TWI693210B - 圖案成形糊 - Google Patents
圖案成形糊 Download PDFInfo
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- TWI693210B TWI693210B TW107141615A TW107141615A TWI693210B TW I693210 B TWI693210 B TW I693210B TW 107141615 A TW107141615 A TW 107141615A TW 107141615 A TW107141615 A TW 107141615A TW I693210 B TWI693210 B TW I693210B
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- forming paste
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Images
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H—ELECTRICITY
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- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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Abstract
本發明揭示用於使金屬奈米線圖案成形之圖案成形糊,該圖案成形糊包括含有胍硫氰酸鹽之錯合劑。使具有金屬奈米線之基板選擇性圖案成形之方法,包括:提供具有帶有金屬奈米線之表面之基板;及將該圖案成形糊選擇性施加至該基板,使得該等金屬奈米線經選擇性切割成圖案。消費型電子產品,包括:具有帶有金屬奈米線之表面之基板。該基板之該等金屬奈米線係藉由將該圖案成形糊施加至該基板來選擇性圖案成形,使得將該等金屬奈米線選擇性切割成圖案。
Description
本發明係關於用於使金屬奈米線圖案成形之圖案成形糊、用於使具有金屬奈米線之基板選擇性圖案成形之方法及消費型電子產品。
銀奈米線膜作為導電膜中氧化銦錫(ITO)之可能替代品或對於其中撓性係重要考慮因素之應用日益受歡迎。該等銀奈米線膜之圖案成形可減慢整個處理時間。此乃因當前技術需要印刷複雜圖案成形層、選擇性去除且然後蝕刻、最後去除遮罩或藉由等待雷射蝕刻出圖案。
本發明係關於使金屬奈米線圖案成形之圖案成形糊,該圖案成形糊包括含有胍硫氰酸鹽之錯合劑。
本發明亦係關於使具有金屬奈米線之基板選擇性圖案成形之方法,其包括提供具有帶有金屬奈米線之表面之基板。將包括含有胍硫氰酸鹽之錯合劑之圖案成形糊選擇性施加至該基板,使得將金屬奈米線選擇性切割成圖案。
本發明亦係關於包括具有帶有金屬奈米線之表面之基板的消費型電子產品。基板之金屬奈米線係藉由將圖案成形糊施加至基板使得將金屬奈米線選擇性切割成圖案而選擇性圖案成形。圖案成形糊包括含有
胍硫氰酸鹽之錯合劑。
圖1顯示包括金屬奈米線之基板之影像,該基板已使用具有硫氰酸鉀之圖案成形糊經圖案成形,該基板具有極明顯之圖案成形;圖2A-2B顯示包括金屬奈米線之基板之掃描電子顯微鏡影像,該基板已使用含有胍硫氰酸鹽(圖2A)或胍硫氰酸鹽及雙(六亞甲基)三胺(圖2B)之圖案成形糊經圖案成形;及圖3A-3C顯示包括金屬奈米線之基板之掃描電子顯微鏡影像,該基板已使用含有胍硫氰酸鹽之圖案成形糊經圖案成形。
出於以下詳細闡述之目的,應瞭解,本發明可設想各種替代變化及步驟順序,惟明顯與所規定相反之情況除外。此外,除在任何操作實例中或其中另有說明之情況以外,在說明書及申請專利範圍中表示(例如)所用成分之量的所有數值在所有情況下皆應理解為由術語「約」修飾。因此,除非指示與此相反,否則以下說明書及隨附申請專利範圍中所闡述之數值參數為可端視欲藉由本發明獲得之期望性質而變化之近似值。最低限度地且並非試圖限制申請專利範圍之等效項之準則的應用,每一數字參數均應至少根據所報告有效數字之數值且藉由應用普通舍入技術來解釋。
儘管描述本發明寬範圍之數值範圍及參數係近似值,但在具體實例中所描述之數值儘可能準確地報告。然而,任一數值固有地含有必然由其各別測試量測中發現之標准偏差引起之某些誤差。
而且,應理解本文所述之任一數值範圍皆意欲包括其中所
包括之全部子範圍。例如,「1至10」之範圍意欲包括所有介於(且包括)所述最小值1與所述最大值10之間之子範圍,亦即,最小值等於或大於1,且最大值等於或小於10。
在本申請案中,除非另有明確說明,否則單數之使用包括複數且複數涵蓋單數。另外,除非另有明確說明,否則在本申請案中使用「或」意指「及/或」,即使在某些情形下可明確使用「及/或」。此外,除非另有特別說明,否則在本申請案中,使用「一(a或an)」意指「至少一者」。舉例而言,「一」胺、「一」錯合劑及諸如此類係指該等物項中之一或多者。而且,如本文所用,術語「聚合物」可係指寡聚物以及均聚物與共聚物兩者。術語「樹脂」可與「聚合物」互換使用。
如本文所用,過渡詞「包含」(及其他相當的術語,例如「含有」及「包括」)係「開放式的」且可包括未規定之物質。儘管依據「包含」來闡述,但術語「基本上由......組成」及「由......組成」亦在本發明之範圍內。
本發明係關於用於使金屬奈米線圖案成形之圖案成形糊,該圖案成形糊包括含有胍硫氰酸鹽之錯合劑。圖案成形糊可藉由選擇性地降解金屬奈米線來切割金屬奈米線,以切斷某些區域中之奈米線。此係藉由產生配體/浸出劑之錯合劑實施,其中配體/浸出劑接觸金屬奈米線,其然後可自基板洗滌,導致金屬奈米線經切割。切割之奈米線之多個部分可遷移或再沈積於附近之完整金屬奈米線,或遷移或再沈積為金屬奈米顆粒或其他含金屬結構。
