200950631 九、發明說明： ，【發明所屬之技術領域】 、 本發明涉及喷墨印刷技術領域、 利用該油墨製作導電線路之方法。 ” 種油墨及 【先前技術】 ^印刷作為—種㈣I藝，其與平版印刷、 Ο 不圖形之轉移。噴墨印刷為非接觸印刷工藝， 只需將所需圓形直接由電腦給出， 制=墨印刷系統之噴嘴，將油墨顆粒由噴嘴喷出並逐點ς 形成圖形ϋ印刷可應用於電路板線路製作中，即 印刷線路圖形。該方法製作線路圖形能夠精確控制線路之 位置及2度，還降低原料浪費，係一種環保之印刷工藝。 目前，噴墨印刷線路圖形係將以單分散之奈米顆粒為 核〜之奈米金屬油墨直接喷射於基板表面形成導電線路。 凊參閱文獻：李江，奈米油墨及其應用技術，材料與製備， 2005，3 : 25-29。惟，銅較金或銀活潑，且奈米銅之比表面 積比一般金屬銅大，於空氣中奈米銅及易被氧化失去金屬 之導電性’所以奈米銅不適合作為油墨’亦不能滿足採用 喷墨印刷之方式製作銅線路。另外’喷射於基板表面之奈 米金屬油墨乾燥後，還需經過3〇〇度高溫燒結，使奈米金 屬顆粒燒結於—起，從而形成連續之導電線路。惟，燒結 過程中’溫度控制不佳會影響導電線路之連續性及導電 6 200950631 性 如燒結溫度過低，奈米金屬顆粒不能完全被燒結於一 ，目反地，燒結溫度過高，基板必須採用 受熱變形材料製成。 门-且不易 【發明内容】 有鑑於此，提供一種油墨及導電線路之製作方法，以 提高導電線路之連續性及導電性實屬必要。 ❹ 以下將以實施例說明一種油墨及導電線路之製作方 法。 、 一種油墨’其包括還原劑與可溶性鈀鹽。 一種製作導電線路之方法，首先將包括還原劑與可溶 性把鹽之油墨藉由喷墨印刷方式於基板表面形成線路圖 形。其次，採用光束照射線路圖形，使該線路圖形中之可 溶性鈀鹽被還原劑還原為金屬鈀粒子’從而獲得預製線 路。再次，於該預製線路之軌跡鍍覆金屬，以形成導電線 ❹路。 與先前技術相比，該油墨包括還原劑與可溶 ， 利用該油墨製作導電線路時，由於還原劑與可溶性鈀^可 完全溶解於油墨中，且不存在奈米金屬易被氧化之問題， 因此該油墨性能穩定，用其製作之線路圖形分佈均勻。該 方法還藉由光束照射線路圖形，引發形成線路圖形之油墨 自身發生氧化還原反應，使油墨中之還原劑將可溶性把鹽 中之纪離子還原成金屬把粒子，並由該金屬把粒子作為催 化中心鍍覆金屬，從而形成連續性好之導電線路，避免採 7 200950631 用高溫燒結形成導電線路，從而使導電線路之製作不必 考慮燒結溫度之影響。 【實施方式】 下面將結合附圖及實施例對本技術方案實施例提供之 -種油墨及㈣該油墨製作導電線路之方法作進一 說明。 — ❹ 本技術方案實施例提供之油墨，其包括還原劑與可溶 性把鹽。該油墨係將還原劑及把鹽與有機溶劑或水溶性介 質混合而製成。由於該油墨為水溶性鈀鹽油墨，該鈀睡完 •全溶解於溶劑中，具有較好分散性，可有效防止直接ς用 奈米金屬粒子油墨時引起之奈米金屬粒子發生團聚之現 象。 由於可溶性把鹽之氧化性較弱，如果將該把鹽與弱還 原性溶液混合’只要沒有高能量光束（如紫外光）之照射， ®氣化把與弱還原性溶液幾乎不發生反應，故包括氯化把與 弱還原性溶液之油墨可保存較長時間而不變質，其避光保 =期至少為三個月。如果將該鈀鹽與強還原性溶液混合， 要有光束之照射，即可使氣化鈀與強還原性溶液發生反 應，故包括氣化鈀與強還原性溶液之油墨保存時間較短， 應於製備後及時使用，縮短油墨之放置時間即可保證喷墨 印刷之=質。由於把離子於溶液令表現為撥色，金屬絲 子（銳單質）為黑色，如果油墨令有金屬纪粒子析出會 使油墨之溶液加深’所以判斷該油墨是否變質，可藉由觀 200950631 察油墨之顏色是否加深即可。 該把鹽可為硫酸把、氣化纪、石肖酸把、祕合物或其 他可溶性把鹽’其摩爾滚度為1〇 m〇l/L至丄⑽几。還原劑 可為捧樣酸納、酒石酸如楚甘 蚁鉀鈉專其他還原劑，其摩爾濃度為 10 mol/L至〇.4mol/L。該麵鹽與還原劑之摩爾比例為玉： 10至1 · 200。光照時’還原劑與把鹽發生氧化還原反應， ❹ ❹ 並餘鹽中之把離子還原為金屬峰子。本實施例中’油 墨包括檸檬酸鈉與氯化把。 另外，於製備過程中還可向該油墨中加人表面活性 劑、黏度調卽劑、連接料或其他試劑，用以調節油墨之表 面f力、黏度等性能，從而提高油墨與待印刷物體表面之 結口力。有機溶劑可為乙醇、丙綱、甘油等可與水相溶之 =性溶劑’水溶性介質可為去離子水、水溶性有機物或兩 者之混口物。而表面活性劑可為陰離子型、陽離子型、非 離子型等，連接料可為聚氨酯、聚乙烯醇等高分子材料。 以下將以包括氣化纪與檸樣酸納之油墨為例介紹本實 施例之油墨中各種組分之配比範圍。摩爾濃度為〇離 至lm〇1/L之氣化把與摩爾濃度為ι〇㈣几至〇 4则】几之 摔樣酸納溶液以摩爾比例為1:1〇至i : 200混合製備油墨 基礎溶液。於上述油墨基礎溶液中還可根據所需油墨之性 能選擇性地加入重量百分比為⑽至50%乙二醇、〇.1%至 2〇%連接料、〇·1%至5〇%黏度調節劑、0.1%至50%保渴劑 及（U%至5%表面活性劑，從而完成油墨之製備。 請參閱圖1至圖4,本實施例提供之採用該油墨製作導 200950631 電線路之方法。 - 第一步··提供基板100。 - 如圖1所示，本實施例中，基板100為電路板製作過 程中需要進行線路製作之半成品。根據所要製作之電路板 之結構可選擇不同結構之基板100。例如，當待製作之電路 板為單層板時，該基板100為一層絕緣層；當待製作之電 路板為多層電路板時，該基板1〇〇為一由多層板和一絕緣 ❹層壓合後所形成之結構’還可為半導體基片。本實施例中， 基板100為需要製作單面線路之單層板。該基板1〇〇具有 用於形成預製線路之表面11〇。當然，該基板1〇〇亦可用於 / 製作雙面板，只要於基板10〇相對設置之兩個表面上製作 即可。 第二步：形成線路圖形200於基板100之表面110。 為增加形成之線路圖形200與基板100之表面110之 結合強度’於基板1〇〇形成線路圖形200之前，可藉由採 ❹用酸、鹼溶液或電漿微蝕基板11〇、清洗等方法對基板11〇 進行表面處理，以除去附著於表面11〇之污物、氧化物、 油脂等。 如圖2所示，分別於基板1〇〇之表面no藉由喷墨印 刷方式形成線路圖形200。具體地，喷墨印刷系統於控制器 之控制下根據所需製作之導電線路之圖形，將油墨自喷嘴 逐點喷灑到表面110,使其沈積於表面110形成線路圖形 200。該油墨為本技術方案提供之油墨。其包括還原劑及可 溶性鈀鹽。該包括還原劑及可溶性鈀鹽之油墨形成之線路 200950631 •圖形200與所需製作之導電線路之圖形相同。 - 該油墨包括還原劑與可溶性鈀鹽，利用該油墨製作導 •電線路時，由於還原劑與可溶性鈀鹽可完全溶解於油墨 中，可避免直接採用奈米金屬粒子形成導電線路時引起之 奈米金屬粒子發生團聚之現象，且不存在奈米金屬易被氧 化之問題，因此該油墨性能穩定，形成包括還原劑及可溶 性鈀鹽之分佈均勻之線路圖形，使線路圖形中各處線路之 ❹#度與寬度相同° 第二步：形成預製線路300於基板1〇〇之表面11〇。 如圖2及圖3所示，採用光束照射形成於基板1〇〇表 面110之線路圖形200,使形成該線路圖形2〇〇之鈀鹽中之 把離子與還原劑於光束照射下發生氧化還原反應，從而把 鹽中之鈀離子被還原為金屬鈀粒子，從而於表面ιι〇上由 該金屬鈀粒子形成預製線路3〇〇。優選地’光束照射時間於 1分鐘至12分鐘。 、 〇 #光束可為紫外光、㈣、^射線等高能光束或其他 光束，只要能使上述氧化還原反應發生即可。本實施例中， 油墨包括氯聽與擰檬酸納。由於檸檬酸納之還原性較 弱，因此需採用高能紫外光作為光源照射包括氣化把與檸 檬酸納之油墨才能使氯域與檸檬酸納發生反應。且體 地，紫外光照射線路圖形2〇〇，形成線路圖形之氯化把 與檸檬酸鈉於紫外光之作用下發生氧化還原反應，使氯化 鈀中之叙離子被檸檬酸鈉還原為金屬絲子，再於光照後 於65度之溫度下乾燥形成預製線路300。經掃描電鏡測量 11 200950631 m路3〇〇之金屬纪粒子之粒徑於6〇奈米 =金=形成預製線路3〇0之金屬絲子亦可不為 屬粒子，只要形成之預製線路300包括金屬鈀粒 子即可。 5 棚第四步：於預製線路3〇〇上鍍覆金屬形成導電線路 刖步驟中’包括還原劑與可溶性把鹽之油墨經喷墨 ❹印刷系統喷射至基板1〇〇之表φ ιι〇形成線路圖形細時， 該線路圖形200為分佈於表面11〇之還原劑與可溶性把鹽 形成。