇、纖維候、瓜耳膝及 石夕膠等中的-種或多種。可以理解，當該墨水中黏度調節劑的含 里較大時該奚水適合用於絲網印刷。本發明實施例中，黏度調 節劑為纖維素鍵。 所述表面活性劑可以為脂肪酸、鱗酸醋、改性聚乙稀醇、聚 矽氧炫、十二院基硫酸納以及聚山梨醇醋中的一種或多種。本發 ©明實施例中，表面活性劑為改性聚乙觸。所述表面活性劑一部 分包裹在奈米碳管表面’使奈米碳管均勻分散在溶液中。另一部 分則分散於墨水中’調節墨水的表面張力，從而使得該墨水可以 適合列印到不同的基底上。 所述溶劑為水，本實施例中，所述溶劑優選去離子水。 可選擇地，該墨水中還可以加入一定量的保濕劑，所述保濕 劑通常為一尚彿點材料，包括多元醇及二元醇鍵醋等中的一種或 ® 多種。保濕劑可以提高該墨水的沸點，減慢墨水蒸發的速度。本 實施例中，於墨水中加入質量百分含量為30%的二元醇醚酯。該 墨水可以於50〜l〇〇°C溫度下使用而不易揮發。 所述墨水採用表面附著有貴金屬離子的奈米碳管作為導電 體’該墨水可用于製備形成包含有貴金屬離子及奈米碳管的導電 線路，5¾導電線路由於含有貴金屬’其導電性較tfj。該墨水的黏 度為1〜40厘泊（cps)，表面張力為20〜60違因/厘米（dyne/cm)。 請參間圖1，本發明實施例進一步提供一種製備導電線路20 201029536 的方法，其包括以下步驟： 步驟一 ’製備一墨水，該墨水包括奈米碳管分散液，該奈米 碳管分散液包括溶劑及均勻分散於溶劑中的奈米碳管，所述墨水 進一步包括貴金屬離子及連接劑，所述貴金屬離子藉由連接劑附 著在奈米碳管表面。 該墨水的製備方法主要包括以下步驟： (一）將連接劑溶解在水中，並加入含貴金屬離子的水溶液 鲁得到一第一混合溶液。 首先’提供一連接劑，並將該連接劑溶于水中，得到一連接 劑的水溶液。 所述連接劑為水溶性聚合物，該聚合物的材料為聚乙烯吡咯 烧酮，聚乙浠醇或聚乙烯亞胺等。 其次，提供一貴金屬鹽溶液，將所述貴金屬的鹽溶液與所述 連接劑水溶液混合。 ® 所述貴金屬鹽溶液中的貴金屬鹽包括銀、鉑及鈀的金屬鹽化 合物中的一種或多種，如硝酸銀、硝酸鉑及硝酸鈀等中的一種或 多種。 最後’授拌該含有貴金屬離子與連接劑的混合液10分鐘至4〇 分鐘’使該貴金屬離子與該連接劑混合均勻，得到一第一混合液。 在所述混合過程中，該第一混合溶液中貴金屬離子與所述連 接劑形成一絡合物，從而使該貴金屬與所述連接劑結合在—起。 所述第一混合液中貴金屬離子的數量不易過多，這樣可以保證大 11 201029536 多數的貴金屬離子和聚合物形成絡合物。因此，所述貴金屬離子 - 的摩爾濃度與聚合物的摩爾濃度的比例為1: 3到1 : 100。攪拌混 • 合溶液的時間由貴金屬離子與聚合物的種類與數量決定，只要能 夠使所述責金屬離子與聚合物充分結合即可。 本實施例製備第一混合溶液方法中，所述連接劑的材料為聚 乙烯比嘻燒酮，貴金屬離子為銀離子，且其以靖酸銀溶液的形式 加入’銀離子的摩爾濃度與聚乙烯吼魏_的摩爾漢度的比例為 ® 1 . 5。授拌混合溶液的時間為3〇分鐘。 (二）添加奈米碳管至上述混合溶液中並分散，得到一第二 混合溶液。 首先’提供一奈米碳管水溶液。 所述奈米碳管為魏化的奈米碳管，該奈米碳管表面帶有親 水性功能團，該功能團包括羧基(_c〇〇H)、羥基(_〇H)、憋基 以及氨基(棚2)等中的-種或多種。將該功能化的奈米碳管放入去 參離子水巾進行超聲分散、細、過祕理，並重復上述步驟4至$ 次，最後將奈米礎管超聲分散于去離子水中，得到一奈米碳管水 溶性分散液。本倾财，絲碳絲崎有概倾基(_c〇〇h) 與羥基(-OH) 〇 所述奈米碳管可以藉由電藏放電法、雷射蒸發法或者化學氣 相沉積法製備。本實施例中，藉由化學氣相沉積法生長奈米碳管 陣列’並將該奈米碳管陣列中的奈米碳管刮落作為原料^奈来碳 管陣列中由於奈米碳管定向排列而沒有相互纏繞，故有利於奈 12 201029536 米石反g在溶液中分散。本實施例中，奈米碳管長度為2⑻奈米。 其* ’添加奈米碳管水驗至貴金屬軒與聚合物溶液形成 .的第混口冷液中’攪拌1〇分鐘至4〇分鐘，形成一第二混合溶 液。 在所述授拌過程中’貴金屬離子與連接劑形成的絡合物纏繞 在不米碳管表面，從而使得貴金屬離子均勻附著在奈米碳管表 面。而且，由於該絡合物的纏繞，減小了奈米碳管之間的吸引力， •從而避免該第二混合液中的複數個奈米碳管由於凡德瓦爾力團娱 在一起，使奈米碳管更好的分散於該第二溶液中。進一步地在 藉由該方法製備的墨水中，奈米碳管不易團聚，有較好的分散效 果0 (二）在所述第二混合溶液中加入適量的黏度調節劑、表面 活性劑、連接劑，並攪拌均勻得到墨水。 在所述第二混合溶液中加入適量的黏度調節劑、表面活性 ® 劑、連接劑，在室温下機械攪拌混合溶液20〜50分鐘，得到墨水。 然後將墨水超聲混合過濾後裝入墨水匣。進一步地，本實施例還 可以於該墨水中加入適量的保濕劑。 本實施例製備的墨水中，所述貴金屬離子的質量百分含量為 1%〜55%，所述溶劑的質量百分含量為50〜80%，所述奈米碳管的 質量百分含量為〇.2~5%，所述黏度調節劑的質量百分含量為 0·1〜30%，所述表面活性劑的質量百分含量為〇.1〜5%，所述連接 劑的質量百分含量為0.1〜30%。該墨水的黏度為1〜40厘泊（cpQ， 13 201029536 表面張力為20〜60達因/厘米（dyne/cm) 〇 本實施例製備的墨水中，由於所述貴金屬離子通過連接劑附 著在碳納米管表面，且該碳納米管均勻分散在所述墨水中。故， 所述貝金屬離子均勻分散於所述墨水中。 步驟二’在一基板1〇表面形成包含奈米碳管14及責金屬離 子的導電線路預製體12。 請參閱圖2，所述基板10為一絕緣材料，形狀與大小不限。 _ 所述基板10材料為矽、氧化矽、石英、藍寶石、陶瓷、玻璃、金 屬氧化物以及高分子材料中的一種或多種。所述在基板1〇上形成 包含該墨水的導電線路預製體12的方法為絲網印刷法或噴墨印表 - 機喷印法。 . 所述導電線路預製體12可以形成一定的圖案。所述導電線路 預製體12包括複數個均勻分佈的奈米碳管14以及附著在奈米碳 管14表面的貴金屬離子（圖未示 參 本實施例中，基板10為一聚醯亞胺薄膜，藉由喷墨印表機在 該聚酿亞胺薄膜上列印圖案。所述圖案中奈米碳管14藉由連接劑 黏附於基板1〇表面，貴金屬離子藉由連接劑附著在奈米碳管14 表面’所述圖案的線寬為1〇微米到1〇〇微米。 步驟三’將基板1〇表面的導電線路預製體12中的責金屬離 子還原為貴金屬顆粒16。 所述導電線路預製體12中的貴金屬離子可以藉由還原劑還 原’亦可以藉由採用高能光照的方法還原，從而在基板表面形成 14 201029536 包含貴金屬顆粒16的線路。所述高能光可以為紫外光、雷射及γ • 射線中的—種或多種。該步驟中，附著在導電線路預製體12中的 . 奈米碳管W表面的貴金屬顆粒16形成化學鍍催化中心，以便化 學鍍。所述還原劑還原的方法可以藉由噴印還原劑於所述導電線 路預製體12的表面實現。 本實施例中，所述南能光為紫外光。藉由紫外光輕照後，銀 離子被還原成奈米級的銀顆粒，該奈米級金屬銀顆粒藉由連接劑 ❿均勻附著在奈米峻管表面。所述連接劑還具有還原所述貴金屬離 2的作用，所述連接劑在高能光的照射下，將一個自由基轉移到 責=屬離子，使貴金屬離子還原為貴金屬，從而使得貴金屬顆粒 附著在奈米碳管的表面.，在基板表Μ彡成包含奈米碳管以及貴金 屬顆粒的線路。在歸光_後，沿著絲辟的徑向，直 技大約為1〇〜20奈米的貴金屬奈来粒子均勻附著在奈米碳管的表 面。高能光照射的方法還原責金屬離子，方法簡單易行，可控性 好’而且成本較低。 ，步驟四，對包含貴金屬顆粒16及奈来碳管Μ的導電線路預 製體12進行金屬化處理，獲得複合導電線路％。 所述金屬化處理的方法為化學鍍或者電鍵。 化學錄可以锻錄、鍵銅或鍍銀等。所述化學鑛的方法具體包 括以下步驟： 首先，提供一化學鍍液。 所述化料喊分秘，可以為化雜舰或化學锻錄液 15 201029536 等。本實施射’細化學鑛液，該化學_㈣主要成分為 硫酸鋼、㈣、乙二胺四乙酸(EDTA)、酒石酸卸納。在該化學鐘 銅液中，硫酸銅的濃度為10g/L，甲盤的濃度為，乙二胺 四乙酸_Λ)的濃•零，酒錢鉀_濃度為2抓。 其次，將所述形財包含貴金屬麵16及奈米碳管Μ的導 電線路預製體12的基板1〇置於化學鍍液中。 