201132794 六、發明說明： 【發明所屬之技術領域】 本發明有關製得含銀結構物之方法，有關包含藉由該 方法可製得之至少一種含銀結構物的電氣及電子產品，及 有關藉由該根據本發明之方法可獲得之含銀結構物的用途 【先前技術】 由於印刷技術使得能簡單且有效率製造廣泛各種不同 結構物，故而其係製造電子結構物（尤其是電路）的重要且 有效率方法。關於這方面，極關注用於製造電子結構物的 印刷方法。爲製造特定結構物（尤其是開關元件），以及爲 獲致各實例中所需之性質，需要電功能印刷墨液以獲得印 刷電子產品。 除了絕緣體及主動半導體材料系統之外，基本的其他 類別電子結構物爲導體。傳導率功能原則上可藉由碳黑或 石墨系統或導電性聚合物（例如PEDOT: PSS或聚苯胺）來 實現’但該等結構物之傳導性對許多應用而言絕對不足。 因此較佳情況係在必須達成低電阻或必須獲致具有高 傳導率之結構物之應用中使用金屬結構物。該等金屬更佳 係由銅或銀組成。 由於印刷系統之表面積因薄層之故而非常大，表面之 反應（例如氧化）扮演重要角色。氧化銀相較於其他氧化物（ -5- 201132794 諸如C u 0或A 12 Ο 3)傳導性非常好，因此對於銀層之傳導 性的減損程度較低。因此，由於銀系統即使在銀結構物表 面氧化之情況下仍保有高傳導率，故其特別適用於印刷導 體跡線。 在許多應用中，例如在RFID天線或太陽能電池電極 中，含銀粒子的銀糊劑係用以獲得含銀結構物。然而，該 等系統首先因粒子-粒子間電阻之故並非尤其具傳導性（僅 約元素銀之體積傳導率的約1 /1 0)，及該等系統其次因微 米大小粒子之故，對於在許多電元件（尤其是電晶體、二 極體及記憶體）中之用途而言太厚且太粗。 原則上，可使用奈米微粒系統代替以製造薄傳導層。 然而，粒子-粒子間電阻仍存在。該含銀奈米粒子之製造 及尤其是其在溶液中之安定化仍然極複雜。 因此替代者應爲化學銀化合物（具有共價性質之化合 物及鹽），此係由於可從彼製造之層的性質若未比奈米微 粒系統更佳，其應展現出至少相似之良好性質，以及相應 印刷墨液之製造遠較簡易且可以較簡易方式安定化之故。 然而，由於例如該膜形成性質對於發展連續扮演重要 角色，並非所有銀鹽或銀化合物都同樣適於製造電子結構 〇 例如’ K.F. Teng 及 R.W. Vest 於 IEEE Transactions on Components, Hybrids, and Manufacturing Technology (Vol_ 11，No. 3，1 98 8)中教示藉由印刷可熱轉化成銀之新 癸酸銀溶液來製造金屬結構。該熱轉化中之溫度影響亦由201132794 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a silver-containing structure, relating to electrical and electronic products comprising at least one silver-containing structure obtainable by the method, and related Use of the silver-containing structure obtainable by the method according to the invention [Prior Art] Since printing technology makes it possible to manufacture a wide variety of different structures simply and efficiently, it is important for the manufacture of electronic structures (especially circuits) And efficient methods. In this regard, great attention has been paid to printing methods for manufacturing electronic structures. In order to manufacture a particular structure (especially a switching element), and to achieve the desired properties in each example, an electrically functional ink is required to obtain a printed electronic product. In addition to insulators and active semiconductor material systems, the basic other classes of electronic structures are conductors. Conductivity functions can in principle be achieved by carbon black or graphite systems or conductive polymers (e.g. PEDOT: PSS or polyaniline), but the conductivity of such structures is absolutely insufficient for many applications. Therefore, it is preferred to use the metal structure in applications where low electrical resistance must be achieved or structures having high conductivity must be obtained. These metals are preferably composed of copper or silver. Since the surface area of the printing system is very large due to the thin layer, the reaction of the surface (e.g., oxidation) plays an important role. Silver oxide is very conductive compared to other oxides (-5-201132794 such as C u 0 or A 12 Ο 3), so the degree of impairment of the conductivity of the silver layer is low. Therefore, the silver system is particularly suitable for printing conductor traces because it retains high conductivity even in the case of oxidation of the surface of the silver structure. In many applications, such as in RFID antennas or solar cell electrodes, silver paste containing silver particles are used to obtain silver-containing structures. However, these systems are not particularly conductive due to particle-to-particle resistance (only about 1/1 0 of the volumetric conductivity of elemental silver), and the latter are due to micron-sized particles. Many electrical components (especially transistors, diodes, and