該把鹽中金屬離子間可能沒有完全結合，其連續性 較差，使轉子經反應生成之金屬把粒子亦為分佈於表面 110之連續性較差之金屬絲子，從而降低由該金屬把粒子 形成之預製線路300之導電性，使整個預製線路3〇〇可能 無法達到良好之電性導通。 因此，如圖4所示，於預製線路300之金屬麵粒子表 ❹面經過電鑛或化學錄之方法鍵覆金屬，使所鑛覆金屬完全 包裹於預製線路300之金屬把粒子外並填充相鄰兩個金属 鈀粒子之間隙，從而形成連續之導電線路400。於鍍覆金屬 時，形成預製線路300之每個金屬鈀粒子作為鍍覆反應之 催化中心，並以該每個金屬鈀粒子為中心於其表面生長出 複數金屬粒子。該複數金屬粒子緻密排列於每個金屬鈀粒 子之表面，使該每個金屬鈀粒子完全被複數金屬粒子包 裹，同時沒有完全結合之相鄰兩個金屬纪粒子之表面分別 生長出之複數金屬粒子將該相鄰兩個金屬把粒子電性連 12 200950631 形成具有良好之電性導通 接’從而於基板100之表面110 之導電線路400。 本實施例中，對包括金屬鈀粒子之 化學鑛銅’於基板,。。之表面U。形進行 ❹200950631 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to the field of inkjet printing technology and a method for producing a conductive line using the ink. "Ink and [Prior Art] ^Printing as a kind of (four) I art, which is related to lithography, 图形 not graphic transfer. Inkjet printing is a non-contact printing process, just need to give the required circular directly from the computer, = nozzle of the ink printing system, the ink particles are ejected from the nozzle and formed into a pattern point by point. The printing can be applied to the circuit board circuit production, that is, the printed circuit pattern. The method of making the line pattern can accurately control the position of the line and 2 degrees. It also reduces the waste of raw materials and is an environmentally friendly printing process. At present, the inkjet printed circuit pattern will directly spray the monodisperse nanoparticle as the core to the surface of the substrate to form a conductive line. 凊Reference: Li Jiang, Nano Ink and Its Application Technology, Materials and Preparation, 2005, 3: 25-29. However, copper is more active than gold or silver, and the specific surface area of nano copper is larger than that of ordinary metallic copper. And easy to be oxidized to lose the conductivity of the metal 'so the nano copper is not suitable as an ink' and can not meet the requirements of inkjet printing to make copper lines. In addition, 'spray on the substrate table After the surface of the nano metal ink is dried, it needs to be sintered at a high temperature of 3 degrees to make the nano metal particles sintered to form a continuous conductive line. However, the poor temperature control during the sintering process will affect the conductive line. Continuity and Conductivity 6 200950631 If the sintering temperature is too low, the nano metal particles cannot be completely sintered, and the sintering temperature is too high. The substrate must be made of heat-deformed material. In view of this, it is necessary to provide a method for fabricating an ink and a conductive line to improve the continuity and conductivity of the conductive line. ❹ Hereinafter, an ink and a method for manufacturing a conductive line will be described by way of examples. The invention comprises a reducing agent and a soluble palladium salt. A method for preparing a conductive line, firstly forming a circuit pattern on the surface of the substrate by inkjet printing comprising a reducing agent and a soluble salt ink. Secondly, the light beam is used to illuminate the line pattern to make the line The soluble palladium salt in the graph is reduced to metal palladium particles by the reducing agent to obtain a prefabricated line Thirdly, the metal is plated on the track of the prefabricated line to form a conductive line. Compared with the prior art, the ink includes a reducing agent and a soluble material. When the conductive line is made by using the ink, the reducing agent and the soluble