在圖案成形糊中使用胍硫氰酸鹽作為錯合劑提供優於未包括胍硫氰酸鹽作為錯合劑之圖案成形糊之優點。使用胺(例如雙(六亞甲
基)三胺)及在活化或退火操作期間蒸發之揮發性有機化合物作為唯一錯合劑不能很好地工作,此乃因自奈米線釋放之銀通常再次沈積於銀奈米線基板上,此導致不希望之電隔離區域。胺可包括揮發性有機化合物,其在活化或退火操作期間蒸發,且然後再次沈積於金屬奈米線基板上,此導致不希望之電隔離區域。硫氰酸鹽係鹽且不會自銀奈米線基板蒸發掉;然而,並非所有硫氰酸鹽之效力均相同,且發現某些硫氰酸鹽不如胍硫氰酸鹽。舉例而言,硫氰酸鉀(KSCN)提供良好銀奈米線隔離,但高度可見。圖1顯示與使用硫氰酸鉀作為唯一錯合劑相關聯之高度可見圖案成形。硫氰酸鈉亦不利地顯示高度可見圖案成形。硫代硫酸銨在60℃及90%相對濕度之條件下提供過度殺傷(overkill)。此外,硫氰酸銨在60℃下在其他條件下不提供殺傷(甚至不提供期望之切割)。氯化鈉(NaCl)作為錯合劑沒有任何效果,且溴化鈉(NaBr)作為錯合劑阻礙活化。多硫化物及氨不能提供局部切割且傾向於提供過度殺傷。
如本文所用,術語「奈米線」係指實質上為固體之細長、奈米大小之物件。典型地,奈米線具有在奈米(nm)範圍中之橫向尺寸(例如,呈寬度、直徑或代表跨越正交方向之平均值之寬度或直徑之形式的橫斷面尺寸)、在微米(μm)範圍中之縱向尺寸(例如,長度)及為3或以上(例如,10或以上)之縱橫比。如本文所用,術語「奈米大小」係指至少一個尺寸在nm範圍中之物件之尺寸。如本文所用,術語「奈米範圍」或「nm範圍」係指自1奈米(「nm」)至1微米(μm)之尺寸範圍。
基於圖案成形糊之總重量,胍硫氰酸鹽在圖案成形糊中之存在量可在1至35重量%範圍內,例如1至30重量%、1至25重量%、1至20重量%、1至15重量%、1至10重量%、4至15重量%或4至10重量%。
基於圖案成形糊之總固體重量,胍硫氰酸鹽在圖案成形糊中之存在量可在5至30重量%範圍內,例如5至25重量%、5至20重量%、5至15重量%、8至30重量%、8至25重量%、8至20重量%、8至15重量%、10至30重量%、10至25重量%、10至20重量%、10至15重量%、15至30重量%、15至25重量%或15至20重量%。
胍硫氰酸鹽作為錯合劑提供有利性質,此乃因其係某些金屬(例如銀)之已知浸出劑/配體。胍硫氰酸鹽選擇性切割銀金屬奈米線,此乃因胍硫氰酸鹽在製程條件下並未完全反應,但是留下少量金屬奈米線以將基板電隔離,同時保持少量殘留金屬奈米線,以使得基板之外觀對肉眼沒有顯著影響。
圖案成形糊可除胍硫氰酸鹽以外包括其他錯合劑。舉例而言,圖案成形糊可包括胺,例如雙(六亞甲基)三胺。儘管胺自身作為錯合劑並不能提供較胍硫氰酸鹽自身作為錯合劑更好的結果(胺可造成不希望之電隔離區域),但含有胺及胍硫氰酸鹽之圖案成形糊可適於使金屬奈米線圖案成形。胺/胍硫氰酸鹽組合物中之胺濃度可保持足夠低,以使得胺不會對金屬奈米線造成過度殺傷,同時有利地賦予基板更好的視覺性質。過度殺傷定義為圖案成形糊在期望處理區域之外之不希望鋪展現象。胺可以基於圖案成形糊之總重量至多12重量%之量存在於圖案成形糊中。胺可以基於圖案成形糊之總重量0.1至12重量%範圍內之量存在於圖案成形糊中。
圖2A及2B顯示使用包括胍硫氰酸鹽(圖2A)或胍硫氰酸鹽及雙(六亞甲基)三胺(圖2B)之圖案成形糊經圖案成形基板之結果。圖2B藉由影像中大量亮點顯示銀再沈積之證據。銀之再沈積可提供基板之經圖案
成形區域與未經圖案成形區域之間之有利折射率匹配。
除胍硫氰酸鹽以外,錯合劑可包括適用於作為錯合劑之其他組分。可經包括作為錯合劑(或作為錯合劑或配體之源)之適宜組分之實例包括含有第15族元素(例如,含氮)化合物或路易斯鹼(Lewis base),且可呈單體、寡聚物及聚合物之形式,其經一或多種類型之含有第15族元素之官能團封端、衍生或取代或在(例如)寡聚物或聚合物之骨架結構中包括一或多個第15族元素原子或含有第15族元素之基團。適宜含有第15族元素之化合物的實例包括有機及無機胺,例如氨、一級有機胺(環狀或非環狀、不飽和或飽和)及多胺(直鏈、具支鏈或樹枝狀)、二級有機胺(環狀或非環狀、不飽和或飽和)及多胺(直鏈、具支鏈或樹枝狀)及三級有機胺(環狀或非環狀、不飽和或飽和)及多胺(直鏈、具支鏈或樹枝狀),例如聚離胺酸、氮雜環丙烷、基於氮雜環丙烷之化合物、經衍生之基於氮雜環丙烷之化合物、聚伸乙亞胺(直鏈、具支鏈或樹枝狀)及上述化合物之磷、砷、銻及鉍類似物一級上述化合物之衍生形式。
適宜胺之實例包括彼等具有下式者:N(R)(R’)(R”),其中R、R’及R”獨立地選自氫基(hydride);烷基、烯基、炔基、芳基,例如直鏈或具支鏈烴基團(例如,包括1-20、1-15、1-10、1-8或1-5個碳原子之烴基團);聚(環氧烷)基團、矽氧烷或聚矽氧烷基團及其衍生物。亦涵蓋上述化合物之磷、砷、銻及鉍類似物,例如其中氮由磷、砷、銻或鉍替代之情形。
適宜多胺之實例包括彼等具有下式者:R2N((CnR2n)xNR)a(CmR2m)yNR2,其中R為氫基;烷基、烯基、炔基、芳基,例如直鏈或具支鏈烴基團(例如,包括1-20、1-15、1-10、1-8或1-5
