201211054 六、發明說明： 【發明所屬之技術領域】 本發明係關於可印刷材料及其製造方法。尤其關注包含 諸如銅、金及銀之金屬之可印刷材料。銀為較佳金屬。二 • #明係關於此類金屬且尤其是銀之可印刷組合物。該等材 ·#在經印刷至基板上時可形成導電路#。關注包括喷墨印 刷之任何適宜印刷方法。 【先前技術】 吾人極大地關注對用以圖案化導電電路（例如，電子電 路）之印刷技術的潛力。尤其關注印刷至低成本基板（諸如 塑膠）上。此類程序可提供比習知程序（諸如電子工業中之 常見之程序）顯著低之製造成本。特定應用包括在印刷式 顯示器、RFID標籤及光伏打裝置中之應用。 導電圖案之施加要求將滿足應用的效能要求之諸如墨水 的高度功能性材料。理想地，用於形成導電路徑之所關注 材料亦易於（例如）藉由印刷來施加，且進一步需要可在低 溫下處理該等材料。 關鍵挑戰中之一者為開發適宜低成本可印刷導電材料。 所謂的鑄幣金屬（銅、銀及金）擁有最高導電性且因而具有 適宜於形成導電路徑之導電性。然而，金被認為過於昂 貴’而儘管銅顯著更低廉，但銅不具有適宜之環境穩定 性。由於此等原因，常常將銀視作用於此類應用之首選材 料。 舉例而言’已使用銀奈米粒子來製造功能性墨水，該等 154912.doc 201211054 功能性墨水可進行噴墨印刷且接著經熱轉變至緻密高導電 陡銀溥膜。基於極小金屬粒子（通常<1〇〇 nm)之低溫燒結 性質來形成該等薄膜，纟中基本上粒子愈小，燒結溫度愈 低。已報道在15(TC之燒結溫度下來自3〇 ^^至兄nm粒子 的、力1.5x10馱姆.厘米之電阻率。其他方法已達成9χΐ〇·6 歐姆·厘米之電阻率（但係在12〇1之較低溫度下）。 儘管基於銀奈米粒子之組合物係有用的，但在製備及利 用此等材料時存在需應對的諸多問題。該等粒子本身之合 成可為複雜的’例如’具有可觀數目個複雜分離。該等程 序作向於浪費地；肖耗其他化學物（諸如穩定劑及溶劑）。小 金屬π米粒子極難以保持膠體穩^，膠體穩定必需包含適 宜表面活性穩定劑。在燒結操作期間必須揮發掉表面活性 齊J抑或必須至；自銀粒子表面移除該表面活性劑。此導 致在膠體穩疋性與燒結便易性之間難以達到平衡。隨著粒 子大小變得更小（尤其對於約2G nm大小或小於約20⑽之 大小），此平衡變得更難以維持。 針對奈米粒子方法之替代方法為使用前驅物材料， 刖驅 驅物材料通常藉由分解且在印刷之後轉變成金屬材料。在 效果上’ Μ學變化來替換藉由燒結達成之物理變化 藉由加熱來誘發化學變化’例如，藉由足以導致金屬前驅 物材料分解以形成金屬之熱量。在此情況下，可藉： 物反應性來控制分解溫度。 存在諸多優點。不存在製造及穩定化奈米粒子之任 求。通常’材料為不含任何固體之液體’所以在施加期間 J54912.doc 201211054 (例如’在印刷期間）無需擔心聚結、沈降或結塊。作為牛 頓液體’該等液體相當易於調配以進行施加（例如，藉由 諸如喷墨印刷之印刷）。 美國專利公開案2006/001726描述經還原劑還原以形成 元素銀金屬之銀前驅物材料。該等前驅物材料包含硕酸銀 及如在彼文獻之表1中所閣明之其他銀材料。提及甲酸銅 作為可能之額外組分。 國際（PCT)公開案WO 2006/093398描述基於胺基甲酸酯 錯口物之銀前驅物系統之使用。胺基甲酸酯基提供呈胺基 甲酉文§曰離子形式之抗衡離子，同時兩性離子形式提供錯合 作用，從而允許易於溶解在冑見溶齊jt。以下展示基本化 學式。 \ Ag+X- + η Ν- 0 D II /3 -C 一0. NH+—R_ · K 0 ' II \ 0 R " II /3 r2〆 \ N- r2〆 一 c—〇- Ag* N- -c—a NH*—r4 + X· NH+—R4 、r5 η-0.7-5.5 如此產生之胺基Ψ酸銀錯合物可容易地溶解於常見溶劑 (諸如乙醇）中’且可經喷墨印刷而產生具有在1〇〇⑽至。 mm之範圍中的厚唐夕相玆时 。 又之銀溥膜。據稱此等薄膜在130°C至 15 0 °C下經乾燥歷時j 〇分鐘$ 3 t ιυ刀釦至30分鐘之時間段時具有約 4x10歐姆.厘米之電阻率。#志_如 电丨且羊。此表不對於某些奈米粒子方法 之顯著改良。 業界在處理溫度 間上要求愈加苛刻 、最終電阻率及達成此最終電阻率之時 ’所有該等性質正冑於不斷降低。因 1549I2.doc 201211054 此’業界存在對改良溫度、所敷設的導電路徑之形成時間 及在§亥導電路徑中達成的電阻率中之一或多者之需求。 【發明内容】 本發明提供適於印刷以形成銀層的組合物及用於製備彼 等組合物之方法。 本發明提供一種用於製造銀基前驅物墨水之獨特化學性 質及方法》可藉由（例如）旋塗或印刷技術來將此等墨水容 易地施加至適宜基板《可接著在顯著低於先前技術所描述 之溫度下且以顯著低於先前技術所描述之反應時間將該等 銀基前驅物墨水熱轉變成獲得極佳電性質之銀。 本發明之特定最終使用應用為提供銀薄膜之印刷施加。 本發明之技術適於印刷至許多類型之基板上，該等基板 包括玻璃、包括諸如PET(聚對苯二曱酸伸乙酯）的聚醋之 塑膠’及供用於電子工業中之膠帶，包括焊接帶，（例如） 諸如由DuPont以商標名Kapton膠帶出售之彼等膠帶的聚醯 亞胺膠帶。 本發明之技術適於許多最終使用之應用，該等應用包括 (例如）在作為可印刷導電墨水之應用、在喷墨印刷、在製 造印刷電路、在製造平板顯示器及RFID器件中之印刷。 本發明提供一種可印刷墨水，其包含： (0液體媒劑；及 (ii)銀前驅物，其為藉由曱酸銀或草酸銀中之至少一者 與穩定劑之反應所形成之銀錯合物。 本發明之組合物已展示為在印刷時表現極佳性質。 154912.doc 201211054 口思地，該銀前驅物以組合物之重量計以〗5 %至3 〇%之 量存在（例如，以組合物之重量計17%至27%)，合意地， 理想上以組合物之重量計以2〇%至25%之量存在。 合意地，該穩定劑係選自任何適宜類型，包括胺、肟、 腙、胍、醯肼、卡巴腙，及其組合。 在一項貫施例中，該穩定劑包含胺。適宜胺包括（例如） 一級胺、二級胺，且包括環胺及其組合。適宜胺包括包括 G-Cw胺之脂肪胺，該等Ci_c“胺包括丁胺及壬胺、二丁 胺、三丁胺、二伸乙基胺、四伸乙基戊胺、辛胺，及其組 合。合意地，該穩定劑為辛胺。 a亥胺可為包括CrCM胺基醇之胺基醇，實例包括乙醇 胺、丙醇胺（包括異丙醇胺），及其組合。 在一項實施例中，該穩定劑包含肟。適宜肟包括醛肟及 酮肟，及其組合。該肟為視情況選自包括C1_C16醛肟或酮 肟之適宜肟的醛肟或酮肟及其組合❶該等肟可包括丙酮 肟、曱基醛肟及曱基乙基酮肟，及其組合。 合思地’該穩定劑以墨水組合物之重量計以5%至丨〇%之 量存在。 合意地’平均奈米粒子大小係5 1101至10 nm之範圍。 合意地，液體介質包含極性溶劑，包括極性有機溶劑且 包括諸如乙醇之醇、丙酮及水，及其組合。合意地，該液 體介質包含乙醇。通常，該液體介質以組合物之重量計占 70%至 80%。 該組合物可進一步包含促導電組分，諸如草酸、甲酸及 154912.doc 201211054 的，此係因為 電性仍可能接 其、’且Ο »然而，應注意，此類組分並非必需 甚至在不存在此類組分之情況下所達成之導 近於塊體銀之導電性。 在適宜時，應瞭解，本發明之一項實施例之所有可選及/ 或較佳特徵可與本發明之另—/其他實施例之可選及 佳特徵組合。 本發明亦係關於一種用於製造可印刷墨水之方法，該可 印刷墨水包含：銀前驅物，其為藉由甲酸銀或草酸銀中/之 至少一者與穩定劑在適宜液體介質中之反應所形成之銀錯 合物β 本發明之方法可進一步包含使曱酸銀或草酸銀與穩定劑 反應以形成銀錯合物之步驟。 合意地，該液體介質形成用於印刷銀前驅物至基板上之 液體媒劑。在反應之後，可減少該液體介質之液體量以增 大銀前驅物濃度。舉例而言，可取出液體介質（例如，藉 由真空抽出），合意地’同時維持在低於約之溫度。 本發明之一個特定方法為用於製造藉由曱酸銀或草酸銀 與胺反應所形成之銀錯合物之方法，該方法包含以下步 驟：在低於約o°c之溫度下使曱酸銀或草酸銀與胺在適宜 液體介質中反應。 本發明亦係關於一種具有可印刷墨水供應器（例如，諸 如墨水盒之可印刷墨水儲器）之印表機，其中該墨水係作 為本發明之墨水。 本發明進一步係關於一種包括印刷材料之施加材料，該 154912.doc 201211054 施加材料包含根據本發明之可£ P刷墨水之印刷產物。本發 明亦係關於本發明之可印刷墨水之印刷產物。可處理該施 加材料’例如，將其暴露於流體形式之促導電組分中。合 意地，該促導電組分為視愔況 优馆， 兄選自草酸及曱酸及其組合的 有機酸。 本發明進-步係關於在施加本發明之墨水組合物至基板 上之後藉由燒結該墨水組合物所形成之材料。在本發明内 包括由施加於已經促導電組分(諸如酸)處理的基板之墨水 所形成之燒結材料。一種適宜酸為甲酸。合意地，該材料 在與該促導電組分接觸的同時加以燒結。舉例而言，該促 =電組分可處於液相中或氣相（包括蒸汽相）中。舉例而 »在以下清况下可發生燒結：在處於具有氣體形式之促 導電組分之封閉氣氛中的同時正燒結施加有墨水的基板。 該促導電組分可為視情況選自草酸及甲酸及其組合的有機 酸。 本發明擴展至-種施加有導電材料的器件，其中導電材 料為本發明之墨水組合物之產物或由本發明之組合物所形 成之燒結材料。 本發明進-步係關於-種用於燒結所施加銀材料之方 法，其中銀材料為藉由甲酸銀或草酸銀中之至少-者㈣ 定劑反應所形成之銀錯合物，其中該方法包括在與促導電 組分接觸的同時燒結該所施加銀材料之步驟。合意地，該 促導電組分為視情況選自草酸及¥酸及其組合的有機酸。 該促導電組分可處於液體形式（例如，在液體介質中）。合 1549丨 2.d〇c 201211054 意地’該促導電組分處於氣體形式（例如，在氣體介質 中）。 【實施方式】 本發明之額外特徵及優點描述於本發明之實施方式中且 將自該實施方式及圖式而變得顯而易見。 身又熟習此項技術者應容易地顯而易見本文中在下文所 揭示之實例僅表示一般化實例，且能夠再現本發明之其他 配置及方法為可能的且納入本發明。 吾人之發明係以Ag+離子之穩定的化學性質為基礎。眾 所周知’此易得之具有N供體配位體之錯合物產生具有在2 至4範圍中的配位數之化合物。詳言之，胺形成下文所展 示之類型的直鏈2配價錯合物··201211054 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a printable material and a method of manufacturing the same. Particular attention is paid to printable materials containing metals such as copper, gold and silver. Silver is a preferred metal. II • #明 relates to a printable composition of such metals and especially silver. These materials can form a conductive circuit # when printed onto a substrate. Focus on any suitable printing method including inkjet printing. [Prior Art] I have great interest in the potential of printing techniques for patterning conductive circuits (e.g., electronic circuits). Particular attention is paid to printing onto low cost substrates such as plastics. Such programs can provide significantly lower manufacturing costs than conventional programs, such as those found in the electronics industry. Specific applications include applications in printed displays, RFID tags, and photovoltaic devices. The application of the conductive pattern requires a highly functional material such as ink that will meet the performance requirements of the application. Desirably, the material of interest for forming the conductive path is also easy to apply, for example, by