TWI629375B - 製備高透光率軟性導電基材的方法及該導電基材 - Google Patents

製備高透光率軟性導電基材的方法及該導電基材 Download PDF

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TWI629375B
TWI629375B TW106117261A TW106117261A TWI629375B TW I629375 B TWI629375 B TW I629375B TW 106117261 A TW106117261 A TW 106117261A TW 106117261 A TW106117261 A TW 106117261A TW I629375 B TWI629375 B TW I629375B
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substrate
copper
group
amine
solution
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TW201900923A (zh
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竇維平
陳柏廷
林良杰
張弘明
林庭筠
林芳瑜
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國立中興大學
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Abstract

本發明提出一種以非導體軟性透明基材上製作銅網格使該基材成為導電基材的方法，該方法排除鈀觸媒的使用；並且，本發明以上述方法所製備的軟性導電基材上具有奈米級或微米級銅線所構成的網格，在可見光透光波長390-750nm範圍內，其透光率高達80%-90%。

Description

製備高透光率軟性導電基材的方法及該導電基材
本發明關於在非導體軟性透明基材上製作銅網格的方法，該方法排除鈀元素的使用；本發明更包括通過上述方法所製備的軟性導電基材，該基材的可見光穿透率達到80-90%。
透明導電薄膜被廣泛應用於顯示器、發光器件、太陽能電池、感測器及電致變色等光電器件領域，因此具有很大商業需求。傳統的塗膜方法製備的銦錫氧化物(ITO)導電薄膜具有良好的導電性能和透光性，被用於各種光電器件中，但因銦的儲量非常有限，又由於市場需求的不斷增加，使得ITO價格持續增長。而ITO薄膜多採用化學沉積方法，該方法對原材料、設備要求均較高，而且所製備的透明導電薄膜均為硬質膜，不能彎曲，使ITO薄膜在柔性電極領域的應用受到限制。
基於ITO薄膜不適用於柔性電極領域的問題，目前已採用透明聚合物膜，例如聚對苯二甲酸乙二酯(PET)，這些透明導電膜具有薄、輕、不易碎裂、富有彈性、可撓曲、易於加工和可做成各種形狀的優點。但是，PET不導電，所以，解決之道便是在其表面加工導電層材料。