個碳原子之烴基團);聚(環氧烷)基團、矽氧烷或聚矽氧烷基團或其衍生物,且n、m、x、y及a係各自獨立地大於或等於0或大於或等於1之整數(例如,0或以上、1或以上、2或以上、3或以上、4或以上、5或以上或6或以上)。該式亦可一般化為RR’N((CnR”2n)xNR''')a(CnR''''2m)yNR'''''R'''''',其中各個R基團獨立地選自氫基;烷基、烯基、炔基、芳基,例如直鏈或具支鏈烴基團(例如,包括1-20、1-15、1-10、1-8或1-5個碳原子之烴基團);聚(環氧烷)基團、矽氧烷或聚矽氧烷基團及其衍生物,且n、m、x、y及a係各自獨立地大於或等於0或大於或等於1之整數(例如,0或以上、1或以上、2或以上、3或以上、4或以上、5或以上或6或以上)。適宜多胺之額外實例包括彼等具有下式者:RR’N-[(R”)x-NR'''-(R'''')y]z-NR'''''R'''''',其中R、R’、R'''、R'''''及R''''''基團獨立地選自氫基;烷基、烯基、炔基、芳基,例如直鏈或具支鏈烴基團(例如,包括1-20、1-15、1-10、1-8或1-5個碳原子之烴基團);聚(環氧烷)基團、矽氧烷或聚矽氧烷基團及其衍生物,且R”及R''''基團獨立地選自伸烷基(例如,亞甲基或-CH2-及伸乙基或-CH2-CH2-)、伸烯基、伸炔基、伸芳基,例如直鏈或具支鏈烴基團(例如,包括1-20、1-15、1-10、1-8或1-5個碳原子之烴基團);聚(環氧烷)基團、矽氧烷或聚矽氧烷基團及其衍生物,且x、y、z係各自獨立地大於或等於0或大於或等於1之整數(例如,0或以上、1或以上、2或以上、3或以上、4或以上、5或以上或6或以上)。亦涵蓋上述化合物之磷、砷、銻及鉍類似物,例如其中上述式中之至少一個氮經磷、砷、銻或鉍替代。
其中R1、R2、R3及S獨立地選自氫基;烷基、烯基、炔基、芳基,例如直鏈或具支鏈烴基團(例如,包括1-20、1-15、1-10、1-8或1-5個碳原子之烴基團);聚(環氧烷)基團、矽氧烷或聚矽氧烷基團及其衍生物,L係選自伸烷基、伸烯基、伸炔基、伸芳基,例如直鏈或具支鏈烴基團(例如,包括1-20、1-15、1-10、1-8或1-5個碳原子之烴基團);聚(環氧烷)基團、矽氧烷或聚矽氧烷基團及其衍生物,A及B獨立地選自氮、磷、砷、銻及鉍,且n係大於或等於0或大於或等於1之整數(例如,0或以上、1或以上、2或以上、3或以上、4或以上、5或以上或6或以上),且其中對於n>1:在n個單元之不同者中之L可相同或不同,且獨立地選自伸烷基、伸烯基、伸炔基、伸芳基,例如直鏈或具支鏈烴基團;聚(環氧烷)基團、矽氧烷或聚矽氧烷基團及其衍生物,在n個單元之不同者中之S可相同或不同,且獨立地選自氫基;烷基、烯基、炔基、芳基,例如直鏈或具支鏈烴基團;聚(環氧烷)基團、矽氧烷或聚矽氧烷基團及其衍生物,且在n個單元之不同者中之B可相同或不同,且獨立地選自氮、磷、砷、銻及鉍。
胺及多胺之具體實例包括氨、乙二胺(或H2N-(CH2)2-NH2)、二伸乙基三胺(或H2N-(CH2)2-NH-(CH2)2-NH2)、辛胺(或CH3-(CH2)7-NH2)、癸胺(或CH3-(CH2)9-NH2)、三伸乙基四胺(或H2N-(CH2)2-NH-(CH2)2-NH-(CH2)2-NH2)、N-甲基乙二胺(或CH3-NH-(CH2)2-NH2)、
N,N’-二甲基乙二胺(或(CH3)2N-(CH2)2-NH2)、N,N,N’-三甲基乙二胺(或CH3-NH-(CH2)2-N(CH3)2)、N,N’-二異丙基乙二胺(或(CH3)2CH-NH-(CH2)2-N-CH(CH3)2)及四乙基五胺(或H2N-(CH2)2-NH-(CH2)2-NH-(CH2)2-NH-(CH2)2-NH2)。胺及多胺之其他具體實例包括乙二胺四乙酸、咪唑(例如,二咪唑及三咪唑)、嘧啶、嘌呤、精胺、脲、離胺酸、乙醇胺鹽酸鹽、乙內醯脲、硫脲及胺氧化物(或氧化胺)。其他實例包括胺化聚合物(例如聚(乙烯胺))及有關共聚物。在一些實施例中,適宜胺及多胺包括彼等缺少羧基(或缺少羰基或缺少-(C=S)-)、或包括每分子不多於2個羧基(或每分子不多於2個羰基或不多於2個-(C=S)-)或每分子不多於1個羧基(或每分子不多於1個羰基或不多於1個-(C=S)-)者。
多胺之額外具體實例包括聚伸乙亞胺,其亦可稱為聚氮雜環丙烷或聚(亞胺基乙烯)。聚伸乙亞胺可以若干分子量使用,可為具支鏈、直鏈或樹枝狀,且可作為衍生物(例如經衍生具有各種側鏈或官能基之聚伸乙亞胺)使用。聚伸乙亞胺之適宜分子量包括800及25,000(數量或重量平均),但涵蓋其他分子量,例如100,000或以下、50,000或以下、25,000或以下、20,000或以下、10,000或以下、5,000或以下或1,000或以下及直至500或以下。
可用作錯合劑之組分的其他實例包括過渡金屬或銨鹵化物(例如,鹵化銀,例如氯化銀或溴化銀)、過渡金屬或銨氧化物(例如,氧化銀)、過渡金屬或銨硫化物(例如,硫化銀)、其他含有銀(例如,Ag+)之化學試劑、鹼金屬(例如,鈉或鉀)或銨硫氰酸鹽、鹼金屬(例如,鈉或鉀)或銨多硫化物、鹼金屬(例如,鈉或鉀)硫化物、鹼金屬(例如,鈉或鉀)或銨硫代硫酸鹽、鹼金屬(例如,鈉或鉀)鹵化物(例如,氯化物或溴化物)、
金屬或銨氰化物、碳酸銨及胺甲酸銨。
圖案成形糊可進一步包括載劑。載劑可包括增稠劑。基於該圖案成形糊之總重量,增稠劑可以至多10重量%、例如至多6重量%、至多5重量%、至多4重量%、至多3重量%、至多2重量%或至多1重量%之量存在於圖案成形糊中。增稠劑可包括2-羥乙基纖維素。然而,可使用其他增稠劑,例如羥乙基纖維素、甲基纖維、乙基甲基纖維素、鹼可溶脹乳液、HEUR增稠劑(非離子聚胺基甲酸酯締合型增稠劑)及黏土。可使用該等增稠劑之組合。增稠劑可包括聚合物黏合劑,包括水溶性聚合物黏合劑,例如聚(乙烯基吡咯啶酮)、聚乙烯醇、聚(乙烯醇-共-乙烯胺)、乙烯-乙烯醇共聚物、聚丙烯酸鈉及碳水化合物(例如水溶性纖維素衍生物,如羧甲基纖維素鈉;及水溶性天然聚合物,如澱粉、澱粉糊、可溶性澱粉及糊精)。聚苯乙烯亦可為適宜增稠劑。
載劑亦可包括溶劑。溶劑可包括保濕劑以將錯合劑保持在溶液中(例如,亦可作為溶劑之保濕劑)。如本文所用,「保濕劑」係指用於保持濕潤之材料。圖案成形糊中可包括不作為溶劑之保濕劑。保濕劑可包括乙二醇、丙二醇、蜂蜜、丁二醇、甘油、脲、銀耳提取物、乳酸鈉、山梨糖醇、吡咯啶酮碳酸之鈉鹽及其組合。保濕劑可基於圖案成形糊之總重量以至多50重量%、例如至多45重量%、至多40重量%或至多35重量%之量存在於圖案成形糊中。保濕劑可以1至50重量%、例如10至45重量%、15至40重量%、20至35重量%範圍內之量存在於圖案成形糊中。
