TWI425079B - 用於蝕刻氧化型、透明及導電性層之可印刷媒質 - Google Patents
用於蝕刻氧化型、透明及導電性層之可印刷媒質 Download PDFInfo
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- TWI425079B TWI425079B TW096140455A TW96140455A TWI425079B TW I425079 B TWI425079 B TW I425079B TW 096140455 A TW096140455 A TW 096140455A TW 96140455 A TW96140455 A TW 96140455A TW I425079 B TWI425079 B TW I425079B
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- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000003631 wet chemical etching Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Description
本發明關於新穎的可印刷蝕刻媒質,其具有改良的性質以用於製造太陽能電池之方法中。此媒質為對應的含粒子組成物,且藉由彼可極為選擇性地蝕刻極細的線條和結構而來損及或傷及毗鄰部位。
於太陽能電池製程中,有需要,特別地,在承載材料上結構化氧化物層。晶矽太陽能電池常由p-傳導性基板所組成,於其內,會在前面擴散一層具均勻厚度的n-傳導物質層,例如,磷層。為了傳導掉在光入射中產生的電流,於晶圓的前側和背側要施加金屬性傳導接觸。為了適合大量製造的便宜製法之目的,該接觸常利用網版印刷製成。
在太陽能電池製造中,除了必須結構化的氧化物層之外,也必須蝕刻氮化矽層。為了蝕刻相應的氮化物層,必須以適當方式修改所用方法及調適蝕刻糊。
晶矽太陽能電池的表面係在製程中,及合宜者也在其完成時,塗覆薄無機層。此等層具有在從20至200奈米範圍內,於大部份情況中,在從50至150奈米的範圍內之厚度。
於晶矽太陽能電池的製程中,因而有利地為在許多程序步驟中於此等太陽能電池無機層內蝕刻細線條。
在太陽能電池表面中的此等開口可用來,例如,產生所謂的選擇性發射極,也稱為兩段式發射極(two stage emitter)。為此目的,係在位於矽上的擴散障壁之部份開口中,於後面擴散步驟中產生高度n-摻雜,較佳者利用磷擴散入。
於本說明中,無機表面係意指矽的氧化型和含氮化物的化合物,特別者氧化矽和氮化矽之表面。此類型擴散障壁的操作方式係諳於此技者所知且在文獻中有述及者[A.Goetzberger;B.Vo β;J.Knobloch;Sonnenenergie:Photovoltaik[太陽能:光生優打(Photovoltaics)],Teubner Studienbcher Stuttgart 1997,pp 40,107]。此等擴散障壁於此可用多種方式製成。
經由,例如,在含氧的氣體環境中,於900℃區內的溫度下,熱處理矽,可得非常密實的二氧化矽層(熱氧化物)。
同樣為諳於此技者所知者為經由CVD程序的二氧化矽沈積。依進行反應的方式而定,於,例如,下列方法之間給予區別-APCVD(大氣壓CVD)-PE-CVD(電漿增強CVD)-LP-CVD(低壓CVD)
此等方法的共同特徵在於所需無機化合物都是得自揮發性先質的氣相,於二氧化矽例中,該先質為,例如,矽烷(SiH4
)或TEOS(原矽酸四乙酯),經由將先質沈積在目標基板上再分解。
代表擴散障壁的二氧化矽層也可利用以液體或溶解在溶劑或溶劑混合物之固體先質進行濕式化學塗覆而得。此等液體系統通常係經由旋塗而施加在要塗覆的基板上。此等系統為諳於此技者所知悉的旋塗玻璃(spin-on-glass)(SOG)。