CN103124470B(US8663485)發明案揭露塑料金屬化立體線路製造方法，包括以下步驟：(1)提供一塑料基材；(2)對所述塑料基材進行表面 前處理；(3)對所述塑料基材表面進行金屬化處理，沉積形成一金屬薄膜層；(4)對所述金屬薄膜層表面進行光阻塗佈處理，形成一光阻保護層；(5)對所述光阻保護層進行曝光/顯影處理，形成一圖案化光阻保護層；(6)對顯露的金屬薄膜層進行蝕刻處理，形成一圖案化金屬線路層；(7)對所述圖案化光阻保護層進行剝除處理；以及(8)對所述圖案化金屬線路層表面進行表層處理，形成一金屬保護層。在步驟(2)表面前處理步驟中，還包括表面脫脂、粗化、敏化以及活化處理。敏化處理是將氯化亞錫混合酸性溶液中的亞錫離子滲入塑料基材表面粗化的多孔凹穴內部達到吸附作用。表面活化處理是將氯化鈀混合酸性溶液中的鈀離子植入反應形成一活性金屬微粒，以利後續進行金屬化鍍層金屬沉積作用。所述金屬化處理，是利用低溫濺鍍或水溶液電鍍的其中一種加工方式，使金屬沉積於所述塑料基材表面形成一金屬薄膜層；所述沉積金屬選自於鎳(Ni)、鈷(Co)、鈀(Pd)、錫(Sn)、銅(Cu)的其中一種或以上金屬之間任一種複合金屬。
上述發明案代表了一項習知技術，該習知技術是指使用鈀化合物為觸媒將PET基材表面金屬化。然而，此習知技術的問題在於鈀化合物昂貴，且後處理不易從PET基材表面去除乾淨，進而造成淺灰色之殘鈀存留於PET基材表面，大幅降低PET之透光性。為解決此問題，必須仰賴價格更為昂貴的除鈀劑移除金屬圖案空格處的殘鈀，但PET基材的透光性仍然不佳。
如第一圖，未經處理的PET透明基材的可見光(390-750nm)透光率約為85%-90%；PET透明基材以氯化鈀為觸媒進行金屬化處理並經曝光、顯影、蝕刻等步驟形成網格狀金屬導電圖案之後，透光率明顯降至60%-70%；經過除鈀程序，透光率約略提昇至65%-75%。然而，透明導電薄膜的可見 光透光率應維持在80%以上，經除鈀之後的導電PET薄膜的透光率顯然不佳。
第二圖，(a)為未經除鈀製程的PET透明基材及其金屬線的光學顯微鏡(OM)圖；(b)及(c)為掃瞄式電子顯微鏡(SEM)影像，分別為150x和1000x。第三圖，(a)(b)(c)(d)為經除鈀製程的PET透明基材及其金屬線的掃瞄式電子顯微鏡(SEM)影像，分別為150x、1000x、3000x、5000x。比對第二圖和第三圖可知，除鈀製程明顯破壞了金屬線，使導電薄膜的導電性受到影響。
本發明之目的是在提出一種製備高透光率軟性導電基材的方法，該方法排除鈀元素的使用；並且，本發明更包括通過上述方法所製備的軟性導電基材，其上具有奈米級或微米級銅線所構成的網格，390-750nm可見光透光率高達80%-90%。
一種製備高透光率軟性導電基材的方法，包括以不步驟：(A)提供一非導體軟性透明基材；(B)通過表面修飾步驟使該基材的表面具有含氧官能基；(C)通過表面改質步驟使胺基官能基吸附鍵結於該基材表面形成一改質層；(D)通過銅離子觸媒接枝步驟使銅離子吸附鍵結於該基材的改質層上；(E)通過還原步驟將銅離子還原為銅原子；(F)通過無電電鍍步驟，於該基材表面沈積一銅膜；以及(G)依序通過曝光、顯影、及蝕刻步驟，使該銅膜成為奈米級或微米級銅網格。
一種以上述方法所製備的軟性導電基材，該軟性導電基材的銅網格對角線長度為200μm-1000μm，銅線寬度2μm-12μm、銅線厚度 2μm-12μm、占空比(銅網格線之投影面積/PET面積)<20%、以及390-750nm可見光透光率為80%-90%。
本發明之方法使非導體軟性透明基材成為高透光率軟性導電基材。