圖案成形糊可進一步包括惰性填充劑,例如硫酸鋇、高嶺土、二氧化鈦、空心球體、二氧化矽、雲母或為圖案成形糊提供容積、賦予有利流變性質及/或不與金屬奈米線反應之任何其他材料。
圖案成形糊可進一步包括潤濕劑以將調配物調整至金屬奈米線膜的特定表面張力。
圖案成形糊可施加至具有經金屬奈米線覆蓋之表面之基板。基板可具有任何形狀及大小且可為透明、半透明或不透明。基板可為撓性、可彎曲、可摺疊、可延伸或剛性的。基板可為導電、半導電或絕緣的。
用於基板之適宜材料之實例包括有機材料、無機材料及混合有機-無機材料。舉例而言,基板可包括熱塑性聚合物、熱固性聚合物、彈性體、或其共聚物或其他組合,例如選自以下者:聚烯烴(例如,聚乙烯(或PE)、聚丙烯(或PP)、聚丁烯及聚異丁烯)、丙烯酸酯聚合物(例如,聚(甲基丙烯酸甲酯)(或PMMA),1型及2型)、基於環狀烯烴之聚合物(例如,環狀烯烴聚合物(或COP)及共聚物(或COC),例如以ARTON及ZEONORFILM商標市售購得者)、芳香族聚合物(例如,聚苯乙烯)、聚碳酸酯(或PC)、乙烯乙酸乙烯酯(或EVA)、離聚物、聚乙烯醇縮丁醛(或PVB)、聚酯、聚碸(polysulphone)、聚醯胺、聚醯亞胺、聚胺基甲酸酯、乙烯基聚合物(例如,聚氯乙烯(或PVC))、氟聚合物、聚碸(polysulfone)、聚乳酸、基於烯丙基二甘醇碳酸酯之聚合物、基於腈之聚合物、丙烯腈丁二烯苯乙烯(或ABS)、三乙酸纖維素(或TAC)、基於苯氧基之聚合物、伸苯基醚/氧化物、塑性溶膠、有機溶膠、可塑性澱粉材料、聚縮醛、芳香族聚醯胺、聚醯胺-醯亞胺、聚芳醚、聚醚醯亞胺、聚芳碸、聚丁烯、聚酮、聚甲基戊烯、聚伸苯基、基於苯乙烯馬來酸酐之聚合物、基於聚烯丙基二甘醇二碳酸酯單體之聚合物、基於雙馬來醯亞胺之聚合物、聚鄰苯二甲酸烯丙基酯、熱塑性聚胺基甲酸酯、高密度聚乙烯、
低密度聚乙烯、共聚酯(例如,以商標TRITAN市售購得者)、聚對苯二酸乙二酯(polyethylene terephthalate glycol)(或PETG)、聚對苯二酸乙二酯(polyethylene terephthalate)(或PET)、環氧、含有環氧之樹脂、基於三聚氰胺之聚合物、聚矽氧及其他含矽聚合物(例如,聚矽烷及聚矽倍半氧烷)、基於乙酸酯之聚合物、聚(富馬酸丙二酯)、聚(二氟亞乙烯-三氟乙烯)、聚-3-羥基丁酸聚酯、聚己內酯、聚乙醇酸(或PGA)、聚乙交酯、聚伸苯伸乙烯、導電聚合物、液晶聚合物、聚(甲基丙烯酸甲酯)共聚物、基於四氟乙烯之聚合物、磺化四氟乙烯共聚物、氟化離聚物、對應於或包括於聚合物電解質膜中之聚合物、基於乙烷磺醯氟之聚合物、基於2-[1-[二氟-[(三氟乙烯基)氧基]甲基]-1,2,2,2-四氟乙氧基]-1,1,2,2,-四氟-以及四氟乙烯之聚合物、四氟乙烯-全氟-3,6-二氧雜-4-甲基-7-辛烯磺酸共聚物、聚異戊二烯、聚乙交酯、聚乙醇酸、聚己內酯、基於二氟亞乙烯之聚合物、基於三氟乙烯之聚合物、聚(二氟亞乙烯-三氟乙烯)、聚(伸苯伸乙烯)、基於酞菁銅之聚合物、賽璐玢(cellophane)、基於銅銨之聚合物、嫘縈(rayon)、及生物聚合物(例如,乙酸纖維素(或CA)、乙酸丁酸纖維素(或CAB)、乙酸丙酸纖維素(或CAP)、丙酸纖維素(或CP)、基於脲之聚合物、木材、膠原、角蛋白、彈性蛋白、硝基纖維素、可塑性澱粉、賽璐珞(celluloid)、竹、生物衍生之聚乙烯、碳化二亞胺、軟骨、硝酸纖維素、纖維素、幾丁質、幾丁聚醣、結締組織、酞菁銅、棉纖維素、彈性蛋白、醣胺聚多醣、亞麻、透明質酸、硝基纖維素、紙、羊皮紙、可塑性澱粉、澱粉、基於澱粉之塑膠、二氟亞乙烯及黏膠)或其任何單體、共聚物、摻合物或其他組合。適宜基板之額外實例包括陶瓷,例如介電或非導電陶瓷(例如,基於SiO2之玻璃;基於SiOx之玻璃;基於TiOx之玻璃;基於SiOx
之玻璃之其他鈦、鈰及鎂類似物;旋塗玻璃;自溶膠-凝膠處理形成之玻璃、矽烷前體、矽氧烷前體、矽酸鹽前體、正矽酸四乙酯、矽烷、矽氧烷、磷矽矽酸鹽、旋塗玻璃、矽酸鹽、矽酸鈉、矽酸鉀、玻璃前體、陶瓷前體、矽倍半氧烷、金屬矽倍半氧烷、多面體寡聚矽倍半氧烷、鹵代矽烷、溶膠-凝膠、氫化矽氧、聚矽氧、錫氧烷、矽硫烷、矽氮烷、聚矽氮烷、茂金屬、二氯化二茂鈦、二氯化二茂釩;及其他類型之玻璃)、導電陶瓷(例如,視情況經摻雜且透明之導電氧化物及硫屬化合物,例如視情況經摻雜且透明之金屬氧化物及硫屬化合物)及其任何組合。適宜基板之額外實例包括導電材料及半導體,例如導電聚合物,如聚(苯胺)、PEDOT、PSS、PEDOT-PSS等。基板可為(例如)n摻雜、p摻雜或未經摻雜。基板材料之其他實例包括聚合物-陶瓷複合材料、聚合物-木材複合材料、聚合物-碳複合材料(例如,形成科琴黑(ketjen black)、活性碳、碳黑、石墨烯及碳之其他形式)、聚合物-金屬複合材料、聚合物-氧化物或其任何組合。基板材料亦可併入還原劑、腐蝕抑制劑、濕氣障壁材料或其他有機或無機化學試劑(例如,具有抗壞血酸之PMMA、具有濕氣障壁材料之COP或具有二硫化物型腐蝕抑制劑之PMMA)。
具有金屬奈米線之基板可用作透明導體或其他類型之裝置。基板可展現經改良性能(例如,較高導電及導熱性及較高透光率),以及提供因其組成及製造方法產生之成本益處。基板可藉由表面嵌入製程製造,其中將金屬奈米線以物理方式嵌入基板中,同時保存基板之期望特性(例如,透明性)並賦予所得基板額外之期望特性(例如,導電性)。金屬奈米線可藉由將金屬奈米線嵌入乾燥組合物或將金屬奈米線嵌入濕潤組合物而嵌入基板中,其中潤濕程度在完全乾燥與完全濕潤之間變化(完全乾燥
與完全濕潤之間之連續體)。基板可藉由其他製程(例如烘箱塗佈製程)製造。
