TWI284423B - Methods and devices for fabricating and assembling printable semiconductor elements - Google Patents
Methods and devices for fabricating and assembling printable semiconductor elements Download PDFInfo
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- TWI284423B TWI284423B TW94118507A TW94118507A TWI284423B TW I284423 B TWI284423 B TW I284423B TW 94118507 A TW94118507 A TW 94118507A TW 94118507 A TW94118507 A TW 94118507A TW I284423 B TWI284423 B TW I284423B
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Classifications
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
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- 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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Description
1284423 , 九、發明說明: 【發明所屬之技術領域】 本發明係關於製造及組合可印刷半導體元件之方法及裝置。 【先前技術】 ,自從1994年首次展出一種經印刷之全聚合物電晶體以 , 來’吾人對一種在塑膠基板上包含可撓性整合電子裝置之 潛在新型電子系統產生濃厚興趣。[Gamier,F.,Hajlaoui, • R·,Yassar,A•及 Srivastava,P·,Science,Vol· 265,pgs 1684- 1686]最近,實質研究已針對開發用於可撓性塑膠電子裝 置之導體、介電質及半導體元件之新型溶液可處理材料。 然而’在可撓性電子裝置之領域中之進展不僅可藉由新型 /谷液可處理材料之開發來驅動,且可藉由新型裝置組件之 幾何形狀、有效的裝置及裝置組件之處理方法及可應用至 塑私基板之尚解析度圖案化技術來驅動。預期此等材料、 裝置組怨及製造方法將在快速出現之新型可撓性整合電子 φ 裝置、系統及電路中扮演重要角色。 對可撓性電子裝置之領域之興趣主要來源於此技術所提 供之若干重要優勢。第一,塑膠基板材料之機械強度提供 不易受機械應力引起之破壞及/或電子效能之降級之電子 裝置。第二,此等基板材料之固有可撓性允許其整合成多 種形狀提供大量有用裝置組態,而基於習知的脆性矽之電 子裝置不可能具有此性質。舉例而言,預期可彎曲可撓性 電子裝置可製造諸如電子紙、彳穿戴電腦及大面積高解析 度顯示器之新型f置,其利用所建立之基於石夕之技術係不 96164.doc 1284423 ^達成的。最後,溶液可處理組件材料與塑膠基板之組合 :藉由可以低成本於大基板區域上產生電子裝置之連續、 兩速之印刷技術來製造。 、
/而,設計及製造展現良好電子效能之可撓性電子裝置 提出大夏重大挑戰。首先,製造習知的基於矽之電子裝置 ”好開發方法不適於大部分塑膠材料。舉例而言,諸如 早晶:或鍺半導體之傳統高品質無機半導體組件通常藉由 在顯者超出大部分塑膠基板之溶融或分解溫度之溫度(大 ;攝氏1〇〇〇度)下生長薄膜來處理。此外,大部分無機半 Z體本質上不溶於便利的溶劑,其允許基於溶液之處理及 道送。第二’儘管多種非晶矽、有機或有機-無機混合半 導體適於倂人塑縣板中,且可在相對低溫下處理,作是 此等材料不具有可提供具有良好電子效能之整合電子裝置 之電子性質。舉例而言,具有此等材料製造之半導體元件 之賴電晶體展現小於基於互補單晶石夕之裝置約三個數量
、的琢效遷移率。由於此等限制,目前將可撓性電子裝置 限制於不需要高效能之转宏 特應用中,諸如用在用於具有非 ^ '、之主動式矩陣平板顯示器之開關元件中,及用 在發光二極體中。 =擴展塑膠基板上之整合電子裝置之電子效能能力 方面取传了進細將其助擴大至更廣泛之電子應用。舉 例而言,已出現若干新型薄膜電晶體( 在塑膠基板材料上進行處理4比具有非_、無^有 機-無機混合半導體元件之薄膜電晶體展現更高之裝置效 96164.doc 1284423 能特徵。-類更高效能可撓性電子裝置係基於藉由脈衝雷 射退火非晶矽薄膜製造之多晶矽薄膜半導體元件。雖然此 類可撓性電子裝置提供增強之裝置電子效能特徵,但是使 用脈衝雷射退火限制了製造此#裝置之簡易及$活性,_ 此顯著增加了成本。另—有希望之新型更高效能可撓性電 子裝置係採用諸如奈米線、奈米帶、奈米粒子及碳奈米管
之溶液可處理奈米級材料作為大量宏觀電子及微電子裝置 中之主動功能組件之裝置。 已將使用離散單晶奈米線或奈米帶估計為—種將展現增 強之裝置效能特徵的可印刷電子裝置提供於塑膠基板上之 可能的方式。Duan等人描述具有複數個選擇性定向之單晶 石夕奈米線或CdS奈米帶作為半導電通道之薄膜電晶體設計 [D職,X.,Niu,C·,Sahl,v·, Chen,j,卩⑽,j, Empedocles,S.及 G〇ldman,j,_阶,v〇i 425,卿 m Μ。作者報告了—種據宣稱適於在塑職板上進行溶液 处之製每方法,其中厚度小於或等於i %奈米之單晶石夕 奈米線或⑽奈米帶分散於溶液中,且利^向流動對準 方法(fl〇wdi⑽d alignment咖偏)組合於—基板表面上 =產生相電晶體之半導電㈣。作者提供之光學顯微圖 ^月所揭示之製造方法製備大體平行方向且相隔約則奈 =半0不米之早層奈米線或奈米帶。儘管作者報告了個 米帶具有相對較高之本質場效遷移率(約為119 Γ人^ ),但是最近已判定整個裝置場效遷移率比d疆 I之本質場效遷移率值"小約兩個數量級"[Mitzi, 96164.doc ‘1284423 ’ Kosbar,L.L·,Murray,C.E·,Copel,Μ· Afzali,A·,
Native’ V〇i· 428, pgs· 299_3〇3]。此裝置場效遷移率比習知 的單晶無機薄膜電晶體之裝置場效遷移率低若干數量級, 且其可月b歸因於在利用Duan等人所揭示之方法及裝置組態 來對準、密集封裝及電接觸離散奈米線或奈米帶中之實踐 挑戰。 亦已將使用奈米晶體溶液作為多晶無機半導體薄膜之前 _ .驅體開發為一種將展現更高裝置效能特徵的可印刷電子裝 置提供於塑膠基板上之可能方式。Ridley等人揭示一種溶 液處理製造方法,其中在塑膠可適應溫度下處理一尺寸約 為2奈米之溶液硒化鎘奈米晶體以提供一用於場效電晶體 之半導體元件。作者報告了 一種方法,其中則匕錦奈米晶 體溶液中之低溫晶粒生長提供了包圍數百奈米晶體之單晶 區域。儘管Ridley等人報告了相對於具有有機半導體元件 之對比裝置已改良之電性質,但藉由此等技術所達到之裝 籲置遷移率(約為i cm2 v-i〆)比習知的單晶無機薄膜電晶體 之裝置場效遷移率低若干數量級。藉由Ridley等人之裝置 組態及製造方法所達成之對於場效遷移率之限制可能由個 別奈米粒子之間所建立之電接觸產生。特定言之,使用有 機端基穩定奈米晶體溶液及防止聚結可阻礙在相鄰奈米粒 子之間建立良好電接觸,良好電接觸對於提供高裝置場效 遷移率是必需的。 儘管Diian等人及Ridley等人提供用於在塑膠基板上製造 薄膜電晶體之方A,但是所述之裝置組態採用包含諸如電 96164.doc 1284423 極、半導體及/或介電質之機械剛性裝置組件之電晶體。 選擇具有良好機械性質之塑膠基板可提供可在屈曲或扭曲 方向執行之電子裝置。然而,預期此移動於個別剛性電晶 體裝置組件上產生機械應變。此機械應變可(例如)藉由破 裂而導致破壞個別組件,且亦可降級或破壞裝置組件之間 之電接觸。 應由上述瞭解,當前此項技術中需要用於在塑膠基板上 • 製造含半導體之整合電子裝置之方法及裝置組態。需要具 有良好電特徵之可印刷半導體元件以允許在可適於在塑膠 聚合物基板上組合之溫度下有效製造裝置。此外,需要將 半導體材料印刷至大面積塑膠基板上之方法以可在大的基 板區域上連續、高速印刷複雜積體電子電路。最後,需要 可在屈曲或變形裝置方向上具有良好電子效能之完全可撓 性電子裝置以使能製造廣泛新型可撓性電子裝置。 【發明内容】 修 本發明提供用於在諸如塑膠基板之基板表面上製造諸如 §有半導體之電子裝置之結構及/或裝置之方法、裝置及 裝置組件。詳言之,本發明提供用於藉由靈活、低成本印 刷方法製造電子裝置、光電子裝置及其它功能電子組件之 可印刷半導體元件。本發明之一目標為提供用於製造半導 體元件的方法及裝置,該等半導體元件諸如具有自約數十 奈米至約數十公分變化之選定實體尺寸之整體單晶無機半 導體,其可經由多種印刷技術高度精確組合於基板表面 上。本發明之另一目標為提供用於利用於大基板區域上提 96l64.doc -10 - 1284423 供良好置放精確度及圖案保真度之乾式轉印接觸印刷及/ 或溶液印刷技術來組合及/或圖案化可印刷半導體元件之 方法。本發明之又一目標為提供包含由一塑膠基板支持之 一或多個可印刷半導體元件之具有良好電子效能之整合電 子及/或光電子裝置,尤其是展現諸如場效遷移率、臨限 電壓及接通/斷開比之良好電子效能特徵之具有可印刷半 導體元件的完全可撓性薄膜電晶體。 Φ 本發明之一態樣提供製造具有諸如可印刷半導體元件之 一或多個可印刷組件之高效能電子及/或光電子裝置或裝 置組件的方法。可藉由本發明之方法製造之電子及光電子 裝置包括(但不限於)電晶體、二極體、發光二極體 (LED)、雷射、有機發光二極體(〇LED)、微電子機械系統 (MEMS)及奈米電子機械系統(NEMS)。特定言之,本發明 提供經由印刷技術將半導體元件及/或其它裝置組件組合 於電子及/或光電子裝置或裝置組件中之方法,該等裝置 φ 或裝置組件展現與藉由習知的高溫處理方法製造之基於單 晶半導體之裝置相當之效能特徵。 在可用於在諸如塑膠基板及半導體基板之具有低熔融或 分解溫度之基板上製造裝置之本發明之一實施例中,本發 明之方法包含以下可獨立執行之製造步驟:〇)形成一或多 個離散、高品質半導體元件_,及(2)將此等帛導體元件及# 它裝置組件組合及/或圖案化於一基板表面上。舉例而 言,本發明包括其中藉由遮蔽及蝕刻藉由諸如高溫(大於 攝氏1000度)薄膜生長、摻雜及其它處理技術之習知的高 96164.doc -11 - 1284423 溫處理方法製造之塊狀單晶無機半導體材料產生獨立、高 品質可印刷無機半導體之方法。製造之後,藉由可在相對 較低溫度下(約小於攝氏400度)執行之印刷技術將此等可印 刷無機半導體組合於一或多個基板表面上。具有獨立可勃 行製備及圖案化/組合步驟之一優勢在於每一步驟可在諸 如溫度及環境污染等級(意即,是否需要無塵室條件)之環 境條件下執行’其可最佳化每一獨立可執行製造步驟之效 φ 率、靈活性及效用。舉例而言,本發明之方法允許半導體 材料在產生高品質單晶半導體所需之高溫下製造。然而, 半導體7G件之圖案化及/或組合可在對於在諸如塑膠基板 之具有低熔融或分解溫度之基板上製造裝置有利之實質較 低溫度下隨後進行。以此方式,可在廣泛基板表面製造高 效能裝置’而不會顯著熔融、分解或破壞基板表面。將半 導體製造與半導體/裝置組合分開之另一優勢在於將半導 體元件整合於高效能裝置及裝置組件中可藉由諸如乾式轉 • 印及溶液印刷技術之廣泛的低成本及靈活組合方法來達 成’此等方法無需無塵室條件且祕在大面積基板上連 、續、高速之裝置製造。在本發明之此態樣之情形中,本發 明之方法適於在包含幾乎任一材料之基板上印刷,該等基 板包括塑膠基板及非塑膠基板,諸如半導體晶圓(例如石夕 晶圓或GaAs晶圓)。 在另一邊樣中’本發明接供用^\勒:人> 祆倂用於整合於高效能電氣及光 電子裝置及裝置組件中之可印刷半導體元件。在本發明之 情形中,術語,,可印刷"係指無需將基板曝露至高溫下(意 96164.doc 1284423 即,在小於或等於約攝氏400度之溫度下)即可被轉印、組 合、圖案化、組織及/或整合於基板上或基板中之材料、
結構、裝置組件及/或整合功能裝置。本發明之可印刷半 導體可包含可藉由乾式轉印接觸印刷及/或溶液印刷方法 組合及/或整合於基板表面上之半導體結構。本發明之例 示半導體元件可藉由”由上而下"處理包括(但不限於)單晶 矽晶圓、絕緣物上矽晶圓、多晶矽晶圓及GaAs晶圓之多種 無機半導體材料而製造。因為由高品質半導體晶圓(例如 利用習知的高溫氣相沈積處理技術產生之半導體晶圓)獲 得的可印刷半導體元件比利用"自下而上"處理技術(諸如習 知的用於製造奈米晶體及奈米線之技術)製備的材料具有 較佳結晶純度及程度,所以此等材料有益於需要良好電子 效能之應用。本發明之,,由上而下,,處理方法提供之另一優 勢在於可印刷半導體元件及可印刷半導體元件陣列可以良 好界定方向及圖案之方式製造,而不像通常用於製造奈米 線及奈米粒子之”自下而上,,處理方法。舉例而言,半導體 元件可製造料如電晶體陣列或二極體陣列之位置及空間 方向直接對應於此等元件在功能裝置或功能裝輯列中之 最終位置及空間方向之陣列中。 可印刷半導體元件可包含且 s八有啫如帶(或條)狀、圓盤 狀、片狀、塊狀、柱狀、圓士七 狀W柱或此等形狀之任意組合之 泛形狀之整體、單晶無機半 /、 丁守篮、、、σ構。本發明之可印刷本 導體元件可具有廣泛f轉 ^ κ體尺寸,例如自約10奈米至約100 微米變化之厚度、自約5 Q太丰丄 丄 ’丁、米至、力1毫米變化之寬度及自 96164.doc -13 - 1284423 勺1微米至約1毫米變化之長度。對某些應用較佳使用厚度 大於約10奈米且寬度大於約5〇〇奈米之半導體元件,此係 =為此等尺寸可提供展現良好電子效能之電子裝置,諸如 場效遷移率大於或等於約⑽em2 V·1 s·1,且較佳大於或 等於約300 em2 v-i 一,且更佳大於或等於8〇〇 ν-ι、〆 之薄膜電晶體。此外,寬度大於約1〇奈米之半導體元件可 藉由具有良好置放精確度及圖案保真度之多種印刷技術組 合於基板上。 發月之可印刷半導體元件亦具備一將該可印刷半導體 件機械連接至一諸如半導體晶圓之母基板的對準保持元 件。對準保持元件可用於在轉印、組合及/或整合處理步 驟過程中保持—可印刷半導體元件之—選定方向及/或位 置。對準保持元件亦可用於在轉印、組合及/或整合處理 〔驟過程中保持界定半導體元件之—選定圖案之複數個半 v體元件的相對位置及方向。在本發明之方法中,對準保 持元件在可印刷半導體元件與一致(c〇nf〇rmab⑷轉印裝置 接觸表面接觸(及黏結)過程中保持選定位置及方向。本 發明之此態樣中之有用對準保持元件可在—致轉印裝置之 移動時與可印刷半導體元件分離,而不會顯著變化可印刷 +導體元件之選定位置及方向。分離操作通常藉由在轉印 裝置移動過程中對準保持元件之斷裂或釋放來達成。 命在本發明之—實施例中,可印刷半導體元件具有-以較 :末端及一窄中央區域為特徵之花生形狀。在此實施例 ’對準保持元件係經由不完全各向同性餘刻較寬末端下 96164.doc -14- J284423
方,且完全各向同性蝕刻中央區域下方來提供。此處理產 生連接至一母基板之半導體元件,且兩點對應於該半導 體兀件之每一末端。在另一實施例中,可印刷半導體元件 具有一沿一中心縱向軸延伸之帶狀。在此實施例中,對準 保持元件將沿縱向軸延伸之帶的兩末端連接至母基板。在 每一實施例中,將帶狀或花生狀半導體元件黏結至轉印裝 置之接觸表面及移動轉印裝置可導致兩個對準保持元件斷 裂’且可印刷半導體元件自母基板釋放。 本發明之可印刷半導體元件可具有獨立可選定實體尺 寸諸如見度、兩度及厚度。在一例示性實施例中,可在 小於約5%之範圍内選擇可印刷半導體元件之實體尺寸。 利用本泉明之方法可製造大量具有高度均一選定實體尺寸 之可印刷半導體元件。在一例示性實施例中,可製造具有 變化小於約1%之實體尺寸之大量可印刷半導體元件。因 此與省知的產生奈米線之方法相反,本發明提供無顯著 大小及形狀分佈之可印刷半導體元件。此方法之—顯著優 勢在於無需建構整合本發明之可印刷半導體元件的結構及 裝置以容許在半導體元件之大小及形狀上之離差 (dispersion)。 本發明之可印刷半導體元件較佳具有至少一平滑表面 (諸如微帶之頂部或底部表面),較佳展現自平均表面位置 小於1〇奈米之偏差,且在某些應用中,更佳展現自平均表 2置小於丨埃之偏差。本發明之可印料導體元件之平 …允許有效電接觸及/或實體整合與其它裝 — 96164.doc -15- 1284423 起建立於一整合電子裝置或光電子裝置中。 或者,本發明之可印刷半導體元件可包含複合半導體元 件’其將一半導體結構以操作方式連接至諸如介電質結 構、傳導結構(如’電極)、額外半導體結構或此等結構之 意組合之一或多個額外結構。τ印刷4合半導體元件提 今易且有效整合於複雜電子或光電子&置中之材料及 裝置組件。此外,本發明之組合方法允許將可印刷半導體 _ 丨件提供料列幾何形狀中,其中相鄰㈣彼此接近,例 如彼此在100奈米至i微米内。舉例而言,本發明之一可印 T半導體元件包含-將—諸如單晶無機半導體之高品質半 導體結構以操作方式連接至一無機介電質結構(諸如二氧 化夕層)之整體結構。因為可於一單個印刷步驟中組合半 V體及’丨電夤組件,且因為使用包含半導體與介電質組件 t整體結構導致自閘極至半導體元件或源極及沒極之漏電 机非吊低之絕緣體組態,所以本發明之此實施例尤其可用 鲁於製造高效能薄膜電晶體。在另一實施例中,本發明之可 印刷半導體元件可包含整合功能裝置,諸如二極體、 LED、電晶體及0LED,其可容易地倂至基板表面上。 在另一態樣,本發明提供一包含一第一電極、一第二電 =及一經定位以與該第一及該第二電極電接觸之可印刷半 V體兀件之電氣裝置。在一用於需要良好電氣裝置效能之 應用的實施例中,可印刷半導體元件包含一具有實體尺寸 及形狀之整體無機半導體結構,其於該第一與該第二電極 之間提供一大於或等於約50%之填充因子,在某些應用 96164.doc _ 16- 1284423 •中,較佳大於或等於約80%。在一實施例中,可印刷半導 體元件具有至少一大於或等於約5〇〇奈米之截面尺寸。在 -實施例中,可印刷半導體元件具有—等於或小於約1〇之 長度與寬度之比,在某些應用中,較佳等於或小於約 1.5。