memories) are too thick and too thick for use. In principle, a nanoparticle system can be used instead of to make a thin conductive layer. However, particle-to-particle resistance still exists. The manufacture of the silver-containing nanoparticles and, in particular, their stabilization in solution are still extremely complicated. The replacement should therefore be a chemical silver compound (a compound having a covalent nature and a salt) which exhibits at least similar good properties since the properties of the layer that can be made from it are not better than the nanoparticulate system, and The manufacture of the corresponding printing ink is much simpler and can be stabilized in a simpler manner. However, since, for example, the film forming properties play an important role in the development of continuous, not all silver salts or silver compounds are equally suitable for the manufacture of electronic structures such as 'KF Teng and RW Vest at IEEE Transactions on Components, Hybrids, and Manufacturing Technology (Vol_ 11, No. 3, 1 98 8) teaches the fabrication of metal structures by printing a solution of silver neodecanoate which can be thermally converted to silver. The temperature effect in this thermal conversion is also affected by
S -6 - 201132794 A.L. Dearden 等人進行硏究（^4&。1*〇111〇1.尺3卩丨<10〇1111111111· 2〇〇5, 26，3 15-3 18)。形成傳導層，但轉化所需之時間太長 (50或至少5分鐘）以致不可能在慣用印刷系統中施行而不 拖延整體程序。此外，可獲致之傳導率在許多情況下並不 充足。 以三氟醋酸銀爲底質之有機金屬墨液係由Kaydanova 等人於 Conference Paper NREL/CP-520-33594 中描述。 Curtis等人在NREL/CP-520-31020中描述特別是包含（1,5-環辛二烯）六氟乙醯丙酮銀之墨液。然而，該等墨液並未 形成令人滿意的結果。S -6 - 201132794 A.L. Dearden et al. conducted an investigation (^4&1*〇111〇1. 3 卩丨<10〇1111111111·2〇〇5, 26,3 15-3 18). The conductive layer is formed, but the time required for the conversion is too long (50 or at least 5 minutes) to be impossible to perform in a conventional printing system without delaying the overall procedure. In addition, the conductivity that can be obtained is not sufficient in many cases. An organometallic ink based on silver trifluoroacetate is described by Kaydanova et al. in Conference Paper NREL/CP-520-33594. Curtis et al., in NREL/CP-520-31020, describe inks comprising, in particular, (1,5-cyclooctadiene) hexafluoroacetamidine silver. However, these inks did not form satisfactory results.
Samsung Advanced Institute of Technology 於 Materials Science and Engineering(B 1 1 7 (2005), 1 1 - 1 6)中 描述一種將銀鹽與胺倂用之方法。爲了在表面上製造結構 化製造銀跡線，先將含胺之銀錯合物施加於該表面，然後 以UV光照射。然而’隨後該層必須與還原劑（諸如肼或氫 硼化鈉）反應以產生元素銀。因此，此處之缺點係使用反 應性高且危險的物質。然而，所形成層不具充分傳導率。 合成含銀層之其他方法係由 Bidoki等人於J. Mikromech. Microeng. 17 (2007)，967-974 中教示。Bidoki 等人描述使用以醋酸銀、乳酸銀、硝酸銀、碳酸酸銀 '氯 化銀或柳酸銀爲底質之含銀溶液，彼等在施加於表面之後 可以還原劑予以轉化。然而’如前文已提及，使用還原劑 不利。 最後，JP 10-312715 A教示藉由照射（較佳爲UV輻射 201132794 )從有機或無機銀化合物製造銀結構物。上述可使用之有 機銀化合物爲醋酸銀、乳酸銀、草酸銀、檸檬酸銀、丙烯 酸銀、酒石酸銀、麩胺酸銀、褐藻酸銀及葡萄糖酸銀。上 述之無機銀化合物爲硝酸銀。然而，形成之結構係呈坑口 形式且不適用於需要精密結構物之目的。此外，此處所述 之結構物的所形成傳導率未令人滿意。 【發明內容】 因此，本發明目的係提供以化學銀化合物爲基礎之方 法，其藉由可與慣用印刷系統（尤其是將可溶性銀化合物 轉化成銀的轉化時間短者）整合的操作可能重現製造具有 特別高傳導率之甚至非常精細的銀結構物。 藉由主要主張權項中所詳述之從至少一種化學銀化合 物製得含銀結構物的方法獲致該目的，該方法包括以下步 驟：a)提供基材，b)將含有該化學銀化合物之組成物施加 於該基材，c)隨意地乾燥塗覆有該組成物的該基材，及d) 將該基材上至少一部分的該含有化學銀化合物之組成物轉 化成含銀結構物，其特徵在於該化學銀化合物爲乳酸銀且 該轉化作用係藉由i)以選自電磁輻射及電子束的輻射照射 該基材上之待轉化的該含乳酸銀組成物部分，及ii)對整 體的該經塗覆基材供應熱能來進行。 應理解本發明內容中之含銀「結構物」意指藉由印刷 方法可獲得之任何含銀構造，即基本上（忽略所獲得塗層 之厚度）爲二維含銀構造（尤其是基材之平坦部分塗層及/或 201132794 基本上由複數個直線子結構物所構成的導體跡線）。應理 解「含銀」結構物意指在轉化後包含元素銀之結構物。 該含銀結構物較佳爲純銀結構物。該等結構物具有藉 由彼可獲致特別良好傳導率的優點。當含有該化學銀化合 物之組成物含有乳酸銀作爲導體的唯一導體前驅物時可獲 致純銀結構物。 用於本發明方法中之基材較佳爲玻璃、矽、二氧化矽 、金屬氧化物或過渡金屬氧化物、金屬或聚合物材料（尤 其是PI或PET)組成之基材。在該例中，含銀結構物可直 接施加於該基材表面或施加於至少部分塗覆基材的導體、 半導體及/或絕緣層。 