金屬奈米線可包括銀奈米線。金屬奈米線可由各種其他導電或半導電材料形成,包括金屬(例如,鎳(或Ni)、鈀(或Pd)、鉑(或Pt)、銅(或Cu)及金(或Au))、金屬合金、半導體(例如,矽(或Si)、磷化銦(或InP)及氮化鎵(或GaN))、類金屬(例如,碲(或Te))、視情況經摻雜且透明之導電氧化物及硫屬化合物(例如,視情況經摻雜且透明之金屬氧化物及硫屬化合物,例如氧化鋅(或ZnO))、導電聚合物(例如,聚(苯胺)、聚(乙炔)、聚(吡咯)、聚(噻吩)、聚(對苯硫醚)、聚(對伸苯基伸乙烯基)、聚(3-烷基噻吩)、聚吲哚、聚(芘)、聚(咔唑)、聚(薁)、聚(氮雜環庚三烯)、聚(茀)、聚(萘)、三聚氰胺、聚(3,4-伸乙基二氧基噻吩)(或PEDOT)、聚(苯乙烯磺酸)(或PSS)、PEDOT-PSS、PEDOT-聚(甲基丙烯酸)、聚(3-己基噻吩)、聚(3-辛基噻吩)、聚(C-61-丁酸-甲酯)、聚[2-甲氧基-5-(2’-乙基-己氧基)-1,4-伸苯基伸乙烯基])及其任何組合。奈米線可具有核-殼構形或核-多殼構形且可併入金屬鹵化物殼或金屬氧化物殼、或其他金屬鹵化物或金屬氧化物部分。
其他結構可用於代替或與奈米線組合。實例包括奈米大小或微米大小之金屬結構(或微米結構),其代替或與奈米線組合。適宜結構之非限制性實例包括經印刷或沈積之金屬網格柵。經印刷或沈積之金屬網格柵可為單沈積合金或雙沈積物。金屬網格柵可具有奈米大小直徑且尺寸為微米大小或在完全燒結或印刷時,儘管金屬網格柵無需為奈米大小。一般而言,結構(例如,奈米結構及微米結構)可由各種材料形成,包括金屬、金屬合金、半導體、類金屬、視情況經摻雜且透明之導電氧化物及硫
屬化合物、導電聚合物、絕緣體及其任何組合。為賦予導電性,奈米結構及微米結構可包括導電材料、半導體或其組合。
導電材料之實例包括金屬(例如,呈銀奈米線、銅奈米線及金奈米線形式之銀、銅及金)、銀-鎳、銀氧化物、具有聚合覆蓋劑之銀、銀-銅、銅-鎳、碳基材料(例如,呈碳奈米管、石墨烯及巴克球(buckyballs)之形式)、導電陶瓷(例如,視情況經摻雜且透明之導電氧化物及硫屬化合物)、導電聚合物及其任何組合。
半導體之實例包括半導電聚合物、第IVB族元素(例如,碳(或C)、矽(或Si)及鍺(或Ge))、第IVB-IVB族二元合金(例如,碳化矽(或SiC)及矽鍺(或SiGe))、第IIB-VIB族二元合金(例如,硒化鎘(或CdSe)、硫化鎘(或CdS)、碲化鎘(或CdTe)、氧化鋅(或ZnO)、硒化鋅(或ZnSe)、碲化鋅(或ZnTe)及硫化鋅(或ZnS))、第IIB-VIB族三元合金(例如,碲化鎘鋅(或CdZnTe)、碲化汞鎘(或HgCdTe)、碲化汞鋅(或HgZnTe)及硒化汞鋅(或HgZnSe))、第IIIB-VB族二元合金(例如,銻化鋁(或AlSb)、砷化鋁(或AlAs)、氮化鋁(或MN)、磷化鋁(或AlP)、氮化硼(或BN)、磷化硼(或BP)、砷化硼(或BAs)、銻化鎵(或GaSb)、砷化鎵(或GaAs)、氮化鎵(或GaN)、磷化鎵(或GaP)、銻化銦(或InSb)、砷化銦(或InAs)、氮化銦(或InN)及磷化銦(或InP))、第IIIB-VB族三元合金(例如,砷化鋁鎵(或AlGaAs或AlxGa1-xAs)、砷化銦鎵(或InGaAs或InxGa1-xAs)、磷化銦鎵(或InGaP)、砷化鋁銦(或AlInAs)、銻化鋁銦(或AlInSb)、砷氮化鎵(或GaAsN)、砷磷化鎵(或GaAsP)、氮化鋁鎵(或AlGaN)、磷化鋁鎵(或AlGaP)、氮化銦鎵(或InGaN)、砷銻化銦(或InAsSb)及銻化銦鎵(或InGaSb))、第IIIB-VB族四元合金(例如,磷化鋁鎵銦(或AlGaInP)、砷磷
化鋁鎵(或AlGaAsP)、砷磷化銦鎵(或InGaAsP)、砷磷化鋁銦(或AlInAsP)、砷氮化鋁鎵(或AlGaAsN)、砷氮化銦鎵(或InGaAsN)、砷氮化銦鋁(或InAlAsN)及砷銻氮化鎵(或GaAsSbN))、及第IIIB-VB族五元合金(例如,氮砷銻化鎵銦(或GaInNAsSb)及砷銻磷化鎵銦(或GaInAsSbP))、第IB-VIIB族二元合金(例如,氯化亞銅(或CuCl))、第IVB-VIB族二元合金(例如,硒化鉛(或PbSe)、硫化鉛(或PbS)、碲化鉛(或PbTe)、硫化錫(或SnS)及碲化錫(或SnTe))、第IVB-VIB族三元合金(例如,碲化鉛錫(或PbSnTe)、碲化鉈錫(或Tl2SnTe5)及碲化鉈鍺(或Tl2GeTe5))、第VB-VIB族二元合金(例如,碲化鉍(或Bi2Te3))、第IIB-VB族二元合金(例如,磷化鎘(或Cd3P2)、砷化鎘(或Cd3As2)、銻化鎘(或Cd3Sb2)、磷化鋅(或Zn3P2)、砷化鋅(或Zn3As2)及銻化鋅(或Zn3Sb2))及第IB族(或第11族)元素、第IIB族(或第12族)元素、第IIIB族(或第13族)元素、第IVB族(或第14族)元素、第VB族(或第15族)元素、第VIB族(或第16族)元素及第VIIB族(或第17族)元素之其他二元、三元、四元或更高階合金(例如硒化銅銦鎵(或CIGS))以及其任何組合。
奈米結構及微米結構可包括(例如)金屬或半導體奈米顆粒、金屬或半導體奈米線(例如,銀、銅、或鋅)、金屬或半導體奈米微板、金屬或半導體奈米棒、奈米管(例如,碳奈米管、多壁奈米管(「MWNT」)、單壁奈米管(「SWNT」)、雙壁奈米管(「DWNT」)及石墨化或經修飾奈米管)、富勒烯、巴克球、石墨烯、微米顆粒、微米線、微米管、核-殼奈米顆粒或微米顆粒、核-多殼奈米顆粒或微米顆粒、核-殼奈米線及具有大體上或實質上為管狀、立方形、球形或錐形之形狀且描述為非晶形、單晶或多晶、四方晶系、六方晶系、三方晶系、斜方晶系、
單斜晶系、或三斜晶系或其任何組合之其他奈米大小或微米大小之結構。