在一實施例中,可印刷半導體元件具有一等於或小 於約0.1之厚度與寬度之比,在某些應用中,較佳等於或 小於約0.01。 _ 本發明之此態樣進一步包含電氣裝置陣列,其包含一第 一電極、一第二電極及經定位以與該第一及第二電極電接 觸之複數個可印刷半導體元件。在一用於需要良好電氣裝 置效能之應料實施财,該#可印刷I導體元件於該第 一與該第二電極之間提供一大於或等於約50%之填充因 子,且在某些應用中,較佳大於或等於約80%。可印刷半 導體元件可相對於一選定對準轴大體縱向定向,該轴諸如 連接該第及該第二電接點之最近點之軸延伸的選定 _對準軸。在一實施例中,可印刷半導體元件之相對位置及 方向可選擇為在小於或等於約5微来内。在-提供半導體 兀件之末端對末端良好對準之實施例中,該等可印刷半導 體π件之每一者延伸一長度,且終止於第一及第二末端。 =此二轭例中,該等可印刷半導體元件之第一末端定位於 第一電極之5微米内,且該等可印刷半導體元件之第二末 端定位於該第二電極之5微米内。 ^ 〜、樣中,本發明提供一具有一可印刷半導體元件 之私曰曰體。在一實施例中,本發明之電晶體包含一源極、 96164.doc (§) -17- 1284423 可印刷半導體元件、—及極及—閘極。在此組態中,源 極與沒極均與可印刷半導體元件電接觸,且由該可印刷半 導體7G件分離’且閘極藉由介電質與可印刷半導體元件分 離該可印刷半導體元件可包含—厚度大於或等於約50奈 米之正體結晶無機半導體結構,在某些應用中,較佳其厚 度大於或等於約100奈米,且在某些應用中,更佳大於或 等於約200奈米。本發明亦包括一具有與源沒及没極接觸 鲁之複數個可印刷半導體元件之電晶體。因為將複數個可印 刷半導體元件用於一單個電晶體中可降低場效電晶體中諸 如源;及、沒極及閘極、以及介電質之各種裝置組件的總位 置精確度容限,所以其可有益於某些應用。本發明亦包括 -中可Mj半V體元件為—可拉伸半導體元件之實施例。 因為可拉伸半導體凡件在屈曲、拉伸或變形裝置方向上可 提供良好裝置效能及機械強度,所以將一或多個可拉伸半 導體元件用於本發明之電晶體中係有益的。 • 在另一實施例中,本發明提供-藉由-諸如聚醯亞胺、 聚碳酸醋或Mylar(聚s旨薄膜)基板之塑膠基板支持及/或與 其實體接觸之高效能電晶體。本發明之此實施例之電晶體 可具有一包含一諸如矽或鍺之單晶無機半導體結構之可印 刷半導體元件。此等裝置組態展現諸如場效遷移率、臨限 電麼及接通/斷開比之良好裝置效能特徵。在一例示性實 施例中,塑膠基板上之薄膜電晶體具有一與一具有一包含 一藉由習知的高溫處理方法製造之結晶半導體之半導體2 件之電晶體的場效遷移率相當之場效遷移率,舉例而言, 96164.doc -18- 1284423 可具有一大於或等於300 cm2 V-1 s·1之場效遷移率,更佳 大於或等於800 cm2 V·1 s-1。
在一實施例中,本發明之此態樣之電晶體之介電質及半 導體組件可包含一整體複合可印刷半導體元件。或者,本 發明之此態樣之電晶體之介電質、閘極及半導體元件可包 含一整體複合可印刷半導體元件。在某些應用中較佳使用 一具有經整合半導體及絕緣體結構之複合可印刷半導體元 件,此係因為其可將展現非常低洩漏之高品質介電質-半 導體介面提供於薄膜電晶體中。此外,使用具有經整合半 導體及絕緣體結構之複合可印刷半導體元件亦提供裝置組 件之有效組合,而無需用於將一介電層整合於一薄膜電晶 體中之旋塗澆鑄步驟。 在另一實施例中,本發明提供可經受顯著應變而不會斷 裂之可拉伸半導體元件。即使在經受諸如大於或等於約 0·5/〇,#父佳為1%且更佳為2%之應變的顯著應變時,本發 明之可拉伸半導體元件亦可展現良好電子效能。在某些應 用中較佳之本發明之可拉伸半導體元件亦具有可撓性,且 因此可沿一或多個軸顯著伸長、屈曲、彎曲或變形。當在 屈曲、伸展、收縮、彎曲及/或變形狀態時,具有可撓性 之可拉伸半導體亦可展現良好電子效能。本發明之可:伸 及可撓性半導體元件可以係可印刷的,且可包含將一半導 體、、’°構以_作方式連接至諸如介電質、電極及其它半導體 之其它裝置組件之複合半導體元件。本發明包括具有可拉 伸及/或可撓性半導體元件之廣泛電子及/或光電子裝置, 96164.doc -19- .1284423 諸如電晶體、二極體、LED、OLED、雷射、微電子機械 褒置及奈米電子機械裝置。 本發明之可拉伸半導體元件包含一具有一支持表面之可 撓性基板,及一具有一曲線形内表面之可印刷半導體結 構。在此實施例中,半導體結構之曲線形内表面之至少— "P刀黏、,Ό至可撓性基板之支持表面。用於本發明之具有曲 線形内表面之例示性半導體結構包含彎曲半導體結構。在 此描述之情形中,"彎曲半導體結構"係指一具有一由施加 -力產生之曲線形構形之半導體結構。彎曲半導體結構可 具有-或多個折疊區域。㈣半導體結構可以—捲曲構形 或以-具敏的構形呈現。諸如f曲半導體結構之具有曲線 形内表面之半導體結構可以一經受諸如小㈣應變、小 於㈣應變或小㈣.1%應變之應變的構形黏結至―可挽性
本發明之可拉伸半導體之曲線形内表面可具有提供可拉 伸性或可撓性之任-輪靡外形’纟包括(但不限於)以至少 一凸起區域、至少1陷區域或至少-凸起區域及至少一 Y陷區域之組合為特徵之輪廓外形。在-實施财,可拉 可撓:半導體元件之曲線形内表面具有一 =或一大體非週期波為特徵之輪廊外形。在此描述之 W中’«波與非週期波可為任—二維或 包括(但不限於)正弦波、方形波、Aries:、數、、斯 二二一波、洛命兹(LGrentzian)波或此等波: 月之可拉伸及可撓性半導體元件包含 96164.doc -20- 1284423 一具有一曲線形内表面之彎曲半導體帶,該曲線形内表面 具有一以一沿帶之長度延伸之大體週期波為特徵之輪廓外 形。此實施例之可拉伸及可撓性半導體元件可沿一沿該帶 之長度延伸之轴伸展或收縮,且可沿一或多個其它軸彎曲 或變形。
本發明之此實施例中之半導體結構的輪廓外形可在經受 機械應力時,或在將力施加至半導體元件時變化。因此, 改變例示性半導體結構之輪料形之能力可使其具有在不 經歷顯著機械破壞、斷裂或電效能之實質降低之情況下伸 展、收縮、屈曲、變形及/或彎曲之能力。半導體結構之 曲線形内表面可連續黏結至支持表面(意即,在沿曲線形 内表面之4乎所有點處黏結)。或者,半導體結構之曲線 I内表面可不連_黏結至支持表面,彡中該曲線形内表面 在沿曲線形内表面之選定點處黏結至支持表面。 本發明亦包括可拉伸電子裝置及/或裝置組件,其包含 -可印刷半導體結構與額外整合裝置組件之組合,額外整 合裝置組件諸如電接點、雪^^ , 电接2 電極、傳導層、介電層及額外半 導體層(如摻雜層、? _ rjN接面專),所有此等額外整合裝置 組件具有由一可繞性其士 土板之支持表面支持之曲線形内表 面。額外整合裝置纟且^ A kk ^ ^ 、、件之曲線形内表面組態使其即使在經 受顯著應變時亦可展5目$+ 展見良好電子效能,諸如當在拉伸或彎 曲組悲時,保持與丰| ^ -、千等體70件之導電性或電絕緣。本發明 之此態樣之額外整人狀罢Μ 正口裝置組件可具有一如上文所述之諸如 捲曲或具皺組態之彎曲έ能 心弓曲組怨,且可利用與用以製造可拉伸 96164.doc -21 - 1284423 半導體元件之技術相似之技術製造。在一實施例中,舉例 而言,包括一可拉伸半導體元件之可拉伸裝置組件可獨立 製造,且隨後互連。或者,含有半導體之裝置可以一平面 組態製造,且隨後處理所得平面裝置以向所有或某些裝置 組件提供曲線形内表面。 本發明之可印刷半導體元件可包括可用於各種裝置環境 及組態中之展現諸如增強之機械、電、磁及/或光學性質 之增強性質的異質半導體元件。異質半導體元件係包含一 半導體及一或多種添加物之多組份結構。在此描述之情形 中’添加物包含元素、分子及錯合物、聚集體及其粒子, 其不同於組合有該等添加物之半導體,諸如具有不同之化 ^组合物及/或物理狀態(諸如,結晶、半結晶或非結晶狀 態)之添加物。本發明之此態樣中之有用添加物包括其它 半導體材料、諸如碎、硼及錄之_及?型摻雜劑、結構增 強劑、介電材料及傳導材^本發明之異f半導體元件包 括八有工間句貝組合物的結構,諸如經均—摻雜之半導體 結構’且包括具有空間非句質組合物的結構,諸如具有濃 度可在-維、一維或三維空間變化之摻雜劑之半導體結構 (意即’半導體元件中之空間非句質摻雜劑分佈)。 在另-隸中,異質半導體元件包含具有額外整合功能 ί置組件之半導體結構’額外整合功能裝置組件諸如介電 曰、電極、電接點、摻雜接觸層、Ρ_Ν接面、額外半導體 :及用於限制電荷之經整合之多層堆疊。本發明之此態樣 額外整合功能裝置組件包括含有半導體之結構與不含半 96164.doc -22- 1284423 導體之結構兩者。在一實施例中,異質半導體元件包含諸 如電晶體、二極體或太陽能電池之功能裝置,或可被效圖 案化、組合及/或互連於基板材料上之多元件功能裝置組 件0
使用可印刷異質半導體元件可在本發明之製造方法中提 供某些優勢。第一,本發明之方法的,,由上而下,,處理方法 允許諸如受空間控制摻雜之幾乎所有類型之半導體處理在 與如下之製造步驟分離之製造步驟中進行:(丨)界定半導體 元件之空間維數,及(ii)將半導體元件組合於基板上並組 合於功能裝置中。本發明之方法中之處理半導體與組合及 互連裝置及裝i組件分離允許對半導體材料之處理在用於 產生含非常高品質半導體之材料的各種條件下進行,其包 括八有良好界疋/辰度及空間摻雜劑分佈之摻雜區域的單晶 半導體’及展現高純度之整合半導體多層堆疊。舉例而 :,處理半導體與組合裝置組件之分離允許在高溫下且在 南度控制雜質含量的條件τ處理半導體。第二,使用包含 複數個整合裝置組件及’或功能裝置之異質半導體元件允 許X冑業上有益之方式有㉗高產出率印刷功能裝置及其 :列。舉例而言,使用包含複數個互連裝置組件之異質半 V體兀件之本發明的裝置製造方法減少淨製造步驟數及/ 或降低製造某些裝置中涉及之成本。 、 〜、樣中,本發明提供經由包括乾式轉印接觸印刷 ^容料刷技術之各種印刷方法將可印刷半導體元件組 疋位組織、轉印、圖案化及/或整合至基板上或基 96164.doc -23- 1284423 反中之方法。本發明之印刷方法可以一大體不影響半導體 兀件之電性質及/或機械特徵之方式將一或多個半導體元 件整合於一基板上或一基板中。此外,本發明之印刷方法 可將半導體元件組合於—基板之敎區域上或組合於其中 且在選定空間方向上。而且,本發明之印刷方法可以一藉 由於選定裝置組件之間建立良好傳導性,於選定裝置組^ 之間建立良好絕緣性,及/或於裝置組件之間建立良好空 間對準及相對定位來提供高效能電子及光電子裝置之 將半導體元件及其它裝置組件整合於-基板中或-基i 上0 在本發明之—實施财,藉由諸如軟微影微轉印或奈米 印方法之乾式轉印接觸印刷方法將半導體元件組合於一 基板表面上。在一種方法中,— 或多個可印刷半導體元件 可與一具有-或多個接觸表面之一致轉印裝置接觸。建立 於接觸表面與可印刷半導體元件之間之-致接觸將半導體 7C件黏結至接觸表面。隨後’將安置於接觸表面上之半導 體兀> 件之至少一部分與基板之一接 筏收表面接觸。在一實施 列中,一致轉印裝置亦於上方安置 文直有+導體元件之接觸表 接收表面之至少—部分之間建立保形接觸。-致轉印 裝置之接觸表面與半導體元件之分離將半導體元件轉印至 接此料導體元件組合於基板之接收表面 ίηί佳用於裝置製造應用之實施例中,將可印刷半 =牛疋:及/或整合於基板上—選定區域中及選定空 間方向上。本發明中使用乾式轉印接觸印刷方法之優勢在 96164.doc -24- 1284423 於可將可印刷半導體元件之圖案以一保持界定圖案之半導 體元件之選定空間方向之方式轉印及組合於基板表面上。 本發明之此態樣對於其中在直接對應於一選定裝置組態或 裝置陣列組態之良好界定位置及相對空間方向製造複數個 可印刷半導體元件之應用尤其有益。本發明之轉印印刷方 法可轉印、定位及組合可印刷半導體元件及/或含有可印 :半導體之功能裝置’其包括(但不限於)電晶體、光波導 管、微電子機械系統、奈米電子機械系統、雷射二極體或 全形(fully formed)電路。 在另-實施例中,本發明提供其中將某些(但非所有)所 提供之可印刷半導體轉印及組合於一基板上或一基板中之 選擇性轉印及組合方法。在此實施例中,一致轉印裝置可 選擇性黏結至所提供之特定可印刷半導體元件。舉例而 5,一致轉印裝置可在其外表面上具有一選定三維凸起圖 案,其具有凹進區域及凸起特徵。在此實施例中,可定位 凹進區域及凸起特徵以使得僅選定的可印刷半導體元件與 凸起圖案所提供之-或多個接觸表面接觸,且隨後將其轉 印及組合於基板表面上。或者,一致轉印裝置可具有—接 觸表面或複數個接觸表面’其具有諸如自接觸表面延伸之 具有經基之化學改質區域及/或具有一或多個黏接表面塗 層之區域的黏結區域之一選定圖案。在此實施例中,僅將 與接觸表面上之黏結區域接觸之此等半導體元件黏結至轉 印裝置’且隨後將其轉印及組合於基板表面上。本發明之 選擇性轉印及組合方法的優勢在☆以位置及空間方向之第 96164.doc -25- 1284423 -集合為特徵之可印刷半導體元件之第 不同於第一圖案且以位置及空間方向之Ha以生 可印刷半導體元件的第二圖案,—集。為特徵之 或裝置陣列組態。 适疋裒置組態 本發明之例示性一致轉印 4 L 1衣置包含-乾式轉印戳記 置用…^生體轉印戳記或複合、多層圖案化裝 置 本發明之一致轉印裝置包括圖案化裝置,其包含 稷數個聚合物層且描述於2〇〇5 Α Φ ^ ^ , 亍月27曰向美國專利商標 c〇mp〇site Patterning s〇ft ㈣叩吻”之第U/出,954號美國專利中請案中,該申請 案之全文以引用的方式倂入本文中。可用於本發明之方法 中之-例示性圖案化裝置包含一諸如聚二甲基石夕氧烧 (PDMS)層之具有一低揚氏模數之聚合物層,在某些應用 中K圭具有—自約1微米至約⑽微米之範圍選擇之厚 度。因為低模數聚合物層提供可與一或多個可印刷半導體 凡件’尤其係具有曲線形、粗縫、平坦、平滑及/或波狀 外形曝露表面的可印刷半導體元件,建立良好保形接觸, 且可與具有諸如曲線形、粗糙、平坦、平滑及/或波狀外 形基板表面之廣泛表面形態之基板表面建立良好保形接觸 之轉印裝置,所以使用低模數聚合物層係有益的。 本發明之轉印裝置可視需要進一步包含一具有一與内表 面相對之外表面的第二聚合物層,其亦具有_高楊氏模 數。在此實施例中,第一聚合物層之内表面及第二聚合物 層之内表面係經排列以使得施加至第二聚合物層之外表面 96164.doc -26- 1284423 之力傳遞至第一聚合物層。因為高模數第二聚合物層提供 具有一足夠大以提供良好黏結、轉印及組合特徵之淨撓曲 剛度之轉印裝置,所以本發明之轉印裝置中使用高模數第 一聚合物層係有益的。舉例而言,使用具有一自約1 χ 1 0_7 Nm至約lxl〇·5 Nm範圍中選擇之淨撓曲剛度的轉印裝置可
使得在與一基板表面建立保形接觸時黏結至接觸表面之半 導體元件及/或其它結構的位置扭曲最小化。此屬性提供 展現高置放精確度及良好圖案保真度之組合可印刷半導體 元件之方法及裝置。本發明之轉印裝置可包含用於提供容 易操縱及維持、良好熱性質,且提供將施加至轉印裝置之 力均一分佈至整個接觸表面之額外聚合物層,如於2〇〇4年 4月27日向美國專利商標局申請之標題為,,c〇mp〇she
Patterning Devices for Soft Lithography”之第 60/565,604號 美國專利申請案中所教示,該申請案被倂入本文中。 本發明之轉印裝置可具有一單個連續接觸表面或複數個 非連續接觸表面。本發明之轉印裝置之接觸表面可藉由一 具備具有選定實體尺寸之凹進區域及凸起特徵之選定三維 凸起圖案來界定。用於本發明之接觸表面可藉由凡得瓦爾 力、共價鍵、黏接劑層、諸如於其表面上安置有羥基之區 域之化學&質區4、偶極·偶極力或各種方式 < 組合黏結 可印刷半導體元件。本發明之轉印裝置可具有接觸表面, 該等接觸表面可具有任-面積。對於某些高速微製造及奈 米製造應用而言,鮫佳自約〗ns, 孕乂 1土目、、〇 1〇 cm至約26〇 cm2範圍中選擇 揍觸表面積。 96164.doc -27- 1284423 * 多種方法可用以幫助將可印刷半導體元件自接觸表面轉 印於基板表面中或該基板表面上。在一例示性實施例中, 基板表面與接觸表面之表面能差異錢至基板表面之轉 印。舉例而言,可有效達成自一具有一較低表面能之由 PDMS層組成的接觸表面轉印至諸如聚醯亞胺、聚碳酸酯 或Mylar表面之具有較高表面能之基板表面。此外,可藉 由在與待轉印之可印刷半導體元件接觸之前及/或此過程 _ 中加熱來軟化或部分熔融一塑膠基板表面,藉此產生嵌入 基板中之半導體元件。允許基板在接觸表面與半導體元件 分離之前冷卻及硬化可促進有效轉印。或者,基板表面可 具有展現增強之基板對半導體元件之親和力之一或多個化 學改質區域。舉例而言,改質區域可由一或多個黏接劑層 覆蓋,或可被改質以使得其經歷與半導體元件之有效共價 鍵、、及引凡付瓦爾力、偶極-偶極力或此其組合以促進 有效轉印及組合。或者,一部分聚合之聚合物前驅體可與 # 半導體元件或其它裝置組件接觸,且隨後聚合,其導致形 成一於其中嵌入有半導體元件之基板。 在一例示性實施例中,製造可印刷半導體元件使其具有 塗覆有一薄的釋放層之頂表面,該釋放層諸如在界定及製 造可印刷半導體元件過程中用作一圖案化至一基板上之遮 罩的光阻層。使一致轉印裝置之接觸表面達成與可印刷半 導體元件之塗覆表面保形接觸。該釋放層有助於將可印刷 半導體元件黏結至轉印裝置之接觸表面。隨後,未塗覆有 釋放層之可印刷半導體元件之表面與一基板之接收表面接 96164.doc -28- 1284423 冑。接著,例如藉由曝露至一諸如丙酮之適當溶劑中來移 除釋放層,#此將可印料導體元件與一致轉印裝置分 離。接收表面可視需要塗覆有一或多個黏接劑層以助於轉 印可印刷半導體元件。 ' 在本發明之另一實施例中,藉由溶液印刷將可印刷半導 體7L件組合於基板表面上。在此描述之情形中,術語"溶 液印刷"意指下述處理,藉此可將諸如可印刷半導體元件 φ 之一或多個結構分散於諸如載體流體或溶劑之載體介質 中’且以一協同方式傳送至基板表面之選定區域。在一例 示性溶液印刷方法中,傳送結構至基板表面之選定區域係 藉由獨立於經受圖案化之基板表面之形態及/或實體特徵 之方法來實現。在另一實施例中,可印刷半導體元件維持 懸浮於溶劑中直至該溶劑蒸發為止,或直至一諸如靜電 力磁力或由聲波&供之力的所施加力將可印刷半導體元 件自溶液拉出且放至基板之選定區域上為止。此種功能性 • 可藉由選擇為避免提前沈降所必需的適當之可印刷半導體 元件之實體尺寸及質篁來提供。以此方式,本發明之溶液 印刷方法與其中由於重力懸浮於載體介質中之元件從溶液 中掉出且統計上地落入基板凹進區域之某些流體自組合方 法在本質上不同。 本發明之將可印刷半導體元件組合於一基板之接收表面 上之方法包含將可印刷半導體元件分散於載體介質中之步 驟,藉此產生在該載體介質中包含半導體元件之懸浮液。 藉由將懸浮液溶液印刷至接收表面上而將半導體元件傳送 96164.doc -29- 1284423