於許多情況中,經施加的SiO2
層也保留為反射減低用鈍化層。此時常為出現在,特別者,熱生長SiO2
情況中之情況。
除了氧化矽層之外,透明傳導層(TCOs)也起著重要作用(例如LC顯示器、觸控面板,等)。除了有二元或三元摻雜的ZnO化合物(諸如,銦-鋅氧化物,Al-ZnO,銻-ZnO)之外,銦-錫氧化物層特別廣用。銦-錫氧化物為由氧化銦(In2
O3
)和氧化錫(IV)(SnO2
)所組成的混合氧化物(不過也可用其他摻雜劑,諸如,氟,如FI:SnO2
)。此等TCO層於下文以ITO為例提及。此等透明半導體具有導電性與透明性之性質。於電子工業中,彼等係用來製造薄膜太陽能電池,液晶螢幕中的透明電極,有機發光二極體和觸控螢幕。作為可強烈反射紅外輻射的半導體,ITO係以散射方式或在大面積上施用作為窗玻璃板的熱防護。有非常廣多種表面,例如,塑膠膜,可同樣地用ITO塗覆以使彼等不會荷靜電。
ITO常由90%的氧化銦(In2
O3
)和10%的氧化錫(IV)(SnO2
)所組成。氧化錫(IV),作為摻雜劑,會在氧化銦晶體結構中產生良好導電性所需的瑕疵(flaw)。典型地約200奈米之薄層具有高透明度且具有約6歐姆/平方厘米(Ohm/cm2
)的表面電阻。
ITO常經由陰極濺鍍施加到相應的基板上-幾乎總是玻璃。不過,ITO也可用高真空氣相沈積來施加,不過經由氣相沈積塗覆的化合物必須熱到高達360℃,此限制其可應用性。
氮化矽層較少在晶矽太陽能電池技術中用為擴散障壁,雖則彼等原則上同樣可適用於此目的。氮化矽層基本上用為鈍化層和抗反射層。
於晶矽太陽能電池的製造中,有利地也為能在氮化矽層中以目標導向方式製造開口。於此可提及的一例子為施加導電性糊。此等金屬糊常在約600℃溫度〝煅燒〞透過氮化矽層,促成對發射極層的電接觸。由於此等高溫,因此以聚合物為基(環氧樹脂或酚樹脂)的金屬塗敷糊不能用於此目的。於燒透程序的實施中也會發生底下矽中的晶體缺陷和金屬污染。此外,該系統的後果為鈍化層會被印在頂部上的金屬糊所完全破壞。所以,更有利者為在氮化矽層中製造出供電接觸用的部份型更窄的開口及保留在邊緣區中的鈍化層,其係由頂部上面的金屬塗敷層所遮罩。
除了由二氧化矽或氮化矽組成的純擴散障壁之外,也可以在晶矽太陽能電池的製造中使用薄玻璃層。
玻璃的定義:玻璃係意指本身為均勻的組成物,例如石英、窗玻璃-硼矽酸鹽玻璃;不過也指在其他基材(如陶瓷、金屬片、矽晶圓)之上,以諳於此技者所知的各種方法(CVD、PVD、旋塗、熱氧化,等)製成的此等材料之薄層。
下文中的玻璃係意指含氧化矽-和含氮化矽的材料,彼等係呈固體非晶型物理狀態,其玻璃成分沒有結晶出且在微結構中因缺乏長程序(long-range order)而具有高無序(disorder)度。
除了純SiO2
玻璃(石英)之外,此等涵蓋含有SiO2
和其他成分,特別是元素諸如鈣、鈉、鋁、鉛、鋰、鎂、鋇、鉀、硼、鈹、磷、鎵、砷、銻、鑭、鋅、釷、銅、鉻、鎘、鐵、鈷、鎳、鉬、釩、鈦、金、鉑、鈀、銀、鈰、銫、鈮、鉭、鋯、釹、鐠,彼等係以氧化物、碳酸鹽、硝酸鹽、磷酸鹽、硫酸鹽及/或鹵化物之形式存在於玻璃中作為玻璃中的摻雜元素;之所有玻璃(例如摻雜玻璃,諸如硼矽酸鹽、磷矽酸鹽和硼磷矽酸鹽等玻璃;有色玻璃;乳白玻璃;水晶玻璃;光學玻璃)。摻雜玻璃為,例如,硼矽酸鹽、磷矽酸鹽和硼磷矽酸鹽玻璃,有色玻璃,乳白玻璃,水晶玻璃和光學玻璃。氮化矽可同樣地包含其他元素,諸如硼、鋁、鎵、銦、磷、砷或銻。
以氧化矽-和氮化矽-為基的系統之定義:以氧化矽為基的系統在下文中係定義為不落於上面所給非晶型SiO2
玻璃的定義下且以二氧化矽為基之所有晶型系統;此等可為,特別者,原矽酸的鹽類和酯類及彼等的縮合產物-通常為諳於此技者所稱的矽酸鹽類-以及石英和玻璃陶瓷。
再者,也涵蓋其他以氧化矽-和氮化矽-為基的系統,特別是原矽酸的鹽類和酯類及彼等的縮合產物。除了純SiO2