printing, and further requires that the materials be processed at low temperatures. One of the key challenges is the development of suitable low cost printable conductive materials. The so-called coin metal (copper, silver and gold) has the highest conductivity and thus has electrical conductivity suitable for forming a conductive path. However, gold is considered too expensive' and although copper is significantly cheaper, copper does not have suitable environmental stability. For these reasons, silver is often used as a preferred material for such applications. For example, silver nanoparticle has been used to make functional inks, and the functional inks can be inkjet printed and then thermally converted to a dense, highly conductive, steep silver tantalum film. These films are formed based on the low-temperature sintering properties of very small metal particles (usually < 1 〇〇 nm), the smaller the particles in the crucible, and the lower the sintering temperature. It has been reported that the resistivity of a force of 1.5 x 10 .·cm from 3 〇 ^ ^ to the brother nm particle at a sintering temperature of TC. Other methods have achieved a resistivity of 9 χΐ〇 6 ohm·cm (but At a lower temperature of 12〇1. Although compositions based on silver nanoparticles are useful, there are many problems to be dealt with when preparing and utilizing such materials. The synthesis of such particles can be complex' For example, 'has a considerable number of complex separations. These programs are wasteful; other chemicals (such as stabilizers and solvents) are consumed. It is extremely difficult to maintain colloidal stability of small metal π-meter particles, and colloid stabilization must contain suitable surface activity. Stabilizer. The surface active must be volatilized during the sintering operation or must be removed; the surfactant is removed from the surface of the silver particles. This results in difficulty in achieving equilibrium between colloidal stability and ease of sintering. The size becomes smaller (especially for a size of about 2G nm or less than about 20 (10)), this balance becomes more difficult to maintain. An alternative to the nanoparticle method is to use a precursor material, The drive material is usually converted into a metallic material by decomposition and after printing. In the effect of 'study changes to replace the physical change achieved by sintering, the chemical change is induced by heating', for example, by enough to cause the metal precursor The material decomposes to form the heat of the metal. In this case, the decomposition temperature can be controlled by the reactivity of the material. There are many advantages. There is no need to manufacture and stabilize the nanoparticles. Usually the material is free of any solids. Liquid 'so during application period J54912.doc 201211054 (eg 'during printing') there is no need to worry about coalescence, sedimentation or agglomeration. As a Newtonian liquid 'these liquids are fairly easy to formulate for application (eg by inkjet printing) U.S. Patent Publication No. 2006/001726 describes a silver precursor material which is reduced by a reducing agent to form an elemental silver metal. The precursor materials comprise silver silicate and other silver materials as specified in Table 1 of the literature. Reference to copper formate as a possible additional component. International (PCT) Publication WO 2006/093398 describes urethane-based scission The use of the silver precursor system. The urethane group provides a counter ion in the form of an amino group, and the zwitterionic form provides a mismatch, allowing for easy dissolution in the smear. Show the basic chemical formula. \ Ag+X- + η Ν- 0 D II /3 -C -0. NH+-R_ · K 0 ' II \ 0 R " II /3 r2〆\ N- r2〆一c—〇 - Ag* N- -c-a NH*-r4 + X· NH+-R4, r5 η-0.7-5.5 The thus produced silver amide silver complex can be easily dissolved in common solvents such as ethanol. And can be produced by inkjet printing at 1 〇〇 (10) to. Thick Tang Xixiang in the range of mm. Another silver enamel film. These films are said to have a resistivity of about 4 x 10 ohm.cm at a temperature of from 130 ° C to 150 ° C for a period of 30 minutes for a period of 30 minutes. #志_如电丨 and sheep. This table does not significantly improve some of the nanoparticle methods. The industry is increasingly demanding temperatures between treatments, final resistivity, and when this final resistivity is reached. ‘All of these properties are steadily decreasing. 1549I2.doc 201211054 There is a need in the industry for one or more of the improved temperature, the formation time of the laid conductive path, and the resistivity achieved in the §H conductive path. SUMMARY OF THE INVENTION The present invention provides compositions suitable for printing to form a silver layer and methods for preparing such compositions. The present invention provides a unique chemistry and method for making silver-based precursor inks that can be easily applied to a suitable substrate by, for example, spin coating or printing techniques, which can then be significantly lower than prior art The silver-based precursor inks are thermally converted to silver that achieves excellent electrical properties at the temperatures described and at significantly lower reaction times as described in the prior art. A particular end use application of the invention is to provide a print application of a silver film. The techniques of the present invention are suitable for printing onto many types of substrates, including glass, plastics