本發明實施辦’在實下將所述形成有導電線路預製體η 的基板1〇置於化學鍍銅液中2分鐘後取出。由於奈米碳管表面Η 均勾附著有貴金屬雛16 _社學·化巾心，藉由化學鑛可 以製備厚度均勻的複合導電線路 本發明實施财金屬銀為奈米級雌，均物著在奈米碟管 表面，形成複數個催化中心。化學鍍時，由於金屬銀雜化作用， 一層金屬銅將絲碳管以及金屬銀包覆，由於金屬銀被金屬銅包 裹在線軸部’該導電線路在使崎，雜子不會從線路中遷移 ❹出來。祕料電線路中包含了金屬銀顆粒，其導雜也進-步 得到增強。騎屬銀齡均勻分佈在絲碳管贼面，形成複數 個催化中心。在金屬銀的催化作用下，化學鍍時使獲得的導電線 路的厚度均勻’獲得的導電線路的導電性較強。 可k的’為進-步增加金屬層的厚度’還可以在化學鍵之後 進灯電鑛。本實細巾，將形成有複合導電線路2㈣基板放 入電鍍槽巾作為陰極電鍍銅1鍍時，電流密度為2〜聊此2， 電鍍時間保持在5~10分鐘，鑛層厚度為漏师。 16 201029536 可以理解，_奈米碳管具有—定的導，本實施例還可 以直接藉㈣鍍使得包含貴金屬難16及奈米碳管w的導電線 路預製體12金屬化’以達到實用的要求。由於本發明實施例令的 導電線路預製體12包括貴金屬顆粒16以及奈米碳管m，其導電 队先别技射僅包括奈米碳管的線路的導電性強，因此，採用 本發月實施例巾包括貴金屬顆粒以及奈米碳管w的導電線路 預製體12電鑛時，電鍍效果更好。• This service provides H-components including: metal ion 'I. Mt. anti-official' solvent' viscosity adjuster' surfactant and linker. Wherein, the mass percentage of the noble metal ion is 1% to S5%, the mass percentage of the navel tube is 0.2 to 5%, and the mass percentage of the solvent is 5〇~8〇 %, the mass percentage of the viscosity modifier is αι~3〇%, the content of the surfactant is 0.1~5%, and the mass percentage of the binder is 〇1~Na . In step 10, the ink can also be added with a quantity-quantity guarantee, and the humectant has a mass content of 0.1 to 40%. The shell metal ion may be a gold ion, a silver ion, a counter ion or a starting ion. In the present invention, the FF lining is a heterodule, and the silver nitrate can be directly dissolved in water to obtain a solution having silver ions. The linking agent is a water-soluble polymer comprising one or more of polyvinylpyrrolidone (PW), polyethylene glycol (pVA), and povidone. In the examples of the present invention, the linking agent is polyvinylpyrrolidone. The linking agent can form a complex with a noble metal ion (such as Au+, Ag+, Pt+ or Pd+) in the ink, and the complex can be wound around the surface of the carbon nanotube so that the noble metal ion uniformly adheres to the surface of the carbon nanotube. . Adding a bonding agent can also improve the adhesion of the ink. After the ink is printed on the substrate, the carbon nanotubes are easily peeled off as the viscosity modifier and other components such as the surfactant are volatilized. The connecting agent can fix the carbon nanotubes on the surface to which the metal ions are attached to the surface of the substrate. The mass percentage of the carbon nanotubes in the ink should not be too high, otherwise it will be blocked by the nozzle of the printer due to the nano 8 201029536 ==; the ink is 1 main; the i S hundred knife contains I can not be too low Because the actual financial needs need to be in the surface of the carbon nanotubes, so that the conductive line formed ^ precious metal: = the conductive line obtained by water preparation from "one kilogram of non-carbon carbon & including single-walled carbon nanotubes" One or more kinds of double-walled carbon nanotubes and multi-walled carbon nanotubes. The carbon nanotubes can be prepared by arc discharge method, lightning evaporation method or chemical vapor deposition method. The diameter is less than 5, and the length of the nanometer is less than 2 micrometers. - The smaller the diameter of the carbon nanotube, the larger the length, the larger the specific surface area, the stronger the adsorption capacity for noble metal ions. The larger the length of the nanotube & tube, the older it is, and the ink is transferred from the container to the __ blockage when used. The hair is cast, _ diameter is less than 50 nm, length is 5〇 ~200nm