(石英、鱗石英(tridymite)、白矽石(cristobalite)),也涵蓋從SiO2
或〝離散〞及/或聯結[SiO4
]四面體,諸如,中矽酸鹽(mesosilicates)、獨矽酸鹽(solosilicates)、環矽酸鹽、無機矽酸鹽、葉矽酸鹽、架狀矽酸鹽(tectosilicate)且包含其他成分,特別者,元素/成分諸如鈣、鈉、鋁、鋰、鎂、鋇、鉀、鈹、鈧、錳、鐵、鈦、鋯、鋅、鈰、釔、氧、羥基、鹵化物所構建成的所有以SiO2
為基的系統。
以氮化矽為基的系統在下文中係經定義為不落在上面所給非晶型氮化矽玻璃/層的定義下之所有晶型和部份晶型(常稱為微晶型)系統。此等包括Si3
N4
,其α-Si3
N4
和β-Si3
N4
等改質形式以及所有晶型和部份晶型SiNx
和SiNx
:H層。晶型氮化矽可包含其他元素,諸如硼、鋁、鎵、錮、磷、砷、和銻。
結構之蝕刻蝕刻劑,即化學侵蝕性化合物,之使用導致暴露於蝕刻劑作用下的物質之溶解。於大部份情況中,其目標為完全移除要蝕刻的層。於碰到對蝕刻劑有實質抗性的層時即達到蝕刻結束。此外,也有諳於經由蝕刻到常經界定的目標厚度以部份移除一層之技藝者所知之方法。
在以氧化矽-和氮化矽-為基的玻璃及其他以氧化矽-和氮化矽為基的系統上之結構體之蝕刻:根據現有技藝狀態,任何所欲結構體都可在以氧化矽-和氮化矽-為基的玻璃中和其他以氧化矽-和氮化矽-為基的系統或其表面及其可變厚度的層之中經由雷射支援的蝕刻方法,或在遮罩後,經由濕式化學法([1]D.J.Monk,D.S.Soane,R.T.Howe,Thin Solid Films 232(1993),1;[2]J.Bhler F.P.Steiner.H.Baltes,J.Micromech.Microeng.7(1997),R1)或經由乾式蝕刻法([3]M.Khler〝tzverfahren fr die Mikrotechnik〞[微型技術用之蝕刻方法],Wiley VCH 1983),而選擇性地蝕刻成。
於雷射支援的蝕刻模組中,在向量取向系統中,雷射光束會逐點地(dot-by-dot)或逐線(line-by-line)地掃在玻璃上的整個蝕刻圖案,此,除了高度精確性外,也需要顯著的調整精力和時間。
濕式化學法和乾式蝕刻法都包括材料密集性,耗時且昂貴的程序步驟:A.不蝕刻部位的遮罩,例如用:.光平版印刷法:產生負型或正型蝕刻結構(依阻劑而定),基板表面的塗覆(例如用液體光阻劑旋塗),光阻劑的乾燥,塗覆的基板表面之曝光,顯像,清洗,隨意地乾燥。
B.結構的蝕刻,用:.浸蝕法(例如在濕式化學檯中濕式蝕刻):將基板浸在蝕刻槽內,蝕刻操作,在H2
O級聯沈槽中重複清除、乾燥.旋塗或噴布法:將蝕刻溶液塗佈在轉動的基板上,可在沒有或有輸入能量(例如IR或UV輻射)之下進行蝕刻操作,此接著為清洗和乾燥.乾式蝕刻法,諸如,電漿蝕刻,在昂貴的真空單元中,或在流動反應器內用反應性氣體蝕刻
C.光阻劑移除:於最後的程序步驟中,必須移除覆蓋基板保護部位的光阻劑。此可利用溶劑,例如,丙酮,或稀的鹼性水溶液來進行。最後將基板清洗和乾燥。
以氧化矽-和氮化矽-為基的玻璃及其他以氧化矽-和氮化矽-為基的系統之全面蝕刻:為了蝕刻以氧化矽-和氮化矽-為基的玻璃及其他以氧化矽-和氮化矽-為基的系統及其不同厚度的層上的完全地整個部位或只到某一深度,主要是使用濕式蝕刻法。其中係將以氧化矽-和氮化矽-為基的玻璃及其他以氧化矽-和氮化矽-為基的玻璃及彼等具不同厚度之層浸在蝕刻槽中,其常含有毒性和高苛性氫氟酸及隨意地其他礦酸添加劑。
所述諸蝕刻法之缺點係來自耗時、材料密集及昂貴的程序步驟,彼等於某些情況中從技術和安全性上而言非常複雜且,此外,也常不連續地實施。
國際專利申請WO 01/83391A述及呈可印刷、均質、無粒子蝕刻糊形式的蝕刻媒質,其具有非牛頓性(non-Newtonian)流動行為,用於蝕刻無機,玻璃狀非晶型或晶型表面,特別是玻璃或陶瓷,較佳者以SiO2
