TWI740406B - 具自組裝保護層之導電結構及自組裝塗層組合物 - Google Patents
具自組裝保護層之導電結構及自組裝塗層組合物 Download PDFInfo
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- TWI740406B TWI740406B TW109107310A TW109107310A TWI740406B TW I740406 B TWI740406 B TW I740406B TW 109107310 A TW109107310 A TW 109107310A TW 109107310 A TW109107310 A TW 109107310A TW I740406 B TWI740406 B TW I740406B
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Abstract
本發明提供一種具自組裝保護層之導電結構及一種自組裝塗層組合物。自組裝塗層組合物包含樹脂、溶劑、以及自組裝添加劑。自組裝添加劑包含烷基胺、氟代烷基胺、氟代苯胺或其衍生物。自組裝添加劑在自組裝塗層組合物中具有濃度為約0.01-100mg/L。導電結構包含基板、導電層、以及自組裝保護層。導電層設置於基板上。自組裝保護層覆蓋導電層，且自組裝保護層包含樹脂、溶劑、以及上述自組裝添加劑。
Description
本發明是有關於一種自組裝塗層組合物及導電結構。
在電子裝置中，通常會在導電層上設置一層保護層以防止導電層(例如，金屬、金屬合金或金屬氧化物)被腐蝕。舉例而言，可以在銅的表面覆蓋一層樹脂材料層，以將銅與環境中的腐蝕介質隔離，進而達到抗腐蝕的效果。然而，即使設置了樹脂材料的保護層在導電層上，導電層中的金屬仍有腐蝕的風險。
根據本發明之某些實施方式，提供一種具自組裝保護層之導電結構，包含基板、導電層、以及自組裝保護層。導電層設置於基板上，包含金屬、金屬合金或金屬氧化物。自組裝保護層覆蓋導電層，其中自組裝保護層包含烷基
胺(alkylamine)、氟代烷基胺(fluoroalkylamine)、氟代苯胺(fluoroaniline)或其衍生物。
根據本發明之某些實施方式，導電層包含塊狀(bulk)、微絲(micro wire)、奈米線(nanowire)、網狀(mesh)、顆粒(particle)、團簇(cluster)、或片狀(sheet)的導電材料。
根據本發明之某些實施方式，導電層是透明導電層，包含一透明基質層與複數條嵌入透明基質層中的銀奈米線。
根據本發明之某些實施方式，自組裝保護層包含75wt%-95wt%的樹脂以及0.1wt-10wt%的自組裝添加劑。
根據本發明之某些實施方式，樹脂包含聚丙烯酸酯、環氧樹脂、酚醛樹脂、聚氨酯、聚醯亞胺、聚醚、聚酯、聚乙烯縮丁醛或其組合。
根據本發明之某些實施方式，自組裝保護層具有厚度為約10奈米至約0.5公分。
根據本發明之各種實施方式，提供一種自組裝塗層組合物，包括樹脂、溶劑、以及自組裝添加劑。自組裝添加劑包含烷基胺(alkylamine)、氟代烷基胺(fluoroalkylamine)、氟代苯胺(fluoroaniline)或其衍生物，且在自組裝塗層組合物中具有濃度為約0.01-100mg/L。
根據本發明之某些實施方式，樹脂包含聚丙烯
酸酯、環氧樹脂、酚醛樹脂、聚氨酯、聚醯亞胺、聚醚、聚酯、聚乙烯縮丁醛或其組合。
根據本發明之某些實施方式，溶劑包含水、乙醇、異丙醇、丙酮、四氫呋喃、N-甲基吡咯烷酮、二甲基甲醯胺、二甲基亞碸、丙二醇甲醚醋酸酯、丙二醇甲醚、乙酸乙酯或其組合。
根據本發明之某些實施方式，自組裝添加劑包含烷基胺(alkylamine)、氟代烷基胺(fluoroalkylamine)、氟代苯胺(fluoroaniline)或其衍生物或其衍生物。
100、200、300:導電結構
110:基板
120、120a、120b:導電層
121、121a、121b:上表面
130:自組裝保護層
120T、130T、T1:厚度
D1:間距
W1、W2:寬度
當讀到隨附的圖式時，從以下詳細的敘述可充分瞭解本揭露的各方面。值得注意的是，根據工業上的標準實務，各種特徵不是按比例繪製。事實上，為了清楚的討論，各種特徵的尺寸可任意增加或減少。