palladium can be used. It is completely dissolved in the ink, and there is no problem that the nano metal is easily oxidized. Therefore, the performance of the ink is stable, and the pattern of the line formed by the ink is uniformly distributed. The method also irradiates the line pattern by the light beam to induce the ink which forms the line pattern itself. The redox reaction occurs, so that the reducing agent in the ink will reduce the ions in the salt to the metal particles, and the metal will be used as the catalytic center to plate the metal, thereby forming a conductive line with good continuity, avoiding the use of 7 200950631 The conductive line is formed by high-temperature sintering, so that the production of the conductive line does not have to take into account the influence of the sintering temperature. [Embodiment] Hereinafter, the ink provided by the embodiment of the present technical solution and (4) the conductive line prepared by the ink according to the embodiment and the embodiment will be described. The method is further explained. — 油墨 An ink provided by an embodiment of the present invention includes a reducing agent and a soluble salt. The ink is prepared by mixing a reducing agent and a salt with an organic solvent or a water-soluble medium. Since the ink is a water-soluble palladium salt ink, the palladium is completely dissolved in a solvent and has good dispersibility, and can effectively prevent the agglomeration of the nano metal particles caused by directly using the nano metal particle ink. Since the solubility of the salt is weak, if the salt is mixed with the weakly reducing solution, as long as there is no irradiation of a high-energy beam (such as ultraviolet light), the gasification will hardly react with the weakly reducing solution, so Inks including chlorination and weakly reducing solutions can be stored for a longer period of time without deterioration, and are protected from light for a period of at least three months. If the palladium salt is mixed with a strong reducing solution, the vaporized palladium and the strongly reducing solution may be reacted by irradiation with a light beam, so that the ink containing the vaporized palladium and the strong reducing solution has a short storage time. It can be used in time after preparation, and the ink placement time can be shortened to ensure the quality of inkjet printing. Since the ion is expressed in the solution, the wire (sharp element) is black. If the ink causes the metal particles to precipitate, the solution of the ink will be deepened. Therefore, whether the ink is deteriorated or not can be observed by looking at the ink in 200950631. Whether the color can be deepened. The salt may be a sulfuric acid, a gasification, a sulphuric acid, a mystery or other soluble salt having a molar rolling degree of from 1 〇 m〇l/L to 丄(10). The reducing agent can be used as a reducing agent for sodium tartaric acid, tartaric acid, such as Chugan ant potassium sodium, and has a molar concentration of 10 mol/L to 〇.4 mol/L. The molar ratio of the face salt to the reducing agent is jade: 10 to 1 · 200. During the illumination, the reducing agent reacts with the redox reaction of the salt, and the ions in the residual salt are reduced to metal peaks. The ink in this embodiment includes sodium citrate and chlorinated. In addition, a surfactant, a viscosity adjusting agent, a binder or other reagent may be added to the ink during the preparation process to adjust the surface