-或氮化矽-為基的系統之表面;及此等蝕刻媒質之用途。特別是在表面的印刷上,因為印刷出的線條、點或結構體具有不足的彈性(resilience)(不足的結構保真度),意即原印線條會發生明顯的變寬(蝕刻物種在基板上流動),使此等無粒子媒質的使用產生問題。
US 5,688,366 A使用含粒子的蝕刻糊來蝕刻透明傳導層,諸如,ITO層。所用蝕刻糊係從含結晶水的熔融氯化鐵,甘油和聚合物粒子製備者。此等組成物適合用來蝕刻具有約1毫米寬度的線條。實驗證明此等蝕刻糊不適合用來清楚且無瑕疵地用來蝕刻具有小於1毫米的寬度之非常細線條,不論其是否採用具有0.01微米至30微米的直徑之聚合物粒子來製備該糊。
本發明目的因而為提供新穎不貴的蝕刻糊以用於在矽太陽能電池上的二氧化矽及/或氮化矽層,特別者,也在傳導層上蝕刻具有小於100微米,特別者小於80微米的寬度之非常均一的細線條,及極細微的結構體。本發明的另一目的為提供新穎的蝕刻媒質,其可在蝕刻後以簡單的方式從處理過的表面移除而不會留下殘渣且比已知的糊具有更具環境友善性質。
該目的係由一種新穎的用於蝕刻氧化型、透明及導電性表面和層且呈蝕刻糊型式之可印刷、可分配之蝕刻媒質所達成,該媒質包含a)磷酸b)至少一種溶劑,c)石墨及/或碳黑,其具有介於80奈米至20奈米之相對粒徑及介於40至100平方米/克的BET比表面積,d)隨意地增稠劑,及e)隨意地添加劑,諸如消泡劑、搖變劑、流動控制劑、除氣劑及黏著促進劑。
於特別具體實例中,此類型的蝕刻媒質包含具有小於50奈米的相對粒徑和介於50至70平方米/克的BET比表面積之石墨或碳黑。業經證明特別有利者為所含石墨或碳黑具有介於30至45奈米的相對粒徑。包含具有40奈米之相對粒徑和62平方米/克之BET比表面積的碳黑粉末之蝕刻媒質具有非常特佳的性質。雖然在早先組成物中需要更高比例的固體,不過,根據本發明,少於8重量%但大於0.5重量%量的具有該等性質之石墨或碳黑粉末的添加可以給出能印刷成極細線條的形式之組成物。具有介於3至7重量%量的石墨或碳黑粉末且介於25至35 Pas的黏度之組成物具有特佳性質。相應的組成物可有利地用以介於120至170℃之溫度下蝕刻ITO層。
該新穎糊調合物在針對表面清潔、印刷精確度及蝕刻操作後的廢水污染上具有明顯改良的性質。令人訝異地,經發現,有加入極細微粒狀無機粉末,特別者細微粒狀石墨及/或碳黑的該蝕刻糊在用於在120至170℃間的溫度蝕刻ITO時,相較於加入市售石墨或碳黑的糊而言,具有改良的清潔性質。處理過的表面之後續清潔係用去離子水進行。
再者,本發明新穎糊調合物的一項基本優點係在於所含無機粉末在蝕刻溫度下不會變化且不會熔化,反而有助於下述事實:該蝕刻糊可用極細線條或極細結構形式施加在表面上而不會流動和旁漏且能夠隨後在蝕刻操作中擴散到作用部位。特別者,具有小於80奈米,特別者小於50奈米,較佳者45奈米至30奈米的相對粒徑,及在從40至100平方米/克,較佳者從50至70平方米/克的BET比表面積,之無機石墨或碳黑粉末的使用可給出改良的結果。非常特佳者為使用具有約40奈米的粒徑和約62平方米/克的BET比表面積之碳黑粉末。此等碳黑粉末的使用給出特佳的蝕刻結果。與最小直徑為3至5微米的聚合物粉末的使用相比,由於奈米粒狀碳黑粒子的添加,可以印刷且蝕刻出明顯更細的線條與更小的結構體,即,達到明顯改良的印刷精密度,且可在ITO上印刷和蝕刻出明顯更小的結構體。因此之故,可望在簡單的顯示器中及在高解析度TFT顯示器中有新穎潛在應用,如圖1至3中顯示者。
本發明糊係使用具有上述性質且符合尺寸和表面要求的市售石墨或碳黑粉末製備者。於此可舉例提及者為商品Super PTM
(得自TIMCAL Graphite & Carbon,Switzerland的傳導性碳黑)。其粒度通常可用習用方法予以測定。例如,其粒度可利用粒子相關光譜術(PCS)測定,使用Malvern zetasizer根據操作手冊進行研究。於此,粒子的直徑係經測定為d50