including polyesters such as PET (polyethylene terephthalate) and tapes for use in the electronics industry, including Solder tape, for example, a polyimide tape such as those tapes sold by DuPont under the trade name Kapton tape. The techniques of the present invention are suitable for many end use applications including, for example, in applications as printable conductive inks, in ink jet printing, in the manufacture of printed circuits, in the manufacture of flat panel displays, and in RFID devices. The present invention provides a printable ink comprising: (0 liquid vehicle; and (ii) a silver precursor which is a silver fault formed by the reaction of at least one of silver citrate or silver oxalate with a stabilizer The compositions of the present invention have been shown to perform extremely well at the time of printing. 154912.doc 201211054 Thoughtally, the silver precursor is present in an amount of from 5% to 3% by weight of the composition (eg , from 17% to 27% by weight of the composition, desirably, preferably in an amount of from 2% to 25% by weight of the composition. Desirably, the stabilizer is selected from any suitable type, including Amine, hydrazine, hydrazine, hydrazine, hydrazine, carbazone, and combinations thereof. In one embodiment, the stabilizer comprises an amine. Suitable amines include, for example, primary amines, secondary amines, and include cyclic amines and A suitable amine includes a fatty amine including a G-Cw amine, and the Ci_c "amine includes butylamine and decylamine, dibutylamine, tributylamine, diethylamine, tetraethylamine, octylamine. And a combination thereof. Desirably, the stabilizer is octylamine. A helamine may be an amino alcohol including a CrCM amino alcohol. Examples include ethanolamine, propanolamine (including isopropanolamine), and combinations thereof. In one embodiment, the stabilizer comprises hydrazine. Suitable hydrazines include aldoxime and ketoxime, and combinations thereof. An aldoxime or ketone oxime selected from the group consisting of C1_C16 aldoxime or ketone oxime and combinations thereof, and the oxime may include acetone oxime, decyl aldoxime and mercaptoethyl ketoxime, and combinations thereof. The stabilizer is present in an amount of from 5% to 丨〇% by weight of the ink composition. Desirably, the average nanoparticle size is in the range of 5 1101 to 10 nm. Desirably, the liquid medium contains a polar solvent, including polar organic Solvents and include alcohols such as ethanol, acetone and water, and combinations thereof. Desirably, the liquid medium comprises ethanol. Typically, the liquid medium comprises from 70% to 80% by weight of the composition. The composition may further comprise Conductive components, such as oxalic acid, formic acid, and 154912.doc 201211054, because electrical properties may still be followed, 'and Ο» However, it should be noted that such components are not required even in the absence of such components The approach reached The conductivity of the bulk silver. Where appropriate, it will be appreciated that all optional and/or preferred features of one embodiment of the invention may be combined with alternative and preferred features of the other/other embodiments of the invention. The invention also relates to a method for producing a printable ink comprising: a silver precursor which is reacted with at least one of silver formate or silver oxalate and a stabilizer in a suitable liquid medium The silver complex formed β The method of the present invention may further comprise the step of reacting silver citrate or silver oxalate with a stabilizer to form a silver complex. Desirably, the liquid medium is formed to print a silver precursor to the substrate. A liquid vehicle. After the reaction, the amount of liquid in the liquid medium can be reduced to increase the silver precursor concentration. For example, the liquid medium can be removed (e.g., by vacuum extraction), desirably' while maintaining a temperature below about. A particular method of the present invention is a method for producing a silver complex formed by reacting silver citrate or silver oxalate with an amine, the method comprising the steps of: causing tannic acid at a temperature below about o ° C Silver or silver oxalate is reacted with an amine in a suitable liquid medium. The present invention is also directed to a printer having a printable ink supply (e.g., a printable ink reservoir such as an ink cartridge), wherein the ink is used as the ink of the present invention. The invention further relates to an application material comprising a printing material, the 154912.doc 201211054 application material comprising a print product of a brush ink according to the invention. The present invention is also directed to a printed product of the printable ink of the present invention. The application material can be treated', e.g., exposed to a conductive component in the form of a fluid. Desirably, the conductive promoting component is an organic acid selected from the group consisting of oxalic acid and citric acid and combinations thereof. The present invention is directed to a material formed by sintering the ink composition after application of the ink composition of the present invention onto a substrate. A sintered material formed by an ink applied to a substrate which has been treated with a conductive component such as an acid is included in the present invention. A suitable acid is formic acid. Desirably, the material is sintered while in contact with the electrically