至基板,藉此將半導體元件組合於該接收表面上。在此實 :例中’溶液印刷可藉由此項技術中已知的多種技術來提 供,包括(但不限於)喷墨印刷、熱轉印印刷及絲網印刷。 ^發明之溶液印刷方法亦可採用自組合對準技術。舉例而 實施例中,具有圖案化疏水及親水基之可印刷半 、_牛之枚直、疋位及對準藉由在具有互補圖案化疏水 區域(諸如以甲基為終端之表面基團)及親水區域(諸如以經 酸為終端之表面基團)之接收表面上對準來達成。本發明 之溶液印刷方法亦可採用含有經分散之可印刷半導體元件 滴知]之毛細管作用以達成校直、定位及對準。 可視需要將多種方法用於本發明以控制基板表面上之半 導體元件及/或其它裝置組件之方向、對準及選擇性沈 、 等方法可製造包含具有精確指定相對位置及空間方 向之複數個互連裝置組件之複雜整合電子及光電子裝置。 :例而言,可採用靜電力、聲波及/或靜磁力以助於將半 =元件及其它裝置組件定㈣基板表面上特定位置及選 疋空間方向上。或者,可在選定區域修改基板表面自身之 性質及/或組合物去 口物以達成精確置放半導體元件及其它 組件。舉例而言, 風 、, 了化予改貝基板表面之選定區域以使得 八對於半導體元件展^撰 展見選擇性親和力。此外,可修改基板 表面之電性質‘ ^ 、 ,在特疋表面區域中形成電位穴)以便 於選擇性萼人、…丄_ W ^ ^ & 對準可印刷半導體元件及其它裝置 組仔。 本發明之印刷方、土 +制& ^ 】方法在I造尚效能電子及/或光電子裝置 96164.doc -30 - 1284423 方面具有多個重要優勢。第一,本發明 需將無機單晶半導體結構 ' 無 政,傅曝路至足夠大而引起顯著破壞或 =級(诸如由斷裂引起之破壞)的機械應變下的情況下便可 此等結構。第二,本發明之印刷方法可以良好 =確度在選定方向將—或多個半導體元件定位 板表面之選定區域上 置的空間偏差小於或等二自絕對正確方向及基板上之位 1偏差小於或專於5微米。第三,本發明之印刷方 包含相對於一諸如對應於一功能裝置或裝置陣列 之空間組態的選定空間組態具有良好保真度之複數個半導 體7L件、其它裝置元件、整合功能裝置或此等裝置之任意 組合的圖案。第四’本發明之印刷方法可在相對較低溫度 下進行(意即’溫度小於約攝氏4〇〇度),且因此可適於廣泛 ^板,尤其適於塑膠基板。最後,本發明之印刷方法提供 製造高效能電子及/或光電子裝置之低成本方法,且無需 無塵室條件。 將可印刷半導體元件組合、定位、組織、轉印、圖案化 及/或整合於基板上或基板内之本發明之組合物及相關方 法可用以製造包含一或多個半導體元件之幾乎任一結構。 此等方法可尤其用於製造複雜整合電子/光電子裝置或裝 置陣列,諸如二極體、發光二極體、太陽能電池、電晶體 (ΕΤ及雙極)及薄膜電晶體陣列。本發明之組合物及相關 方法亦可用於製造諸如互補邏輯電路之系統級積體電子電 路,其中可印刷半導體元件以良好界定空間方向印刷至一 土板上’且經互連以形成一所要電路設計。在本發明之此 96164.doc -31 · (§) 1284423 態樣之-實施例中,可組合及互連具有選定推雜劑濃度及 摻雜劑空間分佈之可印刷N型及p型異f半導體元件以製造 複雜積體電路。在另一實施例中,將包含不同半導體材料 之複數個可印刷半導體元件印刷至相同基板上,且將其互 連以製造複雜積體電路。 然而,本發明之組合方法並不侷限於半導體。相反,此 等方法廣泛適於非半導體之廣泛材料。可藉由本發明之方 φ 法轉印及/或組合之材料包括(但不限於)諸如si〇2之絕緣材 料,諸如導體之接通材料,諸如主動光學材料、被動光學 材料及光纖元件之光學元件,用於感應應用之材料及磁性 材料。因此,本發明之方法、裝置及裝置組件可用以製造 廣泛微尺寸及/或奈米尺寸之結構及結構總成,諸如微流 體裝置及結構、NEMS裝置及NEMS裝置陣列以及MEMS裝 置及MEMS裝置陣列。本發明之轉印及組合方法尤其可用 於藉由順序重疊複數個印刷級產生諸如積體電路之複雜三 g 維結構。 本發明之組合物及相關製造、組合及互連方法可用以在 廣泛基板上製造裝置,尤其係基於半導體之裝置。本發明 之方法之益處在於其可適於在適於大部分可撓性基板之溫 度下組合裝置,該等可撓性基板包括諸如熱塑性材料、熱 固性材料、加強型聚合物材料及複合聚合物材料之聚合物 材料。然而,本發明之方法同樣可應用於在包括陶瓷材 料、玻璃、介電材料、導體、金屬及半導體材料之剛性及 /或脆性基板上製造裝置。此等方法在脆性材料上製造裝 96164.doc 32 - 1284423 置之適用性起因於利用本發明之印刷方法可給予基板非常 低之力。本發明之組合物及製造方法亦可適於在諸如紙、 木材、及橡膠之不經常使用之基板材料上製造裝置。本發 明之組合物及製造方法亦可適於在包括凹陷及凸起表面之 曲線形表面上製造裝置。 在另一態樣中,本發明之製造方法可將可印刷半導體元 件異質整合於功能基板中。舉例而言,本發明之印刷方法 鲁彳將可印刷半導體元件沈積及整合於具有良好界定半導體 區域、傳導區域及/或絕緣區域之基板中。本發明之製造 方法之優勢在於可以高的置放精確度將可印刷半導體元件 印刷至諸如積體電路或積體電路組件之功能基&上選定方 向及位置,此優勢在本發明之乾式轉印接觸印刷方法之情 形中尤其明顯。 @ 本發明之可印刷半㈣元件可由廣泛材料製造^用於製 造可印刷半導體元件之有用前驅體材料包括··半導體晶圓 φ源、’其包括諸如單晶石夕晶圓、多晶石夕晶圓、錯晶圓之塊狀 半導體晶圓;超薄半導體晶圓,諸如超薄石夕晶圓;推雜半 導體晶圓,諸如P型或N型摻雜晶圓及具有選定摻雜劑空間 分佈之晶圓(諸如絕緣物上石夕(如,si_SI02, siGe)之絕緣半 導體晶圓;及基板半導體晶圓,諸如基板上石夕晶圓及絕緣 物上石夕)。而且,本發明之可印刷半導體元件可由利用習 處理半導體裝置所剩餘之帶有财之或未使用的 咼品貝之或經再處理之半導騁姑袓制 干寺體材科製造。此外,本發明之 可印刷半導體元件可由各種非晶圓源製造,諸如非晶、多 96164.doc _ 33 · 1284423 晶及單晶半導體材料(如多晶矽、非晶矽、多晶GaAs及非 晶GaAs)之薄膜,其沈積於一犧牲層或基板(如,siN或 Si02)上,且隨後退火。 本發明亦包括製造可印刷半導體元件及可撓性半導體元 件之方法。此等方法可由諸如絕緣物上矽晶圓、單晶矽晶 圓、多晶石夕薄膜、超薄石夕晶圓及鍺晶圓之廣泛前驅體材料 製造可印刷半導體元件及可撓性半導體元件。此外,此等
方法可產生具有廣泛形狀及實體尺寸之可印刷半導體元 件。而且,本發明之方法可在良好界定相對空間方向低成 本製造可印刷半導體元件之大陣列/圖案。 在另一態樣中,本發明提供一種用於將可印刷半導體元 件組合於基板之接收表面上之方法,其包含步驟:⑴提供 包含-整體無機半導體結構之可印刷半導體元件;⑺將可 印刷半導體元件與-具有—接觸表面之—致轉印裝置接 觸,其中接觸表面與可印刷半導體元件之間之接觸將可印 刷半導體元件減至接觸表面,藉此形成上方安置有可印 刷半導體元件之接觸表面;(3)將安置於接觸表面上之可印 刷半導體元件與基板之接收表面接觸;及⑷將一致轉印裝 置之接觸表面與可印刷半導體 、曾祕 干¥體70件分離,其中將可印刷半 V體70件轉印至接收表面上, 精此將可印刷半導體元件組 合於基板之接收表面上。在一膏 實施例中,本發明之此方法 進一步包含步驟··(1)提供額外 土 4人 P刷+導體元件,其每一 者包含一整體無機半導體結構 件盥一且古一拉_ * 將該#可印刷半導體元 -、/、有一接觸表面之一致韓£(7壯要& & 褥P衣置接觸,其中接觸表 96164.doc -34- 1284423 面與可印刷半導體元件之間之接觸將該等可印刷半導體元 件黏i至β亥接觸表面,且在包含該等可印刷半導體元件之 -選定圖案之相對方向上產生上方安置有該等可印刷半導 體元件之接觸表面;(3)將安置於接觸表面上之可印刷半導 體疋件與基板之接收表面接觸;及⑷將該—致轉印裝置之 接觸表面與該等可印刷半導體元件分離,其中將該等可印 刷半導體元件於包含該選定圖案之相對方向上轉印至該接 收表面上。 在另態樣中,本發明提供一種用於將可印刷半導體元 件組合於基板之接收表面上之方法,其包含步驟:⑴提供 包含一整體無機半導體結構之可印刷半導體元件,其中該 可印刷半導體元件具有至少一大於或等於約5〇〇奈米之截 面尺寸,(2)將該半導體元件分散於溶劑中,藉此產生在該 溶劑中包含該半導體元件之㈣液;及⑺藉由將該懸浮液 溶液印刷至接收表面上而將該半導體元件傳送至該基板, 丨藉此將該半導體元件組合至該接收表面上。在一實施例 中’本發明之此方法進一步包含步驟··⑴提供額外可印刷 半導體元件,其中該等額外可印刷半導體元件之每一者具 有至少一大於或等於約500奈来之截面尺寸;(2)將該等半 導體元件分散於溶劑中,藉此產生在該溶劑中包含該等半 導體元件之懸浮液;及(3)藉由將該懸浮液溶液印刷至該接 收表面上而將該等半導體元件傳送至基板,藉此將該等半 導體元件組合至該接收表面上。 在另一態樣中,本發明提供一種製造可印刷半導體元件 96164.doc -35- 1284423 • 之方法’其包含步驟⑴提供-具有-外表面之晶圓,該晶 ^包含一半導體;(2)藉由應用一遮罩遮蔽該外表面之一選 定區域;(3)各向異性蝕刻該晶圓之外表面,藉此於該晶圓 上產生一凸起結構及該晶圓之至少一曝露表面,其中該凸 起結構具有-遮蔽側及一或多個未遮蔽側,·(4)將一遮罩應 用至該凸起結構之未遮蔽側之至少一部分;及⑺餘刻該晶 圓之曝路表面,藉此自該晶圓釋放該凸起結構之一部分, φ i製造可印刷半導體元件。在此實施例中,可藉由諸如濺 鍍或氣相沈積之傾斜沈積方法或藉由遮罩之一部分在外表 面上流動至未遮蔽侧來將遮罩應用至該凸起結構之未遮蔽 側。 在另一態樣中,本發明提供一種製造可印刷半導體元件 之方法,其包含步驟··(1)提供一具有一外表面之晶圓,該 曰曰圓包含一半導體;(2)藉由應用一第一遮罩遮蔽該外表面 之選定區域;(3)各向異性蝕刻該晶圓之外表面,藉此產生 • 複數個凸起結構;(4)退火該晶圓,藉此產生一經退火之外 表面’·(5)藉由應用一第二遮罩遮蔽該經退火外表面之選定 區域;及(6)各向異性蝕刻該經退火外表面,藉此產生該半 導體元件。 在另一態樣中,本發明提供一種製造可印刷半導體元件 之方法,其包含步驟:(1)提供一具有一外表面之超薄晶 圓,該晶圓包含一半導體且具有一沿一垂直該外表面之軸 的選疋厚度;(2)藉由應用一遮罩遮蔽該外表面之選定區 域·’(3)各向異性蝕刻該晶圓之外表面,其中蝕刻該晶圓貫 96164.doc -36- 1284423 穿沿垂直該外表面之軸之厚度,藉此產生該可印刷半導體 元件。 在另一實施例中,本發明提供一種用於製造可撓性半導 體凡件之方法,其包含步驟··(1)提供一具有一内表面之可 印刷半導體結構;(2)提供一在一伸展狀態之預應變彈性基 板,其中該彈性基板具有一外表面;及將該可印刷半導 體結構之内表面黏結至在一伸展狀態之該預應變彈性基板 之外表面;及允許該彈性基板至少部分鬆弛至一無張力 (relaxed)狀態,其中該彈性基板之鬆弛彎曲該可印刷半導 體結構之内表面,藉此產生一具有一曲線形内表面之半導 體元件。在一例示性實施例中,該預應變彈性基板係沿一 第一軸、沿一垂直於該第一軸之第二軸或沿第一軸與第二 軸兩者伸展。在一伸展狀態之預應變彈性基板可藉由彎曲 彈性基板或滚動該彈性基板形成。本發明之此態樣之方法 可視痛要進一步包含將具有一曲線形内表面之半導體轉印 至一具有可撓性之接收基板之步驟。 【實施方式】 參考圖式’相似之數字指示相似元件,且出現於多於一 個圖式中之相同數字係指相同元件。此外,在下文中廡用 如下定義: ,,可印刷”係關於材料、結構、裝置組件及/或經整合之功 能裝置,其可在基板未曝露至高溫(意即,在小於或等於 約攝氏400度之溫度下)之情況下轉印、組合、圖案化、組 織及/或整合於基板上或基板中。在本發明之一實施例 96164.doc •37- 1284423 中,可印刷材料、元件、裝置組件及裝置可經由溶液印刷 或乾式轉印接觸印刷轉印、組合、圖案化、組織及/或整 合於基板上或基板中。 本發明之"可印刷半導體元件”包含可(例如)利用乾式轉 印接觸印刷及/或溶液印刷方法組合及/或整合於基板表面 上之半導體結構。在一實施例中,本發明之可印刷半導體 元件係整體單晶、多晶或微晶無機半導體結構。在此描述 之情形中,一整體結構係一具有可被機械連接之特徵的單 體元件。本發明之半導體元件可為不摻雜或摻雜的,可具 有選疋之摻雜劑之空間分佈,且可摻雜包括p型及n型摻 雜劑之複數種不同的摻雜劑材料。本發明包括具有至少一 大於或等於約1微米之截面尺寸之微結構可印刷半導體元 件,及具有至少一小於或等於約丨微米之截面尺寸之奈米 、、、。構可印刷半導體元件。可用於多種應用之可印刷半導體 元件包含由對諸如湘習知的高溫處理技術產生之高純度 結,半導體晶圓之高純度塊材材料進行"由上而下"處理所 ^于之7C件。在—實施例中,本發明之可印刷半導體元件 匕含將—半導體以操作方式連接至諸如—傳導層、介電 層、電極、額外半導體結構或此以件任意組合之至少一 額外破置組件或結構之複合社盖 得攸^、、、口構。在一實施例中,本發明 可印刷半導體元件包含可拉申 導體元件。 ⑫料導體^及/或異質半 截面尺寸係指裝置、裝置組件 尺寸包括窗步r… 仟次材枓之截面尺寸。截面 寬度、厚度、半徑及直徑。舉例而言,具有一帶 96164.doc -38- 1284423 狀之可印刷半導體元件的特徵為長度及兩截面尺寸(厚产 及寬度)。舉例而言’具有圓柱形狀之可印料 = 之特徵為長度及截面尺寸直徑(或者半徑)^ 1干 填充因子脑諸如第_與第二電極之㈣元件 材料、元件及/或裝置組件佔據之面積百分比。在本發明 之:實施例中,第一及第二電極係提供為與-或多個可印 刷+導體X件電接觸,該或該等可印刷半導體元件在第一 與第二電極之間提供大於或等於5()%之填充因+,對 些應用,較佳大於或等於8〇0/。。 …、 "由-基板支持,,係指__結構,該結構至少部分呈現於一 j表面=或至少部分呈現於定位於該結構與基板表面 八二入I夕個中間結構上。術語"由-基板支持”亦指部 刀或70王敢入於一基板中之結構。 "溶液印刷"意指製程’藉此諸如可印刷半導體元件之一 ^夕個結構可分散於載體介質中且以—協同方式傳送至一 =表面之選定區域。在一例示性溶液印刷方法中 =送至—基板表面之敎區域藉由獨立於經歷圖案化: :板表:之形態及/或實體特徵之方法來實現。可用於本 谷液印刷方法包括(但不限於)喷墨印刷、熱轉印印 刷及毛細管作用印刷。 ^大體縱向定向·,係指一方向,其使得諸如可印刷半導體 件群之縱向軸定向於大體平行於—選定對準轴。 =義之情形中’大體平行於一選定轴係指一在一絕對 仃向之10度範圍内之方向,較佳在一絕對平行方向之 96164.doc -39- 1284423 5度範圍内。 可拉伸"係指一 而不舍齡 ’、結構、裝置或裝置組件發生應變 而不會斷裂之能力。 料、&M ^ 隹—例示性實施例中,一可拉伸材 竹 、、、°構、農置吱梦番^ 合辦刻 < 置、、且件可經受大於約0.5%之應變而不 合辦刻 —w用’較佳經受大於約1%之應變而不 會斷裂,且對於某此雇田 、—應用,更佳經受大於約3%之應變而 不會斷裂。 術$吾"可撓性”及"可彎 弓曲同義用於本發明說明中,且係 心一材料、結構、桊詈弋 一, 裝置或裝置組件變形為一曲線形狀而不 又引入顯著應變之變形之能力,該應變諸如以一材料、 。構哀置或裝置組件之破裂點為特徵之應變。在一例示 \實加例中’-可撓性材料、結構、裝置或裝置組件可變 /為曲線幵/狀而未引入大於或等於約5%之應變,對於 某些應用,較佳大於或等於約1%,且對於某些應用,更 佳大於或等於約0.5%。 ’’半導體"係指為-在非常低溫度下是絕緣體,但在約 3〇〇開爾文之溫度下具有一可感知導電性之材料的任一材 料。在本發明說明中,術語半導體之使用意欲與軟微影技 術中此術語之使用一致。用於本發明之半導體可包含元素 半導體,諸如矽、鍺及金剛石,·及化合物半導體,諸如四 族之化合物半導體’諸如SiC及SiGe ;三五族半導體,諸 如 AlSb、AlAs、AIN、A1P、BN、GaSb、GaAs、GaN、
GaP、InSb、InAs、InN及InP ;三五族三元半導體合金, 諸如AlxGa!_xAs,一六族半導體,諸如csse、cdS、 96164.doc -40- 1284423 , CdTe、Zn〇、ZnSe、ZnS、及 ZnTe; —七族半導體,諸如
CuCl,·四六族半導體,諸如pbs、扑丁㊁及;層半導 體,諸如Pb〗2、MoS2及GaSe,·及氧化物半導體,諸如cu〇 及Cu2〇。術語半導體包括本質半導體及外質半導體,該等 外質半導體摻雜一或多種選定材料,其包括具有p型摻雜 ‘ 材料及η型摻雜材料之半導體。術語半導體包括包含半導 體之混合物之複合材料。 φ 塑膠’’係指通常在加熱時,可被模製或成形,且硬化為 一所要形狀之任一合成或天然存在之材料或材料之組合。 用於本發明之裝置及方法中之例示性塑膠包括(但不限於) 聚合物、樹脂及纖維素衍生物類。在本發明說明中,術語 塑膠意欲包括複合塑膠材料,其包含具有諸如結構增強 劑、填補劑、纖維、增塑劑、穩定劑或可提供所要化學或 •物理特性之添加劑之—或多種添加劑的—或多種塑膠。 /聚合物’’係指一包含複數個重複化學基團(其通常被稱作 修早體)之分子。聚合物之特徵通常為高分子質量。可用於 明之聚合物可為有機聚合物或無機聚合物,且可為非 一半非日日結日日或部分結晶狀態。聚合物可包含具有相 同化予組成之單體或可包含諸如共聚物之具有不同化學組 成之複數個單體。具有經聯接單體鍵之交聯聚合物尤其可 Z於本發明之某些應用中。可用於本發明之方法、裝置及 衣置組件中之聚合物包括(但不限於)塑膠、彈性體、熱塑 性彈性體、彈性塑膠、恆溫器、熱塑性塑膠及丙烯酸醋。 例不性聚合物包括(但不限於)縮酸聚合物、可生物降解聚 96164.doc -41 - 1284423 合物、纖維素聚合物、氟聚合物、耐綸、聚丙烯腈聚合 物、聚醯胺-醯亞胺聚合物、聚醯亞胺、聚芳酯、聚苯幷 咪唑、聚丁烯、聚碳酸酯、聚脂、聚醚醯亞胺、聚乙烯、 聚乙烯共聚物及經改質之聚乙烯、聚酮、聚甲基丙烯酸甲 酯、聚甲基戊烯、聚苯醚及聚苯硫醚、聚鄰苯二曱醯胺、 聚丙烯、聚胺基甲酸酯、苯乙烯樹脂、颯基樹脂、乙烯基 樹脂或此等之任意組合。