或d90
值。所示粒徑較佳者表為d50
值。
粒徑通常可利用雷射繞射配合線上分析予以測定。於此方面,係將雷射光束射到分布於透明氣體,例如空氣中的粒子雲中。粒子折射該光,小粒子以比大粒子較大的角度折射該光。散射角因而直接關聯於粒子尺寸。所觀測到的散射角會隨著粒子尺寸的減低而呈對數地增加。折射後的光係用配置在各種角度的許多光偵測器予以測量。該等測量較佳地係使用Mie光繞射理論來評定,其係建基於Maxwell的電磁場方程式。此理論係以兩項假設為基礎。第一,假設要測量的粒子係球體,但此於實際上只能應用於少數種粒子。所測量的雷射繞射係用來計算粒子的體積。第二,假設稀的粒子懸浮體。常用來以動態光散射測定在奈米範圍內的粒子尺寸之方法在得自Malvern Instruments Ltd.的小冊〝Dynamic Light Scattering:An Introduction in 30 Minutes〞,DLS技術記要,MRK656-01中有更詳細的說明。
在奈米粒子範圍中的粒度也可藉助於掃描電子顯微照片(SEM照片)予以測定。於此方面,可製備含粒子的乳液且在旋塗程序中在適當表面上塗佈或極薄的層。於蒸發掉溶劑之後,取得SEM照片且測量所記錄到的粒徑。所測量的樣品之相對粒徑係以統計評定予以測定。適用於此目的之測定粒子尺寸的標準化方法與裝置載於ISO 13321,〝Methods for Determination of Particle Size Distribution Part 8:Photon Correlation Spectroscopy,International Organisation for Standardisation[(ISO)1996(First Edition 1996-07-01)],包括測定在奈米測量範圍中的尺寸所用方法。
業經證明特別有利者,根據本發明的奈米粒子碳黑之使用可使得對蝕刻糊組成物的固體添加量明顯減少。令人訝異地,業經發現,若採用奈米粒狀碳黑,相比於在具有可相比黏度的糊中使用聚合物粒子之情況,可將蝕刻糊中的固體百分比減低超過70重量%。此點特別可用於具有在從20奈米至80奈米的相對粒徑及在從40至100平方米/克範圍中的BET比表面積之石墨及/或碳黑的使用。
特別是在使用具有約40奈米的相對粒徑和約62平方米/克的BET比表面積之碳黑粒子於相應的組成物中之時,在與添加具有在3至5微米範圍中的相對粒徑之聚合物粒子以製備具有低於40Pas,特別是約30Pas的黏度之糊時相比較之下,固體添加量可以減低約74%。以此方式,可以製備出明顯更具環境友善性之糊。此也促成從廢水移除懸浮粒子所需的廢水過濾器之使用壽命顯著地延長,更明顯地,用於從清潔經蝕刻的表面所用清洗操作中產生的廢水移除懸浮粒子所用者。
令人訝異地,測量證明經清洗掉的碳黑粒子(活性碳)對於糊的有機增稠劑添加劑和有機溶劑成分具有吸附性作用。其後果為清洗水的BOD5值(毫克/升)可經由單純的粒子過濾予以減低。BOD5值為廢水在5天中的生物需氧量(毫克/升),係根據DIN 38409 H51測量者。在,例如,使用包含聚合物粒子及其他都相同的組成物時測定出14毫克/升的BOD5值,但在使用包含根據本發明添加的碳黑粒子之蝕刻糊時,在每一情況中於清洗水中有相同量的糊(135毫克糊/0.5升清洗水)之時,只測得7至8毫克/升之BOD5值。
經證明特別有效的有效蝕刻成分為,特別者,磷酸,更明確而言,濃度在從約35至50重量%範圍內者。具有在從40至50重量%範圍內的磷酸濃度之組成物業經證明係特別有效者。彼等具有非常特別有利的性質,因為彼等可以良好地印刷在表面上且給出很好的蝕刻結果。特佳者為具有45至46重量%磷酸含量之蝕刻糊。