該基材可以但不一定必須經預處理。然而爲了確保基 材的最適潤濕性，該基材應在施加該組成物之前例如藉由 電暈方法或化學方法（尤其是施加對應之適用底漆）來預處 理。 當該含有化學銀化合物之組成物包含10-30重量％之 乳酸銀，7 0 - 9 0重量％之溶劑及0 - 1重量％之界面活性劑時 可獲致最特別良好之傳導率。 亦已意外地發現，從乳酸銀之經加熱溶液形成的層展 現出特別良好的傳導率。 在該組成物中，可能使用一或多種溶劑，即該組成物 可含有一種溶劑或不同溶劑之混合物。可用於本發明方法 之調配物的溶劑較佳爲非質子性弱質子性溶劑，即選自非 質子性非極性溶劑，即烷類、經取代烷類、烯類、炔類、 -9 - 201132794 不具或具有脂族或芳族取代基之芳族化合物之群組；非質 子性極性溶劑，即醚類、芳族醚類 '經取代醚類、酯類、 酸酐類、酮類、三級胺類、硝基甲烷、DMF(二甲基甲醯 胺）、DMSO(二甲 DMSO(二甲亞颯）或碳酸丙二酯之群組； 及弱質子性溶劑，即醇類、一級胺類及二級胺類及甲醯胺 ，以及水。特佳之可用溶劑爲水、醇類以及甲苯、甲苯、 二甲苯、苯基甲基醚、1，3,5-三甲苯、正己烷、正庚烷、 三（3，6-二噁庚基）胺（TDA)、2-胺基甲基四氫呋喃、苯乙醚 、4-甲基苯基甲基醚、3-甲基苯基甲基醚、苯甲酸甲酯、 N-甲基-2-吡咯啶酮（NMP)、四氫萘、苯甲酸乙酯及二乙醚 。特佳之溶劑爲水、甲醇、乙醇、異丙醇、四氫呋喃醇、 第三丁醇及甲苯以及其混合物。 較適用且可用以獲致經改良表面潤濕性的界面活性劑 可以下列商品名取得：Tego® Wet 2 5 0、Tego® Wet 270、 Tego® Wet 505、Tego® Wet 260、Tego® Wet 2 8 0、Tego® Wet 510、Tego® Wet 265、Tego® Wet 500、Tego® Wet KL 245(均得自 Evonik Goldschmidt GmbH)及 BYK 340、BYK 3 45、8丫1<：347或8丫反348(後者均得自德國沢6861之8丫1^ Additives)。特佳者係使用可以商品名Tego® WET 505從 德國Essen之Evonik Goldschmidt GmbH獲得之醇烷氧基 化物。 該組成物特別有利之處係藉由係選自以下之塗布方法 施加：印刷法（尤其是快乾/凹版印刷、噴墨印刷、套版印 刷、數位套版印刷及網版印刷）、噴霧法、旋塗法（「旋轉A method for using a silver salt and an amine oxime is described by Samsung Advanced Institute of Technology in Materials Science and Engineering (B 1 17 (2005), 1 1 - 16). In order to fabricate a structured silver trace on the surface, an amine-containing silver complex is first applied to the surface and then irradiated with UV light. However, the layer must then be reacted with a reducing agent such as hydrazine or sodium borohydride to produce elemental silver. Therefore, the disadvantage here is the use of highly reactive and dangerous substances. However, the layer formed does not have sufficient conductivity. Other methods of synthesizing silver-containing layers are taught by Bidoki et al., J. Mikromech. Microeng. 17 (2007), 967-974. Bidoki et al. describe the use of silver-containing solutions based on silver acetate, silver lactate, silver nitrate, silver acetate silver chloride or silver sulphate, which can be converted by a reducing agent after application to the surface. However, as already mentioned, the use of a reducing agent is disadvantageous. Finally, JP 10-312715 A teaches the manufacture of silver structures from organic or inorganic silver compounds by irradiation, preferably UV radiation 201132794. The organic silver compounds which can be used as described above are silver acetate, silver lactate, silver oxalate, silver citrate, silver acrylate, silver tartrate, silver glutamate, silver alginate and silver gluconate. The inorganic silver compound described above is silver nitrate. However, the resulting structure is in the form of a pit and is not suitable for the purpose of requiring a delicate structure. Moreover, the resulting conductivity of the structures described herein is not satisfactory. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method based on a chemical silver compound which can be reproduced by an operation integrated with a conventional printing system, particularly a short conversion time for converting a soluble silver compound into silver. An even very fine silver structure with a particularly high conductivity is produced. This object is achieved by a process for producing a silver-containing structure from at least one chemical silver compound as detailed in the main claim, the method comprising the steps of: a) providing a substrate, b) containing the chemical silver compound a composition applied to the substrate, c) optionally drying the substrate coated with the composition, and d) converting at least a portion of the chemical silver