核-殼奈米顆粒及核-殼奈米線之實例包括彼等具有鐵磁性核(例如,鐵、鈷、鎳、錳、以及其氧化物及利用該等元素之一或多者形成之合金)、具有由金屬、金屬合金、金屬氧化物、碳、或其任何組合(例如,銀、銅、金、鉑、導電氧化物或硫屬化合物、石墨烯及其他本文作為適宜材料所列示之材料)形成之殼者。核-殼奈米線之特定實例係具有銀核及圍繞銀核以減少或防止銀核氧化之金殼(或鉑殼或另一類型之殼)者。核-殼奈米線之另一實例係具有銀核(或由另一金屬或其他導電材料形成之核)、具有由以下各項中之一或多者形成之殼或其他塗層者:(a)導電聚合物,例如聚(3,4-伸乙基二氧基噻吩)(或PEDOT)及聚苯胺(或PANI);(b)導電氧化物、硫屬化合物及陶瓷(例如,藉由溶膠-凝膠、化學氣相沈積、物理氣相沈積、電漿增強之化學氣相沈積或化學浴沈積來沈積);(c)呈超薄層形式之絕緣體,例如聚合物、SiO2、BaTiO及TiO2;及(d)金屬薄層,例如金、銅、鎳、鉻、鉬及鎢。該等經塗佈或核-殼形式之奈米線可期望賦予導電性,同時避免或減少與基板之不利相互作用,例如在金屬(例如銀)存在下之潛在黃變或其他變色、氧化(例如,銀/金核/殼奈米線可由於金殼而具有實質上降低之氧化)及硫化(例如,銀/鉑核/殼奈米線可由於鉑殼而具有實質上降低之硫化)。
對於某些實施方案而言,高縱橫比奈米結構係期望的,例如呈奈米線、奈米管及其組合之形式。舉例而言,期望奈米結構包括由碳或其他材料形成之奈米管(例如,MWNT、SWNT、石墨化MWNT、石墨化SWNT、經修飾MWNT、經修飾SWNT及含有聚合物之奈米管)、由金屬、金屬氧化物、金屬合金或其他材料形成之奈米線(例如,銀奈米線、
銅奈米線、氧化鋅奈米線(未經摻雜或經例如鋁、硼、氟及其他摻雜)、氧化錫奈米線(未經摻雜或經例如氟摻雜)、氧化鎘錫奈米線、ITO奈米線、含有聚合物之奈米線及金奈米線)以及其他導電或半導電且具有各種形狀(無論為圓柱形、球形、錐形或其他形狀)之材料。適宜導電結構之額外實例包括彼等由活性碳、石墨烯、碳黑或科琴黑形成者、及由金屬、金屬氧化物、金屬合金、或其他材料形成之奈米顆粒(例如,銀奈米顆粒、銅奈米顆粒、氧化鋅奈米顆粒、ITO奈米顆粒及金奈米顆粒)。
金屬奈米線可併入單層或多層基板。
金屬奈米線可嵌入或以其他方式併入基板之至少一部分中,納入程度為併入嵌入表面之金屬奈米線之10體積%(或更少,例如0.1%)及併入嵌入表面之金屬奈米線之至多100體積%,且可使金屬奈米線以不同表面積覆蓋率暴露,例如0.1%暴露表面積覆蓋率(或更少,例如0%,當嵌入區域完全在表面以下時,或當結構完全由基板封裝時)至至多99.9%(或更多)暴露表面積覆蓋率(例如0.1%至10%、0.1%至8%或0.1%至5%暴露表面積覆蓋率)。舉例而言,就嵌入表面下方之金屬奈米線體積相對於結構之總體積而言,至少一根金屬奈米線可具有在0%至100%範圍內(例如10%至50%或50%至100%)之嵌入體積百分比(或結構群體可具有平均嵌入體積百分比)。
嵌入區域可具有大於所用金屬奈米線之特性尺寸之厚度(例如,大於個別奈米線之直徑或跨越奈米線之平均直徑),其中金屬奈米線大部分或實質上侷限於嵌入區域且具有小於基板之總厚度之厚度。舉例而言,嵌入區域之厚度可不大於基板之總厚度的95%,例如不大於80%、不大於75%、不大於50%、不大於40%、不大於30%、不大於20%、不大於
10%或不大於5%之總厚度。
金屬奈米線可相對於所用金屬奈米線之特性尺寸(例如,相對於個別奈米線之直徑或跨越奈米線之平均直徑)以不同程度表面嵌入或以其他方式併入基板之至少一部分中。舉例而言,就金屬奈米線上在嵌入表面下方之最遠嵌入點之距離而言,至少一根金屬奈米線可嵌入至多於特性尺寸之100%之程度,或可嵌入至不超過特性尺寸之100%之程度,例如特性尺寸之至少5%或10%及至多80%、至多50%或至多25%。作為另一實例,金屬奈米線群體平均可嵌入至多於特性尺寸之100%之程度,或可嵌入至不超過特性尺寸之100%之程度,例如特性尺寸之至少5%或10%及至多80%、至多50%或至多25%。應理解,金屬奈米線嵌入基板中之程度可影響嵌入表面之粗糙度,例如當量測為跨越嵌入表面之高度變化程度時(例如,相對於平均高度之標准偏差)。在一些實施例中,表面嵌入基板之粗糙度可小於嵌入結構之特性尺寸。
至少一根奈米線可自基板之嵌入表面延伸出0.1nm至1cm,例如1nm至100nm、1nm至50nm、50nm至100nm或100nm至100μm。在其他實例中,奈米線群體平均可自基板之嵌入表面延伸出0.1nm至1cm,例如1nm至100nm、1nm至50nm、50nm至100nm或100nm至100μm。在其他實例中,基板之實質上所有表面積(例如,嵌入表面之區)可由金屬奈米線覆蓋或佔據。在其他實例中,至多100%或至多75%之表面積由金屬奈米線覆蓋或佔據,例如至多50%之表面積、至多25%之表面積、至多10%、至多5%、至多3%之表面積或至多1%之表面積由金屬奈米線覆蓋。金屬奈米線不需要自基板之嵌入表面延伸出,且可經定位完全在嵌入表面下方。金屬奈米線在基板中之嵌入程度及表面積覆蓋率可根
據特定應用來選擇。
圖案成形糊可選擇性施加至基板,使得金屬奈米線選擇性切割成圖案。如本文所用,圖案可係指銀奈米線之任何預定配置。圖案成形糊可藉由網版印刷方法(例如,旋轉網版印刷)選擇性施加至基板。圖案成形糊可藉由以下選擇性施加至基板:首先將遮罩施加至基板且然後將圖案成形糊施加至基板,使得經遮蔽區域不會被圖案成形糊接觸,同時暴露區域由圖案成形糊接觸。圖案成形糊可藉由狹縫式模具塗佈、柔版印刷、凹版印刷、唧筒分配印刷、及/或氣溶膠噴射印刷選擇性施加至基板。