本發明之方法排除鈀觸媒的使用，因此所有因為鈀觸媒而產生的高成本、導電基材透光性差、除鈀而致導電基材本身以及銅線破壞、導電性降低...等相關問題，在本發明中都被排除。
本發明方法使基材上的銅膜具有優良之附著力，可通過百格附著力測試，有利於銅線路加工，並且不需再使用昂貴的去除觸媒之藥劑，因為銅觸媒在銅膜蝕刻步驟中會一併被去除。此技術大幅降低成本且達到具有優異透光品質之軟性導電電極。
本發明使用一般工業生產所能接受之有機、無機化合物，對於量產設計屬於環境友善製程，製程時間也比利用鈀觸媒行之的濕式無電電鍍時間短，具有低成本、銅膜與基材之附著力佳、銅膜之導電性佳，方便微、奈米線路設計，蝕刻後無金屬殘留、透光度高等優點，可具體實現為市場所需的透明軟性基材表面銅網格製程技術。
本發明高透光率軟性導電基材可見光波長範圍390-750nm的穿透率為80%-90%，未經處理的PET透明基材的可見光穿透率為85%-90%；以550nm為基準，本發明軟性導電基材的穿透率為88-89%，未經處理的PET的穿透率為90-91%，顯示本發明軟性導電基材的可見光透光率趨近於原PET透明基材的可見光透光率。本發明的透光率更高於現行對透明導電薄膜 可見光透光率的要求(80%)。除此之外，與先前技術使用鈀觸媒的導電基材相較，本發明的透光率提昇近20%。
本發明之方法兼顧了導電基材的透光度和導電性。
第一圖為未處理的PET基材及使用鈀觸媒製備金屬導電圖案的PET基材的可見光透光率。
第二圖(a)為使用鈀觸媒製備金屬導電圖案的PET基材的光學顯微鏡(OM)影像；(b)、(c)分別為掃瞄式電子顯微鏡(SEM)150x、1000x影像；表示進行除鈀製程之前的金屬網格形貎。
第三圖(a)(b)(c)(d)為使用鈀觸媒製備金屬導電圖案的PET基材的掃瞄式電子顯微鏡(SEM)150x、1000x、3000x、5000x影像，表示進行除鈀製程之後的金屬網格形貎。
第四圖為非導體軟性透明基材在本發明各步驟處理後所呈現的外觀樣貎。
第五圖透過掃描式電子顯微鏡(SEM)3000x拍攝本發明基材經無電電鍍沉積之銅膜俯視圖。
第六圖為本發明經無電電鍍沈積銅膜之基材進行百格膠帶附著力測試結果。
第七圖(a)為本發明之方法所製備具銅網格的軟性導電基材之光學顯微鏡(OM)俯視影像；(b)、(c)分別為掃描式電子顯微鏡(SEM)150x、1000x之俯視影像。
第八圖為本發明基材經步驟(B)KOH溶液接觸後的可見光穿透率測試圖。
第九圖為本發明基材經步驟(C)胺基矽烷類化合物溶液接觸後於表面鍵結胺基官能基之後的可見光穿透率測試。
第十圖為本發明軟性導電基材的透光率測試。
第十一圖為本發明軟性導電基材進行電性測試之裝置圖。
本發明一種製備高透光率軟性導電基材的方法，包括以下步驟：(A)提供一非導體軟性透明基材；(B)通過表面修飾步驟使該基材的表面具有含氧官能基；(C)通過表面改質步驟使胺基官能基吸附鍵結於該基材表面形成一改質層；(D)通過銅離子觸媒接枝步驟使銅離子吸附鍵結於該基材的改質層上；(E)通過還原步驟將銅離子還原為銅原子；(F)通過無電電鍍步驟，於該基材表面沈積一銅膜；以及(G)依序通過曝光、顯影、及蝕刻步驟，使該銅膜成為奈米級或微米級銅網格。
關於步驟(A)，所述非導體軟性透明基材是選自聚對苯二甲酸乙二醇酯(PET)、聚碳酸酯(PC)、聚氯乙烯(PVC)、聚乙烯(PE)、透明聚醯亞胺(PI)之擇一。本發明實施例是選用含有二氧化矽(Silica)添加物的聚對苯二甲酸乙二醇酯(PET)複合材料(簡稱PET/Silica複合材)。將該基材以有機溶劑、水溶液洗淨後，置入烘箱乾燥完全。
