TWI631580B - 具有]導電性奈米線網絡之導電性基板，及其製造方法 - Google Patents
具有]導電性奈米線網絡之導電性基板，及其製造方法 Download PDFInfo
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- TWI631580B TWI631580B TW103105496A TW103105496A TWI631580B TW I631580 B TWI631580 B TW I631580B TW 103105496 A TW103105496 A TW 103105496A TW 103105496 A TW103105496 A TW 103105496A TW I631580 B TWI631580 B TW I631580B
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- network
- nanofiber
- nanowire network
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/0412—Digitisers structurally integrated in a display
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/023—Alloys based on aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract
本發明提供一種導電性奈米線網絡、利用其之導電性基板及透明電極、以及其等之製造方法。
本發明之導電性奈米線網絡之特徵在於由實質上未中斷而連續之導電性奈米線隨機地網絡化而成。且，本發明之導電性奈米線網絡之製造方法之特徵在於係將奈米纖維以隨機之網絡狀應用於已被導電層所覆蓋之基板上，並去除未被前述奈米纖維所覆蓋之導電層區域，接著去除前述奈米纖維。進而，控制前述網絡之構造(線徑及網絡密度)，即可製得兼具透明性與導電性之透明電極。
Description
本發明有關於一種利用奈米纖維之導電性奈米線網絡。且，本發明有關於一種利用可適用於電子裝置之前述導電性奈米線網絡之導電性基板及透明電極。進而，本發明有關於上述導電性奈米線網絡、導電性基板及透明電極之製造方法。
薄型電視、手機、智慧型手機、平板電腦等之顯示裝置及觸控面板、太陽電池、電致發光元件、電磁遮蔽、功能性玻璃等中，透明電極均為必備之元件。該等電子裝置所使用之透明電極之導電性材料則以銦錫氧化物(以下簡稱為ITO)為主流。
然而，ITO之原料之銦為稀有金屬，故未來之供給尚存不確定性。且，製作ITO膜之濺鍍等步驟之低生產性則導致成本降低之困難，而須尋求ITO之替代材料。
近年，替代ITO之新透明導電材料在諸如專利文獻1中已提案有使含有金屬系奈米線材料之導電層圖形化
而成之透明導電體及其製造方法。且，刻正檢討設有包含碳奈米管及導電性高分子等之纖維狀導電性物質之透明導電層之透明導電膜，舉例言之，已予以揭露於專利文獻2中。
其等雖表現可替代習知之ITO膜之較高透明性
與較低之電阻，但包含使用金屬系奈米線或碳奈米管等纖維狀導電性物質之透明導電層之透明導電膜則因纖維狀導電性物質乃長度有限之棒狀形態，而於製造步驟中發生纖維狀導電性物質易朝一定方向進行排列之情況，因此，透明導電膜之電特性及光學特性容易產生異向性。其結果，電特性及光學特性將隨透明導電膜之位置及方向而不同，難以管理品質以外，並將餘留可能發生視認性問題之後果。進而，由於長度有限，故纖維狀導電性物質間之接點較少，即導電通路較少，而無法充分發揮纖維狀導電性物質之電特性。