conductive component. For example, the promoting component can be in the liquid phase or in the gas phase (including the vapor phase). For example, sintering may occur in the following conditions: the substrate to which the ink is applied is being sintered while being in a closed atmosphere having a gas-promoting conductive component. The conductive promoting component may be an organic acid selected from the group consisting of oxalic acid and formic acid, and combinations thereof. The invention extends to a device to which a conductive material is applied, wherein the conductive material is the product of the ink composition of the invention or a sintered material formed from the composition of the invention. The invention further relates to a method for sintering a applied silver material, wherein the silver material is a silver complex formed by a reaction of at least one of (4) a formic acid or silver oxalate, wherein the method comprises The step of sintering the applied silver material while in contact with the electrically conductive component is included. Desirably, the conductive promoting component is an organic acid selected from the group consisting of oxalic acid and acetic acid, and combinations thereof. The conductive promoting component can be in liquid form (eg, in a liquid medium). 1549丨 2.d〇c 201211054 The conductive component is intended to be in gaseous form (e.g., in a gaseous medium). The additional features and advantages of the present invention are described in the embodiments of the present invention and will be apparent from the embodiments and drawings. It will be readily apparent to those skilled in the art that the examples disclosed herein are merely representative of the generalized embodiments, and that other configurations and methods of the present invention are possible and are included in the present invention. Our invention is based on the stable chemical properties of Ag+ ions. It is well known that this readily available complex with an N donor ligand produces a compound having a coordination number in the range of 2 to 4. In particular, the amine forms a linear 2 valence complex of the type shown below.
r2〆 I; r3 \ —f 藉由在所要求之溶劑中將該胺以正確化學計量添加至適 宜銀鹽AgX來容易地製備錯合物。 銀前驅物溶液之製備 本發明之一個態樣提供一種所需要之前驅物化學性質， 且在此等實驗中為合意之胺前驅物化學性質。在此態樣R2〆 I; r3 \-f The complex is readily prepared by adding the amine to the appropriate silver salt AgX in the correct stoichiometric amount in the desired solvent. Preparation of Silver Precursor Solutions One aspect of the present invention provides a precursor chemical chemistry that is desirable and is desirable amine precursor chemistry in such experiments. In this aspect
的銀化合物之另一實例為草酸銀。 因為此等材料不可購 154912.doc 201211054 得’所以吾人描述作為本發明之部分的用於以高產率及純 度常規地製造該等材料之合成方法。 自在水溶液中之硝酸銀及甲酸鹽製備曱酸銀。最佳化學 計量為1:3，如下： 3NaHC02 + AgN03 — AgHC02 + NaN03 + 2NaHC02 曱酸銀在水中僅微溶且在混合時沈澱出溶液。曱酸銀為 介穩態化合物，且在低於1:2之任何化學計量下相當快地 分解成銀。超出1:3則未觀察到在產率上之任何改良。然 而’藉由將沈殿物載運至冷環境中（在或接近〇。〇）來實 質上改良產率且限制分解（基本為零）。典型製備如下。 將具有1.71 g(l〇 mmol)硝酸銀之溶液溶解於10 mi蒸館 水中且置於家用冰箱中或較佳置於冰浴中直至其平衡。類 似地’亦製備3.4 g曱酸鹽（30 mmol)之20 ml溶液。接著將 此等物質混合在一起，隨之乳白色沈澱形成。在致冷的同 時快速過濾及洗滌此乳白色沈澱（致冷有助於在使用之前 冷卻過濾、漏斗）〇藉由2x25 ml份之冰冷水，繼之以1 X25 mi 之冰冷乙醇來進行洗滌。80%之產率係基於硝酸銀之初始 量。剩餘銀（亦即，未恢復為曱酸銀固體）剩餘在滤液中， 此係由於曱酸銀甚至在冷水中亦為微溶的。此銀易於自該 濾液恢復，此係由於簡單地靜置其若干小時（或隔夜）造成 其還原成可容易地分離洗滌及循環利用之銀金屬。 甲酸銀感光，且在置於空氣中時會緩慢地變灰接著變 黑。此情形在較高溫度下加劇。出於此原因，未乾燥上文 製備之被乙醇潤濕之固體，較佳立即使用其來製造前驅物 154912.doc •11- 201211054 /今液。然而，將其（被乙醇潤濕）儲存於家用冷卻器中若干 週（在暗處）而無任何明顯分解係可能的。 若應避免顯著分解，則上文描述之前驅物溶液之自草酸 銀的製備並非小事-樁。甲酸銀與（例如）胺配位體之錯合 造成大量放熱。此情形可引發前驅物之過早分解，且明顯 必須避免此過早分解。開發一程序來僅避免任何分解。需 要具有儘可能高的載有銀之前驅物溶液，此係由於此情形 會在每個印刷週期沈積下更多銀且在溶劑蒸發及熱處理時 會最終導致更緻密的薄膜。然而，為避免歸因於放熱錯合 物形成反應所致之分解，需要保持系統儘可能稀以有助於 耗散熱量。另彳’再次需要在冷環境τ執行該方法，此係 再次由於此情形減輕來自放熱之熱量。開發以下程序，該 程序解決此等問題，下文展示該程序之梗概。 在家用冷;東n中置放含1() g乙醇之敞口燒杯達^干小時 以致平衡。接著添加使用上文描述之程序所製備的甲酸銀 (約1.2 g)且混合完全以將其分散。接著將此燒杯置回於該 冷凍器中且靜置1小時以致平衡。同時將—定量（2 8至3幻 之丁胺置於單獨燒杯中且允許平衡。接著將i 15 §經冷: 丁胺添加至醇類漿料。將其充分混合，且將其重新置⑽ 冷康器中。在約i小時至2小時之後’乳白色溶液變得澄 清。此刻現已製備出前驅物之稀溶液。 為濃縮前驅物（或去除溶劑），必需移除所有或部分乙 醇。可使用如在圖2中之經修改旋轉式汽化器來進行 作。該裝置具有冰浴及C〇2肼來維持前驅物之穩定。系 154912.doc •12- 201211054 在此配置中，用冰/水來填充旋轉式汽化器之水浴。不 使用内建式冷凝器。代替地，使用直插式乾冰耕來隔離乙 醇。該程序相對緩慢，且允許選擇移除乙醇中之全部或— 些。此情形允許簡單濃縮至銀之所需料或完全移除以調 配成另一溶劑組合。吾人之標準程序為移除足量乙醇以留 下具約20%銀（以重量計）之乙醇胺錯合物。 亦已使用草酸銀來進行本發明，草酸銀可產生具有與使 用曱酸銀形成且在14(TC退火時所形成之薄膜的導電性類 似之導電性的薄膜。藉由額外的酸處理（見下文），僅在 1 〇〇 C燒結且歷時1 〇分鐘達成相同位準之導電性。 可自在水溶液中之硝酸銀及二水合草酸來製備草酸銀 (亦如在圖8中所闡明）。例示性化學計量為2:3。 {COOH)2 ·2Η20 + AgN03 -> Ag2(C00)2 + HN03 + H20 將二水合草酸3〇 g溶解於35〇 ml水中。單獨地將3〇呂硝 酸銀溶解於120 ml水中。接著將硝酸銀溶液逐滴添加至草 酸溶液’同時攪拌草酸溶液❶當添加該草酸溶液時，草酸 銀立刻形成且白色沈澱立即顯現。在反應完成時，使用1 μηι濾紙過濾該溶液以移除水。用水洗滌濾出物兩次以移 除可溶組分及任何殘餘酸。接著進一步用乙醇洗滌濾出物 兩次。最後將濾餅壓碎成粉末狀態，且在室溫下將粉末真 二乾餘隔仪。因而獲得草酸銀之白色粉末。草酸銀之產率 為>95重量。/〇。 為製備前驅物墨水’將草酸銀粉末溶解於溶劑混合物 中。稱重出25 g草酸銀粉末且將其放入50 g乙醇中。在此 154912.doc 13 201211054 階段該白色粉末並未溶解且沈澱至底部。連續攪拌懸浮液 藉由冰洛來冷卻。接著將5〇 g異丙胺在約⑺分鐘内逐滴 添加至該懸浮液。另外，將12.5 g辛胺添加至該混合物。 草l銀開始/容解。接著將樣品自冰浴巾取出且繼續在室溫 下撥拌約2小時直至獲得淡黃色溶液為止。在室溫下陳放 "亥/合液達2週。在s亥陳放期間觀察到一些暗色沈澱。在陳 放之後，以9000轉每分來離心該溶液歷時i小時以移除固 體内含物。因而獲得淡黃色之透明墨水。該墨水在室溫下 穩疋達一個月以上。儘管如此，但由於草酸銀對光敏感， 所以建議於暗處儲存該墨水。 為評估導電性，吾人浸塗草酸銀墨水於玻璃載片上。吾 人簡單地將玻璃載片（25x25 mm)之一側面浸入在皮氏培養 皿中固持之墨水池中。立即在熱板上在14〇〇c下退火經塗 佈之載片歷時30分鐘。藉由標準4線探針來量測電阻（下文 詳細論述）。藉由Veeco白光干涉計來量測薄膜厚度（下文更 詳細論述）。在下文表格中列出代表性實例之結果。 樣本標號 退火 (°C) 退火(分 鐘） 電阻(Ω) 尺寸 (mmxmm) 厚度 (μιη) 電阻率 (Ω-cm) 1 140 30 0.0118 25x25 1.34 7.06χ10*6 2 140 30 0.0113 25x25 1.23 6.21xl〇·6 3 140 30 0.0090 25x25 2.17 8.72x1ο*6 接著開發一程序以降低草酸銀墨水之燒結溫度》低溫燒 結擴展了墨水至諸如塑膠及紙張之溫度敏感基板之施加。 吾人發現使用酸來促進燒結可將燒結溫度有效地降低至少 1 〇°C。另外，酸處理亦可加速燒結。在100°C或100°C以下 退火歷時僅10分鐘之後已發現薄膜高度導電。 -14 - 154912.docAnother example of a silver compound is silver oxalate. Since such materials are not commercially available, we have described a synthetic method for the conventional production of such materials in high yield and purity as part of the present invention. Silver citrate was prepared from silver nitrate and formate in aqueous solution. The optimum stoichiometry is 1:3, as follows: 3NaHC02 + AgN03 - AgHC02 + NaN03 + 2NaHC02 Silver citrate is only slightly soluble in water and precipitates as a solution when mixed. Silver citrate is a metastable compound and decomposes into silver quite rapidly at any stoichiometry below 1:2. No improvement in yield was observed beyond 1:3. However, the productivity is improved and the decomposition is reduced (substantially zero) by transporting the sediment to a cold environment (at or near 〇.〇). Typical preparations are as follows. A solution having 1.71 g (l〇 mmol) of silver nitrate was dissolved in 10 mi of steaming water and placed in a domestic refrigerator or preferably placed in an ice bath until it was equilibrated. Similarly, a solution of 3.4 g of decanoate (30 mmol) in 20 ml was prepared. These materials are then mixed together and a milky white precipitate is formed. The milky white precipitate was quickly filtered and washed while cooling (cooling aided in cooling the filter, funnel before use), and washed by 2 x 25 ml portions of ice-cold water followed by 1 x 25 mi of ice-cold ethanol. The 80% yield is based on the initial amount of silver nitrate. The remaining silver (i.e., not recovered to silver citrate solids) remains in the filtrate, which is also slightly soluble due to silver citrate even in cold water. This silver is easily recovered from the filtrate, which is reduced to a silver metal which can be easily separated for washing and recycling by simply standing it for several hours (or overnight). Silver formate is sensitive and will slowly gray out and then turn black when placed in air. This situation is exacerbated at higher temperatures. For this reason, the solids moistened with ethanol prepared above are not dried, and it is preferred to use them immediately to make a precursor 154912.doc •11-201211054/present solution. However, it was (sweeted by ethanol) stored in a domestic chiller for several weeks (in the dark) without any significant decomposition. The preparation of the precursor solution from the silver oxalate described above is not trivial-pile if significant decomposition should be avoided. The mismatch between silver formate and, for example, an amine ligand results in a large exotherm. This situation can lead to premature decomposition of the precursor and it is obvious that this premature decomposition must be avoided. Develop a program to avoid just any decomposition. It is desirable to have as high a silver-loaded precursor solution as possible, since this will deposit more silver per print cycle and eventually result in a denser film as the solvent evaporates and heats. However, in order to avoid decomposition due to the exothermic complex formation reaction, it is necessary to keep the system as thin as possible to help dissipate heat. In addition, the method needs to be performed again in the cold environment τ, which again reduces the heat from the heat release due to this situation. The following procedure was developed, which addresses these issues, and a summary of the program is shown below. In the household cold; placed in the east n with an open beaker containing 1 () g of ethanol for a dry hour to balance. Silver formate (about 1.2 g) prepared using the procedure described above was then added and mixed thoroughly to disperse it. The beaker was then placed back in the freezer and allowed to stand for 1 hour to equilibrate. At the same time - quantify (2 8 to 3 butyl butylamine in a separate beaker and allow for equilibration. Then add i 15 § cold: butylamine to the alcohol slurry. Mix it thoroughly and re-set it (10) In the chiller, the milky white solution became clear after about 1 hour to 2 hours. A dilute solution of the precursor has now been prepared. To concentrate the precursor (or remove the solvent), all or part of the ethanol must be removed. This was done using a modified rotary evaporator as in Figure 2. The device had an ice bath and C〇2肼 to maintain the stability of the precursor. 154912.doc •12- 201211054 In this configuration, use ice/water To fill the water bath of the rotary evaporator. No built-in condenser. Instead, use in-line dry ice tillage to isolate the ethanol. The procedure is relatively slow and allows the selection to remove all or some of the ethanol. This allows Simple concentrate to silver or complete removal to formulate another solvent combination. Our standard procedure is to remove enough ethanol to leave an ethanolamine complex with about 20% silver by weight. Has used silver oxalate to enter In the present invention, silver oxalate can produce a film having conductivity similar to that of silver formed using silver silicate and having a conductivity similar to that of the film formed at 14 (TC annealing). With additional acid treatment (see below), only 1 〇 〇C is sintered and achieves the same level of conductivity over a period of 1 minute. Silver oxalate can be prepared from silver nitrate and oxalic acid dihydrate in aqueous solution (also as illustrated in Figure 8). An exemplary stoichiometry is 2:3. {COOH)2 ·2Η20 + AgN03 -> Ag2(C00)2 + HN03 + H20 Dissolve 3〇g of oxalic acid dihydrate in 35〇ml of water. Dissolve 3〇L of silver nitrate in 120 ml of water separately. The solution was added dropwise to the oxalic acid solution while stirring the oxalic acid solution. When the oxalic acid solution was added, silver oxalate was formed immediately and the white precipitate appeared immediately. Upon completion of the reaction, the solution was filtered using 1 μηι filter paper to remove water. The product was discharged twice to remove the soluble component and any residual acid. Then the filtrate was washed twice with ethanol. Finally, the filter cake was crushed into a powder state, and the powder was dried at room temperature. Obtained A white powder of silver oxalate was obtained. The yield of silver oxalate was > 95 wt./〇. To prepare a precursor ink 'silver oxalate powder was dissolved in a solvent mixture. 