關於步驟(B)，表面修飾步驟，是利用紫外光接觸法、化學酸性或鹼性溶液〔如NaOH、KOH、KMnO4/NaOH、KMnO4/HCl、KMnO4/H2SO4、KOH/C2H5OH、或H2SO4/H2O2〕接觸、或有機溶劑〔DMF、DMAC、THF、或(CH2OH)2〕接觸的其中一種方式氧化該基材的表面，使該基材的表面產 生含氧官能基，例如酮基、酯基或是酸基。本發明實施例是將該基材浸泡接觸氫氧化鉀(KOH)溶液，溶液溫度為25-60℃，浸泡時間為1-30分鐘。
關於步驟(C)，表面改質步驟，包括以pH4-6或pH9-11胺基矽烷類化合物之溶液或具胺基官能基之高分子化合物的溶液接觸該基材表面，使胺基官能基鍵結於該基材表面之含氧官能基。接觸手段為浸泡，浸泡時間為10-30分鐘，溶液溫度25-60℃。利用胺基矽烷類化合物之溶液或高分子化合物的胺基官能基與基材表面含氧官能基反應，進行官能基之間的化學鍵結接枝，使該基材表面具有帶電性的官能基。胺基矽烷類化合物是選自3-氨丙基三甲氧基矽烷、3-氨丙基三乙氧基矽烷、4-氨丙基甲基二甲氧基矽烷、3-氨丙基甲基二乙氧基矽烷、N-2-氨乙基-3-氨丙基三甲氧基矽烷、N-2-氨乙基-3-氨丙基三乙氧基矽烷、N-2-氨乙基-3-氨丙基甲基二甲氧基矽烷、N-2-氨乙基-3-氨丙基甲基二乙氧基矽烷、3-二乙烯三胺基丙基三甲氧基矽烷、3-二乙烯三胺基丙基甲基二甲氧基矽烷、乙烯基苄基氨乙基氨丙基三甲氧基矽烷鹽酸鹽、N-(正丁基)-3-氨丙基三甲氧基矽烷、N-(正丁基)-3-氨丙基三乙氧基矽烷、3-(N-環己胺基)丙基三甲氧基矽烷、雙(3-三甲氧基甲矽烷基丙基)胺、雙(3-三乙氧基甲矽烷基丙基)胺、N-苯基-3-氨基丙基三甲氧基矽烷、N,N-二甲基-3-氨丙基三甲氧基矽烷、或N,N-二乙基-3-氨丙基三甲氧基矽烷之擇一。本發明實施例使用3-氨丙基三甲氧基矽烷[(3-Aminopropyl)triethoxysilane]。
具有胺基官能基之高分子化合物本發明實施例是選自式(1)
在式(1)中，n=1~8，m=1~10，R1為三唑(triazole)、咪唑(imidazole)、己內醯胺(caprolactam)、吡啶(pyridine)、吡嗪(pyrazine)之擇一。
pH調整劑已知可選用Formic acid、Acetic acid、Hydrochloric acid、NaOH、KOH等有機、無機酸、鹼類化合物。
關於步驟(C)，更包含於該改質層形成之後的一加熱乾燥步驟，該加熱乾燥步驟是為使胺基官能基更穩定吸附鍵結於該基材。該加熱乾燥步驟為將該基材置入溫度為40~120℃之烘箱內乾燥約5~30分鐘。
關於步驟(D)，銅離子觸媒接枝步驟本發明實施例包括：將該基材浸入包含螯合劑、銅離子、pH值調整劑、以及去離子水的觸媒溶液中，使銅離子錯合物接枝於該基材表面；浸泡時間為5-20分鐘，溶液溫度為20-40℃，pH值為4-10；浸泡後以去離子水清洗；其中，螯合劑是選自式(3)或式(4)；銅離子是選自可產生二價銅離子的可溶性鹽；pH調整劑是選自NaOH、KOH、NH4OH之擇一；