為消除專利文獻1及2所代表之透明導電膜之特
性之異向性，刻正檢討形成規律之導電性金屬之網狀圖形以避免透明導電膜之特性產生異向性之透明導電膜(專利文獻3)。然而，導電性金屬之網狀圖形為規律之圖形，故具有容易產生雲紋之本質性問題。
專利文獻1日本專利特表2009-505358號公報
專利文獻2日本專利特開2011-168421號公報
專利文獻3日本專利特開2006-352073號公報
本發明之目的在一概解決上述之問題，而以簡化之製程及較低之成本提供可適用於電子裝置之導電性奈米線網絡及利用前述導電性奈米線網絡之導電性基板以及透明電極。
本發明人等人為達成上述目的，而致力檢討之結果，發現將實質上未中斷而連續之奈米纖維以隨機之網絡狀應用於已被導電層所覆蓋之基板上，並去除未被前述奈米纖維所覆蓋之導電層區域後，再去除前述奈米纖維，即製得由網絡狀之導電體即實質上未中斷而連續之導電性奈米線隨機地網絡化而成之導電性奈米線網絡，同時控制前述網絡之構造(線徑及網絡密度)，則製得兼具透明性與導電性之透明電極，而完成本發明。
本發明利用實質上未中斷而連續之奈米纖維之隨機之網絡，故製得之導電性奈米線網絡為均向性，利用前述導電性奈米線網絡之透明電極則表現安定之物性值，且，不致產生雲紋。又，與習知之長度受限(長度有限)之奈米線相較，本發明之奈米線在線間之接點較多，而可製得電阻較低之網絡。因此，可減少達成同等之導電性所需之奈米線量(即網絡之密度)，其結果，則可實現較高之透明
性。因此，可提供利用可適用於電子裝置之導電性奈米線網絡之透明電極。甚且，可採用簡化之製程並使用泛用之高分子材料作為奈米纖維原料，故可降低成本。此外，本發明之透明電極可使用彎曲耐性良好之基材，故舉例言之，可適用於觸控面板用透明導電膜、電子紙用透明電極、軟性薄膜太陽電池用透明電極、軟性顯示器用透明電極等要求彎曲耐性之軟性電子裝置。
圖1顯示本發明之導電性奈米線網絡之顯微鏡相片之一例。
以下，詳細說明本發明。
(導電性奈米線網絡)
本發明之導電性奈米線網絡為實質上未中斷而連續之導電性之奈米線隨機地網絡(網目)化而成之導電體。本說明書中所稱之「導電體」，不僅包括導電性奈米線網絡本身，亦包括予以搭載之基板等。本發明之導電性奈米線網絡中，實質上未中斷而連續之奈米線已隨機地網絡化之形態意指不包含由特定圖形或特定圖形之組合所構成之諸如三角形、四角形、六角形等之n角形、圓、楕圓等或其等之組合所構成之格子形狀等表現一定之規律性之網絡(網目)。當然，本發明之導電性奈米線網絡整體為不規律形狀即可，在可獲致其所需之效果之限度內，並不排除局部偶然形成
之規律形狀之網目之存在。本發明之導電性奈米線網絡之一例可藉適當方法將網絡狀之奈米纖維應用於已被導電層所覆蓋之基板上，並去除未被奈米纖維所覆蓋之導電層區域後，再去除網絡狀奈米纖維而製得。習知之金屬系奈米線及碳奈米管等纖維狀導電性物質之長度有限，故包含使用其等之透明導電層之透明導電膜中，將於製造步驟中發生纖維狀導電性物質易朝一定方向排列之情況，而餘留透明導電膜之電特性及光學特性可能產生異向性之問題，但本發明之導電性奈米線網絡構成實質上未中斷而連續之隨機之網目狀之導電體，故實質上不具有異向性，且，由於網目並無規律性，故實質上將不產生雲紋。且，可輕易控制網絡(網目)之密度，而可兼具配合具體用途之良好透光率與導電性。形成本發明之導電性奈米線網絡之奈米纖維亦可為連續之1條奈米纖維，或獨立之複數條奈米纖維。以上情況下，各奈米纖維之重點均為具有充份長度以在隨機地應用於基板上時於線間形成多數接點。
上述導電層雖可列舉為鐵、鈷、鎳、銅、鋅、鉻、