compound-containing composition on the substrate to a silver-containing structure, Characterized in that the chemical silver compound is silver lactate and the conversion is performed by i) irradiating the substrate with the silver fluoride-containing composition to be converted on the substrate with radiation selected from electromagnetic radiation and electron beams, and ii) The entire coated substrate is supplied with thermal energy. It should be understood that the silver-containing "structure" in the context of the present invention means any silver-containing structure obtainable by a printing method, that is, substantially (ignoring the thickness of the obtained coating layer) is a two-dimensional silver-containing structure (especially a substrate). The flat portion of the coating and/or 201132794 is substantially a conductor trace formed by a plurality of linear substructures). It should be understood that the "silver-containing" structure means a structure containing elemental silver after conversion. The silver-containing structure is preferably a pure silver structure. These structures have the advantage that they can achieve particularly good conductivity. A pure silver structure can be obtained when the composition containing the chemical silver compound contains silver lactate as the only conductor precursor of the conductor. The substrate used in the process of the present invention is preferably a substrate composed of glass, ruthenium, ruthenium dioxide, metal oxide or transition metal oxide, metal or polymeric material (especially PI or PET). In this case, the silver-containing structure can be applied directly to the surface of the substrate or to the conductor, semiconductor and/or insulating layer of the at least partially coated substrate. The substrate may, but need not, be pretreated. However, in order to ensure optimum wettability of the substrate, the substrate should be pretreated prior to application of the composition, e.g., by corona or chemical methods, especially by applying a corresponding suitable primer. When the composition containing the chemical silver compound contains 10 to 30% by weight of silver lactate, 70 to 90% by weight of a solvent and 0 to 1% by weight of a surfactant, the most particularly good conductivity can be obtained. It has also been unexpectedly found that a layer formed from a heated solution of silver lactate exhibits particularly good conductivity. In the composition, it is possible to use one or more solvents, i.e., the composition may contain a solvent or a mixture of different solvents. The solvent which can be used in the formulation of the method of the invention is preferably an aprotic weak protic solvent selected from aprotic non-polar solvents, ie, alkanes, substituted alkanes, alkenes, alkynes, -9 - 201132794 Group of aromatic compounds having no or aliphatic or aromatic substituents; aprotic polar solvents, ie ethers, aromatic ethers, substituted ethers, esters, anhydrides, ketones, tertiary amines a group of nitromethane, DMF (dimethylformamide), DMSO (dimethyl DMSO (dimethyl hydrazine) or propylene carbonate; and weak protic solvents, ie, alcohols, primary amines and Secondary amines and formamide, and water. Particularly preferred solvents are water, alcohols and toluene, toluene, xylene, phenyl methyl ether, 1,3,5-trimethylbenzene, n-hexane, n-heptane , tris(3,6-dioxyl)amine (TDA), 2-aminomethyltetrahydrofuran, phenylethyl ether, 4-methylphenyl methyl ether, 3-methylphenyl methyl ether, benzoic acid Methyl ester, N-methyl-2-pyrrolidone (NMP), tetrahydronaphthalene, ethyl benzoate and diethyl ether. Particularly preferred solvents are water, methanol, ethanol, isopropanol, tetra Furanol, tert-butanol and toluene, and mixtures thereof. Surfactants which are suitable for use in obtaining improved surface wettability are available under the following trade names: Tego® Wet 2 5 0, Tego® Wet 270, Tego® Wet 505, Tego® Wet 260, Tego® Wet 280, Tego® Wet 510, Tego® Wet 265, Tego® Wet 500, Tego® Wet KL 245 (both from Evonik Goldschmidt GmbH) and BYK 340, BYK 3 45, 8丫1<:347 or 8丫反348 (the latter are all obtained from 8丫1^ Additives of Germany 6861). The best ones are the alcohols obtained from Evonik Goldschmidt GmbH of Essen, Germany under the trade name Tego® WET 505. The composition is particularly advantageous by application to a coating method selected from the group consisting of printing methods (especially fast drying/gravure printing, ink jet printing, pattern printing, digital offset printing, and screen printing). ), spray method, spin coating method ("rotation"
S -10- 201132794 塗布」）、浸塗法（「浸漬塗布」）及選自由彎液面塗布、狹 縫塗布、狹縫模具式塗布及淋幕式塗布。本發明所使用之 塗布法最佳爲印刷法。 在施加之後且在轉化之前，該經塗覆基材亦可額外經 乾燥。其基本上移除溶劑，且未在此早期階段將乳酸銀轉 化成元素銀。熟悉本技術之人士已習知用於該目的的對應 之方法及條件。此處之乾燥溫度通常不超過loot：。 在本情況下，該乳酸銀係藉由i)以選自電磁輻射及電 子束的輻射照射該基材上之待轉化的該含乳酸銀組成物部 分’及ii)對整體的該經塗覆基材供應熱能來轉化。 該熱能原則上可在照射之前、期間或之後供應。然而 ，於照射待轉化之該含乳酸銀組成物的部分之後供應熱能 獲致特佳之結果。 待轉化的該含乳酸銀組成物部分係以選自電磁輻射（ 較佳爲UV輻射、X射線或γ射線）及電子束的輻射照射。 最佳者爲UV輻射。其較佳係藉由使用汞蒸氣燈注入。 爲獲致特別良好之結果，輻射劑量應爲至少3 J/cm2 。在使用市售1 33 W/cm燈之例中其可例如於20秒內達成 具有特別適用於精細導體跡線之優點的最精細因而較 佳之結構物可藉由透過界定對應之結構的遮罩照射該至少 —部分的含有化學銀化合物之組成物來製造。就厚度爲至 少一微米的結構物而言，較佳係直接曝光方法’其中該遮 罩係直接位於介於輻射源與經塗覆基材之間的光束路徑中 -11 - 201132794 。爲獲得更精細結構物，較佳可能使用縮小光學器件，尤 其是透鏡系統或鏡光學器件，藉由該縮小光學器件可在該 經塗覆表面上獲得該遮罩的縮小影像。該目的之對應設備 及方法已爲熟悉本技術之人士所知且經常稱爲微影術。 熱能可藉由熟悉本技術之人士習知之方法供應，例如 使用熱空氣、熱板、IR輻射或微波處理。在進行照射可獲 致之最終傳導率不受轉化所使用之溫度影響。然而，所使 用之溫度愈高，則更迅速達到可獲致之最終傳導率。爲了 在迅速時間內（不多於供應熱能1 0分鐘）達到可獲致之最終 傳導率，該經塗覆基材應加熱至至少！ 60 °C。 除了克服已提及的缺點之外，本發明方法另外具有在 僅一部分含有該化學銀化合物之組成物係在該基材上轉化 成含銀結構物，且因此僅該部分經照射，該未經照射部分 可簡單地使用適當溶劑洗掉而去除。原則上，由於表面上 包含未轉化乳酸銀之該部分層不具在電子應用中會特別麻 煩的充分傳導率，故此並非必要。然而，爲獲致電子應用 的特別良好導體跡線，基材表面上之未反應乳酸銀較佳可 以適當溶劑（諸如水或上述有機溶劑）洗掉。特佳係使用水 作爲該溶劑。 本發明另外提供電氣或電子產物，其可藉由本發明方 法獲得且包含基材及至少一種藉由本發明方法所施加之銀 結構物。如前文已述，此種基材較佳爲玻璃、矽、二氧化 矽、金屬氧化物或過渡金屬氧化物、金屬或聚合物材料（ 尤其是PI或PET)之基材。該含銀結構物可直接施加於該S -10- 201132794 Coating"), dip coating method ("dip coating"), and selection from meniscus coating, slit coating, slit die coating, and curtain coating. The coating method used in the present invention is preferably a printing method. The coated substrate may also be additionally dried after application and prior to conversion. It essentially removes the solvent and does not convert silver lactate to elemental silver at this early stage. Corresponding methods and conditions for this purpose are well known to those skilled in the art. The drying temperature here usually does not exceed the loot:. In the present case, the silver lactic acid is coated on the whole by i) irradiating the silver-containing silver-containing composition portion 'and ii) to be converted on the substrate with radiation selected from electromagnetic radiation and electron beams. The substrate supplies thermal energy for conversion. This thermal energy can in principle be supplied before, during or after the irradiation. However, the supply of thermal energy after irradiation of the portion of the silver lactate-containing composition to be converted is particularly excellent. The portion of the silver-containing lactic acid composition to be converted is irradiated with radiation selected from electromagnetic