第1A圖為根據本發明的一些實施方式繪示的導電結構剖面圖。
第1B圖為根據本發明的一些實施方式繪示的導電結構剖面圖。
第2圖為根據本發明的一些實施方式繪示的導電結構的環境測試示意圖。
第3圖為根據本發明之一實施方式的導電結構的環境測試結果。
以下將以圖式揭露本發明之複數個實施方式，為明確說明起見，許多實務上的細節將在以下敘述中一併說明。然而，應瞭解到，這些實務上的細節不應用以限制本發明。也就是說，在本發明部分實施方式中，這些實務上的細節是非必要的。並且為求清楚說明，元件之大小或厚度可能誇大顯示，並未依照原尺寸作圖。此外，為簡化圖示起見，一些習知慣用的結構與元件在圖示中將以簡單示意的方式繪示之。
在本文中使用空間相對用語，例如「下方」、「之下」、「上方」、「之上」等，這是為了便於敘述一元件或特徵與另一元件或特徵之間的相對關係，如圖中所繪示。這些空間上的相對用語的真實意義包含其他的方位。例如，當圖示上下翻轉180度時，一元件與另一元件之間的關係，可能從「下方」、「之下」變成「上方」、「之上」。此外，本文中所使用的空間上的相對敘述也應作同樣的解釋。
本發明之一態樣，提供一種自組裝塗層組合物，包括樹脂、溶劑、以及自組裝添加劑。自組裝塗層組合物中各組分的細節詳述如下。
在一些實施方式中，樹脂為紫外光(UV)固化樹脂或熱固化樹脂。在一些實施例中，樹脂包含聚丙烯酸酯(polyacrylate)、環氧樹脂(epoxy)、酚醛樹脂(Novolac)、
聚氨酯(PU)、聚醯亞胺(PI)、聚醚(Polyether)、聚酯(Polyester)、聚乙烯縮丁醛(PVB)或其組合。在一些實施方式中，樹脂可以為光學透明樹脂。
在一些實施方式中，溶劑包含水、乙醇、異丙醇(IPA)、丙酮(acetone)、四氫呋喃(THF)、非質子性溶劑(例如，N-甲基吡咯烷酮(NMP)、二甲基甲醯胺(DMF)、或二甲基亞碸(DMSO)等)、丙二醇甲醚醋酸酯(PGMEA)、丙二醇甲醚(PGME)、乙酸乙酯(EAC)或其組合。
在一些實施方式中，自組裝添加劑包含烷基胺(alkylamine)、氟代烷基胺(fluoroalkylamine)、氟代苯胺(fluoroaniline)或其衍生物。
自組裝添加劑在自組裝塗層組合物中的濃度為約0.01-100mg/L，例如為約0.02、0.05、0.1、0.2、0.5、0.7、1、5、10、20、30、40、50、60、70、80、90、95或99mg/L。本發明之自組裝塗層組合物具有流動性，可以塗佈於導電材料(例如，奈米金屬線)的表面，以抑制其腐蝕。在自組裝塗層組合物中，若自組裝添加劑的濃度小於上述濃度範圍，將無法達到足夠的抑制腐蝕的效果。若自組裝添加劑的濃度大於上述濃度範圍，則具疏水特性的自組裝添加劑將不利於後續的塗佈製程。
本發明之另一態樣亦提供一種導電結構。第1A圖及第1B圖分別為根據本發明的一些實施方式繪示的導電結構100、200的剖面圖。請同時參照第1A-1B圖，導電結構100包含基板110、導電層120、以及自組裝保護層130。
基板110可以為可撓式基板或硬式基板。可撓式基板包含聚對苯二甲酸乙二酯(PET)、聚環烯烴(Cycloolefin Polymer；COP)、環烯烴共聚物(Cyclic Olefin Copolymer；COC)、聚碳酸酯(Polycarbonate；PC)、聚甲基丙烯酸甲酯(poly(methyl methacrylate；PMMA)、聚醯亞胺(Polyimide；PI)、聚對荼二甲酸乙二酯(Polyethylene naphthalate；PEN)、聚偏二氟乙烯(polyvinylidene difluoride；PVDF)、或聚二甲基矽氧烷(Polydimethylsiloxane；PDMS)，但不限於此。硬式基板包含玻璃、晶圓(wafer)、石英、碳化矽(SiC)、陶瓷，但不限於此。