鉬、釕、銠、鈀、銀、鎘、鋨、銥、白金、金、鋁等金屬及該等金屬之合金，或ITO、銦鎵鋅酸鹽氧化物(IGZO)、鈦、氧化鈷、氧化鋅、氧化釩、氧化銦、氧化鋁、氧化鎳、氧化錫、氧化鉭、氧化鈮、氧化釩、氧化鋯等金屬氧化物及氮化鈦、氮化鋯、氮化鋁等金屬氮化物所例示之金屬化合物，但本發明之導電性奈米線網絡之導電層不限於其等，而可應用任何導電性物質。且，就提供利用本發明之導電
性奈米線網絡之透明電極方面，自導電性之觀點而言，宜使用銅、銀、鋁、銦錫氧化物，且，就軟性透明電極(透明導電膜)之提供方面，宜使用鋁、銅等金屬或合金，進而就輕量與低價之觀點而言，使用鋁則更佳。
導電層之基板可列舉樹脂及玻璃等，但若不致於
後述之導電層去除步驟中受損，即無特別之限制，其材料、形狀、構造、厚度等可由公知之條件中適當加以選擇。樹脂可列舉聚對苯二甲酸乙二酯、聚二甲酸乙二醇酯等之聚酯、液晶型芳香族聚酯、液晶型全芳香族聚酯、聚碳酸酯、聚甲基丙烯酸酯及聚丙烯酸乙酯等之聚丙烯酸酯、聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯及聚甲基丙烯酸羥乙酯等之聚甲基丙烯酸鹽、聚丙烯腈、聚乙烯、聚丙烯、聚烯、環烯烴樹脂、聚氯乙烯、聚苯乙烯、聚乳酸、脂肪族聚醯胺、全芳香族聚醯胺、聚醯亞胺、聚二醚酮、聚降冰片烯、聚碸、多硫化物、聚對苯撐苯並二噁唑、聚胺甲酸酯、環氧樹脂、三醋酸纖維素等之醣類高分子、聚偏二氟乙烯等之含氟高分子、聚矽氧烷、聚矽倍半氧烷及聚矽烷等之含矽高分子、聚磷腈等之含磷高分子、丙烯腈-丁二烯-苯乙烯共聚物或該等物質之共聚物或者混合物。其中，共聚物亦可為包括隨機共聚物、交替共聚物、嵌段共聚物、接枝共聚物在內之任何共聚物，其等亦可由2種以上之複數成分所構成。進而，玻璃則可使用通常之鈉鈣玻璃等。此外，亦可採用組合有樹脂與玻璃之基板，積層2種以上樹脂之基板等複合基板。基板之種類不限於上述例示，可視用途而就
透明性、耐久性、成本等選擇最適用之基板，基板之厚度若考量作為透明電極之功能，則宜為1μm以上、2000μm以下。且，利用本發明之導電性奈米線網絡之透明電極尤其在軟性透明電極(透明導電膜)之提供方面，雖就透明性、尺寸安定性、厚度均一性、強度、耐熱性、耐化學性、耐水性等性質而言，可列舉聚酯為適例，但不限於此，可視用途而適當加以選擇。此時，基板之厚度除考量透明性以外，並須考量基板之可撓性或柔軟性，而宜為1μm以上、500μm以下，但視用途而不同，故不限於該範圍。
上述已被導電層所覆蓋之基板之製作方法，即基
板之導電性物質之覆蓋方法，可列舉濺鍍、真空蒸鍍、離子鍍膜等物理性製作法、噴鍍法、浸鍍法、CVD法等化學性製作法及鍍覆等，但若適用於覆蓋之導電性物質而可均一進行覆蓋，則任何方法均可採用。導電層之厚度可視用途而設為最佳之厚度，雖受所覆蓋之導電層之電阻值等之影響，但宜為1nm以上、500nm以下之厚度。
應用於已被導電層所覆蓋之基板上之奈米纖
維，只要可不中斷而以連續之網絡狀來應用，則任何種類之奈米纖維均可採用。惟，先前已例舉之導電性奈米線網絡之製造方法中，須於製得導電性奈米線網絡之最終步驟中藉溶媒等而去除奈米纖維，故將使用與基板所使用之材料不同之材料之奈米纖維。可使用之奈米纖維則可列舉聚對苯二甲酸乙二酯及聚二甲酸乙二醇酯等之聚酯、液晶型芳香族聚酯、液晶型全芳香族聚酯、聚碳酸酯、聚甲基丙