carbon nanotubes to prepare ink, which can evenly disperse the carbon nanotubes, and will not be used when used. The nozzle of the watch machine is clogged, and it can be understood that the ink containing the carbon nanotube has certain adsorption property, so as to facilitate its application in the preparation of the conductive line. Further, the carbon nanotube can be functionalized The carbon nanotube has a hydrophilic functional group on the surface, and the functional group includes one or more of a slow base (_c〇〇, hydroxyHon), an amino group (_nh2), etc. The functional group is formed. On the wall or end of the carbon nanotube tube, it can be understood that the carbon nanotubes are uniformly dispersed in the ink by means of the functional group. In the embodiment of the invention, the surface of the carbon nanotube has a plurality of carboxyl groups (-COOH). And hydroxyl (-OH). 201029536 The viscosity modifier is an organic solvent or a water-soluble polymer to adjust the adhesion of the ink. The weight adjustment is methanol, ethanol, fiber, melon, knee and stone. It is understood that the hydrophobicity is suitable for screen printing when the content of the viscosity modifier in the ink is large. In the embodiment of the invention, the viscosity modifier is a cellulose bond. The surfactant may be fatty acid, vinegar vinegar, modified One or more of ethylene glycol, polyoxoxime, sodium sulfoxide, and polysorbate. In the present invention, the surfactant is a modified polyethylene. Part of the surfactant. The coating on the surface of the carbon nanotubes 'distributes the carbon nanotubes evenly in the solution. The other part is dispersed in the ink' to adjust the surface tension of the ink, so that the ink can be printed on different substrates. In the present embodiment, the solvent is preferably deionized water. Optionally, a certain amount of a humectant may be added to the ink, and the humectant is usually a sacred point material, including a polyol and a binary. One or more of alcoholic vinegars, etc. The humectant can increase the boiling point of the ink and slow down the evaporation rate of the ink. In this embodiment, a glycol ether ester having a mass percentage of 30% is added to the ink. The ink can be used at a temperature of 50 to 1 ° C without being volatile. The ink is made of a carbon nanotube with a noble metal ion attached to the surface as a conductor. The ink can be used to prepare a conductive line containing noble metal ions and a carbon nanotube. The conductive line of the conductive layer is more conductive than tfj. The ink has a viscosity of 1 to 40 centipoise (cps) and a surface tension of 20 to 60 deficient/cm (dyne/cm). Referring to FIG. 1 , an embodiment of the present invention further provides a method for preparing a conductive line 20 201029536, which includes the following steps: Step 1 'Prepare an ink, the ink includes a carbon nanotube dispersion, the carbon nanotube dispersion The invention comprises a solvent and a carbon nanotube uniformly dispersed in the solvent, the ink further comprising a noble metal ion and a bonding agent, the noble metal ion being attached to the surface of the carbon nanotube by a bonding agent. The preparation method of the ink mainly comprises the following steps: (1) dissolving the linking agent in water and adding an aqueous solution containing noble metal ions to obtain a first mixed solution. First, a linker is provided and the linker is dissolved