導電層120設置於基板110上。在一些實施方式中，導電層120包含導電材料，例如金屬、金屬合金或金屬氧化物。在一些實施例中，導電層120可以為鋁、鈀、金、銀、鎳、銅、錫、鐵或其合金，例如：黃銅。在一些實施方式中，導電層120可以包含塊狀(bulk)、微絲(micro wire)、奈米線(nanowire)、網狀(mesh)、顆粒(particle)、團簇(cluster)、或片狀(sheet)的導電材料。在一些實施例中，導電層120是透明導電層，包含一透明基質層與複數條嵌入透明基質層中的銀奈米線。在一些實施方式中，導電層120可以為單層或多層堆疊的結構。在一些實施方式中，導電層120具有厚度120T為約10奈米-5微米，較佳為約20奈米-1微米，更加為約50-200奈米。例如，可以為55、60、70、100、120、150、180或195奈米。
以銀奈米線導電層120為例，銀奈米線彼此搭接可形成銀奈米線導電網路。適當的奈米線的長寬比例如為10至100000。當使用長寬比較高的傳導奈米線時，採用較低密度的奈米線即可實現導電網路，以使得導電網路在可見光範圍440nm至約700nm之間基本為透明。需注意的是，把銀等金屬奈米化後，會大幅提升單位體積下金屬的表面積比，即有較高比率的原子位於材料表面，而使其具有高度的化學活性。另外，在如此小的尺寸下，原子或周邊的電子會出現量子效性，因此其特性也會可能與巨觀材料不同。相較於大尺寸的金屬材料，對於銀奈米線等微尺寸金屬要抑止腐蝕會更為艱鉅，而本發明的自組裝塗層組合物對於巨觀與微觀尺寸的金屬導電層都可提供足夠的保護。
在一些實施方式中，導電層120可以為圖案化導電層，如第1B圖所示。請參考第1B圖，導電結構200包含導電層120a、120b。在一些實施方式中，導電層120a、120b之間具有間距D1為約5-500微米。例如為約6、10、15、30、50、70、100、200、250、300、400、450、480或490微米。在一些實施方式中，導電層120a、120b分別具有寬度W1、W2為約5-1000微米。例如為約6、10、50、100、200、500、700、900、950或990微米。
請繼續參考第1A及1B圖。自組裝保護層130覆蓋導電層120，且包含75wt%-95wt%的樹脂以及0.1wt%-10wt%的自組裝添加劑。例如，自組裝保護層130可以包含76、80、85、90、92、或94wt%的樹脂。例如，
自組裝保護層130可以包含0.2、1.5、1、2、5、7、或9wt%的自組裝添加劑。在一些實施例中，樹脂包含聚丙烯酸酯(polyacrylate)、環氧樹脂(epoxy)、酚醛樹脂(Novolac)、聚氨酯(PU)、聚醯亞胺(PI)、聚醚(Polyether)、聚酯(Polyester)、聚乙烯縮丁醛(PVB)或其組合。在一些實施例中，自組裝添加劑包含烷基硫醇(alkylthiol)、氟代烷硫醇(fluoroalkylthiol)、氟代苯硫酚(fluorothiophenol)或其衍生物。在一些實施方式中，自組裝保護層130為光學透明。
在一些實施方式中，自組裝保護層130可以由上述自組裝塗層組合物形成。詳細地說，可以將上述自組裝塗層組合物以任何合適的方法塗佈於導電層120上，再藉由固化、烘乾等製程形成自組裝保護層130於導電層120的表面。在一些實施方式中，可以直接塗佈自組裝塗層組合物於導電材料的表面，再經由蝕刻製程形成圖案化的導電層120及圖案化的自組裝保護層130。也就是說，自組裝保護層130僅形成於導電層120的上表面121之上，如第1A圖所示。在其他實施方式中，可以先經由蝕刻製程形成圖案化的導電層120a、120b，再塗佈自組裝塗層組合物於導電層120a、120b之上，如第1B圖所示。
在一些實施例中，自組裝保護層130具有厚度130T為約10奈米至約0.5公分。具體而言，導電層120的表面至少包覆厚度為約10奈米的自組裝保護層130。如第1B圖所示，導電層120a、120b的上表面121a、121b之上的
自組裝保護層130分別具有厚度T1，且厚度T1至少為10奈米。此自組裝保護層130可提供堅固的抗腐蝕屏障，強化金屬耐腐蝕的能力，進而保護導電層120，有效抑止金屬腐蝕。
以下結合實驗例對本發明做更詳細的說明，但本發明並不限於以下實驗例。
實驗例1