烯酸酯及聚丙烯酸乙酯等之聚丙烯酸酯、聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯及聚甲基丙烯酸羥乙酯等之聚甲基丙烯酸鹽、聚丙醯胺、聚甲基丙烯醯胺、聚丙烯腈、聚乙烯及聚丙烯等之聚烯、環烯烴樹脂、聚氯乙烯、聚苯乙烯、聚乳酸、脂肪族聚醯胺、全芳香族聚醯胺、聚醯亞胺、聚二醚酮、聚降冰片烯、聚碸、多硫化物、聚對苯撐苯並二噁唑、聚乙炔、聚吡咯及聚塞吩等之導電性高分子、聚胺甲酸酯、環氧樹脂、酚樹脂、醋酸纖維素、硝酸織維素、羥丙織維素、幾丁質．聚葡萄胺糖等之醣類高分子、聚氧化乙烯、聚乙烯醇、聚乙烯吡咯烷酮等之親水性高分子、聚谷氨酸苄酯等之多肽、聚偏二氟乙烯等之含氟高分子、聚矽氧烷、聚矽倍半氧烷及聚矽烷等之含矽高分子、聚磷腈等之含磷高分子、丙烯腈-丁二烯-苯乙烯共聚物或該等物質之共聚物或者混合物。其中，共聚物亦可為包括隨機共聚物、交替共聚物、嵌段共聚物、接枝共聚物在內之任何共聚物，其等亦可由2種以上之複數成分所構成。進而，由諸如三碳醯胺等低分子化合物藉非共價相互作用而自我組合而成之超分子化合物所製得之超分子纖維亦可使用作為奈米纖維。
對已被導電層所覆蓋之基板上應用奈米纖維之
方法雖可列舉藉電紡絲法、共軛熔紡法、熔融吹襲紡絲法而直接加以聚積之方法、將先藉適當方法而業經紡絲之奈米纖維散布於基板上之方法，使預先編成網絡狀之奈米纖維附著於基板上之方法、於基板上旋塗用於形成網絡之高
分子及超分子之膠體等之方法，但不限於其等，若不致對已被導電層所覆蓋之基部造成損傷，則可採用任意之應用方法。尤其，以可在常溫下進行紡絲，並容易控制奈米纖維之直徑及網絡密度之電紡絲法為佳。電紡絲法就奈米纖維之直徑、密度之控制則可為藉調節紡絲液之黏度、導電度、表面張力、溶媒沸點等溶液物性、施加電壓、噴嘴-基板間距離、溶液供給速度等處理條件，而控制奈米纖維之直徑之方法。該等控制因數中，則特別利用紡絲液之黏度與導電度之調整作為泛用之控制方法。具體而言，紡絲液黏度可藉紡絲液中含有之溶質分子(高分子或溶凝膠前驅物)之分子量、濃度及紡絲液之溫度之調整而進行控制，且，紡絲液之導電度可藉對紡絲液中添加電解質而進行控制。一般而言，紡絲液中含有之溶質分子之分子量愈高且濃度愈低，且，在不致妨礙高電場下之感應起電之範圍內紡絲液之導電度愈大，愈可減小奈米纖維之直徑。在可調製均勻之紡絲液時，可適當視用途而選擇溶質分子之分子量及濃度。且，電解質可列舉砒啶、醋酸、胺等有機溶媒及鋰鹽、鈉鹽、鉀鹽、碳酸鹽等無機鹽。可調製均勻之紡絲液時，其等則無限制。奈米纖維之密度可藉控制電紡絲時間而輕易進行控制。奈米纖維之密度將與電紡絲時間一同增加，但電紡絲時間則受使用之電紡絲溶液之種類及濃度甚至裝置之影響，故無法一概而論，但並無特別之限制，可視用途而適當加以選擇。
應用於已被導電層所覆蓋之基板上之奈米纖維
的直徑，雖視導電層之電阻值及用途而不同，但平均直徑宜為5000nm以下，特別擔憂因光散射而導致透明性降低時，設為2000nm以下較佳，進而，設為1000nm以下則尤佳。
所應用之奈米纖維將作為導電層之遮罩使用，故
須與導電層密著。其密著若不足，則製得之導電性奈米線網絡可能發生斷線等瑕疵，而使導電性降低。所應用之奈米纖維對導電層之密著性之提高方法則以諸如在奈米纖維之玻璃轉化溫度以上之溫度下施予熱處理為有效之方式。
熱處理溫度及熱處理時間雖視基板及奈米纖維之熱特性及黏度而不同，但諸如宜在200℃下進行1分鐘以上，就避免熱變性之觀點而言，則宜為200分鐘以下。
去除未被奈米纖維所覆蓋之導電層區域之方法
雖視形成導電層之導電性物質之特性而不同，但舉例言之，可列舉加以浸泡於鹽酸、硝酸等酸性水溶液或氫氧化鈉、氫氧化鉀水溶液中，使導電性物質離子化或錯合離子化等而加以溶解於上述水溶液中之濕式法。浸泡時間及溫度等則可視使用之上述水溶液之種類、濃度及所溶解之導電層之種類及厚度而適當加以選擇，並可視需要而以使用有機系氣體或鹵素系氣體之乾式法予以取代。
去除未被奈米纖維所覆蓋之導電層區域後，為去
除導電性物質已離子化或錯合離子化而成之化合物或水溶液中含有之溶質等雜質，宜以水等充分清洗包含已為奈米纖維所覆蓋之導電性網絡之基板。
接著，去除網絡狀奈米纖維，即可製得反映有網