π彈性體”係指一可拉伸或變形且在無實質永久變形的情 況下返回其原始形狀之聚合材料。彈性體通常經受一實質 彈性變形。用於本發明之例示性彈性體可包含聚合物、共 聚物、複合材料或聚合物與共聚物之混合物。彈性體層係 指一包含至少一彈性體之層。彈性體層亦可包括摻雜劑及 其它非彈性體材料。用於本發明之彈性體可包括(但不限 於)熱塑性彈性體、苯乙烯材料、烯系材料、聚烯烴、聚 胺基甲酸酯熱塑性彈性體、聚醯胺、合成橡膠、pdms、 h-PDMS、聚丁二烯、聚異丁稀、聚(苯乙稀·丁二稀苯乙 烯).、聚胺基甲酸酯、聚氯丁二烯及聚矽氧。 術語"電磁輻射"係指電場與磁場之波。用於本發明之方 法的電磁輻射包括(但不限於)伽瑪射線、χ射線、紫外 光"、可見光、紅外光、微波、無線Μ,或其任意組合。 良好電子效能,,及"高效能"可同義用於本發明說明中, 且係指裝置及裝置組件具有諸如 接通/斷開比之電子特徵,Μ«及 或放大之所要f s 堵如電子訊號開關及> 所要“。展現良好電子效能之本發明之例示性 96164.doc 1284423 可印刷半導體元件可具有大於或等於1〇〇 cm2 v-! S·!之本質 場效遷移率,對於某些應用,較佳大於或等於約3〇〇 ey v s 。展現良好電子效能之本發明之例示性電晶體可具 有大於或等於約100 cm2 之裝置場效遷移率,對於某 些應用,裝置場效遷移率較佳大於或等於約3〇〇 em2 V·、4, 且對於某些應用,更佳大於或等於約800 。展現
良好電子效能之本發明之例示性電晶體可具有小於約5伏 特之臨限電壓,及/或大於約丨x 104之接通/斷開比。 保形接觸"係指建立於表面、塗覆表面、及/或上方安置 有材料之表面之間之接觸,其可用於將結構(諸如可印刷 半導體元件)轉印、組合、組織及整合於一基板表面上。 在一態樣中,保形接觸涉及將一致轉印裝置之一或多個接 觸表面宏觀調適成一基板表面之整體形狀。在另一態樣 ^保形接觸涉及將-致轉印裝置之一或多個接觸表:微 觀绸適成一基板表面以使得與外部空隙緊密接觸。術語保 形接觸意欲與在軟微影技術中之此術語之使用_致。^形 接觸可建立於—致轉印裝置之-或多個裸露接觸表面與二 土板表面之間。或者,保形接觸可建立於一致轉印裝置之 或多個塗覆接觸表面(例如上方沈積有轉印材料、可印 J半V體元件、裝置組件及/或裝置之接觸表面)與一基板 :面之間。或者’保形接觸可建立於一致轉印裝置之
夕個裸路或塗覆接觸表面與—塗覆有_諸如轉印材料、L 體光阻層、預聚物層、液體、薄膜或流體之材料之基板表 面之間。 96164.doc
Cs) 43- 1284423 π置放精確度”係指於一基板之選定區域中產生一圖案之 圖案轉印方法或裝置之能力。,,良好置放,,精確度係指可於 基板之選定區域中產生圖案,且與絕對正確方向之空間 偏差小於或等於5微米(尤其對於在塑膠基板上產生一圖案 而言)之方法及裝置。 "保真度"係指一轉印至一基板表面之圖案與選定的起始 圖案之相似性的量測。良好保真度係指轉印至一基板表面
之圖案與選定的起始圖案之間之以偏差小於⑽奈米為特 徵之相似性。 "揚氏模數"係、—材料、裝置或層之機械性質,其係指一 給定物質之應力與應變之比。揚氏模數可由如下表達式提 供: (II) (應力)一匕F) mm^{ALxA, 其中E為楊氏模數,Lg為平衡長度,為在所施加應力下 之長度變化,F為所施加之力,且A為受力面積。揚氏模數 亦可經由如下方程式以Lame常數形式表達: ρ _ μ〇λ + 2u) · λ^μ ’ (III) :及4 Lame吊數。馬楊氏模數(或"高模數”)及低楊氏 模數(或"低模數丨丨)待—仏中# )糸m疋材枓、層或裝置之揚氏模數量 =相對描述符。本發明中,高揚氏模數大於低楊氏模 ’對於某些應用’較佳大於約10倍,對於其它應用,更 土大於約⑽倍,且對於另外其它應用,更佳大於約嶋 倍0 96164.doc -44- 1284423 在下文描述中,為提供對本發 、十7丄 7 +赞明精確本質之全面解釋闡 述了本發明之裝置、裝置組 方法之大量特定細節。然 以此項技術者㈣解本發明可在無此等料細節之 情況加以實施。
本發明提㈣於製造可印刷何體元件及將可印刷半導 體元件組合於基板表面上之方法及裝置。本發明提供可印 刷之多種半導體元件,其包括單晶無機半導體、包含一以 操作方式連接至-或多個其它裝置組件之半導體結構之複 合半導體元件、及可拉伸半導體元件。本發明之方法、裝 置及裝置組件可產生高效能之電子及光電子裝置及裝置陣 列’諸如可撓性塑膠基板上之薄膜電晶體。 圖1示意性說明用於產生及組合包含單晶矽帶之可印刷 半導體元件的本發明之例示性方法。該處理以提供一具有 一薄單晶矽層105、一内埋式Si〇2層1〇7及矽操縱層1〇8之 絕緣物上矽(soi)基板1〇〇開始。若在薄單晶矽層ι〇5上存 在表面原生氧化物層,則可視需要(例如)藉由將s〇I基板 100之表面曝露至稀(1%)HF來移除該原生氧化物層。充分 剝離該原生氧化物層之後,即可遮蔽S〇i基板ι〇〇之外表面 110之選定區域,藉此於外表面11〇上形成遮罩元件12〇、 遮蔽區域125及曝露表面區域127之一圖案。在圖1所示之 實施例中,外表面110利用提供可抑制外表面11〇之遮蔽區 域12 5餘刻之遮罩兀件12 0之矩形銘及金表面層來圖宰化。 遮罩元件120可具有任一大小及形狀,其包括(但不限於)正 方形、矩形、圓形、橢圓形、三角形形狀,或此等形狀之 96164.doc -45- 1284423 任意組合。在一例示性實施例中,利用微接觸印刷、奈米 接觸印刷技術,或光微影及蝕刻方法(對於Ai^ tfa,·對 於A1用AL-11預混合Cyantec蝕刻劑)來製造提供具有所要 幾何形狀之遮罩元件之Al/Au層的圖案。包含薄金屬膜之 遮罩το件之沈積可藉由諸如Temescal BJD18〇〇之電子束蒸 ,鑛機,(例如)藉由A1(2〇nm; (M nm/s)且隨後為^(1〇〇11叫 1 nm/s)之順序沈積來提供。 • SOI基板100之外表面110係採用各向異性向下蝕刻。如 圖1所示,儘管可選擇性將材料自曝露表面區域127移除, 但遮罩元件120防止餘刻遮蔽區域125,藉此產生具有微傾 斜側壁141之包含單晶矽結構之複數個凸起特徵。在凸 起特徵具有厚度147約為100奈米之侧壁141之例示性實施 例中,將曝露表面區域127曝露至四甲基錢氯氧化物 (TMAH)約3.5分鐘。在此實施例中,#刻於具有舰以遮 罩兀件120之單晶石夕之凸起特冑14〇上產生平滑側壁,較佳 _自平均表面位置之偏差小於1G奈米。#下方叫層1〇7被 (例如)利用遭(49〇/〇)HF部分或完全各向同性钱刻掉時,凸 ^特徵140可起離於基板100。凸起特徵140之起離產生包 各具有一由遮罩元件覆蓋之表面之離散單晶矽結構之可印 刷半導體το件15G。本實例中之遮罩元件—、A·。層可 ::除或可(例如)作為薄膜電晶體中之源極與汲極而直接 4 \最終裝置結構中。如圖1所示,可印刷半導體元 件\5\可藉由乾式轉印接觸印刷技術(由箭頭165示意性指 )或藉由,谷液澆鑄方法(由箭頭166示意性指示)組合於諸 96164.doc -46- 1284423 • 如塑膠基板之基板表面160之接收表面上。兩種組合方法 可在周圍環境中在室溫時進行,且因此可適於包括低成 本、可撓性塑膠基板之廣泛基板。 使用乾式轉印接觸印刷方法組合可印刷半導體元件具有 下述益處:在可印刷半導體元件起離於S〇I基板之前利用 其已知方向及位置。在此情況下,與軟微影轉印印刷技術 之程序相似之程序可用以將可印刷半導體元件自SOJ(在蝕 0 刻Si〇2之後,但在起離矽之前)移至裝置基板上之所要位 置。詳言之’一致彈性體轉印元件將物件自S〇][表面拾 取,且將其轉印至一所要基板。同樣地,可印刷半導體元 件可藉由利用界定於目標基板表面上之容器(receptacle)襯 塾之Au冷焊而直接轉印至薄塑膠基板上。 在一例示性方法中,使得可印刷半導體元件1 50之至少 一部分達到與一諸如彈性體轉印戳記、聚合物轉印裝置或 複合聚合物轉印裝置之一致轉印裝置175之接觸表面17〇保 # 形接觸,藉此將可印刷半導體元件150之至少一部分黏結 至接觸表面170上。安置於一致轉印裝置175之接觸表面 170上之可印刷半導體元件15〇可較佳以於接觸表面與 基板160之接收表面之間建立保形接觸之方式達到與基板 16〇之一接收表面接觸。接觸表面17〇與和基板16〇之接收 表面接觸之可印刷半導體元件150分離,藉此將可印刷半 導體元件15〇組合至該接收表面上。本發明之此實施例可 在包s可印刷半導體元件15〇之接收表面上於良好界定位 置及空間方向產生一圖案。在圖!所示之實施例中,可印 96164.doc 1284423 刷半導體元件150以操作方式連接至存在於基板i6〇之接收 表面之金襯墊162。 圖2提供一說明一種用於將可印刷半導體元件組合於一 基板之-接收表面上之選擇性乾式轉印接觸印刷方法的示 意圖。、將複數個可印刷半導體元件綱製造於母基板3〇5 上成以良好界定位置及空間方向為特徵之可印刷半導體 70件300之第一圖案31〇。具有一具有複數個離散黏結區域 _ 325之接觸表面32G之—致轉印裝置315可達到與在母基板 305上之可印刷半導體元件鳩之至少—部分保形接觸。接 觸表面320上之黏結區域325以對可印刷半導體元件31〇之 親和力為特徵,且其可為化學改質區域,諸如為具有自 PDMS層表面延伸之經基之區域,或為塗覆有—或多個黏 接層之區域。保形接觸可轉印與接觸表面32〇上之黏結區 域325接觸之可印刷半導體元件31〇之至少一部分。轉印至 接觸表面32G之可印刷半導體元件310可達成與基板335之 |接收表面330接觸,該基板可為一諸如塑膠基板之可撓性 基板。半導體兀件3 10與接觸表面32〇之隨後分離導致將該 半導體元件310組合於基板335之接收表面33〇上,藉此產 生以良好界疋位置及空間方向為特徵之可印刷半導體元 件之第二圖案340,其不同於可印刷半導體元件340之第一 圖案。如圖2所示,保留於母基板305上之可印刷半導體元 件340之特徵為不同於可印刷半導體元件之第一及第二圖 案之可印刷半導體元件之第三圖案345。隨後,利用包括 選擇性乾式轉印方法之本發明之印刷方法,可將包含第三 96164.doc -48- 1284423 圖案345之可印刷半導體元件34〇轉印及/或組合至基板ns 或另一基板上。
360之圖案較佳對應於在諸如薄膜電晶體陣列組態之裝置 組態或裝置陣列組‘態中之可印刷半導體元件扇之相對位 置及空間方向。 圖3A至圖3C係展示用於本發明之選擇性乾式轉印接觸 印刷方法之裝置、裝置組態及裝置組件之示意圖。圖从展 示母基板305上之複數個可印刷半導體元件3〇〇,其中選定 之可印刷半導體元件扇具有一或多個黏接塗層⑽。^ 3A所示,黏接塗層35()提供於—良好界^圖案中。圖戰 示具有一具有提供於良好界定圖案中之複數個離散黏結區 域325之接觸表面320的一致轉印裝置315。圖几展示一具 有-包含提供&良好界定圖案中之凸起特徵36()之三維^ 起圖案355之一致轉印裝置315。在圖3C所示之實施例中, 凸起圖案355提供可視需要塗覆有_或多個黏接層之複數 個接觸表面320。黏接塗層35〇、黏結區域325及凸起特徵 刷之本 圖4A1 圖4A1及圖4A2展示一用於利用乾式轉印接觸印 發明之組合方法的可印刷半導體元件之較佳形狀。 提供-透視圖’且圖4A2提供一俯視圖。可印刷半導體元 件包含一具有一第-末端505、巾央區域510及第二末端 515之沿一中心縱向軸5〇2延伸之帶5〇〇。如圖4A所示,帶 5〇〇之寬度可選擇性沿其長度變化。特定言之,第一及第 二末端505及515比中央區域51〇寬。在一例示性方法中, 帶500藉由㈣母基板52〇而形成。在此實施例中,母基板 96164.doc
-49- 1284423 各向同性曝露至蝕刻劑直至帶500藉由包含接近第一及第 末端505及515之犧牲層525之兩個對準保持元件而僅附 著至母基板520為止。此時,在製造過程中,停止蝕刻過 程,且帶500可達到與一致轉印裝置接觸及/或黏結至其 上。當轉印裝置自母基板520移除時,犧牲層525被破壞, 且帶500被釋放。此方法亦可應用於具有如❹所示之形狀 之複數個可印刷半導體元件之乾式轉印接觸印刷。本發明 之此方法的優勢在於在轉印、組合及整合步驟過程中可精 確保持母基板520上之複數個帶5〇〇之方向及相對位置。犧 牲層厚度之例示性範圍可為約! _降至約⑽⑽,且帶寬 度在約2叫與10〇 μιη之間。令人感興趣的是帶之斷裂通常 發生於物件之極端(非常接近帶附著至母晶圓之點/邊緣)。 寬的帶在起離過程中通常不發生扭曲,且其黏結至戮記。
圖4Β1及圖4Β2展示-用於利用乾式轉印接觸印刷之本 Τ明之組合方法的可印刷半導體元件之較佳形狀。圖4m 提供透視圖,且圖4β2提供一俯視圖。可印刷半導體元 件包含沿一平行中心縱向軸528延伸之帶527。帶藉由 將沿中心縱⑲528之帶之至少_末端連接至母基板a;的 對準保持元件53 0而固持於及方向。對準保持 =件530於帶527之圖案化過程中藉由未沿其中心縱向轴界 疋帶之一個或兩個末端而製造。一旦該等帶與一轉印裝置 之接觸表面接觸’且隨後自母基板52()移出,則對準保持 元件530被破壞,且釋放帶527。 可印刷半導體元件15〇 為了實現藉由溶液印刷之組合, 96164.doc -50- 1284423 .之至少一部分分散於載體介質中,藉此產生在載體介質中 包含半導體元件150之懸浮液190。藉由將懸浮液溶液印刷 至基板160之接收表面上而將可印刷半導體元件15〇傳送至 基板,且進行組合。溶液印刷可藉由包括(但不限於)喷墨 印刷、熱轉印印刷及絲網印刷之此項技術中已知之多種技 術來提供。在圖1所示之實施例中,可印刷半導體元件j5〇 以操作方式連接至呈現於基板160之接收表面上的金襯墊 162。 籲 圖5A至圖5C呈現包含具有選定實體尺寸之單晶矽微帶 之多種可印刷半導體元件150的光學及掃描電子顯微圖。 可印刷半導體元件係展示於乙醇懸浮液中且澆鑄於各種類 型之基板上。圖5A展示矽棒(寬度為2微米;厚度為2微 米;長度約為15毫米)之溶液澆鑄傾斜罩面之光學顯微 圖。該插入影像展示分散於乙醇溶液中之可印刷矽條(其 約有1千萬)。圖5B中之低解析度SEM影像說明溶液澆鑄至 • 一裸露矽晶圓上之某些平微帶(厚度340奈米;寬度5奈 米,長度約15毫米)之機械可撓性範圍。圖5C呈現一此等 物件之一者之高解析度SEM影像。應注意由各向異性濕式 钱刻程序產生之極端平滑側壁。 利用本發明之方法亦可形成線狀、片狀及圓盤型式之可 印刷半導體元件。藉由利用大面積軟微影技術,可以—單 一低成本處理序列來產生横向尺寸降至5〇 nm,且幾乎可 為任一幾何形狀之大量(意即十億)可印刷半導體元件。本 發明之方法亦可製造具有如20奈米一樣小之橫向尺寸之可 96164.doc -51 · 1284423 •印刷半導體元件。對於用於可撓性電子系統中之薄膜電晶 體而言,包含長(約10微米)條及窄(約i微米)條之單晶矽的 可印刷半導體元件尤其有用。 圖6呈現一厚度約為25微米之塗覆有PDMS之聚醯亞胺薄 片上之包含單晶矽微帶之經轉印可印刷半導體元件的影 像。此上部插入圖片說明此系統之本質可撓性。下部插圖 展示冷焊於一薄Ti/Au塗覆之Mylar薄片上之可印刷石夕密集 • 微帶(25微米寬、約2微米間隔)之俯視顯微圖。如圖6所 示’包含石夕被f之可印刷半導體元件可良好對準且轉印於 受控方向。即使當基板顯著彎曲時,在利用掃描電子顯微 術仔細檢查時未觀測到由於組合而引起之可印刷半導體元 件之斷裂。利用一 Au塗覆之薄Mylar薄片可獲得相似結果 (無需一彈性體層),如底部插入顯微圖片所說明。以此方 式可實現覆蓋密度接近1〇〇〇/0。 本發明亦提供包含一以操作方式連接至諸如介電元件、 春傳導元件(意即電極)或額外半導體元件之一或多個其它裝 置組件之半導體結構的複合可印刷半導體元件。尤其可用 於製造薄膜電晶體之本發明之一例示性可印刷半導體元件 包含一整合半導體及介電元件。此等複合可印刷半導體元 件長:供具有高品質、無、茂漏介電質之電晶體,且避免需要 用於製造薄膜電晶體中之介電元件之分離旋塗步驟。此 外’使用複合可印刷半導體元件可使得藉由低成本印刷技 術有效的將裝置製造於大的基板區域上。 下文參考文獻係關於自組合技術,其可用於本發明之方 96164.doc -52- ⑧ 1284423 法中以經由接觸印刷及/或溶液印刷技術轉印、組合及互 連可印刷半導體元件:(1) "Guided molecular self-assembly: a review of recent efforts’’,Jiyun C Huie Smart Mater. Struct. (2003) 12,264-271; (2) "Large-Scale
Hierarchical Organization of Nanowire Arrays for Integrated Nanosystems",Whang, D·; Jin, S.; Wu, Y.; Lieber, C. M. Nano Lett. (2003) 3(9), 1255-1259; (3) ’’Directed Assembly of One-Dimensional Nanostructures into Functional Networks”,Yu Huang, Xiangfeng Duan, Qingqiao Wei,及 Charles M. Lieber,Science (2001) 291, 630-633 ;及(4) "Electric-field assisted assembly and alignment of metallic nanowires’’,Peter A. Smith 等人, Appl. Phys. Lett. (2000) 77(9),1399-1401。 本申請案中所引用之所有參考文獻之全文以引用的方式 且以其未與本申請案中之揭示内容產生不一致之程度倂入 本文中。提供於本文中之某些參考文獻以引用的方式倂入 以提供關於本發明之起始材料、額外起始材料、額外試 劑、額外合成方法、額外分析方法及額外用途之來源的詳 情。普通熟習此項技術者易瞭解除了本發明特定描述之外 的其它方法、裝置、裝置元件、材料、程序及技術可應用 於如本文中所廣泛揭示之本發明之實施且無需進行不當之 實驗。意欲將本文所特定描述之方法、裝置、裝置元件、 材料、程序及技術之所有已知技術的功能之均等物涵蓋於 本發明中。 96164.doc -53- 1284423 分別於2004年6月4曰、2004年8月11曰、2005年2月4 日、2005年3月18曰及2005年5月4日申請之第60/577,〇77 號、第 60/601,061號、第 60/650,305號、第 60/663,391 號及 第60/677,617號美國專利申請案之全文以引用的方式且其 未與本申請案中之揭示内容產生不一致之程度倂入本文 中0