radiation (preferably UV radiation, X-ray or gamma ray) and an electron beam. The best is UV radiation. It is preferably injected by using a mercury vapor lamp. For particularly good results, the radiation dose should be at least 3 J/cm2. In the case of using a commercially available 1 33 W/cm lamp, it is possible to achieve, for example, within 20 seconds, the finest and thus preferred structure having the advantages particularly suitable for fine conductor traces by passing through a mask defining the corresponding structure It is produced by irradiating the at least part of the composition containing the chemical silver compound. For structures having a thickness of at least one micron, a direct exposure method is preferred wherein the mask is located directly in the beam path between the radiation source and the coated substrate -11 - 201132794 . In order to obtain a finer structure, it is preferred to use a reduction optic, in particular a lens system or mirror optics, by which a reduced image of the mask can be obtained on the coated surface. Corresponding devices and methods for this purpose are known to those skilled in the art and are often referred to as lithography. Thermal energy can be supplied by methods well known to those skilled in the art, such as using hot air, hot plates, IR radiation or microwave treatment. The final conductivity that can be achieved by irradiation is not affected by the temperature used for the conversion. However, the higher the temperature used, the faster the ultimate conductivity can be achieved. In order to achieve the ultimate conductivity that can be achieved in a fast time (no more than 10 minutes of heat supply), the coated substrate should be heated to at least! 60 °C. In addition to overcoming the disadvantages already mentioned, the method according to the invention additionally has a composition in which only a part of the chemical silver compound is contained on the substrate and converted into a silver-containing structure, and therefore only the portion is irradiated, which is not The irradiated portion can be removed simply by washing it off with a suitable solvent. In principle, this portion of the layer containing unconverted silver lactate on the surface does not have sufficient conductivity which is particularly troublesome in electronic applications, and thus is not necessary. However, in order to obtain particularly good conductor traces for electronic applications, the unreacted silver lactate on the surface of the substrate is preferably washed away with a suitable solvent such as water or the above organic solvent. Tetra uses water as the solvent. The invention further provides an electrical or electronic product obtainable by the process of the invention and comprising a substrate and at least one silver structure applied by the method of the invention. As already mentioned above, such a substrate is preferably a substrate of glass, ruthenium, ruthenium dioxide, metal oxide or transition metal oxide, metal or polymeric material (especially PI or PET). The silver-containing structure can be directly applied to the