絡狀奈米纖維之隨機之軌跡之導電性奈米線網絡。去除網絡狀奈米纖維之方法則須適當考量所使用之奈米纖維之溶解性及基板與導電層之溶解性而選擇適當之溶媒。即，適當選擇可溶解奈米纖維之溶媒且不致溶解基板及導電層之溶媒，以進行奈米纖維之溶解去除。
(利用導電性奈米線網絡之透明電極)
利用本發明之導電性奈米線網絡之透明電極可視用途而使前述導電性奈米線網絡之密度等最佳化而製得，並為使用玻璃等剛性基板之透明電極及使用樹脂等可撓性基板之透明電極(透明導電膜)。為予以應用作為透明電極，雖視用途而不同，但宜採用可見光區域(約400nm~700nm)之透光率為50%以上之透明電極，具有70%以上之透明性則更佳。且，表面電阻率雖隨用途而不同，但宜為1000Ω/□以下，500Ω/□以下則更佳。利用本發明之導電性奈米線網絡之透明電極可藉諸如前述之基板、導電層、奈米纖維之各種組合而製得，故雖無法限定個別之條件，但在不失作為透明電極之功能之範圍內，適當設定基板之種類與厚度、導電層之種類與厚度、奈米纖維之直徑與網絡之密度等，即可適當加以使用。且，利用本發明之導電性奈米線網絡之透明電極因網目不具規律性，實質上將不產生雲紋。
以下，以實施例進而具體說明本發明，但本發明並不受限於該等實施例，可在申請專利範圍所揭露之本發明要旨之範圍內適當進行各種變更。且，各實施例之導電
性奈米線網絡之各種物性值乃藉以下所揭露之方法而測得。
<平均直徑>
使用掃瞄型電子顯微鏡(JEOL公司出品之JCM-5700)而隨機於50部位測定直徑，並算出平均值。
<透光率>
使用紫外線可見光分光光度計(日本分光社出品之V-570)測定400nm至700nm之透光率。以作為基板使用之樹脂膜作為背景值而加以扣除，而以550nm之透光率作為導電性奈米線網絡之透光率。
<表面電阻率>
將透明導電膜裁成5cm見方作為測定用試樣。隨機選擇10部位，使用四探針法電阻儀(三菱化學社出品之Loresta EP MCP-T360型)抵壓四探針探測器而測定表面電阻率，並以10部位之平均作為表面電阻率。
第1實施例
使用作為導電層而為厚100nm之鋁所覆蓋之厚25μm之聚對苯二甲酸乙二酯作為基板，並使用1mL容量之注射器，且在電極間距離10cm、電位差15kV、液體輸送速度3.33μL/分之條件下藉電紡絲法(直流高壓電源：Matsusada Precision HAR-100P 0.3、注射幫浦：Minato Concept MCIP-III)於基板上聚積5秒之聚甲基丙烯酸甲酯(重量平均分子量9萬1500)(和光純藥出品)之奈米纖維。製得之纖維之平均纖維徑為600nm。在此，聚甲基丙烯酸甲酯之電紡絲用
溶液使用濃度25wt%之DMF(N’,N’-二甲基甲醯胺)(和光純藥出品)溶液。接著，在200℃下就包含聚積有奈米纖維之鋁導電層之聚對苯二甲酸乙二酯基板進行1分鐘之熱處理，而使奈米纖維與鋁導電層密著。其結果，平均纖維徑則增大為1200nm。然後，在常溫下將包含聚積有奈米纖維之鋁導電層之聚對苯二甲酸乙二酯基板浸泡於1M氫氧化鉀水溶液中2分鐘，而溶解去除未被奈米纖維所覆蓋之鋁部分，再以水加以清洗。最後，藉丙酮溶解去除奈米纖維，便製得未中斷而連續之隨機之導電性奈米線網絡(平均寬度：1150nm)。進行作為透明電極之評價之結果，透光率為78%，表面電阻率為51Ω/□。又，製得之導電性奈米線網絡表現了因應聚對苯二甲酸乙二酯基板之可撓性之柔軟性。進而，製得之透明電極中未形成可覺察之雲紋。
第2實施例