當一材料、組合物、組份或化合物群揭示於本文中時, 應瞭解,此等群之所有個別成份及其所有子群係單獨揭 示。當一 Markush群或其它群用於本文時,該群之所有個 別成份及該群之所有可能組合及可能子組合意欲個別包括 於本揭示内容中。除非另有聲明,否則本文所描述或例示 之組份之每一調配物或組合可用於實施本發明。無論何時 於本說明書中給出一諸如溫度範圍、時間範圍或組合物範 圍之範圍,所有中間範圍及子範圍,以及包括於給定範圍 中之所有個別值意欲包括於本揭示内容中。 曰如本文所使用之”包含”係與"包括”、”含有"或,,特徵為,, 同義’且係包括的或可擴充的,且不排除額外的、未敍述 元件或方法步驟。如本文所使用之”由…組成”排除未在主 張之兀件中指定之任-元件、步驟或成份。如本文使用之 大體由···組成”不排除在本f上不影響中請 =新賴特徵之材料或步驟。本文之每一實例中:二 二包含,,"大體由…組成”及”由…組成”可由其它兩術語之 任一者替代。 1具有一可印刷半導體元件之薄膜電晶體 96164.doc -54- (S) 1284423 猎由實驗研究驗證本發明之可印刷半導體元件於薄 晶體中提供半導體通道之能力1言之,本發明之—目炉 為提供能_由£卩刷方法在—可撓性塑膠基板上製造之^ 膜電晶體。而且’本發明之—目標為在詩基板上提供且 有與藉由習知高溫處理方法製造之薄臈電晶體相似或優: 其之場效遷移率、接通/斷開比及臨限電·之高效能薄膜 電晶體。 •,圖7呈現一具有一可印刷半導體元件之薄膜電晶體之光 學顯微圖影像。所說明電晶體531包含源極532、汲極 533、可印刷半導體元件534、介電質(在圖7之顯微圖中未 展示)及閘極(在圖7之顯微圖中亦未展示)。薄膜電晶體係 由一包含一塗覆有氧化銦錫(IT〇,約1〇〇奈米厚)作為一閘 極及光固化環氧樹脂作為閘極介電質(su 8 _ 5 · Microchem Corp)之Mylar薄片之基板支持。該介電質之 電容(2.85 nF/cm2)係利用形成於該裝置附近之電容器測試 • 結構來估計。此裝置使用一溶液澆鑄可印刷半導體元件, 其包含一由一具有340奈米裝置層厚度及14至22 〇hm €111之 電阻率之p型摻雜S0I晶圓(s〇itec)製造之約5毫米長、2〇微 米寬及340奈米厚之微帶。25奈米厚之以〇2層藉由在一水 平石英管式爐中乾式氧化而生長於矽之頂部。a1(2〇奈 米)/Au(180奈米)之源極及汲極由起離技術界定。半導體通 道之長度為50微米,且其寬度為2〇微米。 圖8及圖9展示自具有一可印刷半導體元件之本發明之薄 膜電晶體收集之電學量測結果。該裝置之操作與具有一頂 96164.doc -55- 1284423 部接觸組態之背閘極式SOI裝置相似。該半導體在一長度 等於50微米之通道中使用一寬度等於20微米之單晶石夕微 帶。在此情況下之可印刷半導體元件可藉由溶液澆鑄方法 圖案化。該等源極/沒極接點藉由光微影及起離來界定。 圖8提供一展示一在一預氧化si晶圓上製造之裝置之電 _电壓(IV)特徵的曲線。圖9提供一展示一在一塗覆有 ιτο閘極及聚合物介電質之Mylar薄片上製造之裝置在 VDS=0.1 V下量測之轉印特徵的曲線。此曲線之斜率界定 一 180 cm2/Vs之有效裝置遷移率(利用源極及汲極之實體寬 度,在此情況下其等於半導體元件微帶之寬度)。如對p型 摻雜矽上之A1(功函數為4.2 eV)金屬化所預期之,至可印 刷半導體元件之接點之Al/Au金屬化提供至矽之適度之低 電阻蕭特基障壁(Schottky barrier)接觸。熟知鋁可快速擴 政於矽中,但無需特別注意避免區域化之鋁_石夕之相互作 用,因不進行後金屬化高溫退火步驟。此裝置之接通/斷 開比稍微小於103。圖9之轉印特徵分析指示將一平行板模 型用於介電電容之之線性場效遷移率。此分 析忽略了接觸及處理引起之臨限電壓改變之影響。 ^吏利用最適當接觸,仍有理論論據表明將非常高縱橫 、、^、卩極端長之長度對寬度之比)之半導電元件倂入通 道區域中(意即奈米管或奈米線)之電晶體應具有不同於習 知裝置之回應的回應。A 了避免此等影響,吾人選擇包含 一 電曰曰體通道長度數量級相同之寬度之微帶的可印刷 半‘體7G件。此處所觀測之性質(遷移率、標準化轉導、 96164.doc -56 - 1284423 接通/斷開比)為在si蝕刻後但在起離前於S0I基板上製造之 薄膜電晶體之性質的約3/4。在此等量測中,内埋式以〇2氧 化物充田電負,且矽支持基板充當閘極。此結果顯示用 以產生可印刷半導體元件,及將其轉印至裝置基板之處理 步驟未顯著改變矽或由初始圖案化及矽蝕刻步驟所得之其 表面的性質。此結果亦指示具有SU8介電質之凡得瓦爾力 介面可支持良好裝置性質。 藝 本發明之實例的製造方法之主要優勢在於,其將矽之晶 體生長及處理與塑膠基板及其它裝置之組件分離。此外, 本發明之處理可印刷半導體元件之方法在處理序列及可能 之材料選擇中具有高度靈活性。舉例而言,一 Si02層可形 成於矽之一個侧面(例如,藉由在起離Si元件之前或將S0I 内埋式氧化物及Si裝置層一起提昇之前生長熱氧化物)以得 到整合介電質,其利用與本文所說明之用於整合源極/汲 極金屬化之策略相似之策略。以此方式引入之介電質可避 瞻免在塑膠基板上之多種溶液澆鑄薄介電質中與洩漏、滯 後、摻雜、捕集等相關之重大挑戰。
圖10A至圖10H提供說明一種用於製造具有複合可印刷 半導體元件之薄膜電晶體陣列之本發明之方法的示意圖。 如圖10A所示,閘極547沈積於諸如Kapton、Mylar或PET 之一薄片可撓性基板之表面548上。閘極可藉由此項技術 中已知之任一方式圖案化於可撓性基板上,該等方式包括 (但不限於)光微影、微轉印印刷、奈米轉印印刷、軟微 影’或此等方法之組合。如圖1〇B所示,該方法進一步包 96164.doc (§) -57- 1284423 •含製造包含以操作方式連接至Si〇2介電元件56〇之單晶矽 結構555之複數個複合可印刷半導體元件55〇之步驟。如圖 說明,複合可印刷半導體元件550具有-沿中心縱向軸 5 5 1 L伸選疋長度5 5 2之帶狀。複合可印刷半導體元件 550具有一選定厚度553及一作為厚度函數而變化之寬度。 如圖10C所示,該方法進一步包含經由乾式轉印接觸印 刷或溶液印刷將複合可印刷半導體元件55〇組合於閘極 φ 及基板548之步驟。定向複合可印刷半導體元件550以使得 Si〇2介電元件560與閘極547接觸。如圖1〇D所示,該方法 進一步包含將一正性光阻薄層561旋塗於基板548之圖案化 表面上之步驟。或者,可利用一滚筒將該正性光阻薄層 561塗覆至基板548之圖案表面。光阻561未被閘極547遮蔽 之區域曝露至一經由基板548之下側562傳輸之電磁輻射射 束下。本發明之此方法較佳使用光學透射性基板548,尤 其是一在紫外線及/或電磁波譜之可見區域下至少部分透 參 明之基板548。如圖10E所示,該方法進一步包含顯影該薄 光阻層之步驟。如此圖所示,薄光阻層561之被閘極遮蔽 之區域未被顯影。如圖10F所示,該方法進一步包含乾式 或濕式蝕刻整合Si〇2介電質之步驟,藉此斷開源極與汲極 之接觸。在圖10F所說明之實施例中,此藉由將基板548之 圖案化表面曝露至CF4電漿下而實現。如圖10G所示,該方 法進一步包含藉由蔽蔭遮罩蒸鍍而界定源極及汲極之步 驟。因為在下一製造步驟中會界定半導體通道,所以半導 體元件、源極及汲極之對準無需非常精確。如圖10H所 96164.doc -58 - 1284423 示,該方法進-步包含,(例如)藉由曝露至諸如丙綱之溶 劑中而起離正性抗㈣,從而界定半導體通道之步驟。
圖UA至圖UD提供說明一種用於製造一包含經整合之 閘極、閘極介電質、半導體、源極及沒極之可印刷裝置之 本毛明之方法的圖。如圖u A所示,高品質閘極介電質藉 由SOI晶圓之表面熱氧化而生長。接著,沈積閘極材料(諸 如金屬或摻雜多晶石夕)。隨後,利用(例如)微影方法遮蔽頂 表面之選^區域。在-實施例中,在—單獨遮蔽步驟中, 界定具有受控間隔之同一圖案之陣列。隨後藉由各向異性 濕式及/或乾式蝕刻製造可印刷半導體元件。較佳地,三 個不同選擇㈣過程可順序進行録刻閘極材料、間極介 電負及頂部石夕層之曝露區域。 如圖11B所示,微影方法可用以界定電晶體通道。在此 处里y驟中,蝕刻掉(乾式或濕式蝕刻)閘極材料之曝露區 域。隨後如圖11C所示,加熱光阻高於其玻璃態化溫产, 藉此起始迴烊製程。光阻之迴焊距離可藉由仔細選擇^ 層之適當厚度、光阻層之玻璃態化溫度或迴焊製程之溫度 及持續時間來選擇。隨後,利用HF溶液㈣閘極 曝露區域。 者,如圖11D所示,進行金屬化製程,之後起離沈積 /且上之金屬以完成可印刷裝置之製造。源極及汲極自 對準㈣,幻原極與汲極之間之間隔可藉由調整迴焊製 之諸如溫度及持續時間之不同參數來選擇。 如圖UD所示之可印刷裝置可藉由本發明之乾式轉印或 96l64.doc (§> -59- 1284423 溶液印刷方法轉印及組合至一諸如塑膠基板之基板上。圖 Μ至11D中說明之自動對準製程呈現一整合實現諸如 MOSFET裝置之可印刷裝置所必需之所有元件之簡單方 法。本發明之此製造方法之顯著優勢在於需要不適於塑膠 基板之溫度(如’需要溫度大於約攝氏伽度)之所有製程步 驟可在將裝置起離及轉印至基板上之前而於咖基板上執 行。舉例而言,諸如源極及汲極接觸區域之摻雜、矽化物
層之形成及裝置之高溫退火之額外處理步驟可在將元件轉 印至一塑膠基板上之前執行。 實例2 ··可拉伸可印刷半導體元件 本發明提供當被拉伸、屈曲或變形時,可提供良好效能 之可拉伸可印刷半導體元件。而且,本發明之可拉伸可印 刷半導體元件可被調試成廣泛裝置組態以提供完全可撓性 之電子及光電子裝置。 圖12提供一展示一本發明之可拉伸可印刷半導體元件之 原子力顯微圖。可拉伸可印刷半導體元件7〇〇包含一具有 一支持表面710之可撓性基板705,及一具有一曲線形内表 面720之彎曲半導體結構715。在此實施例中,彎曲半導體 結構715之曲線形内表面720之至少一部分黏結至可撓性基 板705之支持表面710。曲線形内表面72〇可在沿内表面72〇 之選定點或沿内表面720之幾乎所有點來黏結支持表面 710。圖12所說明之例示性半導體結構包含一寬度等於約 100微米及厚度等於約1〇〇奈米之單晶矽之彎曲帶。如圖12 所‘明之可撓性基板係一具有一約1毫米厚度之PDm§基 96164.doc • 60· 1284423 板。曲線形内表面720具有一以一沿該帶之長度延伸之大 體週期波為特徵的輪廓外形。如圖12所示,該波之振幅約 為500奈米且峰值間隔約2〇微米。圖13展示一提供一具有 曲線形内表面720之彎曲半導體結構715之展開圖之原子力 顯微圖。圖14展示一本發明之可拉伸可印刷半導體元件陣 -列之原子力顯微圖。圖14之原子力顯微圖之分析表明彎曲 半導體結構被壓縮約〇.27%。圖15展示本發明之可拉伸可 φ 印刷半導體元件之光學顯微圖。 曲線形表面720之輪廓外形允許彎曲半導體結構715沿變 形軸730伸展或收縮而不經受實質機械應變。此輪廓外形 亦可允許半導體結構在除了沿變形軸73〇外之其它方向上 彎曲、屈曲或變形,而無由應變導致之顯著機械破壞或效 能損耗。本發明之半導體結構之曲線形表面可具有提供諸 如可拉伸性、可撓性及/或可彎曲性之良好機械性質,'及/ 或提供諸如當屈曲、拉伸或變形時呈現良好場效遷移率之 籲 i好電子效能之任一輪廊外形。例示性輪庵外形之特徵可 為複數個凸起及/或凹陷區域,及包括正弦波、高斯波、 A—函數、方波、洛侖兹波、週期波、非週期波或此等波 之任意組合之廣泛的各種波形。可用於本發明之波形可相 對於兩個或三個實體尺寸變化。 圖16展示本發明之可拉伸可印刷半導體元件之原子力顯 微圖,該可拉伸可印刷半導體元件具有一黏結至一在其支 持表面7U)上具有-三維凸起圖案之可撓性基板7〇5的彎曲 半導體結構715。該三維凸起圖案包含凹進區域75〇及凸起 96164.doc -61 - 1284423 特徵760。如圖16所示,彎曲半導體結構715被黏結至支持 表面710之凹進區域750中及凸起特徵760上。 圖17展示一說明一種本發明之製造可拉伸半導體元件之 例示性方法的流程圖。在該例示性方法中,提供一在伸展 狀態之預應變彈性基板。預應變可藉由包括(但不限於)滾 •壓及/或預彎曲彈性基板之此項技術中已知之任一方法來 實現。用於本發明之方法中之例示性彈性基板係一厚度等 • 於約1毫米之PDMS基板。該彈性基板可藉由沿一單個軸伸 展或藉由沿複數個軸伸展而發生預應變。如圖17所示,可 印刷半導體結構之内表面之至少一部分黏結至在一伸展狀 L下之預應變彈性基板之外表面。黏結可藉由半導體表面 之内表面之間之共價鍵結、凡得瓦爾力、利用黏接劑或此 等方法之任意組合而實現。在彈性基板係pDMSi 一例示 性實施例中,PDMS*板之支持表面係經化學改質使得其 具有自其表面延伸之複數個羥基以便於與矽半導體結構之 鍵結。返回參看圖17,在黏結預應變彈性基板及半導 f結構之後,允許彈性基板至少部分鬆弛至一無張力狀 ^在此實施例中,彈性基板之鬆弛使該可印刷半導體結 冓之内表面4曲,藉此產生一具有一曲線形内表面之半導 體兀*件。 如圖1 7所不,製造方法可視需要包括一二次轉印步驟, 中具有一曲線形内表面720之半導體結構71 5可自彈性基 2轉印至較佳為_可撓性基板之另_基板。此二次轉印步 鉢可藉由使得具有曲線形内表面720之半導體結構715之一 96164.doc ... m -62- 1284423 曝路表面與黏結至半導體結構715之曝露表面之另一基板 之一接收表面相接觸而實現。黏結至另一基板可藉由包括 (仁不限於)共價鍵、經由凡得瓦爾力黏結及使用黏接劑弋 此項技術中之任一方法來完成。 、 本發明之可拉伸半導體元件可有效整合於大量功能裝置 及咸置組件中,諸如電晶體 '二極體、雷射、、 NEMS、LEDS及OLEDS。本發明之可拉伸半導體元件具有 超出習知的剛性無機半導體之某些優勢。第一,可拉伸半 導體元件可具有可撓性,且因此比習知的剛性無機半導體 更不易由屈曲、彎曲及/或變形引起結構破壞。第二,因 為彎曲半導體結構可處於輕微之機械應變狀態以提供一曲 線形内表面,所以本發明之可拉伸半導體元件可呈現比習 知的無應變無機半導體高之本質場效遷移率。最後,因為 可拉伸半導體元件可在裝置溫度循環時自由伸展及收縮, 所以其可能提供良好熱性質。 實例3 :製造可印刷半導體元件之方法 本發明提供由包括單晶晶圓、基板上矽晶圓、鍺晶圓、 多晶矽薄膜及超薄矽晶圓之廣泛起始材料製造可印刷半導 體元件之方法。特定言之,本發明提供在選定方向及相對 位置製造大量可印刷半導體之低成本方法。 圖1 8A展示一由一 si_Ge磊晶基板製造可印刷半導體元件 之例示性方法。在此方法中,Si磊晶層之選定區域藉由沈 積諸如包含金屬、Si〇2或SiN之薄膜之遮罩材料而遮蔽。U 此遮蔽步驟界定待製造可印刷半導體元件之形狀及某此實 96164.doc -63 - 1284423 體尺寸(+例如’帶之長度及寬度)。Si-Ge遙晶基板之曝露Si 二1由乾式或濕式化學餘刻方法各向異性姓刻。以此 方式產生矽之凸起特徵,較佳具有平滑側壁,其可藉由起 技術有效自Si-Ge磊晶基板釋放,如利用藉由在5〇。。下 之nh4〇h.h2〇2:h2〇 1:1:4提供之選擇性SiGe濕式㈣。源 極、汲極、閘極、介電元件或此等元件之任意組合可視需
