TWI527821B - 銀化合物、銀墨水及可撓式基板之噴印方法 - Google Patents
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Description
本發明係關於一種銀化合物,特別是關於一種以銀錯合物做為前驅物之銀墨水及其應用於可撓式基板之噴印方法。
在積體電路(ICs)的製造中,以往是使用電鍍及蝕刻的傳統製程,由於其伴隨著微影(Lithography)處理,需藉由複雜且精準的堆疊電路層來形成電路,因此在成本及時間的耗費較高。相反地,直接在基板上噴印具有導電特性的金屬薄膜,以加熱燒結來形成電路圖案的方式,製程簡單且成本低,故而非常具有其發展潛力。
銀墨水是在噴印製程中經常被使用的噴印墨水。在先前技術中,形成導電性銀多以高溫加熱還原的方式進行,且多應用在硬性矽基材上,而硬性矽基材有不可繞曲之缺點。然而,若應用於可撓式基板的電路製程中,則因可撓式基板的耐熱性而需要考慮後續加熱燒結形成電路的溫度是否適宜。例如,聚醯亞胺(PI,polyimide)軟基材依其聚合程度最高可耐250℃~300℃。
在先前技術Polyhedron.2002,21,1289-1297與J.Mater.Chem.,1999,9,1771-1780中提出利用銀單邊接2,2,6,6-四甲基-3,5-庚二酮酸(簡稱TMHD,2,2,6,6-tetramethyl-3,5-heptanedionato)或接類似結構(簡稱HFAC,1,1,1,5,5,5-Hexafluoroacetylacetone)的錯合物,此類錯合物可被使用在化學氣相沉積,表示其具有低溫裂解的特性,但HFAC因包含鹵素氟之官能基而具有汙染毒性,並不適合在目前環保訴求之下使用。此外,先前技術中的銀錯合物的缺點是其結構中在另一端接上其他較大的官能基,因
此導致難以裂解而無法測量電阻或是具有較差的電阻。
故,有必要提供一種銀化合物,在低溫容易裂解而形成具有優良導電性的金屬薄膜,以解決習用技術所存在的問題。
本發明之主要目的在於提供一種銀化合物,其係利用銀離子與2,2,6,6-四甲基-3,5-庚二酮酸及二乙烯三胺形成銀錯合物,是一種環保的化合物,其能夠在低溫裂解,適合於應用在噴墨印刷的銀墨水中。
本發明之次要目的在於提供一種銀墨水,其係利用上述銀化合物調配而成,在低溫燒結後可將銀離子還原成銀金屬,應用於大尺寸的電子元件的噴印製程中可降低成本及時間的耗費,並形成具有優良導電性的導電圖案。
為達上述之目的,本發明的一實施例提供一種銀化合物,其結構如下式(I):
本發明的另一實施例提供一種銀墨水,用以在一可撓式基板上形成一導電圖案,該銀墨水包含如上所述之銀化合物、正己胺以及一增稠劑。
在本發明之一實施例中,該增稠劑為乙基纖維素。
在本發明之一實施例中,該銀墨水係以旋轉塗佈方式塗佈於該可撓式基板上。
在本發明之一實施例中,該銀化合物、正己胺以及該增稠劑的重量比例為60:39:1。
在本發明之一實施例中,該銀墨水係以噴印方式塗佈於該可撓式基板上。
在本發明之一實施例中,該銀化合物、正己胺以及該增稠劑
的重量比例為45:54:1。
在本發明之一實施例中,該可撓式基板的材質係選自聚醯亞胺、聚醚碸、聚對苯二甲酸乙二酯或軟性銅箔。
本發明的再一實施例提供一種可撓式基板的噴印方法,其包含步驟:加熱該可撓式基板至60℃;噴印如上所述之銀墨水於該可撓式基板上,以形成一導電圖案;以及在空氣中繼續加熱至一預定溫度,使該銀化合物還原,以形成銀的金屬薄膜。
在本發明之一實施例中,該可撓式基板的材質係選自聚醯亞胺、聚醚碸、聚對苯二甲酸乙二酯或軟性銅箔。
在本發明之一實施例中,該預定溫度介於150至250℃。
在本發明之一實施例中,該銀墨水係藉由旋轉塗佈或壓電式噴印方式噴印於該可撓式基板上。
為了讓本發明之上述及其他目的、特徵、優點能更明顯易懂,下文將特舉本發明較佳實施例,作詳細說明如下。
本發明第一實施例係提供一種銀化合物,其主要結構如下式(I):
如上式(I)所示,為銀離子(Ag+)與2,2,6,6-四甲基-3,5-庚二酮酸(簡稱TMHD)及二乙烯三胺(簡稱DIEN)所共同形成之銀的錯合物[Ag(DIEN)](TMHD)。根據本發明一實施例之銀化合物[Ag(DIEN)](TMHD)具有可在較低的溫度進行裂解的配位基,其加熱還原後所生成的銀金屬薄
膜經由電性測量得到優秀的導電性,其導電率為4.62×10-6歐姆公分(Ωcm),若經過噴印處理後導電率為7.44×10-6歐姆公分,同時具有良好的導電性及更接近一般銀塊材的電阻值。
再者,本發明之銀化合物[Ag(DIEN)](TMHD)的合成流程如下:
在本發明一實施例中,首先以3.36克(20毫莫耳)的硝酸銀溶於1.12毫升之乙腈及20毫升甲醇的混合溶劑中,維持在0℃的冰浴下,加入4.4毫升(20毫莫耳)TMHD配位基/2.8毫升(20毫莫耳)三乙胺/20毫升甲醇的預先混合液,在0℃的冰浴下攪拌反應30分鐘,接著快速抽氣過濾取得Ag(TMHD)之白色固體。將所取得之白色固體抽乾溶劑,秤重後保存於通氮氣的三頸瓶中,然後置於0℃的冰浴下打入20毫升的甲苯並使其攪拌,接著再打入等莫耳數當量的DIEN液體一起攪拌,一個小時後將多餘的溶劑以真空抽取去除,得到一白色固體即為銀化合物[Ag(DIEN)](TMHD),其產率約88%。
本發明第二實施例係提供一種銀墨水,其係包含如式(I)結構之銀化合物,且另包含正己胺以及一增稠劑。
其中,正己胺係用作為有機溶劑,可使大量的式(I)之銀化合物溶解於此有機溶劑中,藉以提高噴墨的銀濃度。此外,本發明第二實施例之銀墨水所添加之該增稠劑,可例如為乙基纖維素,係用來調整該銀墨水整體的黏度,以利於配合噴印機台產生最佳的噴印性質。
根據本發明第二實施例之銀墨水,較佳係可應用於可撓式基板的電路噴印及製作方法中。其中,該可撓式基板可例如是超薄玻璃基板、金屬基板或塑料基板,而最常被應用於半導體電子元件的塑料基板中,其材質可例如是聚醯亞胺(PI,polyimide)、聚醚碸(PES,Polyethersulfone)或聚對苯二甲酸乙二酯(PET,Poly(Ethylene Terephthalate))等等,金屬基板的材質可例如是軟性銅箔基板。該銀墨水係以旋轉塗佈方式塗佈於該可撓式基板上,當該銀墨水作為旋轉塗佈(spin coating)配方時,該銀化合物、正己胺以及該增稠劑的重量比例為60:39:1。若該銀墨水以噴印(spraying)方式塗佈於該可撓式基板上時,該銀化合物、正己胺以及該增稠劑的重量比例為45:54:1。
本發明第三實施例係提供一種可撓式基板的噴印方法,其大致包含步驟:(S1)、加熱該可撓式基板至60℃;(S2)、噴印上述第二實施例中之銀墨水於該可撓式基板上,以形成一導電圖案;以及(S3)、在空氣中繼續加熱至一預定溫度,使該銀化合物還原形成銀的金屬薄膜。
在本實施例中,該銀墨水係包含如式(I)結構之銀化合物,且另包含正己胺以及一增稠劑。
再者,在噴印銀墨水之前加熱該可撓式基板的步驟(S1)可使得銀墨水之咖啡環效應降低,因而可以形成較為均勻的導電圖案,其導電率7.44×10-6歐姆公分(Ωcm),同時具有良好的導電性及更接近一般銀塊材的電阻值。該可撓式基板的材質可例如為聚醯亞胺、聚醚碸、聚對苯二甲酸乙二酯或軟性銅箔。該預定溫度係介於150至250℃,可例如是200℃或230℃,然不限於此。該銀墨水係可藉由旋轉塗佈或壓電式噴印方式噴印於該可撓式基板上。該導電圖案可為任意形狀之電路佈局。
依照本發明所提供之銀化合物、銀墨水及可撓式基板之噴印方法,並且所調配之銀墨水在熱處理後具有接近一般銀塊材的電阻率,應用於可撓式基板之噴印製程中,能夠降低電路燒結的溫度,並提高製程之可靠度。此外,以低溫加熱的方式來獲得導電性優良的金屬線路,可以克服目前高溫加熱還原在可撓性基材上的限制,是一種容易應用且快速便利的低成本方法,省去了在蝕刻製程上所花費的時間與多種化學品的汙染,可應用的產品非常廣泛,所有需要導電線路的元件皆可適用。另外,也可應用為晶圓微小電路缺陷的修復,使得其不良率降低。
雖然本發明已以較佳實施例揭露,然其並非用以限制本發明,任何熟習此項技藝之人士,在不脫離本發明之精神和範圍內,當可作各種更動與修飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
Claims (10)
- 一種銀化合物,其結構如下式(I):
- 一種銀墨水,其包含如申請專利範圍第1項所述之銀化合物、正己胺以及一增稠劑。
- 如申請專利範圍第2項所述之銀墨水,其中該增稠劑為乙基纖維素。
- 如申請專利範圍第2項所述之銀墨水,其中該銀化合物、正己胺以及該增稠劑的重量比例為60:39:1。
- 如申請專利範圍第2項所述之銀墨水,其中該銀化合物、正己胺以及該增稠劑的重量比例為45:54:1。
- 如申請專利範圍第2項所述之銀墨水,其中該可撓式基板的材質係選自聚醯亞胺、聚醚碸、聚對苯二甲酸乙二酯或軟性銅箔。
- 一種可撓式基板的噴印方法,其包含步驟:加熱該可撓式基板至60℃;噴印如申請專利範圍第2項所述之銀墨水於該可撓式基板上,以形成一導電圖案;以及在空氣中繼續加熱至一預定溫度,使該銀化合物還原形成銀的金屬薄膜。
- 如申請專利範圍第7項所述之可撓式基板的噴印方法,其中 該可撓式基板的材質係選自聚醯亞胺、聚醚碸、聚對苯二甲酸乙二酯或軟性銅箔。
- 如申請專利範圍第7項所述之可撓式基板的噴印方法,其中該預定溫度介於150至250℃。
- 如申請專利範圍第7項所述之可撓式基板的噴印方法,其中該銀墨水係藉由旋轉塗佈或壓電式噴印方式噴印於該可撓式基板上。
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