與第1實施例同樣使用以鋁為導電層之聚對苯二甲酸乙二酯作為基板，並使用1mL容量之注射器，且在電極間距離15cm、電位差4.5kV、液體輸送速度5μL/分之條件下藉電紡絲法於基板上聚積3分鐘之聚苯乙烯(重量平均分子量2300萬)之奈米纖維。製得之纖維之平均纖維徑為300nm。在此，聚苯乙烯之電紡絲用溶液使用濃度0.20wt%之DMF/四氫呋喃(質量比1對1)溶液。接著，在200℃下就包含聚積有奈米纖維之鋁導電層之聚對苯二甲酸乙二酯基板進行30分鐘之熱處理，而使奈米纖維與鋁導電層密著。其結果，平均纖維徑則增大至600nm。然後，在常溫下將包含
聚積有奈米纖維之鋁導電層之聚對苯二甲酸乙二酯基板浸泡於1M氫氧化鈉水溶液中3分鐘，而溶解去除未被奈米纖維所覆蓋之鋁部分，再以水加以清洗。最後，以三氯甲烷溶解去除奈米纖維，即製得未中斷而連續之隨機之導電性奈米線網絡(平均寬度：600nm)。進行作為透明電極之評價之結果，透光率為80%，表面電阻率為62Ω/□。且，製得之導電性奈米線網絡表現了因應聚對苯二甲酸乙二酯基板之可撓性之柔軟性。進而，製得之透明電極中未形成可覺察之雲紋。
第3實施例
與第2實施例相同而進行處理，製得未中斷而連續之隨機之導電性奈米線網絡。但，聚苯乙烯之濃度為0.25wt%。且，製得之纖維之平均纖維徑為300nm。熱處理後之纖維之平均纖維徑與奈米線之平均寬度為600nm。進行作為透明電極之評價之結果，透光率為76%，表面電阻率為45Ω/□。且，製得之導電性奈米線網絡表現了因應聚對苯二甲酸乙二酯基板之可撓性之柔軟性。進而，製得之透明電極中未形成可覺察之雲紋。
製得之導電性奈米線網絡之顯微鏡相片顯示於圖1。可觀察未中斷而連續之奈米纖維已隨機地網絡(網目)化之形態。
第4實施例
與第3實施例相同而進行處理，製得未中斷而連續之隨機之導電性奈米線網絡。但，電紡絲法之奈米纖維之聚積
時間為1分鐘。製得之纖維之平均纖維徑為300nm。熱處理後之纖維之平均纖維徑與奈米線之平均寬度為600nm。進行作為透明電極之評價之結果，透光率為93%，表面電阻率為125Ω/□。且，製得之導電性奈米線網絡表現了因應聚對苯二甲酸乙二酯基板之可撓性之柔軟性。進而，製得之透明電極中未形成可覺察之雲紋。
第5實施例
與第3實施例相同而進行處理，製得未中斷而連續之隨機之導電性奈米線網絡。但，電紡絲法之奈米纖維之聚積時間為5分鐘。製得之纖維之平均纖維徑為300nm。熱處理後之纖維之平均纖維徑與奈米線之平均寬度為600nm。進行作為透明電極之評價之結果，透光率為68%，表面電阻率為24Ω/□。且，製得之導電性奈米線網絡表現了因應聚對苯二甲酸乙二酯基板之可撓性之柔軟性。進而，製得之透明電極中未形成可覺察之雲紋。
第6實施例
與第2實施例相同而進行處理，製得未中斷而連續之隨機之導電性奈米線網絡。但，聚苯乙烯之濃度為0.98wt%。且，製得之纖維之平均纖維徑為750nm。熱處理後之纖維之平均纖維徑與奈米線之寬度為1500nm。進行作為透明電極之評價之結果，透光率為35%，表面電阻率為6Ω/□。且，製得之導電性奈米線網絡表現了因應聚對苯二甲酸乙二酯基板之可撓性之柔軟性。進而，製得之透明電極中未形成可覺察之雲紋。
第7實施例
與第6實施例相同而進行處理，製得未中斷而連續之隨機之導電性奈米線網絡。但，電紡絲法之奈米纖維之聚積時間為1分鐘。製得之纖維之平均纖維徑為750nm。熱處理後之纖維之平均纖維徑與奈米線之平均寬度為1500nm。進行作為透明電極之評價之結果，透光率為64%，表面電阻率為27Ω/□。且，製得之導電性奈米線網絡表現了因應聚對苯二甲酸乙二酯基板之可撓性之柔軟性。進而，製得之透明電極中未形成可覺察之雲紋。
第8實施例
與第6實施例相同而進行處理，製得未中斷而連續之隨機之導電性奈米線網絡。但，電紡絲法之奈米纖維之聚積時間為0.5分鐘。製得之纖維之平均纖維徑為750nm。熱處理後之纖維之平均纖維徑與奈米線之平均寬度為1500nm。進行作為透明電極之評價之結果，透光率為77%，表面電阻率為76Ω/□。且，製得之導電性奈米線網絡表現了因應聚對苯二甲酸乙二酯基板之可撓性之柔軟性。進而，製得之透明電極中未形成可覺察之雲紋。