in water to obtain an aqueous solution of a linker. The linking agent is a water-soluble polymer, and the material of the polymer is polyvinylpyrrolidone, polyethylene glycol or polyethyleneimine. Next, a noble metal salt solution is provided, and the salt solution of the noble metal is mixed with the aqueous solution of the binder. The noble metal salt in the noble metal salt solution includes one or more of a metal salt compound of silver, platinum and palladium, such as one or more of silver nitrate, platinum nitrate and palladium nitrate. Finally, the mixture containing the noble metal ions and the linking agent is mixed for 10 minutes to 4 minutes to uniformly mix the noble metal ions with the linking agent to obtain a first mixed liquid. In the mixing process, the noble metal ions in the first mixed solution form a complex with the linking agent, thereby bringing the noble metal into association with the linking agent. The amount of noble metal ions in the first mixed liquid is not so excessive, so that a large number of noble metal ions and a polymer form a complex are ensured. Therefore, the ratio of the molar concentration of the noble metal ion - to the molar concentration of the polymer is 1:3 to 1:100. The time for stirring the mixed solution is determined by the kind and amount of the noble metal ion and the polymer as long as the metal ion can be sufficiently combined with the polymer. In the method for preparing the first mixed solution in the embodiment, the material of the connecting agent is polyethylene than ketone ketone, the noble metal ion is silver ion, and the molar concentration of silver ion and polyethylene are added in the form of silver phthalate solution. The ratio of Moore's Moore is 1.7. The time for mixing the mixed solution was 3 minutes. (2) Adding a carbon nanotube to the above mixed solution and dispersing to obtain a second mixed solution. First, an aqueous solution of carbon nanotubes is provided. The carbon nanotube is a Weihua carbon nanotube having a hydrophilic functional group on the surface, and the functional group includes a carboxyl group (_c〇〇H), a hydroxyl group (_〇H), a sulfhydryl group, and One or more kinds of amino groups (shed 2) and the like. The functionalized carbon nanotubes are placed in a deionized water towel for ultrasonic dispersion, fineness, and subtlety, and the above steps are repeated 4 to 0 times. Finally, the nano tube is ultrasonically dispersed in deionized water to obtain a Nano carbon tube water-soluble dispersion. The carbon nanotubes have a basic tilting group (_c〇〇h) and a hydroxyl group (-OH). The carbon nanotubes can be prepared by a battery discharge method, a laser evaporation method or a chemical vapor deposition method. . In this embodiment, the carbon nanotube array is grown by chemical vapor deposition and the carbon nanotubes in the carbon nanotube array are scraped off as raw materials. The carbon nanotube array is oriented in the carbon nanotube array. Arranged without intertwining, it is beneficial for Nai 12 201029536 Mi Shi anti-g dispersed in the solution. In this embodiment, the length of the carbon nanotubes is 2 (8) nm. It is added to the first mixed liquid cold solution of the precious metal tube and the polymer solution to be stirred for 1 to 4 minutes to form a second mixed solution. During the mixing process, the complex formed by the noble metal ion and the linking agent is entangled on the surface of the carbon nanotube so that the