在式(3)中，其中R1是選自多烷基、環烷基、烷基羧酸、烷基胺酸之擇一；R2是烯胺酸、烷基、胺酸、胺基、羧基、多元醇、酮基之擇一；
在式(4)中，其中R1是多烷基、烯基、胺基、環烷基之擇一；R2是胺基、羧基、醇基、多元醇之擇一。
關於步驟(E)，還原步驟，本發明實施例包括：將該基材浸泡於一還原劑溶液中，將該銅離子錯合物還原為奈米銅原子；該還原液包含濃度為0.01-0.5M的還原劑，pH值為7-10，浸泡時間1-10分鐘，溫度為20-80℃；浸泡後以去離子水清洗；所選之還原劑為二甲胺硼烷(Dimethylaminoborane,DMAB)、聯氨(Hydrazine,N2H4)、次磷酸鈉(NaPO2H2)、或硼氫化鈉(NaBH4)之擇一或組合。
步驟(D)銅離子觸媒接枝及步驟(E)還原步驟，使該基材表面覆蓋具有高催化活性之奈米銅金屬觸媒。
關於步驟(F)，無電電鍍步驟，本發明實施例採用與現有技術同樣的處理即可，沒有特別限制。化學鍍銅液的液溫通常為20~60℃、優選為25~40℃。鍍銅液的攪拌可以採用空氣攪拌、快速液流攪拌、利用攪拌葉片等進行的機械攪拌等。化學鍍銅液的組成沒有特別限制，可以使用公知的化學鍍銅液。化學鍍銅液基本上含有可溶性銅鹽、螯合劑、pH調整劑、還原劑和添加劑。
關於步驟(G)，曝光、顯影、蝕刻步驟，本發明實施例可按照任何一種已知的的方式進行，在本發明中沒有特別的限制。
第四圖為非導體軟性透明基材在本發明上述實施例各步驟處理 後所呈現的外觀樣貎。由右至左，分別為：(a)經步驟(B)修飾後之非導體軟性透明基材；(b)經步驟(C)改質而表面帶有胺基官能基的基材；(c)經步驟(D)銅離子觸媒接枝的基材；(d)經步驟(E)還原後因活性奈米銅而使基材呈現灰色；(e)經步驟(F)無電電鍍形成銅膜於基材表面。
第五圖透過掃描式電子顯微鏡(SEM)3000x拍攝本發明上述實施例之基材經無電電鍍沉積銅膜俯視圖。顯示銅膜均勻披覆於基材表面。
第六圖為本發明上述實施例經無電電鍍沈積銅膜之基材進行百格膠帶附著力測試結果。上圖是基材的銅金屬膜經百格切割後，下圖是沾黏後的膠帶，完全沒有銅剝落的情形。
第七圖(a)為本發明上述實施例之方法所製備具銅網格的軟性導電基材之光學顯微鏡(OM)俯視影像；(b)、(c)分別為掃描式電子顯微鏡(SEM)150x、1000x之俯視影像。銅網格在基材的表面上相連分佈，佈滿整個基材的表面。該軟性導電基材的銅網格對角線長度為250μm-1000μm，銅線寬度2μm-12μm、銅線厚度2μm-12μm、占空比<20%(所謂占空比=銅網格線之投影面積/PET面積)。較佳的，本發明銅網格對角線長600μm，銅線寬10μm，銅線厚度約3μm。
第八圖，為本發明上述實施例基材經步驟(B)KOH溶液接觸後的可見光穿透率測試。可見光波長範圍390-750nm，穿透率為82%-92%，未經處理的PET透明基材的可見光穿透率為85%-90%(請參第一圖)；以視覺最敏感的波長550nm為基準，本發明經步驟(B)的基材的穿透率為90%，未經處理的PET的穿透率為90%。顯示本發明基材經步驟(B)處理成為具有含氧官能基的基材後對於可見光穿透率沒有負面影響。
第九圖為本發明上述實施例基材經步驟(C)胺基矽烷類化合物溶液接觸後於表面鍵結胺基官能基之後的可見光穿透率測試。可見光波長範圍390-750nm，穿透率為85%-95%，未經處理的PET透明基材的可見光穿透率為85%-90%(請參第一圖)；以550nm為基準，本發明經步驟(C)的基材的穿透率為92-94%，未經處理的PET的穿透率為90%。顯示本發明基材經步驟(C)處理成為具有含氧官能基的基材後對於可見光穿透率沒有影響。