第9實施例
與第2實施例相同而進行處理，製得未中斷而連續之隨機之導電性奈米線網絡。但，電紡絲法之奈米纖維之聚積時間為2分鐘。且，聚苯乙烯之電紡絲用溶液使用濃度0.05wt%之DMF/四氫呋喃(質量比1對3)溶液。進而，熱處理溫度設為160℃。製得之纖維之平均纖維徑為170nm。熱處
理後之纖維之平均纖維徑與奈米線之平均寬度為300nm。進行作為透明電極之評價之結果，透光率為84%，表面電阻率為109Ω/□。且，製得之導電性奈米線網絡表現了因應聚對苯二甲酸乙二酯基板之可撓性之柔軟性。進而，製得之透明電極中未形成可覺察之雲紋。
如以上實施例之結果所示，已發明前所未有之未中斷而連續之隨機之導電性奈米線網絡，同時可知利用該網絡之透明電極亦甚為實用。
本發明可以簡化之製程及較低之成本提供前所未有之未中斷而連續之隨機之導電性奈米線網絡與利用該導電性奈米線網絡之導電性基板及透明電極，而可適用於顯示裝置及觸控面板等電子裝置。且，對於特別要求彎曲耐性之軟性電子裝置而言極為實用。
Claims (9)
- 一種導電性基板，係於基板上搭載一具有均一厚度之導電性奈米線網絡，且該導電性奈米線係由鋁所構成，該導電性奈米線係由一實質上未中斷而連續之導電性奈米線隨機地網絡化而成，其中，該導電性基板在可見光區域具有50%以上之透光率，且具有500Ω/□以下之表面電阻率。
- 如請求項1之導電性基板，其中前述基板為透明。
- 如請求項1之導電性基板，其中前述基板為可撓性樹脂基板。
- 如請求項1之導電性基板，其中前述導電性基板構成一透明電極。
- 一種含有一導電性奈米線網絡之一導電性基板的製造方法，其包含步驟：a)提供一已被導電層所覆蓋之一基板，該導電層含有一金屬；b)將具有平均直徑不大於5000nm之奈米纖維以隨機之網絡狀聚積於已被該導電層所覆蓋之該基板上；c)對該基板施予熱處理，使奈米纖維密著於該導電層；d)透過溶解，去除該基板上未被該奈米纖維所覆蓋之導電層區域；e)透過以一溶媒來溶解，自該基板去除該奈米纖維，以製造該具有均一厚度之導電性奈米線網絡。
- 如請求項5之方法，其中前述金屬含有鋁。
- 如請求項5或6之方法，其中，前述奈米纖維係以電紡絲法形成。
- 如請求項5或6之方法，其中，前述熱處理係在前述奈米纖維之玻璃轉化溫度以上實施。
- 如請求項5或6之方法，其中，前述導電性基板在可見光區域具有50%以上之透光率，且具有500Ω/□以下之表面電阻率。
Applications Claiming Priority (2)
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| KR102364746B1 (ko) * | 2015-02-10 | 2022-02-17 | 동우 화인켐 주식회사 | 도전시트 및 도전패턴 |
| KR101715224B1 (ko) * | 2015-03-30 | 2017-03-13 | 고려대학교 산학협력단 | 투명 전극 제조 방법 및 투명 전극 제조 장치 |
| KR20170067002A (ko) | 2015-12-07 | 2017-06-15 | 울산과학기술원 | 전자 빔을 이용한 도전성 나노와이어 네트워크의 제조방법, 이를 적용한 투명 전극 및 전자 장치 |
| CN105607357B (zh) * | 2016-01-06 | 2018-12-18 | 京东方科技集团股份有限公司 | 一种阵列基板、其制作方法及显示装置 |