noble metal ions uniformly adhere to the surface of the carbon nanotube. Moreover, due to the entanglement of the complex, the attraction between the carbon nanotubes is reduced, thereby avoiding that the plurality of carbon nanotubes in the second mixture are brought together by the Van der Waals force group, The carbon nanotubes are better dispersed in the second solution. Further, in the ink prepared by the method, the carbon nanotubes are not easily agglomerated and have a good dispersing effect. (2) adding an appropriate amount of a viscosity modifier, a surfactant, and a linking agent to the second mixed solution. And stir to get the ink. An appropriate amount of a viscosity modifier, a surface active agent, and a linking agent are added to the second mixed solution, and the mixed solution is mechanically stirred at room temperature for 20 to 50 minutes to obtain an ink. The ink is then ultrasonically mixed and filtered and placed in an ink cartridge. Further, this embodiment can also add an appropriate amount of a humectant to the ink. In the ink prepared in this embodiment, the mass percentage of the noble metal ions is 1% to 55%, the mass percentage of the solvent is 50 to 80%, and the mass percentage of the carbon nanotubes is 2. 2~5%, the mass percentage of the viscosity modifier is 0·1~30%, the mass percentage of the surfactant is 〇.1~5%, and the mass of the connecting agent is 100% The content of the fraction is 0.1 to 30%. The viscosity of the ink is 1 to 40 centipoise (cpQ, 13 201029536, the surface tension is 20 to 60 dynes/cm (dyne/cm). In the ink prepared in this embodiment, the noble metal ions are attached to the carbon through the bonding agent. a surface of the nanotube, and the carbon nanotube is uniformly dispersed in the ink. Therefore, the shell metal ion is uniformly dispersed in the ink. Step 2 'forms a carbon nanotube 14 on the surface of a substrate 1 and is responsible for The conductive line preform 12 of metal ions. Referring to Fig. 2, the substrate 10 is an insulating material, and the shape and size are not limited. The substrate 10 is made of tantalum, yttria, quartz, sapphire, ceramic, glass, metal. One or more of an oxide and a polymer material. The method of forming the conductive line preform 12 containing the ink on the substrate 1 is a screen printing method or an inkjet printer-jet printing method. The conductive line preform 12 may form a pattern. The conductive line preform 12 includes a plurality of uniformly distributed carbon nanotubes 14 and noble metal ions attached to the surface of the carbon nanotubes 14 (not shown) In the example, the substrate 10 is a polyimide film printed on the polyimide film by an ink jet printer. The carbon nanotube 14 is adhered to the substrate by a bonding agent. The surface, the noble metal ions are attached to the surface of the carbon nanotube 14 by a bonding agent. The line width of the pattern is 1 〇 micrometer to 1 〇〇 micrometer. Step 3 'Responsible for the conductive line preform 12 on the surface of the substrate 1 〇 The metal ions are reduced to noble metal particles 16. The noble metal ions in the conductive line preform 12 can be reduced by a reducing agent, and can also be reduced by high-energy illumination to form a line on the surface of the substrate 14 201029536 comprising noble metal particles 16 The high-energy light may be one or more of ultraviolet light, laser light, and gamma-ray. In this step, the precious metal particles 16 on