第十圖為通過本發明上述實施例之製備方法所製備具銅網格的軟性導電基材的透光率測試。可見光波長範圍390-750nm，穿透率為80%-90%，未經處理的PET透明基材的可見光穿透率為85%-90%；以550nm為基準，本發明軟性導電基材的穿透率為88-89%，未經處理的PET的穿透率為90-91%。顯示本發明軟性導電基材的可見光透光率趨近於原PET透明基材的可見光透光率，由此可證，銅金屬觸媒在蝕刻步驟時幾乎被全部移除，沒有殘留在基材上。本發明的透光率更高於現行對透明導電薄膜可見光透光率的要求(80%)。除此之外，與先前技術使用鈀觸媒的導電基材相較，本發明的透光率提昇近20%。
以上透光率測試結果證實，本發明方法之步驟(B)至步驟(E)對確保本發明軟性導電基材的可見光高穿透率起了關鍵性的作用。
第十一圖，將本發明上述實施例之軟性導電基材進行電性測試之裝置圖，測試元件為LED燈泡，本發明通電後成功點亮LED燈泡，證明本發明軟性導電基材可當作軟性透明電極。

Claims (10)

  1. 一種製備高透光率軟性導電基材的方法，包括以下步驟：(A)提供一非導體軟性透明基材；(B)通過表面修飾步驟使該基材的表面具有含氧官能基；(C)通過表面改質步驟使胺基官能基吸附鍵結於該基材表面形成一改質層；該表面改質步驟包括以pH4-6或pH9-11胺基矽烷類化合物之溶液接觸該基材表面，使胺基官能基鍵結於該基材表面；胺基矽烷類化合物是選自3-氨丙基三甲氧基矽烷、3-氨丙基三乙氧基矽烷、4-氨丙基甲基二甲氧基矽烷、3-氨丙基甲基二乙氧基矽烷、N-2-氨乙基-3-氨丙基三甲氧基矽烷、N-2-氨乙基-3-氨丙基三乙氧基矽烷、N-2-氨乙基-3-氨丙基甲基二甲氧基矽烷、N-2-氨乙基-3-氨丙基甲基二乙氧基矽烷、3-二乙烯三胺基丙基三甲氧基矽烷、3-二乙烯三胺基丙基甲基二甲氧基矽烷、乙烯基苄基氨乙基氨丙基三甲氧基矽烷鹽酸鹽、N-(正丁基)-3-氨丙基三甲氧基矽烷、N-(正丁基)-3-氨丙基三乙氧基矽烷、3-(N-環己胺基)丙基三甲氧基矽烷、雙(3-三甲氧基甲矽烷基丙基)胺、雙(3-三乙氧基甲矽烷基丙基)胺、N-苯基-3-氨基丙基三甲氧基矽烷、N,N-二甲基-3-氨丙基三甲氧基矽烷、或N,N-二乙基-3-氨丙基三甲氧基矽烷之擇一；(D)通過銅離子觸媒接枝步驟使銅離子吸附鍵結於該基材的改質層上；銅離子觸媒接枝步驟包括：將該基材浸入包含螯合劑、銅離子、pH值調整劑、以及去離子水的觸媒溶液中，使銅離子錯合物接枝於該基材表面；浸泡時間為5-20分鐘，溶液溫度為20-40℃，pH值為4-10；浸泡後以去離子水清洗；其中，螯合劑是選自式(3)或式(4)；銅離子是 選自可產生二價銅離子的可溶性鹽；pH調整劑是選自NaOH、KOH、NH4OH之擇一； 在式(3)中，其中R1是選自多烷基、環烷基、烷基羧酸、烷基胺酸之擇一；R2是烯胺酸、烷基、胺酸、胺基、羧基、多元醇、酮基之擇一； 在式(4)中，其中R1是多烷基、烯基、胺基、環烷基之擇一；R2是胺基、羧基、醇基、多元醇之擇一；(E)通過還原步驟將銅離子還原為銅原子；(F)通過無電電鍍步驟，於該基材表面沈積一銅膜；以及(G)依序通過曝光、顯影、及蝕刻步驟，使該銅膜成為奈米級或微米級銅網格。