S -12- 201132794 基材表面或施加於至少部分塗覆基材的導體、半導體及/ 或絕緣層。將體會該電氣或電子產物不必包含該含銀結構 物作爲最後施加的最上層塗層，但同樣地可在施加該含銀 結構物之後至少部分地塗覆以至少一種導體、半導體及/ 或絕緣層。 本發明另外提供藉由本發明之方法所製造之含銀結構 物的用途，用於製造電子組件，尤其是RFID標籤、電晶 體、二極體、記憶體、顯示器及感應器。 以下實例詳細說明本發明主題且其本身不具限制效果 【實施方式】 實施例 實施例1 藉由旋塗將15 %之均勻濃度的銀鹽溶液（二甲苯中之 新癸酸銀、水中之乳酸銀）施加於玻璃基材，且在下表所 指定之條件下轉化以獲致同樣於下表提出之傳導率。 新癸 酸銀 乳画 虔銀 傳導率 fS/cml 熱轉化 時間 傳導率 fS/cml 熱轉化 時間 僅使用UV輻射 (15 J/cm2) 無傳導層 - 50 畢 僅熱處理(160°C) 83 000 100 000 30分鐘 60分鐘 0.5 30分鐘 UV 輻射(15 J/cm2) 然後熱處理(160°) 17 000 63 000 20分鐘 110分鐘 140 000 20分鐘 -13- 201132794 與對應之新癸酸銀溶液對照，因此可能藉由UV輻射 與隨後之熱能的組合將乳酸銀溶液轉化成具有特別高傳導 率的傳導結構物。 若有任何在熱處理後未進行UV處理之僅具低傳導率 的乳酸銀，亦關注其應用。 實施例2 藉由添加氧化銀（德國Seelze之Riedl de HSen)至溶解 於水中之乳酸（德國Seelze之Sigma Aldrich)來合成乳酸 銀》藉由過濾移除未轉化氧化銀。將水蒸發且在3 5 °C於減 壓下乾燥該乳酸銀。 在3 5 °C下將所獲得之物質用以製成1 7重量％之乳酸 銀水溶液。藉由每千份添加1份界面活性劑（德國Essen之 Tego Wet 505, Evonik Goldschmidt GmbH)來降低該溶液之 表面能，以獲致基材之較佳潤濕作用。 在旋塗步驟之前，通過疏水性0.4 5 μπι PVDF過濾器（ 德國 Schwalbach 之 Millipore Millex HV PVDF)過爐該溶 液。 旋塗係使用以下參數進行：1)在2秒內加速至7 5 0 rpm ; 2)在750 rpm旋轉20秒；3)在5秒內減速至0 rpm 。在熱烘焙之後，以表面測平儀（KLA Tencor，San Jose/CA，USA, P15)測定該層厚度。獲致1 00- 1 20 nm之層 厚度。 以UV光照射係以市售汞蒸氣燈（133 W/cm)在UV帶 -14-S -12- 201132794 Substrate surface or conductor, semiconductor and/or insulating layer applied to at least partially coated substrate. It will be appreciated that the electrical or electronic product does not necessarily comprise the silver-containing structure as the last applied topmost coating, but may likewise be at least partially coated with at least one conductor, semiconductor and/or insulation after application of the silver-containing structure. Floor. The invention further provides the use of a silver-containing structure produced by the method of the invention for the manufacture of electronic components, particularly RFID tags, electro-crystals, diodes, memories, displays and inductors. The following examples illustrate the subject matter of the present invention and have no limiting effect per se. [Embodiment] Example 1 A silver salt solution of 15% uniform concentration (silver neodecanoate in xylene, silver lactate in water) by spin coating Applied to a glass substrate and converted under the conditions specified in the table below to achieve conductivity as also presented in the table below. Neodymite silver emulsion 虔 silver conductivity fS/cml thermal conversion time conductivity fS/cml thermal conversion time using only UV radiation (15 J/cm2) non-conducting layer - 50 only heat treatment (160 ° C) 83 000 100 000 30 minutes 60 minutes 0.5 30 minutes UV radiation (15 J/cm2) and then heat treatment (160°) 17 000 63 000 20 minutes 110 minutes 140 000 20 minutes-13- 201132794 Compared with the corresponding silver neodecanoate solution, it is possible The silver lactate solution is converted to a conductive structure having a particularly high conductivity by a combination of UV radiation and subsequent thermal energy. If there is any low-permeability silver lactate that has not been UV treated after heat treatment, it is also concerned with its application. Example 2 Undeformed silver oxide was removed by filtration by adding silver oxide (Riedl de HSen, Seelze, Germany) to lactic acid dissolved in water (Sigma Aldrich, Seelze, Germany). The water was evaporated and the silver lactate was dried under reduced pressure at 35 °C. The obtained material was used to make a 17% by weight aqueous solution of silver lactic acid at 35 °C. The surface energy of the solution was reduced by adding 1 part of a surfactant (Tego Wet 505, Evonik Goldschmidt GmbH, Essen, Germany) per thousand to achieve a better wetting of the substrate. The solution was passed through a hydrophobic 0.45 μπι PVDF filter (millipore Millex HV PVDF from Schwalbach, Germany) prior to the spin coating step. Spin coating was performed using the following parameters: 1) Acceleration to 7500 rpm in 2 seconds; 2) 20 seconds rotation at 750 rpm; 3) Deceleration to 0 rpm in 5 seconds. After hot baking, the layer thickness was measured with a surface leveler (KLA Tencor, San Jose/CA, USA, P15). A layer thickness of 1 00 - 1 20 nm is obtained. UV light is irradiated with a commercially available mercury vapor lamp (133 W/cm) in the UV belt -14-