the surface of the carbon nanotube W attached to the conductive line preform 12 are formed by electroless plating. A catalytic center for electroless plating. The method of reducing the reducing agent can be carried out by printing a reducing agent on the surface of the conductive line preform 12. In this embodiment, the south energy light is ultraviolet light. After being lightly irradiated by ultraviolet light, the silver ions are reduced to nano-sized silver particles, and the nano-sized metallic silver particles are uniformly attached to the surface of the nano-tube by a bonding agent. The connecting agent also has a reduction of the precious metal. Under the action of 2, the connecting agent transfers a radical to the genus ion under the irradiation of high-energy light, and reduces the noble metal ion to a noble metal, so that the noble metal particle adheres to the surface of the carbon nanotube. The surface is formed into a line containing carbon nanotubes and precious metal particles. After returning to the light, along the radial direction of the wire, the noble metal particles with a direct technique of about 1 〇 20 nm are uniformly attached to the nano carbon. The surface of the tube. The method of high-energy light irradiation restores the metal ions, the method is simple and easy, the controllability is good, and the cost is low. In step 4, the conductive line preform 12 including the noble metal particles 16 and the carbon nanotubes is metallized to obtain a composite conductive line %. The metallization process is electroless plating or electrical bonding. The chemistry record can be forged, keyed copper or silver plated. The method of the chemical ore specifically includes the following steps: First, an electroless plating solution is provided. The chemical material shouts secrets, and can be used for chemical or chemical forging liquids 15 201029536 and the like. In the present embodiment, the fine chemical mineral liquid is produced, and the main component of the chemical _(4) is sulfuric acid steel, (4), ethylenediaminetetraacetic acid (EDTA), and tartaric acid. In the chemical clock copper solution, the concentration of copper sulfate is 10 g/L, the concentration of the plate is, the concentration of ethylenediaminetetraacetic acid, and the concentration of potassium is _. Next, the substrate 1 of the conductive line preform 12 including the noble metal surface 16 and the carbon nanotubes is placed in an electroless plating solution. In the present invention, the substrate 1 on which the conductive wiring preform η was formed was placed in an electroless copper plating bath for 2 minutes and then taken out. Since the surface of the carbon nanotubes is adhered to the precious metal chicks, a composite conductive line having a uniform thickness can be prepared by chemical ore. The invention implements the financial metal silver as a nano-level female, and the matter is On the surface of the nanotube, a plurality of catalytic centers are formed. During electroless plating, due to the hybridization of metallic silver, a layer of metallic copper coats the carbon nanotubes and the metallic silver. Since the metallic silver is wrapped by the metallic copper, the conductive shaft is in the spur, the miscellaneous will not migrate from the line. Come out. The secret electric circuit contains metallic silver particles, and its impurity is also stepped up and enhanced. The silver age of the rider is evenly distributed on