要在起離之前整合於半導體元件中。此製造方法之優勢在 於可清潔及再利用母基板。 圖1犯展示—㈣於由㈣基板,較佳為—單晶石夕基板 製造可印刷半導體㈣之例示性方法。在此方法中,首先 1 )在於自約攝氏8〇〇度至約攝氏12〇〇度之範圍中所選擇 :溫度下’在-石英管式爐中乾式氧化石夕晶圓。接著,將 :閉極材料薄層沈積於㈣晶圓之經氧化表面上。例示性 f極材料包括金屬或經摻雜之多晶矽。該閘極材料薄層可 2光阻選擇性圖案化。此圖案化步驟界㈣製造可印刷 體几件之形狀及某些實體尺寸(例如,帶之長度及寬 度)。該閘極材料薄層及介電層係經各向異 :產生包含-光阻層、間極材料層、介電層切層:且: 平滑側壁之凸起特徵。接著,例如藉由退火至在自 阻# ΐ0ί)度至約攝氏13G度之範圍所選擇之溫度來迴焊光 心迴焊光阻可將光阻之一部分轉印至凸起特徵之侧 ΐ法j18B所示’曝露之Si表面係利用濕式或乾式姓刻 半2向同性韻刻’藉此釋放凸起特徵及產生複合可印刷 h體元件,且其較佳具有平滑表面。石夕之 96164.doc •64· 1284423 可利用HN〇3:NH4F:H2〇 64:3:33溶液來實現。此製造方法 之優勢為矽基板起始材料之相對低成本,及在平坦化 (ECMP)之後再利用母基板之能力。 圖18C展不由塊矽基板,較佳為一單晶矽基板製造可印 " 料導體元件之另—例示性方法。在此方法中,利用光阻 • 冑擇性圖案化塊矽基板之外表面。此圖案化步驟界定待製 造可印刷半導體元件之形狀及某些實體尺寸(例如,帶之 φ 長度及寬度)。較佳利用諸如反應性離子蝕刻及電感耦合 電漿蝕刻之乾式蝕刻方法各向異性蝕刻該圖案化基板表 面,藉此產生凸起特徵,較佳為具有平滑侧壁之凸起特 , 徵。凸起特徵之側壁之至少一部分藉由沈積諸如金屬、 ’ ⑽或_之薄層之遮罩材料來遮蔽。在-實施例中,遮 罩材料可藉由傾斜蒸鍍或濺鍍沈積技術與樣本旋轉結合而 塗覆至凸起特徵之側壁以確保沈積所有曝露侧壁。如圖 18C所示,曝露Si表面係利用濕式或乾式蝕刻方法各向同 • 性蝕刻,藉此釋放凸起特徵及產生可印刷半導體元件,且 其較佳具有平滑表面。矽之各向同性蝕刻可利用 HN〇3:NH4F:H2〇 64:3:33溶液來實現。此製造方法之優勢 為矽基板起始材料之相對低成本,及在平坦化(EcMp)2 後再利用母基板之能力。 圖18D展示由塊矽基板,較佳為一單晶矽基板製造可印 刷半導體元件之另-例示性方法。在此方法中,利用光阻 選擇性圖案化塊石夕基板之外表面。該圖案化基板表面係經 • 各向異性蝕刻,藉此產生凸起特徵。接著,例如藉由在一 96164.doc -65- 1284423 、艮英爐中於約攝氏11GG度之溫度下,且在氮氣中將石夕基板 ^ 下步,經退火之矽基板之表面藉由利用光阻遮蔽 選疋區域來圖案化。此圖案化步驟界定待製造可印刷半導 體元件之形狀及某些實體尺寸(例如,帶之長度及寬度)。 ^圖18D所示,經退火之石夕基板之圖案化表面係利用濕式 或乾式蝕刻方法各向異性蝕刻,藉此產生可印刷半導體元 件且其較佳具有平滑表面。此製造方法之優勢為矽基板 • 起始材料之相對低成本,在平坦化(ECMP)之後再利用母 基板之月b力’及在退火步驟之後整合源極、沒極、閘極及 介電質裝置組件之能力。此外,濕式蝕刻可用於利用i 1〇 矽晶圓之第一蝕刻步驟中。 圖18E展示一種由一超薄矽基板製造可印刷半導體元件 之例示性方法。在此方法中,利用光阻選擇性圖案化超薄 矽基板之外表面。此圖案化步驟界定待製造可印刷半導體 元件之形狀及某些實體尺寸(例如,帶之長度及寬度)。圖 _ 案化基板表面係經各向異性蝕刻穿過超薄矽基板之厚度, 藉此產生可印刷半導體元件。對於此製造方法之某些應用 具有由自約10微米至約500微米之範圍中選擇之厚度之超 薄矽基板是較佳的。此製造方法之優勢為超薄矽基板起始 材料之相對低成本。 圖1 8F及1 8G展示由多晶矽薄膜製造可印刷半導體元件 之例示性方法。在此方法中,一多晶矽薄層沈積於一諸如 玻璃或梦基板之支持基板上’其具有諸如包含或|§丨〇2 之塗層之犧牲表面層。隨後,退火多晶薄膜,且藉由沈積 96164.doc -66- 1284423 t如包含金屬、Si〇2或SiN之薄膜之遮罩材料而選擇性遮 蔽曝露表面之選定區域。此遮蔽步驟界定待製造可印刷半 導體元件之形狀及某些實體尺寸(例如,帶之長度及寬 度)。該圖案化表面係藉由乾式或濕式化學蝕刻方法各向 異性餘刻,以產生犧牲層所支持之石夕之凸起特徵,且較佳 為具有平滑側壁之凸起特徵。各向同性钮刻犧牲層可釋放 凸起特徵,藉此產生可印刷半導體元件。此製造方法之優 勢為可清潔及再利用支持基板。或者,多晶石夕薄層可直接 沈積於si〇2基板上。如圖18G所示,相似之退火、圖案 化、各向異性蝕刻及起離步驟可用以產 :牛、。源極、沒極、閑極、介電元件或此等元件之 了視需要在此等方法之任—者中在起離步驟之前整合於半 導體元件中。 圖聰⑴及圖聰(2)說明—種用於利用本發明之可印刷 丰導體疋件製造單晶半導體薄膜之方法。如圖應⑴所 不’將非晶或多晶半導體薄膜製備於包含諸如si〇2之絕緣 ^科之基板表面上。該薄的非晶或多晶半導體膜可藉由包 =但不限於)諸如氣相沈積或騎沈積之沈積技術之此項 技術中已知的任一方法遨据 抑 万居㈣。亦參看圖18H(1),將包含一 單晶半導體結構之可印刷半導體 曰+ # 1』千¥體70件轉印至覆蓋有薄的非 日日或夕晶半導體膜之基板表面上。 奵於此方法之某些應 用,使用具有一長橫向尺寸之單 半V體、、、吉構是較佳的。 本發明亦包括其中將包含一單曰 日日牛ν體結構之可印刷半導 體兀件在沈積非晶或多晶半導體薄膜之前轉印至基板表面 96164.doc (§) -67- 1284423 上之方法。 如圖18H(2)所示,舉例而言,藉由在諸如高於攝氏1〇〇〇 度溫度之高溫下退火,而將一薄的非晶或多晶半導體膜退 火,且同時與單晶半導體結構接觸。在本發明之此實施例 中單曰曰半導體結構充當一種子(seed),其促進整個薄膜 •自一非晶或多晶狀態至一良好組織之單晶狀態之相轉變。 如圖18H(2)所示,相轉變跟隨移動穿過晶圓整個表面之高 • 咖梯度之前方(fr〇nt)。不同之高溫爐或聚焦光學系統可用 以產生獲得半導體薄膜之有效相變換所需之溫度梯度。此 方法之優勢為其可顯著降低產生諸如單晶矽或鍺薄膜之單 晶半導體薄膜之成本。 圖181展示一種由GaAs基板製造包含微線之可印刷半導 體元件之例示性方法。如此圖巾所示,GaAs基板之曝露表 ㈣用諸如光阻之料材料圖案化。圖案化操作可藉由微 接觸或奈米接觸印刷或經由習知的光微影技術來實現,其 _ ^圖卿斤示。該圖案化表面係利用濕絲刻方法各向異 性钱刻。在所展示之此例示性方法中,冑壁之凹入外形係 利用H3P〇4-H2〇2-H2〇溶液獲得,且姓刻所形成之凸起特徵 直至GaAS基板釋放該等凸起特徵為止,藉此產生GaAS微 友如所示之,光阻層可藉由用丙酮清洗及曝露至〇2反應 性離子钱刻來移除。此技術之優勢在於基板可在平坦 化(ECMP)之後再利肖。此技術亦可用以由一w基板製造 微線。 圖18J展示一種用於製造包含單晶矽帶之可印刷半導體 96164.doc -68 - 1284423 凡件之替代性方法。此方法中之起始材料係—叫11〇)晶 圓。如圖m所示,si⑽)晶圓之外表面利用在處理過程 中充當-遮罩之Si〇2薄媒來選擇性圖案化。此遮蔽步驟界 定待製造可印刷半導體元件之外形及某些實體尺寸(例 如帶之長度及見度)。隨後’藉由乾式或濕式化學蝕刻 方法各向同性飯刻Si⑴0)晶圓之曝露(意即,未遮蔽)表 2。此處理步驟產生石夕之凸起特徵,其較佳具有藉由具有 一^深度之—系列渠溝分離之平滑側壁。隨後,石夕凸起 特徵藉由各向同性㈣及起離處理自si⑴〇)晶圓釋放,藉 此產生可印刷半導體兀件。源極、〉及極、開極、介電元件 或此等元件之任意組合可視需要在起離之前整合於半導體 兀件中。此製造方法之優勢在於可清潔及再利用母基板。 圖⑻亦展示該處理方法中在各點處之si(uG)之财顯微 圖。 圖18K展示一種用於製造包含單晶石夕帶之可印刷半導體 元件之替代性方法。此方法中之起始材料係—si(iu)晶 圓。舉例而言,利用習知的光微影遮蔽與濕式敍刻方法之 組合來選擇性各向同性㈣該Si(lll)晶圓。此處理步驟產 生矽之凸起特徵。如圖18K所示,矽凸起特徵之側壁、表 面或兩者均利用一鈍化製程來塗覆。可印刷單晶矽帶可藉 由各向同性蝕刻及起離處理而自si(111)晶圓釋放。圖18二 亦展示僅在起離操作之前藉由此方法所產生之單晶 SET顯微圖。 實例4:製造半導體奈米線及微線之方法 96164.doc m -69- 1284423 本發明之一目的在於提供製造允許用於廣泛的各種裝 置、裝置組件及裝置設置的具有良好機械及電性質之半導 體奈米線及微線之方法。本發明之一目的更意欲提供組合 奈米線及微線以建構包含此等元件之選定單層結構、多層 結構及功能裝置之方法。為評估本發明之方法之效用,製 造了 GaAs及InP之奈米線及微線,且相對於其在各種裝置 組態中之電導率及機械可撓性來進行估計。此外,藉由製 _ 造包含單層結構及多層結構之大量複雜奈米線/微線總成 來估計本發明之方法將大量奈米線及微線組合於對應於大 基板表面積的良好界定之位置及方向中之能力。說明了製 造及組合GaAs及InP奈米線及微線之本發明之方法以提供 對於線寬度、長度及空間方向之良好控制。此外,所製造 之GaAs及InP奈米線及微線在整合於微電子裝置中時,展 示良好機械及電性質。 圖19提供一說明產生GaAs奈米線陣列且將其轉印至一 • 基板之例示性方法之步驟的示意圖,該基板諸如包含塗覆 有固化聚胺基甲酸酯(PU)薄層之聚對苯二甲酸乙二酯 (PET)薄片之塑膠基板。如圖19所示,該處理以表面沿 (100)方向疋向之一片GaAs晶圓開始(American Technology,Fremont,CA)。界定沿(〇丨方向定向線型式 之一 Sl〇2餘刻遮罩製備利用包含體積比為Η3Ρ〇4(85重量 〇/c〇:H202(30 重量 %):η2〇 =1:13:12 之 Η3Ρ〇4Η202 之水溶液 進行各向異性蝕刻的結構(圖19中步驟i)。當以此方式應用 時,此蝕刻化學顯出高的各向異性,藉此產生在si〇2遮罩 96164.doc (§) -70- 1284423 條下清晰界定之GaAs的反向凸台狀外形。足夠蝕刻時間 下,每一反向凸台之兩側壁交叉,使得形成具有三角形截 面之線。此三角形截面在圖19之畫面A(左側)之頂部插圖 中予以說明。 在一實施例中,圖案化Si〇2線由塊Si〇2薄膜包圍,其使 得每一 GaAs線之兩末端被連接至母晶圓。此連接限制該等 線’且保持si〇2之圖案所界定之空間方向及布局。圖2〇a 提供一由利用孤立Si〇2線圖案化之GaAs晶圓所獲得之獨立 GaAs線之掃描電子顯微圖。值得注意的是,⑸心之橫向 底切與垂直蝕刻發生,此使得可將所得GaAs線之寬度減小 至奈米級,即使Si02線是具有微米寬度。 可將藉由本發明之方法製備之GaAs線陣列轉印印刷至 塑膠薄片,且保持陣列中個別線之方向及相對位置。在圖 19所說明之實施例中,一致彈性體轉印元件被置放於GaAs 晶圓上以拾取該等線,該一致彈性體轉印元件如一平的聚 二甲基矽氧烷片或 PDMS,Sylgard 184,A/B = 1:1〇(Dow
Corning)(如圖19之步驟丨丨所示)。在此實施例中,需要 PDMS薄片與Si〇2遮罩層之間具有相對較強之黏結以斷開 在線末處至下方基板之結晶連接。 清潔PDMS戳記及具有帶有弱氧電漿之Si〇2遮罩之GaAs 晶圓可藉由一縮合反應促進於PDMS與Si02之間形成共價 石夕氧烷(Si-0-Si)鍵(參看圖19之中間插圖)。因此,本發明 包括下述方法,其中將彈性體轉印元件、具有Si〇2遮罩之 半導體晶圓或兩者均曝露至弱氧電漿以將具有Si〇2遮罩之 96164.doc -71 - 1284423 半導體晶圓有效且機械強的轉印至彈性體轉印元件。介面 上之鍵密度與PDMS表面上之-OnSKOHVn的量成比例,其 很大程度上依賴氧電漿之強度及處理時間。長時間進行強 電漿處理可導致鍵結太強以致於不能將線自PDMS釋放至 所要塑膠基板。所控制之實驗指示藉由02產生之電漿在10 mTorr之壓力、10 seem之流速及10 W之功率強度下 (Uniaxis 790,Plasma-Therm Reactive Ion Etching System) 分別處理PDMS及塗覆有Si02之GaAs晶圓3秒及60秒產生最 佳結果。在此等實施例中,經電子束蒸鍍之Si02遮罩層與 GaAs之間之相互作用足夠強以防止轉印處理過程中之分 層。在PDMS戳記與具有Si02遮罩之GaAs晶圓接觸約2小時 之後自GaAs基板剝落該PDMS戳記可將該等所有線起離(如 圖19之步驟iii中所說明)。 本發明之方法使製造及組合大量奈米線及/或微線切實 可行。舉例而言,轉印步驟(圖19之步驟iii)之後可研磨 GaAs晶圓以再產生一用於線製造之另一流程(圖19之步驟 iv)之平面。上述之晶圓研磨與線製造之組合使得可能自單 片晶圓產生大量GaAs線。舉例而言,若一各向異性蝕刻及 研磨循環消耗2 μηι厚度之GaAs,則一片具有10 cm直徑及 45 0 μιη厚度之 GaAs 晶圓(可構自 American Xtal Technology) 可產生足夠多線(具有約400 nm寬度及100 μηι長度之約22 億條線)以密集覆蓋具有1.76 m2面積之塑膠基板之整個表 面。此等情形通常為本實例所述之結果。因此,線製造之 後進行晶圓研磨步驟之該重複應用可以高成本效率使用塊 96164.doc -72- 1284423 晶圓。 如圖19之步驟v及vi中所示,具有Si〇2遮罩元件之GaAs 線可有效轉印至一基板’諸如外表面具有一黏接層之塑膠 基板。在一實施例中,將具有黏結GaAs線之PDMS戳記曝 4至周圍環境中一天時間,或利用乙醇沖洗以將PDms表 面重組為其原生、疏水狀態。此PDMS表面之疏水性質大 體防止PDMS與通常為親水性之黏接劑強烈相互作用。當 • 將經恢復之PDMS戳記靠一黏接劑層置放時,僅附著至 Si〇2遮罩條之GaAs線可被黏接劑弄濕,該黏接劑層諸如旋 塗於一塑膠基板(如,厚度約175 μιη之pet,Mylar film,
Southwall Technologies,Palo Alto,CA)上之PU層(可購自
Nolarland產品,Cranbury,NJ)。Ρϋ層之厚度可藉由控制旋 轉速度而自1微米至數十微米變化。利用一紫外線燈 (Model Β 100 ΑΡ,Black-Ray,Upland,CA)照明樣本 1小時 可固化PU層,且於經固化之PU與GaAs線及Si〇2遮罩條之 • 間及於經固化之PU與下方之PET薄片之間形成一強黏結 (圖19中步驟V)。剝落PDMS戳記使得GaAs線及si〇2條嵌入 於經固化之PU基質中,且保持與起離前線之次序及結晶方 向相似之次序及結晶方向(圖19之步驟vi)。自pDMS戳記分 離Si〇2可由兩種作用達成:丨)減小的與在1>〇]^[8與81〇2之間 之介面處之稀疏矽氧鍵相關聯之黏接強度,且其在重組 PDMS表面之處理過程中會進一步減弱;及⑴超薄以〇2層 (厚度為右干奈米),其在si〇2内聚破壞之後保留於PDMS 上,且其可為非晶的、鬆散的及易碎的。將塑膠薄片浸入 96164.doc -73- 1284423 緩衝氧化物蝕刻劑溶液(BOE,NH4F(40重量。/〇):HF(49重量 %) = 10:1)15分鐘可移除Si〇2遮罩條,且使GaAs奈米線之 清潔(100)頂表面朝向外部(圖19之步驟vii)。 製造及乾式印刷GaAs線陣列之此種簡單的,,由上而下,,之 •方法提供多個優勢。舉例而言,線之幾何形狀(意即,長 • 度、寬度及形狀)及其空間組織可由初始微影步驟來界定 以滿足所要之電子或光學端應用之設計。該轉印印刷技術 φ 可在保持由微影界定之圖案的情況下,產生高達100%之 良率。塑膠基板上之經轉印線之經良好定向結晶面(意 即,頂(100)表面)提供一非常平之頂表面(具有一與原始晶 圓平坦度相似之平坦度),此對於裝置製造非常有用。而 且,Si〇2遮罩條防止GaAs線之頂表面被諸如用於處理中之 PDMS、PU及溶劑之有機物污染。將GaAs線嵌入經固化之 PU中來將其固定,藉此防止其沿橫向或垂直方向移動,尤 其在塑膠基板被彎曲或扭曲時。值得注意的是pu& pET僅 • 為可用於本發明之材料之實例。因此,熟習此項技術者應 瞭解,如NEA l55(Norland®)之其它黏接劑及如〖叩仏一或 聚醯亞胺薄膜之其它類型之塑膠薄片可用於本發明之方法 中〇 不同於先前技術中之,,自下而上”方法,本發明之,,由上 而下’’方法可產生具有自若干微米至數十公分之均一長度 (意即,原始晶圓直徑)的GaAs奈米線。圖20A展示具有約 400 nm寬度及2 cm長度之可隨機組合於母晶圓上之獨立 GaAs奈米線的一 SEM影像。長奈米線在乾燥處理過程中形 96164.doc . 74 1284423 成曲線形結構’其指示該等線之窄寬度可提供之高度可撓 性。如圖20A之下部插圖所示,圓形奈米線具有2〇叫小之 4曲半徑,其表不具有約4〇〇 nm寬度之奈米線可承受約 1.3%之應變。圖20A之上部插圖提供一在奈米線起離前之 截面的掃描電子顯微圖影像,其清晰展示了由各向異性蝕 刻形成GaAs之反向凸台外形及底切的過程。
在本毛月之態樣中,GaAs線之寬度可藉由選擇性調 整Si02遮罩線之寬度,選擇性調整餘刻時間或兩者來控 制。利用本發明之方法可獲得數百微米與數十奈米之間之 寬度。控制钱刻時間提供一自具有微求寬度之叫圖案產 生奈米線之容易方法。圖細至圖2〇E展示藉由蝕刻利用2 μη!寬之Si〇2_案化之GaAs晶圓所獲得之個別線的掃描 電子顯微圖影像。該等線τ利用上述程序轉印至一 pDMs 表面以精確量測其頂表面之平均寬度(被稱作[4。圖2〇ρ 提供一展示藉由本發明之方法製造之線的頂表面之平均寬 度〜對蝕刻時間之依賴性的曲線。此曲線指示具有小至 nm見度之GaAs線可利用本發明之方法之此實施例而獲 得。寬度與餘刻時間之間的線性關係與先前關於在H3P〇4_ H2〇2_H2〇溶液中之GaAs的蝕刻動力學之研究一致,意 即,當h2〇2與h3P〇4之間之莫耳比(Wh2〇2/㈣p〇4)大於2 3, 且當H20(rH20)之莫耳分數等於或小於〇9時(用於吾人實驗 之韻刻劑之叫斯/㈣刚及如分別為7』及G 9),㈣率與 蝕刻時間成比例。統計結果展示對於具有約5〇 之寬度 之線’該等線之寬度分佈(由沿其長度之平均而判定)為: 96164.doc -75- 1284423 於9%’其稍窄於已報告之提供約16.8 nm之平均寬度之一 π自下而上”類型奈米線中之大於14%之變化。 圖20Β至圖20D所示之掃描電子顯微圖影像亦展示該等 線之三角形截面在薄化處理過程中被保持,其指示即使對 於獨立GaAs線而言,蝕刻亦為高度各向異性的。對該等線 之密切觀測展示,其側壁上存在一定粗链性。此粗糙性多 數直接來自用以界定Si〇2遮罩條之微影程序;一些係由於 遮罩線之未對準及自身钱刻所引起。此粗糖性判定可利用 本發明之此實施例獲得之最小連續線寬度。如圖2〇F所 示,沿個別線之寬度變化與平均線寬之間之比(σ 亦高 度依賴餘刻時間。當該比小於100%時,可製備連續GaAs 奈米線。圖20F中所提供之曲線指示應用本發明之此實施 例所獲付之奈米線寬度可減小至約40 nm。具有不同平均 覓度之奈米線展現沿個別線之大體相同的寬度變化(意 即,約40 nm),其接近沿個別si〇2遮罩線之寬度變化(意 即,約36 nm)。此對比證實線侧壁之粗糙性主要由以⑺遮 罩條之粗糙邊緣引入,而與餘刻時間無關。因此,使用降 低了遮罩條粗糙性之微影程序可降低線邊緣之粗糙性。值 得注意的是,此實例中所述之轉印印刷方法曝露用於最終 基板(意即,圖19之PET)上之電連接及裝置製造之線的原 始、超平未餘刻頂表面。 圖21A至圖21G展示印刷於PDMS及PU/PET基板上之多種 GaAs線陣列之影像。此情況下之線具有約4〇〇 nm2寬度及 約100 μηι之長度。沿(i〇〇)GaA^B圓上之i i)方向定向 96164.doc -76· 1284423 的相應之Si〇2遮罩線具有2 μηι之寬度及1〇〇 μιη之長度。圖 21八係一取自經由以〇2遮罩層黏結至平]?1)]^戳記之〇^^ 線陣列的掃描電子顯微圖影像,其指示線之次序被保持。 圖21Α之插圖以相對較高放大率展示三條線之末端,其清 晰顯示其末端處之斷裂。如圖21 b所示,自經固化之pu剝 落PDMS戳記使得具有Si〇2遮罩條之平滑表面(如pdmS般 平滑)朝向外部。如圖21C所示,用BOE蝕刻掉Si02層曝露 GaAs線之原始頂表面。圖2m呈現一自嵌有GaAs線之 PU/PET基板收集之光學影像,其指示大面積線陣列可利 用圖19所說明之方法常規印刷於PU/PET基板上。亦可將 具有其它圖案之GaAs線陣列(例如,由具有不同長度之線 組成的貼片)轉印至PU/PET基板。 重複轉印處理以藉由旋塗一新的PU層而將多層GaAs線 陣列印刷於同一 PET基板上。此等方法提供產生包含奈米 線及/或微線之多層結構的重要途徑。圖21E及圖21F給出 具有雙層GaAs線陣列之多層結構的典型影像。在一實施例 中’藉由相對於第一層將第二層旋轉不同角度(對於E及F 分別為約90。度及約45。)來獲得此等多層結構。