視情況,可實施活化或退火操作以促進圖案成形糊之反應或其他活性,例如藉助在高於室溫或高於25℃、至少30℃、至少40℃、至少50℃、至少60℃、至少70℃或至少80℃且至多150℃、至多140℃、至多130℃、至多120℃、至多115℃、至多110℃或至多100℃之溫度下並持續至少30秒、至少45秒、至少1分鐘、至少1.5分鐘、至少2分鐘、至少3分鐘、至少4分鐘或至少5分鐘且至多2小時、至多1.5小時、至多1小時、至多50分鐘、至多45分鐘、至多40分鐘、至多35分鐘、至多30分鐘、至多20分鐘、至多10分鐘、至多5分鐘或至多2分鐘之持續時間實施加熱或其他熱或賦能處理。視情況,可實施清潔、洗滌或沖洗操作以自基板去除任何殘餘圖案成形糊,例如藉助使用加壓水或其他適宜溶劑,且可實施淬滅操作以進一步淬滅圖案成形糊之反應或其他活性。
經圖案成形基板可用於消費型電子產品中,例如其電路板或天線。經圖案成形基板可用於(例如)太陽能電池(例如,薄膜太陽能電池及晶體矽太陽能電池)、顯示裝置(例如,平板顯示器、液晶顯示器(或LCD)、電漿顯示器、有機發光二極體(或OLED)顯示器、電子紙
(electronic-paper或e-paper)、量子點顯示器(例如,QLED顯示器)及撓性顯示器)、固態發光裝置(例如,OLED發光裝置)、觸控感測器裝置(例如,投射電容式觸控感測器裝置、玻璃觸控感測器裝置、覆蓋層觸控(touch-on-lens)投射電容式觸控感測器裝置、on-cell或in-cell投射電容式觸控感測器裝置、自電容式觸控感測器裝置、表面電容式觸控感測器裝置及電阻式觸控感測器裝置)、智慧窗(或其他窗)、擋風玻璃、航空航天用透明件、電磁干擾屏蔽件、電荷消散屏蔽件及防靜電屏蔽件以及其他電子、光學、光電子、量子、光伏及電漿裝置。基板可端視特定應用而經調諧或最佳化,例如在光伏裝置之背景下之功函數匹配或基板之調諧以與其他裝置組件或層形成歐姆接觸。
適宜電子產品之非限制性實例包括(但不限於)包括觸控螢幕(例如行動電話螢幕、平板電腦螢幕、電腦螢幕及諸如此類)之電子產品。
基板可在觸控感測器裝置中用作電極。觸控感測器裝置通常經實現為與顯示器整合之交互輸入裝置,其允許使用者藉助接觸觸控螢幕來提供輸入。觸控螢幕通常係透明的,以允許光及影像藉助裝置傳輸。
期望導電跡線間之足夠電隔離以隔離電信號,從而達成觸控感測或像素切換中之空間解析度。期望經圖案成形基板之足夠透明性以達成較高顯示器亮度、反差比、影像品質及功率消耗效率,同時期望足夠導電性以維持高信號雜訊比、切換速度、刷新率、響應時間及均一性。對於其中期望電圖案成形但不期望光學上(例如,對人眼可見)可觀察到之圖案成形之應用而言,期望足夠圖案不可見性或低圖案可見性。尤其期望人眼幾乎或實質上不可區分之電隔離圖案。自基板之多個部分在很大程度上
或實質上去除金屬奈米線之圖案成形方法一般係不期望的,此乃因在典型室內照明或在高強度光照明(例如太陽光暴露或暴露於來自其他源之高強度可見光)下,材料經去除之部分可在視覺上藉由人眼與未去除材料之部分區分開。另外,期望低成本、可溶液處理之圖案成形方法或組合物,以(例如)提供與噴墨印刷、網版印刷或凹版印刷之相容性。
呈現以下實例以展現本發明之一般原理。本發明不應被視為受限於所呈現之具體實例。除非另有指示,否則實例中之所有份數及百分比皆以重量計。
圖案成形糊係藉由將7.24克去離子水及28.96克乙二醇添加於配備有攪拌器之10盎司聚丙烯容器中來製備。將4.24克2-羥乙基纖維素(HEC)(黏度平均分子量(Mv)90,000)經由攪拌器併入。一旦HEC溶解,便經由攪拌器將10克胍硫氰酸鹽併入並混合直至溶解。一旦胍硫氰酸鹽溶解,便混入0.25克SULFOPON 30 S03。在添加SULFOPON 30 S03之後直接混入0.57克TEGO Airex 902 W。混入48.74克BLANC FIXE MICRO(硫酸鋇),直至觀察到混合物之均質分散液為止。然後將材料轉移至三輥磨機並藉助磨機進行處理並置於新的10盎司聚丙烯容器中。
1 乙二醇,自Shell Chemicals Company(Houston,TX)市售購得
3 表面活性劑,自BASF(Ludwigshafen,Germany)市售購得
4 AgNW銀浸出劑/配體,自TOKU-E(Bellingham,WA)市售購得
5 硫酸鋇,自Huntsman Corporation(The Woodlands,TX)市售購得
6 Deaerator,自Evonik Industries(Essen,Germany)市售購得
圖案成形糊材料係藉由將7.65克去離子水及30.58克乙二醇添加至配備有攪拌器之10盎司聚丙烯容器中來製備。將4.48克2-羥乙基纖維素(HEC)(黏度平均分子量(Mv)90,000)經由攪拌器併入。一旦HEC溶解,便經由攪拌器將4.97克胍硫氰酸鹽併入並混合直至溶解。一旦胍硫氰酸鹽溶解,便混入0.26克DYNAX DX4005N。在添加DYNAX DX4005N之後直接混入0.60克TEGO Airex 902 W。混入51.47克BLANC FIXE MICRO(硫酸鋇),直至觀察到混合物之均質分散液為止。然後將材料轉移至三輥磨機並藉助磨機進行處理並置於新的10盎司聚丙烯容器中。
7 潤濕及流平添加劑,自Dynax Corporation(Pound Ridge,NY)市售購得
圖3A-3C顯示包括金屬奈米線之基板之掃描電子顯微鏡影像,該基板使用實例2之含有胍硫氰酸鹽之圖案成形糊經圖案成形。圖3A-3C分別顯示經實例2之圖案成形糊處理並在115℃下活化1分鐘、1.5分鐘及2分鐘之基板。如可看出,在活化期間,切割量隨時間而變化。圖3A顯示在1分鐘時達成之一定切割量,在1.5分鐘之後達成更多切割(圖3B),且在2分鐘之後達成進一步切割(圖3C)。
下表3顯示實例1及2中所包括之若干組分之組成優點。
圖案成形糊係藉由將7.24克去離子水及28.96克乙二醇添加於配備有攪拌器之10盎司聚丙烯容器中來製備。將4.24克2-羥乙基纖維素(HEC)(黏度平均分子量(Mv)90,000)經由攪拌器併入。一旦HEC溶解,便經由攪拌器將10克硫氰酸鉀併入並混合直至溶解。一旦硫氰酸鉀溶