the face of the silk carbon tube, forming a plurality of catalytic centers. Under the catalysis of metallic silver, the thickness of the obtained conductive line is uniform during electroless plating, and the conductive line obtained is more conductive. It is also possible to increase the thickness of the metal layer for the step-by-step. The actual fine towel, the composite conductive circuit 2 (four) substrate is formed into a plating smear as a cathode electroplating copper 1 plating, the current density is 2 ~ chat 2, the plating time is maintained at 5 to 10 minutes, the thickness of the ore layer is leaked . 16 201029536 It can be understood that the carbon nanotube has a constant guide. In this embodiment, the conductive wiring preform 12 containing the noble metal and the carbon nanotube w can be directly metallized by the (four) plating to achieve practical requirements. . Since the conductive line preform 12 of the embodiment of the present invention includes the noble metal particles 16 and the carbon nanotubes m, the conductive team does not illuminate the line including only the carbon nanotubes, and thus the conductivity is strong. When the towel comprises precious metal particles and the conductive circuit preform 12 of the carbon nanotube w, the plating effect is better.
本發明實施_備導路財法具扣下伽：第一藉 由光照的方式’在基板表⑽成含有絲碳管與貴金屬顆粒的線 路該方法所需設備簡單，反應快而且方便控制；第二，利用化 學鍛膜或紐增加了線路的導紐，還對線財的貴金屬顆粒進 仃了保護’從而避免了責金屬離子的遷移問題。第三，所述製備 導電線路的方法藉蛾料含有奈純管及貴金屬離子的導電線 ^預製體’將該貴金屬離子還貴金制粒後，責金屬顆粒均 :的附者在奈祕管表面，形成複數健化巾心、，再藉由化學梦 的方材以得到厚度均句的導電線路，其導電性較強。 ^ ,、二上所述’本㈣確已符合發明專狀要件，遂依法提出專 月准以上所述者僅為本發明之較佳實施例，自不能以此 限制本案之巾請專鄉圍。舉凡熟悉本紐藝之人士援依本發明 之精，所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍内。 【圖式簡單說明】 圖1為本發明實施例中製備導電線路的方法的流程圖。 17 201029536 圖2為本發明實施例中製備導電線路的工藝流程圖 【主要元件符號說明】 基底 10 導電線路預製體 12 奈米碳管 14 貴金屬顆粒 16 導電線路 20The invention has the advantages of simple device, quick response and convenient control; the first method of the method is to use a light-emitting method to form a line containing a carbon carbon tube and a precious metal particle on the substrate table (10). Second, the use of chemical forging film or New Zealand has increased the guide of the line, and also protected the precious metal particles of the line of money, thus avoiding the migration of metal ions. Thirdly, the method for preparing a conductive line borrows a molybdenum material containing a neat tube and a noble metal ion conductive wire to form a preform, and the noble metal ion is further granulated into a precious metal, and the metal particles are all attached to the tube. On the surface, a plurality of Jianhua towel cores are formed, and the conductive wires of the chemical dream are obtained to obtain a conductive line having a thickness uniform sentence, and the conductivity is strong. ^ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , . Anyone who is familiar with this New Art will be able to cover the essence of the invention, and equivalent modifications or variations shall be included in the scope of the following patent application. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a method of preparing a conductive line in an embodiment of the present invention. 17 201029536 FIG. 2 is a flow chart of a process for preparing a conductive line according to an embodiment of the present invention. [Description of main components] Base 10 Conductive line preform 12 Carbon nanotubes 14 Precious metal particles 16 Conductive lines 20
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