圖21G提供 具有藉由在圖21E及圖21F所示之樣本上重複印刷處理所獲 得之三層GaAs線陣列之PU/PET基板的影像。PU層之厚度 控制該等線陣列之間之間隔,而PU層之厚度可藉由調整旋 轉速度來控制。當然,此類型之多層性能不需要任一形式 之蠢晶生長,且PU將該等陣列隔離於不同階層中。此製造 能力可用於大量裝置製造應用中。 96164.doc -77- 1284423 ’ 本發明之線製造及印刷技術可用以藉由利用適當之各向 異性蝕刻劑在塑膠基板上產生其它半導體材料之線陣列。 舉例而言,可藉由在1% (ν/ν) Βι*2之甲醇溶液中蝕刻具有 沿(Ο ϊ Ϊ)方向之Si〇2遮罩線之(ΐ〇〇)ιηΡ晶圓來製造具有三 角形截面之InP線。圖22A至圖22C展示PMDS及PU/PE丁基 板上之InP線陣列之掃描電子顯微圖影像。此等線由藉由 50 μηι長及2 μηι寬之Si〇2線圖案化之InP晶圓來製造。所示 • 之線長度及寬度分別為約3 5 μηι及約1 · 7 μηι。在線末端外 形及橫向底切方面,InP在Bo之甲醇溶液中的蝕刻行為顯 著不同於GaAs在Η3Ρ〇4_Η2〇2之水溶液中的蝕刻狀態。舉 例而言,蝕刻處理即使利用一與用於製造〇&八8線(圖21)之 蝕刻遮罩相似之蝕刻遮罩仍將所有Ιηρ線之末端自母晶圓 斷開。而且,InP之底切程度小KGaAs之底切程度,其指 示藉由利用乍Si〇2條比藉由控制钱刻時間更容易製備具有 小寬度(小於500 nm)之InP線。 • 利用GaAs線陣列(與圖21所示之線陣列相似,其由載體 密度為1.1-5.6 X 1〇17 cm3之摻雜Sj^n_GaAs晶圓製造)在 PU/PET基板上製造之一簡單兩端子二極體裝置之機械可 撓性可藉由量測作為彎曲半徑之函數的電力性質來估計。 此等結構係利用根據圖19之方法界定之GaAs線陣列製造。 光微影及金屬沈積於此等線上界定由Ti/Au(5 nm/i5〇 nm) 製造且間隔10 μηι之兩個蕭特基接點。圖23A提供一包含 GaAs線陣列之例示性兩端子二極體裝置之示意圖及影像。 在沈積電極之前,將基板浸入濃HCL溶液1〇分鐘以移除 96164.doc -78- 1284423 ’ GaAs線表面上之原生氧化物層。 圖23B展示在不同彎曲半徑記錄之電流-電壓曲線。 此等曲線均顯出預期之二極體特徵。此等曲線之間之微小 差異表明即使當基板之彎曲半徑(7?)為〇95 em時,亦幾乎 無GaAs奈米線被破壞。此情況下PET表面上之應變約為 0.92%,其小於對圖20A之插圖中所示之單獨GaAs奈米線 所估計具有之應變。此等結果進一步確定藉由本發明之 φ ’’由上而下’’製造方法產生的GaAs奈米線具有可撓性且可與 可彎曲塑膠薄片整合。應注意,資料展示當第一次彎曲基 板後將其鬆弛時,電流較彎曲前自初始裝置記錄之電流小 約40%。圖23C展示在以不同彎曲半徑彎曲後再進行鬆弛 之後對兩端子二極體裝置量測的電流_電壓([厂)曲線。出 於比較之目的,圖23C中之黑色曲線表示對應於彎曲前之 I置組態的電流·電壓曲線。然而,第一次彎曲之後以彎 曲半徑進行多次彎曲/伸直循環中特徵曲線無變化表明 # 僅一次的電流減少可由在電極與線之間之介面處之性質的 初始變化引起。 傳統光微影技術及各向異性化學蝕刻與此等材料之塊狀 高品質單晶晶圓結合使用形成製造具有三角形截面之GaAs 及InP微線及奈米線之具有吸引力的,,由上而下,,方法。藉 由適當選擇微影及蝕刻條件(如蝕刻時間)可選擇性調整該 等線之尺寸及其組織。所獲得之母基板上之線陣列可在高 保真度下有效轉印印刷至塗覆有一黏接劑薄層之塑膠基 板’該等線礙入該薄層中。母晶圓可在研磨之後重複利 96164.doc -79- 1284423 用,其使得一單個晶圓產生大量線。此,,由上而下,,奈米線/ k線之乾式”轉印印刷表示一種新型轉印方法,其在保持 線之次序及結晶方向及其作用表面之純度方面提供超出 "自下而上"奈米線之"濕式,,組合的諸多優勢。詳言之,對 於使用寬於100-200 nm之線的宏觀電子應用而言,本發明 之由上而下”製造方法具有若干具有吸引性之特徵。此處 說明之塑膠基板上之線系統說明了其良好的可彎曲性及對 於用於此類應用之巨大潛力。 實例5 ·用於可印刷半導艘元件之溶液印刷方法 本發明提供可將可印刷半導體元件轉印及組合於多個基 板之大的區域上之溶液印刷方法。本發明之此態樣提供可 應用至廣泛半導體裝置及裝置組件之連續、高速製造方 法0 在本發明之此態樣之-種方法中,可印刷半導體元件係 提供有-操縱元件4此描述之情形中,術語"操縱元件" 係指-組件,其允許液相傳送至一基板表面之後一可印刷 半導體7L件之位置及/或方向的受控操縱。在—實施例 中,-半導體元件係提供為具有一或多個均包含可回應一 磁場、電場或兩者之材料層的操縱元件。本發明之此態樣 可用於提供利㈣電力及/或靜磁力而在基板表面上將可 印刷半導體元件對準、定彳 了+疋位及/或定向之方法。或者,本 發明提供其中半導體元件係提供為具有-或多個均包含回 應雷射二級體誘導動量轉印方法之材料層之操縱元件的方 法。本發明之此態樣用於提供藉由將具有—或多個操縱元 96l64.doc 1284423 • 件之可印刷半導體元件曝露至一系列雷射脈衝而在基板表 面上將可印刷半導體元件對準、定位及/或定向的方法(例 如,雷射鑷夾方法)。或者,本發明提供其中半導體元件 係提供為具有一或多個均包含一回應毛細管作用所產生之 • 力之小液滴之操縱元件的方法。本發明包括利用具有一或 , 多個操縱元件,或諸如回應不同類型場之操縱元件之一或 多個不同類型之操縱元件的可印刷半導體元件之方法及裝 Φ 置操縱元件可提供於本發明之多種類型的可印刷半導體 元件中,其包括(但不限於)微結構、奈米結構、微線、奈 米線、微帶及奈米帶。 在本發明之此態樣中’一或多個均具有一或多個操縱元 件之可印刷半導體元件分散於溶液或載體流體中,且被傳 送至一基板表面。傳送可印刷半導體元件與溶液/載體流 體之混合物可將可印刷半導體元件隨機分佈於基板表面 上。接著,藉由施加由存在可印刷半導體元件之操縱元件 鲁引起之力而將心機分佈於基板表面上之半導體元件協同移 入基板表面上之選定位置及方向。本發明之此態樣用於將 具有操縱元件之可印刷半導體元件對準於良好排序陣列中 或對準於對應於-選定裝置或裝置組件組態之位置及方向 T。舉例而言,藉由施加具有適當分佈之強度及方向的磁 昜可將/、有或夕個包含一磁材料層之操縱元件的可印刷 半導體元件移入基板表面上選定位置及方向中。在此實施 例中’可藉由將-或多個鐵磁元件或電磁元件定位至基板 附近(諸如,定位於基板表面之後,基板表面上,及/或沿 96164.doc -81 - 1284423 基板側)來施加具有選定分佈之強度及方向之磁場,藉此 產生對應於可印刷半導體元件或—選定裝置或裝置組件組 。之所要、《§· Π、圖案或結構的選定分佈之強度及方向。 在本發明之此態樣中’溶劑、載體流體或兩者可在經由操 縱元件之操縱選㈣定可㈣半㈣元件之前、 之中或之後藉由包括蒸發或解吸附方法之此項技術中已知 的任一方法來移除。
圖2 4提供-說明一種用於溶液印刷具有包含磁性接頭 (magnetic tag)之操縱元件的可印刷|導體元件之本發明之 例示性=法的示意圖。如圖24所示,提供可印刷半導體元 件其每者均具有包含薄錄層之複數個磁性接頭。在一 實施例中,薄制係提供於—微尺寸或奈米尺寸之半導體 、。構表面h此實例中將鎳用作操縱元件僅為了以實例來 "兒明’且任一結晶或非晶鐵磁材料均可用於此等方法中, 其包括(但不限於)Co、Fe、Gd、Dy、MnAs、MnBi、
MnSb > Cr02 . MnOFe2〇3 > NiOFe2〇3 . Cu0Fe203 , MgOFe2〇3及諸如過渡金屬_非金屬合金之非晶鐵磁合金。 如圖24中示意圖之步驟!所示,複數個均具有操縱元件 之可印刷半導體元件分散於溶液中,且_於-基板表面 上。此步驟以隨機分佈位置及方向之方式將可印刷半導體 元件提供至基板表面上。如圖24中示意圖之㈣π所示, 隨後將一磁場施加至可印刷半導體元件,較佳為一具有選 定分佈強度及方向之磁場。在圖24之示意性展示中:、藉: 將一或多個磁鐵的磁極定位於其上具有可印刷半導體^基 96164.doc -82- 1284423 板表面的相對側來施加具有選定分佈強度及方向之磁場。 作為鐵磁材料’磁場與包含操縱元件之鎳層之相互作用產 生將可印刷半導體移入基板表面上所要位置及方向之力。 在圖24所示之實施例中,施加一磁場以將可印刷半導體元 件定向於以大體平行對準可印刷半導體元件之長側為特徵 之良好排序陣列中。如圖24中之示意圖的步驟ΠΙ所示,可 將電連接以建立一電連接的方式及以保持藉由施加磁場所 產生之方向的方式沈積於包含該經排序陣列之可印刷半導 體元件的末端上。 圖25提供說明將本發明之溶液印刷方法用以產生具有包 含薄鎳層之操縱元件之可印刷半導體元件的微結構的良好 排序陣列之若干光學影像。呈現於圖2 5左侧畫面中之光學 影像對應於在未施加磁場的情況下可印刷半導體分散於一 基板表面上之基板表面。如此等影像中所示,可印刷半導 體元件係隨機分佈於基板表面上。呈現於圖25右側晝面中 之光學影像對應於施加一磁場時可印刷半導體分散於一基 板表面上之基板表面。與呈現於左侧晝面中之影像相比, 對應於其中施加一磁場之情況的光學影像展示將可印刷半 導體元件提供在對應一良好排序陣列之選定方向及位置。 對比呈現關25左㈣面與右㈣面中之影像指示施加一 具有選疋分佈強度及方向之磁場可產生將個別可印刷半導 體元件移入選定位置及方向之力。 熟習裝置製造技術者將瞭解,圖25右侧晝面中之可印刷 半導體元件之位置及方向僅為利用本發明之溶液印刷方法 96164.doc •83- 1284423 可達成之方向及位置之一個實例。選擇可印刷半導體元件 上之操縱元件之適當位置及選擇具有選定分佈強度及方向 之適當磁場可用以實質上產生半導體元件位置及方向之任 一分佈。 實例6·於可撓性塑膠基板上製造高效能單晶矽電晶體
本發明之一目標在於提#包含組合⑨可挽性基板上之可 印刷、高品質半導體元件之可彎曲宏觀電子、微電子及/ 或奈米電子裝置及裝置組件。此外,本發明之_目標在於 提供可彎曲電子裝置,諸如顯出與藉由習知的高溫處理方 法製造之薄膜電晶體之場效遷移率、#通/斷開比及臨限 電壓相似或優於其之場&遷移#、接通/斷開&及臨限電 壓的可彎曲薄膜電晶體。最後,本發明之一目標在於提供 適於在低溫下於大面積可撓性基板上進行有效高產出率處 理的可f曲電子裝置,諸如在室溫下於塑膠基板上處理。 實驗研究驗證本發明之方法、裝置及組合物可提供以彎 曲及平面組態為特徵顯出高裝置效能之有用的宏觀電子及 或祕電子凌置及裝置組件。此等量測結果表明本發明提 供顯出良好對準能力之乾式轉印接觸印刷技冑,其可藉由 將包括單晶Si帶、Ga_AsAInP線及單壁碳奈米管之多種高 πα枭半導體沈積於塑膠基板上而組合可彎曲薄膜電晶體。 舉例而a,此等實驗研究結果指示包含經乾式轉印可印刷 早^矽7L件之空間良好界定陣列之可彎曲薄膜型電晶體顯 出:裝置效能特徵,諸如在線性區域中估計之約24〇 cm2/Vs 之平均裝置有效遷移率及約為〇 V之臨限電壓。而且,此 96164.doc -84- 1284423 • 等研究展示本發明之薄膜電晶體當經受向前及向後f曲 時’顯出與利用有機半導體製造之裝置相當之可彎曲性 (意即,發生失效時之應變),以及機械穩固性及可挽性。 大面積可撓性基板上之高效能印刷電路表示_種新型電 裝置,其可廣泛應用於感應器、顯示器、醫療褒置及i . β領域。在塑膠基板上製造所需電晶體提出了對達成此等 宏觀電子系統之挑戰。過去若干年中已探索之某些方法係 φ 基於用以在玻璃/石英基板上製造習知的基於矽之薄膜電 晶體(TFT)的處理步驟類型的經修改之、低溫版本。與為 製造單晶矽薄膜而開發之方向性凝固方法(意即,利用連 • 續波雷射、聚光燈、電子束或石墨條加熱器之Si〇2上之Si 薄膜之帶熔融再結晶)相關聯之高溫使得此方法不適於用 於塑膠基板。基於雷射之方法已達到一定的成功,但均一 性、產出率及使用低成本塑膠提出顯著連續實驗挑戰。雖 然將預成型電路直接完全晶圓轉印至塑膠基板上可產生某 • 些有用裝置,但是此方法難以符合大面積規定,且其不能 保持對於低成本'大面積宏觀電子裝置非常重要之印刷類 型製造次序。有機半導體材料提供一製造可撓性電子裝置 之替代途徑’其中基於有機之電子材料可經由室溫沈積而 自然地與多種塑膠基板整合。然而,此等普遍已知之有機 半導體材料僅能達到較小之裝置遷移率。舉例而言,即使 '是此等材料之高品質單晶對於η型及P型裝置亦僅分別具有 1 cm2/Vs至 2 cm2/Vs及約 1〇 cm2/Vs至約 20 cm2/Vs之範圍内 的遷移率。 -85- 96l64.doc 1284423 諸如流體自組合技術之其它製造技術將用於製造高遷移 率材料之高溫步驟與對於在塑膠基板上建構裝置所需之低 溫處理分離。然而,此等方法不允許有效控制沈積之物件 的組織或位置。 圖26A說明用以製造本發明之例示性可彎曲薄膜電晶體 裝置之步驟。第一,光微影技術於絕緣物上矽晶圓(具有 100 nm頂部Si層及145 nm内埋式氧化物之Soitec unibond SOI)表面上界定一光阻圖案。此抗蝕劑充當藉由SF6電漿 (Plasmatherm RIE系統,在50 mTorr腔室底壓、100 W RF 功率下之40 seem SF6流進行25 s)乾式餘刻SOI晶圓之頂部 矽層的遮罩。濃HF溶液蝕刻内埋式氧化物,且自其基板釋 放(但未完全浮起)可印刷單晶矽半導體元件。一平的聚二 甲基矽氧烷(PDMS)片可達成與該晶圓之頂表面保形接 觸,且隨後被仔細剝離以拾取經互連之帶陣列。光阻與 PDMS之間之相互作用足以將兩物件黏結在一起以高效移 除。 塗覆有氧化銦錫(IT0 ;厚度約為100 nm)之聚對苯二曱 酸乙二酯(PET ;厚度約為180 μηι)塑膠薄片充當裝置基 板。利用丙酮及異丙醇清洗該裝置基板,且用去離子水將 其沖洗,隨後利用氮氣流乾燥其以清潔其表面。利用弱氧 電漿(Plasmatherm RIE系統,在 100 mTorr腔室底壓、50 W RF功率下之20 seem 02流進行10 s)處理ITO促進了其與一 環氧樹脂之旋塗澆鑄介電層(利用66%之SU8-2000稀釋劑稀 釋之Microchem SU8-5以3000 RPM進行30 s)之間之黏接。 96164.doc -86- 1284423 此感光環氧樹脂可在50°C下,在約】八典、 社、0 1分鐘過程中預固化於
一熱板上。將麵S及其表面上之可印刷單晶料導體元 件與熱壤氧樹脂層進行接觸’且隨後剝離該PDMS使得將 可印刷單晶料導體元件轉印至該環氧樹腊。此結果表明 矽與軟環氧樹脂層之間之黏結力(歸因於環氧樹脂圍繞可 印刷單晶梦半導體元件邊緣之流動,某些為機械的)比光 阻與PDMS戳記之間之黏結力大。環氧樹脂層在⑽。〔下5 分鐘内完全固化,將其曝露至來自透明基板之背部之紫外 線下10 s,且隨後將其在115°c下進行後烘培5分鐘以交聯 該聚合物。光阻遮罩(其可方便地防止可印刷單晶矽半導 體元件之頂表面在轉印步驟過程中受到污染)溶於丙酮 中’且隨後利用去離子水多次沖洗樣本。 利用沈積於可印刷單晶矽半導體元件之頂表面上之 Ti(約70 nm; Temescal電子束蒸發器)形成源極及汲極。經 圖案化於Ti上之光阻遮罩(shipley S1818)之蝕刻(1:1:1() HF:H2〇2:DI ;約2 S)界定了此等電極之幾何形狀。此製造 的最後步驟涉及經一光阻遮罩乾式蝕刻(利用上文給定RI]g 參數之SF6)以在裝置位置處界定矽島。圖26B呈現薄膜電 晶體之底部閘極裝置組態及部分裝置陣列之高倍放大及低 倍放大光學影像之示意性說明。 圖27A呈現本發明之可彎曲薄膜電晶體之電流電壓特徵 曲線,其展示一如藉由應用忽略接點影響之標準場效電晶 體模型估計之在飽和區域為14〇 cmVVs,在線性區域為26〇 cm2/Vs之有效裝置遷移率。然而,在此等裝置中之蕭特基 96164.doc -87- 1284423 • 接點之高電阻(約90 Qcm)對裝置響應有顯著影響。圖27B 呈現若干裝置之轉印特徵曲線,其以線性刻度(左侧軸)及 對數刻度(右側軸)繪製。該插圖中之圖展示臨限電壓具有 一接近0 V之窄分佈。轉印特徵曲線中之小的(在土1〇 v時 • 間段内電流小於4°/❶)滯後作用指示在矽(具有原生氧化物) • 與環氧樹脂介電質之間之介面處的低密度捕獲電荷。標準 化次臨限斜率之較小值(小於等於13 vnF/dec cm2)保證此 _ 介面之良好品質,其可主要由矽與其原生氧化物之間之介 面來決疋。圖27C展示藉由本發明之方法製造之若干可彎 曲薄膜電晶體之線性有效遷移率之分佈。高斯擬合指示中 間值240 cmVVs,標準差30 em2/Vs。一些低值與電極或裝 置之其它組件中之可見缺陷相關聯。可藉由利用與用以製 備電晶體閘極介電質相同之基板及方法建構256個(2〇〇χ ^ 200 μΠ1)方形電容器陣列來研究環氧樹脂介電質之均一 性。圖27C中之插圖顯示量測之電容值。高斯擬合展示小 • 於2%之標準差可保證環氧樹脂層之良好電及物理性質之 均一性。在多個頻率(介於1 kHz與1 MHz之間)下進行之電 容量測指示介電常數之小的(小於3%)頻率依賴性。 . 本發明之可彎曲薄膜電晶體之機械可撓性及穩固性可藉 • 由執=向前及向後彎曲測試來研究。圖28A呈現一說明可 印刷^晶石夕半導體元件之顯著可撓性之溶液洗鑄帶的高解 析度2描電子顯微圖(左侧插圖)。圖28A之右側插圖展示 的j弓曲在此研究中估計之可彎曲薄膜電晶體之實驗配置 的圖片4 了最大化當彎曲塑膠薄片時薄膜電晶體中所引 96164.doc rc -88- 1284423 起之應變,將一相對厚(約180 μιη)之塑膠基板用於此等研 究中。圖28Β展示當經受拉伸及壓縮應變時,環氧樹脂介 電電容之小(約小於1%)的線性變化(參看頂部插圖)。彎曲 半徑及應變值利用彎折薄片之有限元模型來計算。將彎折 薄片之彎曲輪廓(對於若干彎曲半徑)與利用有限元方法所 獲得之輪廓進行對比可確定該等模擬之精確度。圖28β之 下部插圖呈現對於閘極及汲極之偏壓都為4 V時量測之裝 置之飽和電流的變化。在可彎曲薄膜電晶體可運作時之拉 伸應變之最大值可由ΙΤΟ閘極失效(其在約_0·9%之拉伸應 變值下失效)來限制。即使在壓縮應變高達1 ·4%時,可彎 曲薄膜電晶體仍運作良好。此可彎曲性程度與最近報告之 基於幷五本之有機電晶體之可弯曲性程度相當。本發明之 可彎曲薄膜電晶體之失效可能僅在非常高應變下發生,如 Takahiro等人最近說明之自SOI晶圓之頂層蝕刻之微米尺寸 單晶矽物件可經受住顯著高的拉伸應力(大於6%)[τ.