解,便混入0.25克SULFOPON 30 S03。在添加SULFOPON 30 S03之後直接混入0.57克TEGO Airex 902 W。混入48.74克BLANC FIXE MICRO(硫酸鋇),直至觀察到混合物之均質分散液為止。然後將材料轉移至三輥磨機並藉助磨機進行處理並置於新的10盎司聚丙烯容器中。
包括金屬奈米線之兩個基板(面板A及B)各自使用比較實例3之圖案成形糊沿面板之長度在細長之平行單元中經圖案成形,並在115℃下活化1.25分鐘。用去離子水洗滌並用無絨布乾燥,在Fluke 189萬用表上測試面板之點對點電阻。利用每一面板在316.7(面板A)及260.5(面板B)處之點對點電阻量測在一個單元內實施電阻(以歐姆計)之電隔離量測。在毗鄰單元之間,點對點電阻(以歐姆計)在258.8-316.2(面板A)及247.2-296.5(面板B)之範圍內。面板A及B之電阻率指示使用KSCN之圖案成形糊沒有如使用胍硫氰酸鹽之實例1及2之圖案成形糊在低溫下所發生的那樣切斷金屬奈米線。
本發明進一步包括以下條款之標的物:
條款1:一只用於使金屬奈米線圖案成形之圖案成形糊,
該圖案成形糊包含含有胍硫氰酸鹽之錯合劑。
條款2:條款1之圖案成形糊,其進一步包含載劑,該載劑包含:增稠劑;及溶劑。
條款3:條款1或2之圖案成形糊,其中該錯合劑進一步包含胺。
條款4:條款3之圖案成形糊,其中該胺包含雙(六亞甲基)三胺。
條款5:條款3或4之圖案成形糊,其中該圖案成形糊包含基於該圖案成形糊之總重量0.1至12重量%之該胺。
條款6:前述條款中任一者之圖案成形糊,其中該圖案成形糊包含基於該圖案成形糊之總重量1至35重量%之該錯合劑。
條款7:條款2至6中任一者之圖案成形糊,其中該圖案成形糊包含保濕劑,其中該圖案成形糊包含基於該圖案成形糊之總重量至多50重量%之該保濕劑。
條款8:前述條款中任一者之圖案成形糊,其中該圖案成形糊切割金屬奈米線。
條款9:條款8之圖案成形糊,其中該等金屬奈米線包含銀、金、銅、及/或鎳奈米線。
條款10:條款2至9中任一者之圖案成形糊,其中該圖案成形糊包含基於該圖案成形糊之總重量至多10重量%之該增稠劑。
條款11:一種使包含金屬奈米線之基板選擇性圖案成形之方法,其包含:提供具有帶有金屬奈米線之表面之基板;及將包含含有胍硫氰酸鹽之錯合劑之圖案成形糊選擇性施加至該基板,使得將該等金屬奈
米線選擇性切割成圖案。
條款12:條款11之方法,其進一步包含:在該圖案成形糊選擇性施加至該基板之後,去除該圖案成形糊。
條款13:條款11或12之方法,其中該等金屬奈米線包含銀奈米線。
條款14:條款11至13中任一者之方法,其中該圖案成形糊係藉由網版印刷選擇性施加至該基板。
條款15:條款11至14中任一者之方法,其中在將該圖案成形糊選擇性施加至該基板之前,將遮罩施加至該基板。
條款16:一種消費型電子產品,其包含:具有帶有金屬奈米線之表面之基板,其中該基板之該等金屬奈米線係藉由將包含含有胍硫氰酸鹽之錯合劑之圖案成形糊施加至該基板來選擇性圖案成形,使得將該等金屬奈米線選擇性切割成圖案。
條款17:條款16之消費型電子產品,其中該錯合劑進一步包含胺。
條款18:條款16或17之消費型電子產品,其中該等金屬奈米線包含銀奈米線。
條款19:條款16至18中任一者之消費型電子產品,其中該基板包含電路板或天線。
條款20:條款16至19中任一者之消費型電子產品,其中該消費型電子產品包含觸控螢幕。
儘管上文已出於說明目的闡述本發明之特定實施例,但對彼等熟習此項技術者而言顯然將可對本發明細節作出多種改變,而不背離
如隨附申請專利範圍中所界定之本發明。
Claims (20)
- 一種用於使金屬奈米線圖案成形之圖案成形糊,該圖案成形糊包含含有胍硫氰酸鹽之錯合劑。
- 如請求項1之圖案成形糊,其進一步包含含有以下組分之載劑: 增稠劑;及 溶劑。
- 如請求項1之圖案成形糊,其中該錯合劑進一步包含胺。
- 如請求項3之圖案成形糊,其中該胺包含雙(六亞甲基)三胺。
- 如請求項3之圖案成形糊,其中該圖案成形糊包含基於該圖案成形糊之總重量0.1至12重量%之該胺。
- 如請求項1之圖案成形糊,其中該圖案成形糊包含基於該圖案成形糊之總重量1至35重量%之該錯合劑。
- 如請求項2之圖案成形糊,其中該圖案成形糊包含保濕劑,其中該圖案成形糊包含基於該圖案成形糊之總重量至多50重量%之該保濕劑。
- 如請求項1之圖案成形糊,其中該圖案成形糊切割金屬奈米線。
- 如請求項8之圖案成形糊,其中該等金屬奈米線包含銀、金、銅及/或鎳奈米線。
- 如請求項2之圖案成形糊,其中該圖案成形糊包含基於該圖案成形糊之總重量至多10重量%之該增稠劑。
- 一種使包含金屬奈米線之基板選擇性圖案成形之方法,其包含: 提供具有帶有金屬奈米線之表面之基板;及 將包含含有胍硫氰酸鹽之錯合劑之圖案成形糊選擇性施加至該基板,使得將該等金屬奈米線選擇性切割成圖案。
- 如請求項11之方法,其進一步包含: 在將該圖案成形糊選擇性施加至該基板之後,去除該圖案成形糊。
- 如請求項11之方法,其中該等金屬奈米線包含銀奈米線。
- 如請求項11之方法,其中該圖案成形糊係藉由網版印刷選擇性施加至該基板。
- 如請求項11之方法,其中在將該圖案成形糊選擇性施加至該基板之前,將遮罩施加至該基板。
- 一種消費型電子產品,其包含: 具有帶有金屬奈米線之表面之基板, 其中該基板之該等金屬奈米線係藉由將包含含有胍硫氰酸鹽之錯合劑之圖案成形糊施加至該基板來選擇性圖案成形,使得將該等金屬奈米線選擇性切割成圖案。
- 如請求項16之消費型電子產品,其中該錯合劑進一步包含胺。
- 如請求項16之消費型電子產品,其中該等金屬奈米線包含銀奈米線。
- 如請求項16之消費型電子產品,其中該基板包含電路板或天線。
- 如請求項16之消費型電子產品,其中該消費型電子產品包含觸控螢幕。
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