請參考第2圖，導電結構300包含基板110、導電層120a、120b、以及自組裝保護層130。基板110為聚對苯二甲酸乙二酯(PET)基板，厚度為50微米。導電層120a、120b為奈米銀線導電層，分別具有厚度為約30奈米、寬度為約200微米，且導電層120a、120b之間的間距為約30微米。導電層具有面電阻為70Ω/□。自組裝保護層130包含98%的聚甲基丙烯酸甲酯樹脂(壓克力樹脂)以及2%的2,3,4,5,6-五氟苯胺(2,3,4,5,6-Pentafluoroaniline)。自組裝保護層130的厚度為約40奈米。也就是說，導電層120a、120b的上表面之上具有厚度約為10奈米的自組裝保護層130。
比較例1
比較例1的導電結構與實驗例1的差異在於，比較例1的導電層上僅具有聚甲基丙烯酸甲酯樹脂作為保護層，其中不包含任何自組裝添加劑。
將實驗例1與比較例1的導電結構在溫度為85℃、相對溼度為85%、直流電壓為12V進行環境測試，結果如第3圖所示。請參考第3圖，在經過160小時後，比較
例1的陽極電阻變化量為88%，而實驗例1的陽極電阻變化量為17%。由環境測試結果可知，具有自組裝保護層的導電結構可以使導電衰退大幅降低。自組裝保護層可以保護被其包覆的導電層，有效抑止導電層的金屬腐蝕。
如上所述，根據本發明的實施方式，提供一種自組裝塗層組合物及一種包含自組裝保護層的導電結構。此導電結構可以應用於任何電子裝置中，例如，顯示裝置。和現有技術相比，本發明的自組裝保護層提供堅固的抗腐蝕屏障，可以保護導電結構中導電層，改善導電層被腐蝕的問題。
另注意的是，由於微觀尺寸會改變材料特性，傳統在大尺寸塊狀金屬層上可用來抑止金屬腐蝕的一些疏水處理，施加在奈米線金屬層時可能不足以保護奈米線金屬層，導致奈米線金屬層電阻大幅增加、斷路或發黃而降低透明度。而經過本發明的實驗證實，本發明的自組裝保護層可有效保護塊狀、微絲、奈米線、網狀、顆粒、團簇、或片狀之各式導電層，大幅降低導電層電阻隨著時間增加的比例。
此外，由於本發明的自組裝保護層可設置於成品的導電層上，而不僅僅是疏水處理後即清除的過渡製程，因此可提供更長效的保護。再者，由於本發明的自組裝保護層可作為成品疊構的一部分，因此自組裝保護層的材料、組成與比例均因應電性、光學特性、折射率、材料附著性與可撓性的需求而設置，以克服習知導電結構的電性、光學特性、折射率、材料附著性與可撓性等問題，體現更具可靠度的導電結構。
雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，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。
100:導電結構
110:基板
120:導電層
121:上表面
130:自組裝保護層
120T、130T:厚度
Claims (8)
- 一種具自組裝保護層之導電結構，包含：一基板；一導電層，設置於該基板上，該導電層包含金屬、金屬合金或金屬氧化物；以及一自組裝保護層，覆蓋該導電層，其中該自組裝保護層是由一自組裝塗層組合物形成，該自組裝塗層組合物包含：一樹脂；一溶劑；以及一自組裝添加劑，其中該自組裝添加劑選自由烷基胺(alkylamine)、氟代烷基胺(fluoroalkylamine)、及氟代苯胺(fluoroaniline)組成之群組，且該自組裝添加劑在該自組裝塗層組合物中具有一濃度為約0.01-100mg/L。
- 如請求項1所述之導電結構，其中該導電層包含塊狀(bulk)、微絲(micro wire)、奈米線(nanowire)、網狀(mesh)、顆粒(particle)、團簇(cluster)、或片狀(sheet)的導電材料。
- 如請求項1所述之導電結構，其中該導電層包含複數條銀奈米線。
- 如請求項1所述之導電結構，其中該導電 層為一透明導電層。
- 如請求項1所述之導電結構，其中該自組裝保護層包含75wt%-95wt%的樹脂以及0.1wt-10wt%的自組裝添加劑。
- 如請求項5所述之導電結構，其中該樹脂包含聚丙烯酸酯、環氧樹脂、酚醛樹脂、聚氨酯、聚醯亞胺、聚醚、聚酯、聚乙烯縮丁醛或其組合。
- 如請求項1所述之導電結構，其中該自組裝保護層具有一厚度為約10奈米至約0.5公分。
- 如請求項1所述之導電結構，其中該溶劑包含水、乙醇、異丙醇、丙酮、四氫呋喃、N-甲基吡咯烷酮、二甲基甲醯胺、二甲基亞碸、丙二醇甲醚醋酸酯、丙二醇甲醚、乙酸乙酯或其組合。
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