25 g of silver oxalate powder was weighed and placed in 50 In the ethanol, the white powder is not dissolved and precipitates to the bottom at this stage 154912.doc 13 201211054. The continuously stirred suspension is cooled by ice. Then 5 〇g of isopropylamine is added dropwise to about (7) minutes. In addition, 12.5 g of octylamine was added to the mixture. The grass 1 silver was started/capacited. The sample was then taken out of the ice bath towel and the mixture was allowed to stir at room temperature for about 2 hours until a pale yellow solution was obtained. At room temperature, put "Hai/Hybrid for 2 weeks. Some dark precipitates were observed during the singering. After the aging, the solution was centrifuged at 9000 rpm for 1 hour to remove the solid content. Thus, a pale yellow transparent ink is obtained. The ink is stable for more than one month at room temperature. However, since silver oxalate is sensitive to light, it is recommended to store the ink in the dark. To evaluate conductivity, we dipped silver oxalate ink onto a glass slide. We simply immerse one side of the glass slide (25x25 mm) into the inkwell held in the Petri dish. Immediately on the hot plate, the coated slide was annealed at 14 ° C for 30 minutes. The resistance is measured by a standard 4-wire probe (discussed in detail below). Film thickness was measured by a Veeco white light interferometer (discussed in more detail below). The results of representative examples are listed in the table below. Sample label annealing (°C) Annealing (minutes) Resistance (Ω) Dimensions (mmxmm) Thickness (μιη) Resistivity (Ω-cm) 1 140 30 0.0118 25x25 1.34 7.06χ10*6 2 140 30 0.0113 25x25 1.23 6.21xl〇· 6 3 140 30 0.0090 25x25 2.17 8.72x1ο*6 A procedure was then developed to reduce the sintering temperature of silver oxalate inks. Low temperature sintering extends the application of ink to temperature sensitive substrates such as plastics and paper. We have found that the use of acid to promote sintering effectively reduces the sintering temperature by at least 1 〇 °C. In addition, acid treatment can also accelerate sintering. The film was found to be highly conductive after only 10 minutes of annealing at 100 ° C or below. -14 - 154912.doc
S 201211054 吾人開發兩個程序來降低草酸銀之燒結及增大燒結薄膜 之導電性.（1)用甲酸蒸氣來促進燒結；（2)用甲酸液體來 促進燒結。 以下為程序（1)之實例：在處於曱酸蒸氣飽和狀態之蒸 氣月二至中置放熱板。在此實例中，藉由在該腔室内使甲酸 沸騰來產生甲酸蒸氣。（亦可在腔室外產生曱酸蒸氣且（例 如）藉由諸如空氣之載氣來將該蒸氣饋入至腔室中。）將該 熱板之溫度控制在13〇°C。在用草酸銀墨水浸塗之後，在 無酸瘵氣之空氣中在另一熱板上在13〇它下乾燥該薄膜歷 時約2分鐘。接著將該薄膜轉移至在該腔室内之熱板且退 火歷時30分鐘。下文表格中之資料清楚地說明在具有曱酸 之環境中退火改良薄膜之導電性。 甲酸 電阻(Ω) 控制 無蒸氣 >0.13Ω* 實例 具蒸氣 0.032 *對於在此溫度下退火之薄膜，電阻並不一致，自〇13 Ω 至達到百萬歐姆之值。 以下為程序（2)之實例：將草酸銀墨水之薄膜浸塗於玻 璃載片上。接著在熱板上退火該薄膜。該熱板溫度為 13〇°C、120°C或l〇〇°C。退火時間為10分鐘、2〇分鐘或3〇 为鐘。將該薄膜移離該熱板，且將該薄膜冷卻至室溫。將 經冷卻薄膜浸入於甲酸液體中。最後再次在熱板上乾燥該 薄膜歷時2分鐘。下文表格中之資料再次說明曱酸促進薄 膜之燒結。電阻自在百萬歐姆之區域中的值降低至·2歐 154912.doc 15 201211054 姆之位$ $時，燒結溫度自14G<>C降低至13G°c，或甚至 100 C及100 C以下。退火時間自3〇分鐘降低至1〇分鐘或更 短0 退火 (°C) 退火時間 (分鐘） 用曱酸浸沒 在浸沒之後 乾燥Cc) 乾燥時間 (分錄、 電阻(Ω) 100 30 否 無 > 55M 100 30 100 2 0 035 100 20 是 100 02 0.055 100 10 〜 是 100 02 0.034 130 30 否 無 無 6M 130 10 130 6 0.018 銀薄膜之性質 上文描述之濃縮前驅物儘管未經調配以用於喷墨印刷， 但容易地㈣諸如玻璃之常見基板。此性質允許吾人使用 旋塗作為用於評估薄膜性質之快捷且便利之技術。將上文 製備之前驅物樣品旋塗於玻璃載片上，且接著隨後在 100 C及13G C之兩個溫度下加熱此等玻璃載片歷時1〇分 鐘。藉由標準4線法來量測經塗佈載片之電阻以消除接觸 電阻。4線量測系統由Lucas Labs 3〇2電阻率測試台S 201211054 We developed two procedures to reduce the sintering of silver oxalate and increase the electrical conductivity of the sintered film. (1) use formic acid vapor to promote sintering; (2) use formic acid liquid to promote sintering. The following is an example of the procedure (1): a hot plate is placed in the middle of the steam in the saturated state of the sulphuric acid vapor. In this example, formic acid vapor is produced by boiling formic acid in the chamber. (The citric acid vapor can also be generated outside the chamber and, for example, fed into the chamber by a carrier gas such as air.) The temperature of the hot plate is controlled at 13 °C. After dip coating with silver oxalate ink, the film was dried under 13 Torr on another hot plate in an acid free xenon atmosphere for about 2 minutes. The film was then transferred to a hot plate in the chamber and fired for 30 minutes. The information in the table below clearly illustrates the conductivity of the annealed modified film in a tannic acid environment. Formic acid resistance (Ω) control No vapors > 0.13 Ω * Example With vapor 0.032 * For films annealed at this temperature, the resistance is not uniform, from 〇 13 Ω to a value of one million ohms. The following is an example of the procedure (2): a film of silver oxalate ink is dip coated on a glass slide. The film is then annealed on a hot plate. The hot plate temperature is 13 ° C, 120 ° C or l ° ° C. The annealing time is 10 minutes, 2 minutes or 3 minutes. The film was removed from the hot plate and the film was cooled to room temperature. The cooled film was immersed in a formic