為了製備該蝕刻糊,乃將各成分依序於依下述方式充足混合之下予以彼此混合:於添加蝕刻成分中只能中度地增加溫度,但在混合中要形成具有適當黏度的糊。
如已經指出者,若其中含有具有在從20奈米至80奈米範圍內的相對粒徑及在40至100平方米/克的BET比表面積之石墨和碳黑,則該蝕刻糊可印刷出特別細的線條和結構體。此處,該粒子的表面本質不僅對於作為蝕刻糊之性質具有重要性,而且,如上所述者,會顯著地影響該糊的環境接受性。
因此,為製備本發明糊,較佳地要使用具有小於50奈米的相對粒徑和在50至70平方米/克範圍內的BET比表面積之石墨及/或碳黑。特佳者為具有在從30奈米至45奈米範圍內的相對粒徑的粉末且非常特佳者為具有40奈米的相對粒徑和62平方米/克的BET比表面積之碳黑粉末,因為此等組成物可導致特低之BOD5值之故。
為了導致有利的糊性質,呈石墨及/或碳黑形式的固體粒子在組成物中的含量必須小於8重量%。較佳地於糊中加入3至7重量%的奈米粒狀石墨或碳黑粉末。特別者,約5至6重量%的添加可給出具有在從25至35Pas範圍內的黏度之蝕刻糊,其可極好地印刷,如圖1至圖3中的蝕刻圖所非常清楚地顯示者。不過,0.5重量%的較少量奈米粒狀碳黑或石墨之添加也已可導致,與使用含相同量的聚合物粒子之糊相比之下,在印刷中的改良行為。即使此等小量的粒子也能促成有減小的線條寬度之印刷。
除了奈米粒狀石墨或碳黑外,該糊可包含增稠劑和隨意的添加劑,諸如消泡劑、搖變劑、流動控制劑、除氣劑和黏著促進劑。可摻入之溶劑為水及/或有機溶劑。例如,本發明糊中除了磷酸和碳黑或石墨粉等基本組份之外可包含水、聚乙烯基吡咯烷酮和1-甲基吡咯烷酮。雖則1-甲基吡咯烷酮可能與磷酸的含量相同,但聚乙烯基吡咯烷酮常以少於10重量%之量,較佳者以約5至6重量%的量存在。
對所欲目的具有有利性質的添加劑為消泡劑,諸如可在商品名TEGOFoamex N之下取得者,搖變劑,諸如BYK410、BorchigelThixo2,流動控制劑,諸如TEGOGlide ZG400,除氣劑,諸如TEGOAirex 985,及黏著促進劑,諸如BayowetFT929。
對於諳於此技者毋須說者,此等添加劑也可用其他市售,具有相同作用的產品予以置換。於此方面必要者為此等添加劑的添加要改良產品性質。
在所進行的實驗中指定地採用之添加劑也在下面所給實施例中揭露出。此等對於蝕刻糊的可印刷性可能具有正面影響。添加劑的比例以蝕刻糊總重量為基準,在0至5重量%範圍內。
本發明蝕刻煳可用已知方式印刷在晶圓表面上。特別者,彼等可應用在<50微米的細線條印刷中。此可用於,例如,具有下列參數的網版中:網目計數:鋼織 350網目/吋絲直徑:16微米乳液厚度:10微米印刷中的網版分隔:75微米
圖1至3顯示出有印刷出各具不同厚度的線條之製造結果。此外,從這些圖可以看出,使用本發明糊可以蝕刻出小於100微米間隔的線條而不須用到光阻劑層。如此一來,使用本發明蝕刻糊可以用簡單方式製造出經高解析蝕刻出的結構體。
為了更佳地了解且為了闡明本發明,下面給出實施例,彼等都在本發明的保護範圍之內。此等實施例也用來闡述可能的變黑形式。不過,由於所述本發明原理的一般正確性,此等實施例不適合用來將本申請案的保護範圍縮減到只為此等之內。
對暗於此技者毋須說者,在所給實施例與本說明部份的其餘部份兩者之中,糊組成物中所含成分之量總是加起來全部都到100%,且即使在所示百分比範圍可能出現更高的值,也不可能更大。
包含無機奈米粒狀固體添加劑的蝕刻糊28克 去離子水223克 1-甲基-2-吡咯烷酮1.6克 乙二醇於此溶劑混合物依序攪拌加入下列成分:465克 磷酸(85%)和1克 聚乙烯基吡咯烷酮其中聚乙烯基吡咯烷酮係於激烈攪拌下摻入。接著將50克 碳黑加到透明均勻混合物中,再攪拌2小時。
該即可使用的糊可以使用280網目不鏽鋼織網予以印刷。原則上,也可以使用聚酯或相似的網材料。關鍵因素在於所選網版材料對於蝕刻組成物所含蝕刻成分係呈情性者。