| CN108701510A (zh) * | 2016-03-24 | 2018-10-23 | Jxtg能源株式会社 | 透明导电性膜、透明导电性膜的制造方法、金属模具、及金属模具的制造方法 |
| CN107342115A (zh) * | 2016-05-03 | 2017-11-10 | 上海大学 | 一种透明导电和低发射率微网及其制备方法 |
| CN106340628B (zh) * | 2016-10-28 | 2019-04-02 | 南方科技大学 | 锂离子电池用含硅复合负极材料、制备方法及包含其的电池 |
| US10776552B2 (en) | 2016-12-05 | 2020-09-15 | Synopsys, Inc. | Nano-wire resistance model |
| US10685163B2 (en) | 2017-03-01 | 2020-06-16 | Synopsys, Inc. | Computationally efficient nano-scale conductor resistance model |
| KR101955104B1 (ko) * | 2017-08-10 | 2019-03-06 | 울산과학기술원 | 고투과도 및 저저항 특성을 갖는 투명 전극의 제조방법 및 이를 이용하여 제조된 고투과도 및 저저항 특성을 갖는 투명 전극 |
| GB2594941B (en) * | 2020-05-11 | 2022-05-11 | Provost Fellows Found Scholars & Other Members Board College Holy & Und | Method of preparing nanowire networks and networks prepared thereby |
| JP7432717B2 (ja) * | 2020-05-22 | 2024-02-16 | 北越コーポレーション株式会社 | ナノネットワーク及びその製造方法 |
| JP2022086460A (ja) | 2020-11-30 | 2022-06-09 | 株式会社リコー | エレクトロクロミック素子及びエレクトロクロミック調光レンズ |
| CN113701929B (zh) * | 2021-09-16 | 2022-06-14 | 湖南大学 | 一种基于SBCs-GaN micro-LED的柔性压力可视化传感器及其制备方法 |
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| FR2876863B1 (fr) | 2004-10-19 | 2007-01-12 | Saint Gobain | Dispositif de gravure d'une couche conductrice et procede de gravure |
| JP2006352073A (ja) | 2005-05-20 | 2006-12-28 | Fujifilm Holdings Corp | 導電性パターン材料、透光性導電性膜、透光性電磁波シールド膜、光学フィルター、透明導電性シート、エレクトロルミネッセンス素子、及び平面光源システム |
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| JP6265968B2 (ja) | 2018-01-24 |
| CN105283927B (zh) | 2018-02-13 |
| TW201447928A (zh) | 2014-12-16 |
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