  2. 如請求項1所述之方法，其中，該步驟(B)的表面修飾步驟是將該基材浸泡接觸氫氧化鉀(KOH)溶液。
  3. 如請求項2所述之方法，其中，氫氧化鉀(KOH)溶液溫度為25-60℃，浸泡時間為1-30分鐘。
  4. 如請求項1所述之方法，其中，步驟(C)表面改質步驟接觸手段為浸泡，浸泡時間為10-30分鐘。
  5. 一種製備高透光率軟性導電基材的方法，包括以下步驟：(A)提供一非導體軟性透明基材；(B)通過表面修飾步驟使該基材的表面具有含氧官能基；(C)通過表面改質步驟使胺基官能基吸附鍵結於該基材表面形成一改質層；表面改質步驟包括以pH4-6或pH9-11胺基官能基高分子化合物之溶液接觸該基材表面，使胺基官能基鍵結於該基材表面；胺基官能基高分子化合物是選自式(1) 在式(1)中，n=1~8，m=1~10，R1為三唑(triazole)、咪唑(imidazole)、己內醯胺(caprolactam)、吡啶(pyridine)、吡嗪(pyrazine)之擇一；(D)通過銅離子觸媒接枝步驟使銅離子吸附鍵結於該基材的改質層上；銅離子觸媒接枝步驟包括：將該基材浸入包含螯合劑、銅離子、pH值調整劑、以及去離子水的觸媒溶液中，使銅離子錯合物接板於該基材表面；浸泡時間為5-20分鐘，溶液溫度為20-40℃，pH值為4-10；浸泡後以去離子水清洗；其中，螯合劑是選自式(3)或式(4)；銅離子是選自可產生二價銅離子的可溶性鹽；pH調整劑是選自NaOH、KOH、NH4OH之擇一； 在式(3)中，其中R1是選自多烷基、環烷基、烷基羧酸、烷基胺酸之擇一；R2是烯胺酸、烷基、胺酸、胺基、羧基、多元醇、酮基之擇一； 在式(4)中，其中R1是多烷基、烯基、胺基、環烷基之擇一；R2是胺基、羧基、醇基、多元醇之擇一；(E)通過還原步驟將銅離子還原為銅原子；(F)通過無電電鍍步驟，於該基材表面沈積一銅膜；以及(G)依序通過曝光、顯影、及蝕刻步驟，使該銅膜成為奈米級或微米級銅網格。
  6. 如請求項5所述之方法，其中，該步驟(B)的表面修飾步驟是將該基材浸泡接觸氫氧化鉀(KOH)溶液。
  7. 如請求項6所述之方法，其中，氫氧化鉀(KOH)溶液溫度為25-60℃，浸泡時間為1-30分鐘。
  8. 如請求項5所述之方法，其中，步驟(C)表面改質步驟接觸手段為浸泡，浸泡時間為10-30分鐘。
  9. 如請求項1或5所述之方法，其中，步驟(E)還原步驟包括：將該基材浸泡於一還原劑溶溶中，將該銅離子錯合物還原為奈米銅原子；該還原液包含濃度為0.01-0.5M的還原劑，pH值為7-10，浸泡時間1-10分鐘，溫度為20-80℃；浸泡後以去離子水清洗；所選之還原劑為二甲胺硼烷(Dimethylaminoborane,DMAB)、聯氨(Hydrazine,N2H4)、次磷酸鈉 (NaPO2H2)、或硼氫化鈉(NaBH4)之擇一或組合。
  10. 一種以請求項1或5之方法所製備的軟性導電基材，該軟性導電基材的銅網格對角線長度為250μm-1000μm，銅線寬度2μm-12μm、銅線厚度2μm-12μm、占空比<20%、以及390-750nm可見光透光率為80%-90%。
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