所製蝕刻糊經證明在長期貯存後具穩定性,其有利的蝕刻性質都保留著。於下面的表中給出具有有利性質的根據本發明組成物之其他實施例。
圖1顯示出經蝕刻到ITO層內,具有20.93微米寬度之蝕刻線條。
圖2顯示出之條彼此併排的37.95微米寬度之蝕刻線條,各線條之間分隔98.25微米。
圖3顯示出具有38.4微米寬度為蝕刻線條之連續結構體。
從所示蝕刻圖可以看出本發明蝕刻糊適合用於連續地蝕刻即使極細的線條而在蝕刻徑迹過程中沒有發生線條終止現象。
Claims (8)
- 一種用於蝕刻氧化型、透明及導電性表面和層且呈蝕刻糊型式之可印刷、可分配之蝕刻媒質,其包含a)磷酸,b)至少一種溶劑,c)具有介於20奈米至80奈米的相對粒徑和介於40至100平方米/克的BET比表面積之石墨及/或碳黑,d)隨意地增稠劑,及e)隨意地添加劑,諸如消泡劑、搖變劑、流動控制劑、除氣劑及黏著促進劑。
- 根據申請專利範圍第1項之蝕刻媒質,其包含具有小於50奈米的相對粒徑和介於50至70平方米/克的BET比表面積之石墨或碳黑粉末。
- 根據申請專利範圍第1項之蝕刻媒質,其包含具有介於30至45奈米的相對粒徑之石墨或碳黑粉末。
- 根據申請專利範圍第1項之蝕刻媒質,其包含具有40奈米的相對粒徑和62平方米/克的BET比表面積之碳黑粉末。
- 根據申請專利範圍第1至4項中任一項之蝕刻媒質,其包含少於8重量%但大於0.5重量%量之石墨或碳黑粉末。
- 根據申請專利範圍第1至4項中任一項之蝕刻媒質,其包含3至7重量%量且黏度為25至35Pas之石墨或碳黑粉末。
- 一種申請專利範圍第1至6項中任一項之蝕刻媒質於半導體製造期間供蝕刻透明、導電性氧化型層上之用途。
- 一種申請專利範圍第1至6項中任一項之蝕刻媒質於介於120至170℃之溫度下蝕刻銦錫氧化物(ITO)上之用途。
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MY (1) | MY149959A (zh) |
PL (1) | PL2089491T3 (zh) |
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Also Published As
Publication number | Publication date |
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US8795549B2 (en) | 2014-08-05 |
WO2008052637A1 (de) | 2008-05-08 |
KR101465276B1 (ko) | 2014-11-26 |
KR20090087016A (ko) | 2009-08-14 |
HK1136004A1 (en) | 2010-06-18 |
DE102006051735A1 (de) | 2008-05-08 |
JP2010508664A (ja) | 2010-03-18 |
CN101600779B (zh) | 2013-06-26 |
JP5190063B2 (ja) | 2013-04-24 |
TW200827431A (en) | 2008-07-01 |
CN101600779A (zh) | 2009-12-09 |
PL2089491T3 (pl) | 2013-08-30 |
ES2416310T3 (es) | 2013-07-31 |
US20100068890A1 (en) | 2010-03-18 |
EP2089491A1 (de) | 2009-08-19 |
MY149959A (en) | 2013-11-15 |
EP2089491B1 (de) | 2013-04-10 |
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