S 201132794 系統（UV-Tech Silberberger + Co, Stuttgart，Model 6019) 中進行。所使用劑量介於〇與1 5 J/cm2之間。 該UV劑量係以得自EIT(Pfungstadt)之UV定位盤， 同時考慮到UVA' UVB及UVC光（波長230-390 nm)而決 定。 然後，該等膜係在精確熱板（PrSzitherm PZ28-2，Harry Gestigkeit，Diisseldorf)上在介於 120 與 220°C(尤其是 140 、160及180 °C)之不同設定溫度下烘焙。 以安裝在熱板上方且連接至電源電錶（型號 2400, Keithley Instruments，Cleveland/Ohio, USA)之四點測量頭 (型號 SP4-62-0 8 5-TBY, Sel-Tek，Motherwell, UK)進行即 時傳導率測量。 結果= 在恆溫下供應熱能形成之乳酸銀膜的傳導率取決於 UV劑量及照射時間。最適結果（即，在短時間內有充足傳 導率）可在至少3 J/cm2之照射劑量下於1 60°獲致（參考圖 1 )。 在恆定UV劑量（15 J/cm2)下，藉由至少160°C之溫度 可在足夠短時間內獲致最適傳導率（參考圖2) ° 藉由適當選擇性溫度及UV強度，如此可整合該方法 與慣用印刷方法。 實施例3 -15- 201132794 有機場效電晶體係藉由在n型摻雜矽晶圓上塗覆乳酸 銀建構，所需之結構物係使用遮罩藉由U V帶系統曝光’ 且以水洗掉未顯影之區域。該結構物於熱轉化之後的傳導 率爲約2歐姆/方形’且該兩個指狀結構物（源極及汲極）係 電絕緣。 從5%氯仿溶液旋塗聚-3-己基噻吩（Sepiolid P100, BASF，Ludwigshafen)且在黃光室中予以分析。該電晶體之 通道長度爲17〇μιη。長寬比爲150μπι(參考圖3)。 藉由透過光罩選擇性曝光，製造源極-汲極結構物， 從該等結構物可能建構薄膜電晶體。 【圖式簡單說明】 圖1顯示在160°C不同的UV劑量下之乳酸銀的傳導 率圖。 圖2顯示在恆定UV劑量（1 5 J/cm2)及不同溫度下之傳 導率圖。 圖3顯示由選擇性曝光及清洗之後的乳酸銀所組成之 電晶體的指狀結構物。S 201132794 system (UV-Tech Silberberger + Co, Stuttgart, Model 6019) was carried out. The dose used is between 〇 and 15 J/cm2. The UV dose was determined by UV positioning discs from EIT (Pfungstadt), taking into account UVA' UVB and UVC light (wavelength 230-390 nm). The films were then baked on a precision hot plate (PrSzitherm PZ28-2, Harry Gestigkeit, Diissseldorf) at different set temperatures between 120 and 220 ° C (especially 140, 160 and 180 ° C). Performed with a four-point measuring head (model SP4-62-0 8 5-TBY, Sel-Tek, Motherwell, UK) mounted above the hot plate and connected to a power meter (Model 2400, Keithley Instruments, Cleveland/Ohio, USA) Instant conductivity measurement. Result = The conductivity of the silver lactate film formed by supplying heat at a constant temperature depends on the UV dose and the irradiation time. The optimum result (i.e., sufficient conductivity in a short period of time) can be obtained at 1 60° at an irradiation dose of at least 3 J/cm 2 (refer to Fig. 1). At a constant UV dose (15 J/cm2), the optimum conductivity can be obtained in a sufficiently short time by a temperature of at least 160 ° C (refer to Figure 2). By combining the appropriate temperature and UV intensity, this can be integrated. Method and conventional printing method. Example 3 -15- 201132794 An airport effect cell system is coated with a silver lactate on an n-type doped germanium wafer, and the desired structure is exposed by a UV tape system using a mask and washed away with water. Undeveloped area. The structure has a conductivity of about 2 ohms/square after thermal conversion and the two finger structures (source and drain) are electrically insulated. Poly-3-hexylthiophene (Sepiolid P100, BASF, Ludwigshafen) was spin-coated from a 5% chloroform solution and analyzed in a yellow light chamber. The channel length of the transistor is 17 〇 μιη. The aspect ratio is 150 μm (refer to Fig. 3). Source-drain structures are fabricated by selective exposure through a reticle from which thin film transistors may be constructed. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the conductivity of silver lactate at different UV doses at 160 °C. Figure 2 shows a plot of conductivity at a constant UV dose (15 J/cm2) and at different temperatures. Fig. 3 shows a finger structure of a crystal crystal composed of silver lactate after selective exposure and cleaning.
S -16-S -16-