f force and viscosity of the ink, thereby improving the surface of the ink and the object to be printed. The knot is strong. The organic solvent may be a water-soluble solvent such as ethanol, propyl or glycerin. The water-soluble medium may be deionized water, a water-soluble organic substance or a mixture of the two. The surfactant may be anionic, cationic or nonionic, and the binder may be a polymer material such as polyurethane or polyvinyl alcohol. Hereinafter, the ratio of the components in the ink of the present embodiment will be described by taking an ink including gasification and sodium citrate as an example. The molar concentration is 〇 至 〇 〇 L 之 气 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Base solution. The above ink base solution may also be selectively added in a weight percentage of (10) to 50% ethylene glycol, 0.1% to 2% by weight of the binder, 〇·1% to 5〇% viscosity adjustment according to the properties of the desired ink. a 0.1% to 50% quenching agent and (U% to 5% surfactant to complete the preparation of the ink. Please refer to FIG. 1 to FIG. 4, the method for manufacturing the 200950631 electric circuit using the ink provided in the embodiment) - First step ·· Providing the substrate 100. - As shown in Fig. 1, in the embodiment, the substrate 100 is a semi-finished product that needs to be fabricated during the circuit board manufacturing process. Different structures may be selected according to the structure of the circuit board to be fabricated. The substrate 100 is, for example, when the circuit board to be fabricated is a single-layer board, the substrate 100 is an insulating layer; when the circuit board to be fabricated is a multi-layer circuit board, the substrate 1 is a multi-layer board and a The structure formed by laminating the insulating crucibles may also be a semiconductor substrate. In this embodiment, the substrate 100 is a single-layer board in which a single-sided wiring is required. The substrate 1 has a surface 11 for forming a prefabricated line. Oh, of course, the substrate 1〇〇 can also be used / Making a double panel, as long as it is fabricated on the opposite surfaces of the substrate 10 。. The second step: forming the wiring pattern 200 on the surface 110 of the substrate 100. To increase the formed circuit pattern 200 and the surface 110 of the substrate 100 Before the formation of the line pattern 200 on the substrate 1 , the substrate 11 can be surface-treated by picking with an acid, an alkali solution or a plasma micro-etching substrate 11 , cleaning, or the like to remove the adhesion to the surface 11 . The dirt, oxide, grease, etc. of the crucible. As shown in Fig. 2, the wiring pattern 200 is formed by inkjet printing on the surface no of the substrate 1 respectively. Specifically, the inkjet printing system is under the control of the controller. According to the pattern of the conductive lines to be fabricated, the ink is sprayed from the nozzle point by point to the surface 110, and deposited on the surface 110 to form a wiring pattern 200. The ink is an ink provided by the technical solution, which includes a reducing agent and soluble palladium. Salt. The line formed by the ink including the reducing agent and the soluble palladium salt 200950631 • The pattern 200 is the same as the pattern of the conductive line to be fabricated. - The ink includes a reducing agent and soluble palladium Salt, when the conductive electric circuit is made by using the ink, since the reducing agent