acid liquid. Finally, the film was again dried on a hot plate for 2 minutes. The information in the table below again illustrates the sintering of the tannic acid promoting film. The resistance is reduced from the value in the area of one million ohms to 2 ohms. 154912.doc 15 201211054 When the position is $$, the sintering temperature is reduced from 14G<>C to 13G°c, or even below 100 C and 100 C. Annealing time reduced from 3 minutes to 1 minute or less 0 Annealing (°C) Annealing time (minutes) Immersion with tannic acid to dry after immersion Cc) Drying time (entry, resistance (Ω) 100 30 No No > 55M 100 30 100 2 0 035 100 20 is 100 02 0.055 100 10 〜100 02 0.034 130 30 No No 6M 130 10 130 6 0.018 Properties of silver film The concentrated precursor described above, although not formulated for use Inkjet printing, but easily (iv) a common substrate such as glass. This property allows us to use spin coating as a quick and convenient technique for evaluating the properties of the film. The above prepared precursor sample is spin coated onto a glass slide, and The glass slides were then heated at two temperatures of 100 C and 13 G C for 1 minute. The resistance of the coated slides was measured by a standard 4-wire method to eliminate contact resistance. 4-wire measurement system Resistivity test bench by Lucas Labs 3〇2
Signatone Corp，Gilroy，CA)及 Kehhley 2010 萬用錶 (Keithiey lnstruments Inc·，Cleveland，〇H)組成。接著在薄 膜中蝕刻出一條線以使得基板得以暴露且充當厚度量測之 基線。藉由Wyko ΝΤ9100光學測繪器（Veec〇Signatone Corp, Gilroy, CA) and Kehhley 2010 Multimeter (Keithiey lnstruments Inc., Cleveland, 〇H). A line is then etched into the film to expose the substrate and serve as a baseline for thickness measurement. By Wyko ΝΤ9100 Optical Mapper (Veec〇
Inc·，Plainview，NY)來量測薄膜相對於暴露基板的完整部 分之步高。在量測樣品（通常為長矩形）之尺寸之後，可按 ㈣，以計算電阻率，其中R為所量測之電阻，【為薄膜厚 度，且C〗為幾何校正因數。此程序允許對薄膜電阻率之相 154912.doc -16· 201211054 當準確的量測。在圖3中展示針對典型丁胺甲酸銀前驅物 之結果。 此工作之最顯著成果為在低溫下獲得高導電性薄膜（如 在圖4令展示）。據本發明之發明者所知，不存在可在接近 1 〇〇 C之任何概度下及/或在接近丨〇分鐘之任何時間中達成 次於10·5歐姆·厘米之任何其他印刷技術。該等薄膜雖然具 極佳電性質但仍有些粗糙。 該等結果相當不符直覺，此係因為較低溫度導致較佳薄 膜淡質{僅有較低電阻率且亦有較高薄膜密度（在 下製備之薄膜具有9χ1〇·6歐姆.厘米之電阻率）。在奈米粒 子之燒結中未觀察到此性質，且在先前技術組合物之材料/ 組合物中之任一者中亦未觀察到此性質。 此狀況之原因在現階段仍為值得思考之問題，然而，據 推斷，此原因源自溶劑（在此狀況中為乙醇）的相對低彿 點。 儘管前驅物化學性質及用於其製造之程序在低溫下且在 短時間中導致所要的低電阻率，但感覺此方法仍可進一步 挖掘。藉由理解自液體前驅物轉變至固體銀薄膜之機制之 視角’此源自對此等系統所進行之—些基礎工作。 、自最初始終咸信前驅物分解初始地伴隨銀奈米粒子之形 成而進订。k著分解繼續’此等個別粒子變大且接著彼此 合併且最終形成連接的燒結粒子之網路。 注意，在前驅物之分解期間不存在阻止剛剛形成的銀粒 子之生長及聚結的任何穩定劑/分散劑。 154912.doc •17- 201211054 不存在對於習知地與銀奈米粒子一起使用的穩定劑/分 散劑之類型的任何要求，且因此熟習此項技術者會省略此 要求。在任何情況下，熟習此項技術者將預期任何穩定劑/ 分散劑會因為其性質而不利地影響銀粒子之生長。 雖然如此，本發明之發明者仍決定添加特定穩定劑，且 驚奇地發現形成更合意之銀產物。 本發明之發明者添加已知充當穩定劑之辛胺。辛胺已知 為良好封端劑兼穩定劑’ ^已成功地用於製備穩^的銀奈 米粒子。 ' 向上文描述之溶液前驅物添加10%(以銀重量計）之辛 胺。將此材料如同先前旋塗至玻璃上，且應用相同熱處理 法（13(TC及10(rC歷時1〇分鐘）。如同.先前量測電阻及輪 廓。結果展示於圖5及圖6中。 結果 在100 C，吾人獲得約3倍塊體銀電阻率，同時在 130C，吾人獲得2倍塊體銀電阻率。假定在1〇分鐘内達成 :等數據，結果為出色的’且據本發明之發明者所知在先 則技術中不存在任何接近此良好結果之結果。 ^併入辛胺（不論其是否為奈米粒子穩定劑）已顯著地改變 薄膜性質。所得薄膜薄得多且平滑得多’該等性質進一步 為此項技術之具吸引力的特徵。顯見，該等薄膜相對於無 添加劑之彼等薄膜更加緻密，儘管未有結論性證據 證明已發生經由奈米結構的原位產生而可能的某種形式之 排序。 154912.doc -18- 201211054 圖7展示在玻璃上之分區銀薄膜（按上文描述利用曱酸銀 及辛胺製備）之SEM影像，且該等銀薄膜暴露於如下加熱 法中：左上10(TC加熱歷時1分鐘，右上i〇0°c加熱歷時1〇 分鐘’左下130°C加熱歷時1分鐘，且右下i30°CM熱歷時 1〇分鐘。該等SEM展示在1分鐘内，墨水形成奈米粒子。 在如此短之時間粒子已開始燒結在一起以形成連續導電性 網路。較長的退火時間（10分鐘）造成粒子完全融合在一起 且形成大的連續域。 °司包含」及詞「具有/包括」在本文中參考本發明使 用時用以指定所陳述特徵、整體、步驟或組件之存在但不 排除一或多個其他特徵、整體、步驟、組件或其群組之存 在或添加。 應瞭解’出於清晰起見而在單獨實施例之背景中描述的 本發明之某些特徵亦可在單一實施例中之以組合來提供。 相反’出於簡略起見而在單一實施例之背景中描述的本發 明之各種特徵亦可獨立地或以任何適宜子組合來提供。 【圖式簡單說明】 圖1為根據本發明之用於製備銀前驅物（曱酸）溶液之方 法的示意圖表示。 圖2為用於溶劑移除之經修改旋轉式汽化器之影像。 圖3為說明藉由曱酸銀墨水製備且在ι〇〇=退火之銀薄膜 的所置測輪廓及電性質（使用四線法量測電阻且藉此計算 出電阻率）之曲線圖（γ軸為以微米計之高度；X軸為以微米 計之掃描範圍）。 154912.doc -19· 201211054 圖4為說明使用甲酸銀墨水製備且在⑼^^燒結之銀薄膜 的所量測輪廊及電性質之曲卿抽為以微米計之高度； X軸為以微米計之掃描範圍）。 圖為說月使用包括胺之甲酸銀墨水製備且在⑽。C燒結 ▲薄膜的所量測輪廓及電阻率之曲線圖軸為以微米計 之同度，X軸為以微米計之掃描範圍）。 圖6為說明使用包括胺之甲酸銀墨水製備且在130t燒結 之銀薄膜的所量測輪廟及電阻率之曲線圖（Y抽為以微米計 之尚度，X軸為以微米計之掃猫範圍）。 圖7為在玻璃上的分區銀薄膜之一系列SEM(掃描電子顯 微鏡）影像，左上為l〇〇C歷時1分鐘，右上為1〇〇它歷時1〇 刀鐘，左下為130。〇歷時1分鐘，而右下為13〇〇c歷時1〇分 鐘。 圖8為製備草酸銀墨水之示意性表示。 154912.doc 20·Inc., Plainview, NY) measures the step height of the film relative to the exposed portion of the substrate. After measuring the size of the sample (usually a long rectangle), press (4) to calculate the resistivity, where R is the measured resistance, [is the film thickness, and C is the geometric correction factor. This procedure allows for accurate measurement of the film resistivity phase 154912.doc -16· 201211054. The results for a typical silver butyl amide precursor are shown in Figure 3. The most notable result of this work was the acquisition of highly conductive films at low temperatures (as shown in Figure 4). As far as the inventors of the present invention are aware, there are no other printing techniques that can reach less than 10·5 ohm·cm at any time close to 1 〇〇 C and/or at any time close to 丨〇 minutes. These films are somewhat rough despite their excellent electrical properties. These results are quite unintuitive, because the lower temperature results in better film quality {only lower resistivity and higher film density (the film prepared below has a resistivity of 9χ1〇·6 ohm.cm) . This property was not observed in the sintering of nanoparticles, and was not observed in any of the materials/compositions of prior art compositions. The reason for this situation remains a question worth pondering at this stage, however, it is inferred that this reason stems from the relatively low point of the solvent (ethanol in this case). Although the precursor chemistry and the procedure used for its manufacture result in the desired low resistivity at low temperatures and in a short period of time, it is felt that this method can be further excavated. By understanding the mechanism of the transition from a liquid precursor to a solid silver film, this stems from some of the basic work done by such systems. Since the beginning, the precursor decomposition has been initially ordered with the formation of silver nanoparticles. The decomposition continues [these individual particles become larger and then merge with each other and eventually form a network of connected sintered particles. Note that there is no stabilizer/dispersant that prevents the growth and coalescence of the newly formed silver particles during the decomposition of the precursor. 