and the soluble palladium salt can be completely dissolved in the ink, the phenomenon of agglomeration of the nano metal particles caused by directly forming the conductive line by the nano metal particles can be avoided, and There is no problem that the nano metal is easily oxidized, so the performance of the ink is stable, and a circuit pattern including a uniform distribution of the reducing agent and the soluble palladium salt is formed, so that the lines of the lines in the line pattern are the same as the width. : forming a prefabricated line 300 on the surface 11 of the substrate 1 . As shown in FIG. 2 and FIG. 3 , the line pattern 200 formed on the surface 110 of the substrate 1 is irradiated with a light beam, so that the palladium forming the line pattern 2 is formed. The ions in the salt undergo a redox reaction with the reducing agent under the irradiation of the light beam, thereby reducing the palladium ions in the salt to the metal palladium particles, thereby forming a prefabricated line 3 from the metal palladium particles on the surface. Preferably, the beam irradiation time is from 1 minute to 12 minutes. 〇 # Beams can be high-energy beams or other beams such as ultraviolet light, (four), and ^-ray, as long as the above-mentioned redox reaction can occur. In this embodiment, the ink includes chlorine listen and sodium sulphate. Since the reduction of sodium citrate is weak, it is necessary to use high-energy ultraviolet light as a light source to illuminate the chlorine field with sodium citrate to react the chlorine domain with sodium citrate. In addition, the ultraviolet light illuminates the circuit pattern 2〇〇, and the chlorination of the line pattern and the sodium citrate undergo oxidation-reduction reaction under the action of ultraviolet light, so that the sulphide in the palladium chloride is reduced to metal by sodium citrate. The filaments are dried at a temperature of 65 degrees after the light to form a prefabricated line 300. Scanning electron microscopy 11 The diameter of the metallographic particles of the 200950631 m road is 6 〇 nanometer = gold = the metal wire forming the prefabricated line 3 〇 0 may not be a genus particle, as long as the formed prefabricated line 300 includes metal Palladium particles can be used. 5 The fourth step of the shed: plating the metal on the prefabricated line 3 to form a conductive circuit. In the step, the ink including the reducing agent and the soluble salt is sprayed onto the substrate by the inkjet printing system to form a sheet φ ιι〇. When the line pattern is fine, the line pattern 200 is formed by a reducing agent and a soluble salt distributed on the surface 11〇. The metal ions in the salt may not be completely combined, and the continuity is poor, so that the metal formed by the reaction of the rotor is also a metal wire which is distributed on the surface 110 with poor continuity, thereby reducing the formation of particles by the metal. The conductivity of the prefabricated line 300 makes it impossible for the entire prefabricated line 3 to achieve good electrical conduction. Therefore, as shown in FIG. 4, the surface of the metal surface particle of the prefabricated line 300 is bonded to the metal by means of electro-mine or chemical recording, so that the metal coated metal is completely wrapped around the metal of the pre-made line 300 and the particles are filled and filled. The gap between the two metal palladium particles is adjacent to form a continuous conductive line 400. When metal is plated, each of the metal palladium particles of the prefabricated line 300 is formed as a catalytic center of the plating reaction, and a plurality of metal particles are grown on the surface of the metal palladium particles. The plurality of metal particles are densely arranged on the surface of each of the metal palladium particles, so that each of the metal palladium particles is completely surrounded by the plurality of metal particles, and the plurality of metal particles respectively grown on the surfaces of the adjacent two metallographic particles are not completely combined. The two adjacent metals electrically connect the particles to 12 200950631 to form a conductive line 400 having a good electrical conduction connection to the surface 110 of the substrate 100. In this embodiment, a chemical ore copper comprising metal palladium particles is applied to the substrate. . Surface U. Shape
地’將形成預製線路3GG之基板1GG置於^婆〇〇°具體 於50度之溫度下進行化學鍵銅2分鐘，二::二 形成完全電連通之導電線路400。導電線預I線路· 之粒徑為50至150奈米。該鍍液還可 ：銅= 劑與絡合劑。銅化合物可為硫酸銅、氯化銅等 =還原 為曱醛、乙醛酸等；絡合劑可為乙烯二胺四乙酸二鈉睡了 鈉等：合物。當然，還可於渡液中加入穩定；、 光冗劑4，以滿足化學鍍之需要。具體地，該、 組分為：硫酸銅l〇g/L、酒石酸鉀鈉22g/L、=二二=液之 酸二鈉鹽5〇g/L、曱醛15mL/：L及甲醇1〇mL/L、胺四乙 體採用重量體積比’即’單位體積溶液中含該固體t二固 單液體採用體積體積比，即’單位體積溶液中：該 液體之體積，單位mL/L。 ° =-步研究油墨及光束照射對預製線路·物理性 能及導電線路400物理性能之影響。本實施例還進 究採用包括不同配比之氣化鈀與擰檬酸 , 紫外光照射時間，於基板之表面11G上二^同之 3〇〇之物理性能，以及由該預製線路3⑼形成導電線^線路 之物理性能，並對該研究及分析結果分別列於表工玉 中。其中’導電線路權之方塊電阻採用四探針法H。2 13 200950631 方塊電阻亦稱之為方阻，用於表示一正方形之薄膜導電材 料邊到邊之間之電阻，其單位為Ω/口（歐姆每平方，ohms Per square)。該檸檬酸鈉溶液之濃度可根據所需油墨中檸檬 酸納溶液所占比例及氯化鈀之濃度計算得到。 表1.1含不同氣化鈀（1〇 m〇1/L)與擰檬酸鈉配比之油墨形成 _^預製線路300及導電線路400之物理性能(紫外光照射6分鐘） 線路400The substrate 1GG, which forms the prefabricated line 3GG, is placed at a temperature of 50 degrees to chemically bond copper for 2 minutes, and the second::2 forms a fully electrically conductive conductive line 400. The conductive pre-I line has a particle size of 50 to 150 nm. The plating solution can also be: copper = agent and complexing agent. The copper compound may be copper sulfate, copper chloride or the like = reduced to furfural, glyoxylic acid, etc.; the complexing agent may be sodium diamine tetraacetic acid, sodium, etc. Of course, it is also possible to add stability to the liquid; and a light redundancy agent 4 to meet the needs of electroless plating. Specifically, the components are: copper sulfate l〇g/L, potassium sodium tartrate 22 g/L, = two-two = liquid acid disodium salt 5 〇 g / L, furfural 15 mL /: L and methanol 1 〇 The volume ratio of the solid/volume ratio of the mL/L and the amine tetraethylene to the unit volume solution is the volume-volume ratio, that is, the volume per unit volume of the liquid, in units of mL/L. ° = - Step Study of the effects of ink and beam illumination on the prefabricated circuit, physical properties, and physical properties of the conductive line 400. In this embodiment, the physical properties of vaporized palladium and citric acid including different ratios, ultraviolet light irradiation time, and the same on the surface 11G of the substrate are used, and the conductive line is formed by the prefabricated line 3 (9). The physical properties of the line ^ line, and the results of the research and analysis are listed in the table jade. Among them, the square resistance of the conductive line weight adopts the four-probe method H. 2 13 200950631 The square resistance, also known as square resistance, is used to represent the resistance of a square film of conductive material from side to side, in ohms per square (ohms per square). The concentration of the sodium citrate solution can be calculated from the proportion of the sodium citrate solution in the desired ink and the concentration of palladium chloride. Table 1.1 Ink formation with different vaporized palladium (1〇 m〇1/L) and sodium citrate ratio _^ Physical properties of prefabricated line 300 and conductive line 400 (UV light irradiation for 6 minutes) Line 400