154912.doc • 17- 201211054 There are no requirements for the type of stabilizer/dispersant conventionally used with silver nanoparticles, and therefore those skilled in the art will omit this requirement. In any event, those skilled in the art will recognize that any stabilizer/dispersant will adversely affect the growth of silver particles due to their nature. Nonetheless, the inventors of the present invention have decided to add specific stabilizers and have surprisingly discovered the formation of more desirable silver products. The inventors of the present invention added octylamine known to act as a stabilizer. Octylamine is known to be a good blocking agent and stabilizer '^ has been successfully used to prepare stable silver nanoparticles. Add 10% (by weight of silver) of octylamine to the solution precursor described above. This material was spin-coated onto the glass as before, and the same heat treatment method was applied (13 (TC and 10 (rC for 1 minute). As before, the resistance and profile were measured. The results are shown in Figures 5 and 6. At 100 C, we obtained about 3 times the bulk silver resistivity, and at 130C, we obtained 2 times the bulk silver resistivity. Assume that it is achieved within 1 minute: equal data, the result is excellent' and according to the present invention It is known to the inventors that there are no results close to this good result in the prior art. ^Incorporation of octylamine (whether or not it is a nanoparticle stabilizer) has significantly altered the properties of the film. The resulting film is much thinner and smoother. Many of these properties are further attractive features of the technology. It is apparent that these films are more dense than their films without additives, although there is no conclusive evidence that in situ generation via nanostructures has occurred. And some sort of possible ordering. 154912.doc -18- 201211054 Figure 7 shows an SEM image of a partitioned silver film on a glass (prepared using silver citrate and octylamine as described above), and the silver films are exposed to In the following heating method: the upper left 10 (TC heating lasts 1 minute, the upper right i 〇 0 °c heating lasts 1 ' minutes 'lower left 130 ° C heating for 1 minute, and the lower right i30 ° CM heat lasts 1 〇 minutes. These SEM It is shown that within 1 minute, the ink forms nanoparticles. In such a short period of time, the particles have begun to sinter together to form a continuous conductive network. The longer annealing time (10 minutes) causes the particles to completely fuse together and form a large The continuation of the continuation of the present invention is intended to be used in the context of the present invention, and is used in the context of the present invention, but does not exclude one or more other features, integers, steps, The presence or addition of a component or a group thereof. It is to be understood that certain features of the invention are described in the context of a single The various features of the invention described in the context of a single embodiment may also be provided independently or in any suitable sub-combination. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is used in accordance with the present invention. A schematic representation of a method of preparing a silver precursor (tannic acid) solution. Figure 2 is an image of a modified rotary vaporizer for solvent removal. Figure 3 is an illustration of a silver silicate ink prepared by ITO = annealing A graph of the measured profile and electrical properties of a silver film (measured using a four-wire method and thereby calculating the resistivity) (the gamma axis is the height in microns; the X axis is the scan range in microns) 154912.doc -19· 201211054 Figure 4 is a diagram showing the measured rim and the electrical properties of the silver film prepared by using silver formate ink and sintered in silver. The height is in microns; the X axis is Scanning range of micrometers. The picture shows the monthly measurement using the amine formic acid silver ink and the measured profile and resistivity of the film sintered at (10) C. The axis of the graph is the same degree in micrometers, and the X-axis is Scanning range in micrometers). Figure 6 is a graph showing the measured wheel and resistivity of a silver film prepared by using a silver formate ink comprising an amine and sintered at 130t (Y pumping is in the order of micrometers, and X-axis is sweeping in micrometers). Cat range). Figure 7 is a series of SEM (Scanning Electron Microscope) images of a partitioned silver film on glass. The upper left is l〇〇C for 1 minute, the upper right is 1〇〇, it lasts 1〇 knife clock, and the lower left is 130. It lasted for 1 minute, while the lower right was 13〇〇c for 1 minute. Figure 8 is a schematic representation of the preparation of silver oxalate ink. 154912.doc 20·