氣化把與 擰檬酸“ 配tb 金屬把粒子 粒徑（單 位：奈米） 銅粒子粒徑 (單位：奈米） 方塊電阻 (單位：Ω /□)Gasification and citric acid "with tb metal particles particle size (unit: nano) copper particle size (unit: nano) sheet resistance (unit: Ω / □)
表1.2不同紫外光照射時間形成之預製線路3〇〇及導電線路 〇〇之物理性能（油墨包括氣化鈀（1〇 m〇1/L)與檸檬酸鈉配比工： 40 ’並加入20%乙二醇） 光照射時 間 (單位：分鐘） 預製線路300 導電 線 路400 金屬鈀粒子粒 徑 —:奈米） _ 200 至 30Π -60 至 70 銅粒子粒徑 (單位：奈米） --------- 方塊電阻 (單位：Ω /□) 50 至 1〇〇 0.319 50 至 1〇〇 0.882Table 1.2 Physical properties of prefabricated lines 3导电 and conductive lines formed by different ultraviolet light irradiation times (ink includes gasified palladium (1〇m〇1/L) and sodium citrate ratio: 40 ' and added 20 % Glycol) Light irradiation time (unit: minute) Prefabricated line 300 Conductive line 400 Metal palladium particle size -: Nano) _ 200 to 30 Π -60 to 70 Copper particle size (unit: nanometer) --- ------ Square resistance (unit: Ω / □) 50 to 1 〇〇 0.319 50 to 1 〇〇 0.882
山，π加掙稼毆納之含量有助於使氯化鈀 中把離子完全被還原為金屬㉟粒子，使㈣於金屬把粒子 之鋼粒子粒控減小，從而有利於形成緻密之金屬層。隨銅 粒子粒徑之減小，導電線路400之方塊電阻相應減小。惟， 200950631 當檸檬酸鈉之含量過大時，氯化鈀中鈀離子已經完全被還 原為金屬把粒子’多餘之檸檬酸鈉會附於或包裹於金屬鈀 粒子表面’使部分金屬鈀粒子被隔離，減少鍍覆時作為催 化中心之金屬把粒子之數量，從而減低鏡層之緻密程度， 即使導電線路400銅粒子之粒徑未變化，導電線路4〇〇之 方塊電阻亦會明顯增加。 另外’氯化把與檸檬酸納配比為1 : 20時，氣化把中 ❿之鈀離子未能充分得與擰檬酸鈉反應’使化學鍍反應速度 慢，所鍍覆之金屬薄且連續性差，無法實現電性導通之導 電線路400,因此，無法準確測量導電線路4〇〇之銅粒子粒 徑及導電線路400之方塊電阻。此時，只要相應之增加光 束之照射時間即可。而氯化鈀與檸檬酸鈉配比為1 : 40時， 檸檬酸鈉含量充足，使氣化鈀中之鈀離子與擰檬酸鈉充分 反應，僅20秒即於基板100之表面11〇形成連續之鍍層， 獲得電性導通之導電線路400。 © /由墨中添加乙二醇，該乙二醇具有比檸檬酸鈉還弱之 還原陡，於咼能光照下亦可將氯化鈀中鈀離子還原為金屬 鈀粒子，從而對降低最終製作形成之導電線路4〇〇之方塊 電阻值有促進作用。 從表1,2可看出，相同油墨隨光照時間之增加，氣化鈀 之鈀離子與檸檬酸鈉充分反應，使金屬鈀粒子之粒徑減 嘴。而導電線路400之方塊電阻之阻值增加不明顯，形成 3線路4〇〇之銅粒子沒有變化。即，當採用相同之油墨 形成預製線路300 _，光束照射時間之增加，利於形成預 15 200950631 製線路300巾之.金屬絲子，並減小該金制粒子 而對开/成該導電線路400之方塊電阻景多響不大。 從上述研究結構可看出，選擇合適之油墨及光照時間 有利於形成預製線路綱中之金屬妃粒子，使該預製線 3 〇 〇形成連續性較好之導電線路4 00。 、、 由此完成基板100之表面110具有較高導電性及均勻 性之導電線路400之製作，以供後續加工使用。該製作方In the mountains, the content of π plus crops can help to completely reduce the ions in the palladium chloride to the metal 35 particles, so that (4) the metal particles of the particles reduce the particle size of the particles, thereby facilitating the formation of a dense metal layer. . As the particle size of the copper particles decreases, the sheet resistance of the conductive line 400 decreases accordingly. However, 200950631 When the content of sodium citrate is too large, the palladium ions in palladium chloride have been completely reduced to metal. The particles 'excess sodium citrate will be attached to or wrapped around the surface of the metal palladium particles' to isolate some of the metal palladium particles. The particle size of the metal as the catalytic center during the plating is reduced, thereby reducing the density of the mirror layer. Even if the particle size of the copper particles of the conductive line 400 is not changed, the sheet resistance of the conductive line 4 明显 is also significantly increased. In addition, when the ratio of chlorination to sodium citrate is 1:20, the palladium ion of the ruthenium is not sufficiently reacted with sodium citrate to reduce the electroless plating reaction rate, and the plated metal is thin and The continuity is poor, and the electrically conductive conductive line 400 cannot be realized. Therefore, the particle size of the copper particles of the conductive line 4 and the sheet resistance of the conductive line 400 cannot be accurately measured. At this time, it is only necessary to increase the irradiation time of the beam. When the ratio of palladium chloride to sodium citrate is 1:40, the content of sodium citrate is sufficient, and the palladium ion in the vaporized palladium is fully reacted with sodium citrate, and is formed on the surface of the substrate 100 in only 20 seconds. Continuous plating provides electrically conductive conductive lines 400. © / Adding ethylene glycol from the ink, the ethylene glycol has a weaker reduction than sodium citrate, and can also reduce the palladium ion in the palladium chloride to metal palladium particles under the illumination of the ruthenium, thereby reducing the final production. The square resistance value of the formed conductive line 4〇〇 is promoted. It can be seen from Tables 1 and 2 that the same ink increases with the irradiation time, and the palladium ion of the vaporized palladium reacts sufficiently with sodium citrate to reduce the particle diameter of the metal palladium particles. On the other hand, the resistance of the square resistance of the conductive line 400 is not significantly increased, and the copper particles forming the three lines are not changed. That is, when the same ink is used to form the prefabricated line 300 _, the increase of the beam irradiation time is advantageous for forming the wire of the pre-15 200950631 line 300, and reducing the gold particle to separate/form the conductive line 400 The square resistance view is not loud. It can be seen from the above study structure that selecting the appropriate ink and illumination time is advantageous for forming the metal ruthenium particles in the prefabricated circuit, so that the prefabricated line 3 〇 〇 forms a conductive line 400 with good continuity. Thus, the fabrication of the conductive trace 400 having a higher conductivity and uniformity on the surface 110 of the substrate 100 is completed for subsequent processing. The producer
法採用化學反應與鍍覆合之方式替代高温燒結之方法使 奈米金屬鈀粒子結合於一起，以提高線路連續性，解決燒 結過程中燒結溫度難以控制之問題，提高導電線路之 性及導電性。 、 綜上所述，本發明確已符合發明專利之要件，遂依法 提出專利申請。惟，以上所述者僅為本發明之較佳實施方 式，自不能以此限制本案之申請專利範圍。舉凡熟悉本案 技藝之人士援依本發明之精神所作之等效修飾或變化，皆 ❹應涵蓋於以下申請專利範圍内。 【圖式簡單說明】 圖1係本技術方案實施例提供之基板之結構示意圖。 圖2係圖1中基板形成線路圖形之結構示意圖。 圖3係圖1中基板形成預製線路之結構示意圖。 圖4係圖1中基板形成導電線路之結構示意圖。 【主要元件符號說明】 基板 100 16 200950631 表面 110 線路圖形 200 預製線路 300 導電線路 400The method uses chemical reaction and plating to replace the high-temperature sintering method to combine the nano metal palladium particles to improve the continuity of the line, solve the problem that the sintering temperature is difficult to control during the sintering process, and improve the conductivity and conductivity of the conductive line. . In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic structural view of a substrate provided by an embodiment of the present technical solution. FIG. 2 is a schematic structural view of a circuit pattern formed by the substrate in FIG. 1. FIG. FIG. 3 is a schematic structural view showing the formation of a prefabricated circuit in the substrate of FIG. 1. FIG. 4 is a schematic structural view of a substrate forming a conductive line in FIG. [Main component symbol description] Substrate 100 16 200950631 Surface 110 Line pattern 200 Prefabricated line 300 Conductive line 400
1717