Namazu,Υ· Isono,及 Τ· Tanaka J· MEMS 9, 450 (2000)] 〇 雖然未完全已知在吾人製造的裝置中之在應變下輸出電 流之小的變化的原因,但是已知的在應變下之遷移率之變 化可有助於(但未能完全解釋)此等變化。在此實例中描述 之此類型的裝置可提供新的機會以研究當彎曲塊Si晶圓時 不容易達成之應變值下的發生機械應變之矽中之電荷傳 輸。 總而言之,此實例說明藉由本發明提供之矽之簡單且有 效的並行印刷方法形成於塑膠基板上之可彎曲單晶矽電晶 96164.doc -89 - 1284423 體之高裝置效能及有益機械性質。以吾人看來,此等裝置 之效能超過顯出相似程度之機械可彎曲性之最好裝置(基 於石夕或其它裝置)之效能。與其它方法相比,對可印刷石夕 半導體元件之形狀、實體尺寸及組合物(如,摻雜或不推 雜)的由上而下之控制,及印刷技術可提供顯著優勢。此 外所得裝置之機械可撓性係良好的。而且,此等大體相 似之方法可應用於其它無機半導體(如GaAs、GaN等),且 _ 可用以製造廣泛可撓性微電子及宏觀電子裝置及裝置組 件,諸如太陽能電池、二極體、發光二極體、互補邏輯電 路、貝訊儲存裝置、雙極接面電晶體及FET電晶體。因 此,本發明之方法及裝置可用於製造可撓性電子產品之廣 泛製造應用中。 、 實例7 ·可印刷異質半導體元件及包含可印刷異質半導體 元件之裝置 本發明提供包含多材料元件之異質可印刷半導體元件及 _ 相關裝置及裝置組件。此實例之可印刷異質半導體元件包 含一具有摻雜劑之半導體層,該摻雜劑具有一選定空間分 佈,且該等可印刷異質半導體元件在宏觀電子、微電子2 /或奈米電子裝置中提供增強功能。 本發明之方法製造顯出有用電子性質之異質可印刷半導 體元件之能力可藉由實驗研究來證實。此外,本發明之方 法在將可印刷元件組合於功能裝置中之可應用性可藉由製 造包含具有用於接觸之整合摻雜區域之可印刷單晶矽半導 體元件之可撓性薄膜電晶體來說明。 96164.doc -90- 1284423 乍為衣觀電子裝置之大面積、機械可撓性電子系統可廣 〆乏應用於消費型電子褒置、感應器、醫療裝置及其它領域 中。各種有機、無機及有機/無機混合材料可充當用於此 等=統之半導體。將本發明”由上而下,,之技術方法用於產 生單晶矽微/奈米元件(線、帶、片狀等,其全體被稱作可 印刷石夕半導體70件)係一已說明為用於在可撓性基板上製 造高效能薄膜電晶體之替代方法。此製造方法亦已說明為 了應用於其匕重要半導體材料,諸如GaAs、bp、及 碳奈米管。 本發明之方法之一重要特徵為其使用高品質、基於晶圓 之半導體材料源,該等材料源可生長且與隨後裝置組合步 驟分開處理。分離的半導體處理與組合步驟允許裝置在適 於諸如塑膠基板之大部分可撓性裝置基板之相對低溫度 (如,至溫士攝氏3〇度)下組合。本發明包括下述方法,其 中尚品質半導體不僅生長,且亦可在獨立於隨後製造步驟 φ 之製造步驟中以其它途徑來進行處理,隨後製造步驟涉及 可撓性基板上之可印刷半導體元件之組合。在一實施例 中’本發明包括下述方法,其中在高溫處理過程中將摻雜 劑引入半導體中,且隨後將所得經摻雜之半導;體材料用以 產生可組合於多種有用電子裝置中之可印刷異質半導體元 件。用於摻雜半導體之處理步驟包括高溫處理及其中將摻 雜劑以控制其一、二或三維空間分佈(意即,控制植入面 積及植入深度)之方式來引入之處理。在一種方法中,在 獨立於低溫基板而執行之步驟中藉由在晶圓製造級執行之 96164.doc -91 - ⑧ 1284423 旋塗摻雜程序來選擇性接觸摻雜半導體。接觸換雜提供對 摻雜劑在半導體材料中空間分佈之精確控制,i因此,隨 後之圖案化及餘刻步驟允許製造具有整合捧雜區域之高品 質可印刷異質半導體元件。溶液印刷及乾式轉印接觸印刷 方法理想地適於將此等可印刷異質元件組合於諸如薄膜電 晶體之顯出可達到之良好裝置效能及良好可彎曲性之裝置 中。 ’ • 圖29A呈現一用於在一 PET基板上產生包含可印刷異質 半導體元件之電晶體之製造方法的示意性表示。在此實施 例中,可印刷異質半導體元件包含具有經摻雜之源極(s) 及沒極(D)接點之晶體石夕。圖29A中所說明之方法將一溶液 可處理旋塗摻雜劑(SOD)用以摻雜一絕緣物上矽晶圓 (SOI ;具有1〇〇 nm頂部si層及2〇〇 nm内埋式氧化物之 Soitec unibond)之頂部矽層之選定區域。因此,旋塗摻雜 劑(SOD)提供磷摻雜劑,且一旋塗式玻璃(s〇G)充當一遮 • 罩以控制摻雜劑擴散於石夕中之位置。此經摻雜之S 〇1提供 可印刷異質半導體元件源。 為產生可印刷異質半導體元件,首先將一旋塗式玻璃 (S0G)溶液(Filmtronic)旋塗澆鑄於SOI晶圓上,且將其曝 露至700 °C下進行4分鐘之快速熱退火(RTA)以形成一均一 薄膜(300 nm厚)。經微影圖案化之光阻層(Shipley 1805)之 蝕刻(6:1緩衝氧化物蝕刻劑(b〇E)進行50秒)打開SOG中之 源極及汲極窗。剝離光阻之後,藉由旋塗澆鑄均一地沈積 含構SOD(Filmtronic)。在950°C下進行5秒之RTA使得來自 96164.doc -92- 1284423 . S0D之磷經由由微影技術界定之開口擴散於80(}中及下方 石夕内。SOG阻斷在其它區域中之擴散。將晶圓快速冷卻至 室溫,浸入BOE中90秒以移除SOG&s〇D兩者,且隨後利 用去離子水徹底清洗以完成摻雜處理。 利用本發明之方法將可印刷異質半導體元件組合於塗覆 ,有氧化銦錫(ITO; 100 nm,閘極)及環氧樹脂(SU8; 6〇〇 nm,閘極介電質)之PET塑膠基板上。環氧樹脂不僅提供 φ ”電質,而且有助於轉印印刷可印刷異質半導體元件。
Ti(100 nm)之源極及汲極係藉由對準光微影步驟之後回蝕 刻而形成於經摻雜之接觸區域上。圖29B展示具有利用本 發明之技術製造之異質可印刷半導體元件之若干裝置的光 '學影像。 利用標準轉印線模型(TLM)估計摻雜量及接觸電阻。詳 言之’量測印刷於一塑膠基板上之包含均一摻雜結晶矽之 ’ 可印刷異質半導體元件上之Ti接觸襯墊之間之電阻,該等 修 丁丨接觸襯墊具有介於5微米與100微米之間之間隔(l)及200 微米之寬度(W)。圖30A中之插圖展示用以特徵化接觸電 阻之可印刷異質半導體元件與接觸襯墊之排列的影像。線 性電流(I)對電壓曲線(V)(未圖示)指示接觸為歐姆接觸,且 摻雜量較高。電阻對L之依賴性可描述為:及⑼+ (%/,其中及# (=厂/々為兩個接觸襯塾之間之電阻,也 為接觸電阻,且&為薄片電阻。圖30Α展示作為L之函數的 標準化電阻IUW。線性擬合W給出Rs = 228 士 5 Ω/sq及 . ReW〜1.7 士 0.05 Ω-cm。標準化接觸電阻的值Rcw小於吾 96164.doc •93- 1284423 人所觀測之以相似方式處理之未摻雜可印刷單晶矽半導體 疋件之接觸電阻多於一個數量級。為簡單起見,若假定摻 雜係均一地遍佈於100 nm之摻雜可印刷矽半導體元件,則 對應於1019/cm3摻雜量之電阻率約為2·3 X 1〇-3。圖 30B展不飛行時間二次離子質譜儀(T〇F_SIMS)量測結果, 其展示將圖案化SOG用作一擴散障壁(參看,圖29A之示意 圖)將摻雜劑定位至矽中之所要區域。在圖3〇B所示之影像 中’亮的紅顏色指示磷濃度較高。 圖31A至31D展示對應一環氧樹脂/IT〇/pET基板上之包 含可印刷接觸摻雜矽半導體元件之電晶體之量測結果。圖 31A繪製本發明之裝置(l=7 μπι,W=200 μιη)之電流-電壓特 徵曲線。有效裝置遷移率beff)在線性區域約為24〇 cm2/Vs,且在飽和區域約為230 cm2/Vs,其藉由應用標準 場效電晶體模型來判定。圖31B展示通道長度介於2 μηι與 97 μηι之間,通道寬度為200 μηι之本發明之裝置的轉印特 徵曲線。在所有情形下,接通/斷開電流比約為1〇4。當L自 97 μηι變化至2 μιη時,臨限電壓自約2 V單調變化至約0 V。 圖31C呈現在不同閘極電壓下為L之函數的在開狀態及小的 汲極電壓下量測之裝置電阻(R接通),乘以W· R接通W對L在每 一閘極電壓下之線性擬合提供關於本質裝置遷移率與接觸 電阻之資訊。在此簡單模型中,FU通由通道電阻(其與L成 比例)及與源極及汲極相關聯之經組合之接觸電阻Rc的串 聯相加組成。圖31C展示根據線性擬合概念判定之Re對比 需估計之所有通道長度之通道電阻可忽略。圖31C中之插 96164.doc -94- 1284423 圖展示隨閘極電壓變,化之 ▲ 31C中線性擬合之斜率 广性之變化,其根據圖 所示,此等# 數來匈定。如圖31C之插圖t 所不此專貝科之線性擬合給 cm2/v > 口承貝裝置遷移率約為270 cm/Vs且本質臨限電壓約為2V。 圖3 ID對比直接根據線性 計之具有未摻雜與接觸換雜之=里測之轉印特徵曲線估 電^的=印刷單晶石夕半導體元件之 养雜二。ί ff(意即,未去除接觸影響)。對於未 摻雜^置’通道長戶:T白 200 2/'" 微米減為5微米,^快速自 2〇〇 cm /Vs減為 50 em2/Vs。在 在通道長度小於約50微米時, 接觸開始支配裝置行為。名 27〇 2 … 觸払雜情況下,遷移率約為 S ’且在此範圍中隨通道長度之變化小於2〇%, …根據圖31C之插圖判定之本質 料額外證明此等穿w屎+可如必 寺貝 立 寺4置展不了忽略接觸電阻之影響。應注 思’除了不同遷移率以夕卜,玉 口 注忍到具有摻雜接觸之裝 置比具有未摻雜接觸之裝置在其性質上更穩定、更均一, 且更不易受處理條件之影響。 機械可撓性是此類型之裝置之—重要特徵。吾人對接觸 摻雜降Si電晶體執行了系統性彎曲測試,#彎曲方向為使 得裝置處於壓縮及拉伸狀態。吾人亦進行了某些疲勞測 ‘實例6中提供了實驗配置之細節。_A展示作為應變 (或^考曲半徑)之函數之有效裝置遷移率的變化,其藉由在 未弓曲狀恕下之值^來標準化。負的及正的應變分別對 應拉伸及壓縮。對於此應變範圍(對應於2〇〇微米厚之基 板’ ¥曲半徑降至約! em),吾人觀測到臨限電 96164.doc -95- 1284423 •壓及接通/斷開比僅發生小的(在多數情況下小於2〇%)變 化。機械可撓性程度與對於塑膠基板上之有機及心Si電晶 體所報告之機械可撓性程度相當。圖32B呈現在裝置處引 起自0與0.98%之間之壓縮應變之幾百次彎曲循環(使得半 徑為9.2 mm)後的標準化有效遷移率。觀測到裝置 ,性質幾乎沒有發生變化;在35〇個循環之後,、臨 限電壓及接通/斷開比之變化小於2〇%。此等結果指示包含 _ 可印刷異質半導體元件之本發明之電晶體的良好疲勞穩定 性。 此實例說明旋塗摻雜劑方法可用於塑膠基板上之電晶體 中之接觸摻雜可印刷單晶矽半導體元件。尺度分析指示本 發明之方法產生未被接觸限制之裝置,其說明本發明之方 法可應用於在塑膠基板上製造高頻矽裝置。此特徵結合裝 置之非常良好之機械可撓性及疲勞穩定性使得此接觸換雜 可印刷異質半導體方法成為製造廣泛可撓性宏觀電子、微 電子及/或奈米電子系統之有價值的途徑。 本發明亦提個於將可㈣半導體元件整合於多種裝置 及裝置組態中之異質整人t、、么 JU ^ PO ^ 買正σ方法。本發明之此態樣提供用於 製造其中㈣材料組合且互連於同—平臺上之廣泛裝置之 製造途徑。本發明之異質整合方法利用溶液印刷及、/或乾 式轉印接觸印刷以建立兩種或兩種以上之不同材料之電、 光學及/或機械互連性之方式組合兩種或兩種以上之 !:=!明之可印刷半導體元件可與不同半導體材料或 包括介電質、導體、陶究、玻璃及聚合物材料之其它類: 96l64.doc -96 - 1284423 材料整合。 在此概念之一實施例中,異質整合涉及將一可印刷半導 體元件轉印及互連至一具有不同組合物之半導體晶片,例 如將一系統組合於一晶片類型裝置上。在另一實施例中, 在不同種類半導體晶圓(如,矽晶圓及GaN晶圓)上製造複 •數個獨立裝置及/或裝置組件,且隨後將其一起整合於諸 如接收晶圓之同一接收基板上。在另一實施例中,異質整 • 合涉及藉由將可印刷元件於特定方向組合且將該等可印刷 元件與包含積體電路之其它組件有效互連而將一或多個可 印刷半導體元件引入預成型之複雜積體電路。本發明之異 . 負整合方法可採用用於組合及互連微尺度及/或奈米級可 印刷半導體元件之此項技術中已知的大量其它技術,其包 括(但不限於)晶圓黏結方法、使用黏接劑及中間黏結層、 .退火步驟(高溫及低溫退火)、剝離氧化物外塗層之處理、 半導體摻雜技術、光微影技術及經由連續薄膜層轉印之額 _ 外多層處理。 圖33提供一利用本發明之一異質整合方法製造之包含直 接黏九於矽晶圓(丨〇 〇)上之氮化鎵微結構之複合半導體結 構的SEM衫像。為製造圖33所示之複合半導體結構,利用 感應耦合電漿蝕刻而由矽〇11)晶圓上之⑽微加工包含 GaN之可印刷半導體凡件,且利用在熱水性(攝氏ι〇〇 度)下各向異f生濕式餘刻而自石夕釋放。可印刷GaN元件自母 晶片移除,且藉由利用_PDMS戳記乾式轉印接觸印刷而 • p刷s #收石夕晶片上。可印刷GaN元件與石夕晶片之間之 96164.doc -97-
1284423 ==分子間吸引力提供,而無需使用黏接劑層。圖 iJL 咖影像展示本發明之可印刷半導體元件及 p刷組合方法可異質整合不同半導體材料。 1Γ製造具有可印刷半導趙元件之高效能太陽能電池 ,明之-目標為提供在具有多種組合物之大面積基板 ,可難_基板)上製造太陽能電池、太陽能電池陣 i及具有太陽能電池之經整合電子裝置的方法。此外,本 =之Γ目標為提供異質可印刷半導體元件,其能夠提供 L與猎由習知的高溫處理方法製造之太陽能電池相當之 光電一極體回應之太陽能電池中的P-N接面。 本發明之可印刷半導體元件提供太陽能電池中的包含具 :高品:介面之p_N接面之異質可印刷半導體元件: 月匕力可藉由實驗研究來驗證。太陽能電池係利用用於製造 P^N接面t兩種不同製造途徑來㈣,且藉由此等途捏製 、虞置的光電一極體回應可被估計。此實例中所提供之 實驗結果說明本發明之可印刷異質半導體元件及相關組合 方法可用於提供太陽能電池中之高品質P-N接面。 口 圖34A提供一示意性說明用於製造一包含一可印刷 接面之太陽能電池之製造途徑中處理步驟的處理流程圖。 如圖34A所示,諸如單晶矽晶圓之高品質半導體材料係以 產生一定位為直接與一P型摻雜半導體區域相鄰之N型摻雜 半導體區域之方式提供及處理。對於製造展現良好效率之 太陽能電池而言,較佳P型及!^型區域實體接觸,且在兩者 之間具有一突變介面,而不存在未摻雜半導體。隨後,將 96164.doc -98 - 1284423 、、£處理之半導體材料圖案化且 之實體尺寸。經由起離技術之隨後 P-N接面的單體結構’該接面具有一直接與‘ 體層相鄰之P型掺雜層。隨後,利用 等 -,^ ^ 4 ^乃之洛液印刷或 乾式轉印接觸印刷方法將可印刷p_N接面組入 I σ主一基板
上。如圖34Α所示,Ρ型及Ν型摻雜半導體層上之接點(意 :’電極)可藉由在可印刷Ρ·Ν接面的起離處理之前沈積: 單體結構上,或藉由在組合於基板上之後沈積至可印刷ρ_ Ν接面上來界定。在一實施例中,利用氣相沈積一或多種 金屬來界定接點。 圖34Β展示一藉由圖34Α中所說明之製造途徑產生之一 太%肖b電池裝置組態的示意圖。具有侧摻雜劑之5微米厚 之P!摻雜半導體層係以直接與具有構摻雜劑之兩個N型摻 雜半導體層接觸之方式提供。接點係直接提供於N型摻雜 層,及與形成P-Ν接面之P型摻雜半導體層接觸之兩個富集 P型摻雜層上。引入磷及硼摻雜接觸區域克服了系統的接 觸電阻。圖34C展示電流對偏壓之曲線,其展示在照明具 有圖34B所示之組態之一太陽能電池裝置時所觀測之光電 二極體回應。如圖34C所示,當太陽能電池被照明且具有 正偏壓時,產生電流。 圖3 5 A提供一示意性說明用於製造一包含獨立可印刷ρ 型及N型摻雜半導體層之太陽能電池之一替代製造途徑中 處理步驟的處理流程圖。如圖35A所示,諸如單晶矽晶圓 之局品質半導體材料係以產生離散N型摻雜及ρ型摻雜半導 96164.doc -99- 1284423 體區域之方式提供及處理。隨後,將經處理之半導體材料 圖案化且蝕刻以界定分離的p型摻雜層及N型摻雜層之實體 尺寸。經由起離技術之隨後處理產生一分離可印刷p型推 雜半導體層及/或一分離可印刷N型摻雜半導體層。隨後, 藉由將一第一摻雜半導體元件(P型或N型摻雜)印刷至一具 有一不同組合物之第二摻雜半導體元件上以使得其與第一 推雜元件接觸來組合一 P-N接面。在一實施例中,藉由印 刷P型及N型摻雜半導體層兩者,例如藉由將一第一摻雜半 導體層印刷至一基板上且隨後將一第二捧雜半導體層印刷 至該第一摻雜半導體層上來組合p_N接面。或者,可藉由 將-第-摻雜半導體層印刷至一包含一第二穆雜半導體層 之基板上來組合P-N接面。將-良好介面提供於此等元件 之間之P型及N型摻雜層之任一方向可用於本發明,其包括 (但不限於)一將第一摻雜半導體元件與第二換雜半導體元 件之頂部接觸之方向。 結合N型及P型摻雜可印刷半導體元件可經由此項技術 中熟知之晶圓黏結技術來實現(參看,如"仏㈣❿^⑽ and Engineering R·· Jan Haisma and G.A.C.M. Spierings 37 第1-60頁(雇))。P型及N型摻雜半導體層可視需要在印刷 之前、之中或之後處理以剝離其上諸如外氧化物層之任意 外絕緣層’該等外絕緣層可干擾於p_N摻雜層之間建立2 :有:“質介面之p_N接面。視需要,在某些實施例 中,舉例而言,可藉由加熱將存在於待接合之 表面上之任意水在此等元件接觸之前消除以 96164.doc •100- 1284423 中之介面的品質。第一及第二摻雜半導體元件之組合可利 用本發明之溶液印刷或乾式轉印接觸印刷方法進行。本發 明之此態樣之製造途徑可視需要進一步包含退火接面 之步驟以於P型與N型摻雜半導體層之間建立一良好介面。 退火較佳在足夠低以致不顯著破壞支持P-N接面之基板的 溫度下進行’舉例而言,在小於約攝氏2〇〇度之溫度下進 行以用於將P-N接面組合於塑膠基板上。或者,P-N接面可 • 在與基板分離之處理步驟中退火。在此實施例中,允許經 退火之P-N接面冷卻,且隨後藉由溶液印刷或乾式轉印接 觸印刷方法將其組合於基板上。如圖35 A所示,p型及 払雜半導體層上之接點(意即,電極)可藉由在起離處理之 前沈積至個別摻雜半導體層上,或藉由在組合於基板上之 後沈積至可印刷P-N接面上來界定。在一實施例中,利用 氣相沈積一或多種金屬來界定接點。 圖35B展示一藉由將一 n型摻雜半導體層印刷於一矽晶 • 圓之P型摻雜半導體層之頂部上所產生之一太陽能電池裝 置的示意圖。將複合結構退火至約攝氏1〇〇〇度之溫度以於 N型與P型摻雜半導體層之間產生一具有高品質介面之p_N 接面。經由氣相沈積鋁層將電接點直接提供於每一摻雜半 導體層之頂部上。圖35C展示圖35B中示意性描繪之太陽 能電池之一俯視圖的SEM影像。該SEM影像展示定位於p 型摻雜半導體層之頂部上的N型摻雜半導體層,且亦展示 每一播雜半導體層頂部上之鋁接點。圖35D提供一電流對 偏壓的曲線,其說明了圖35C中所示之太陽能電池之光電 96164.doc 1284423 二極體回應。如圖35D所示,當太陽能電池被照明且具有 正的偏壓時,可產生電流。圖35E提供一在利用不同強度 光照明圖35C所示的太陽能電池所觀測之作為時間函數之 光電流的曲線。 用於本發明之太陽能電池之諸如可印刷摻雜半導體元件 及可印刷P-N接面之可印刷半異質半導體元件之實體尺寸 視多個變數而定。第一,厚度必須足夠大以使p_N接面可 吸收單位面積上之可感知份數的入射光子。因此,p型及N 型摻雜層之厚度至少部分視下方半導體材料之光學性質 (諸如其吸收係數)而定。在某些有用之應用中,可印刷矽 元件之厚度自約20微米至約100微米變化,且砷化鎵元件 之厚度自約1微米至約100微米變化。第二,在某些裝置應 用中,可印刷元件之厚度必須足夠小以使其在特定裝置應 用中展現有用之可撓程度。即使對於諸如單晶半導體之脆 性材料而言,亦使用薄的(小於1〇〇微米)元件提供可撓性,& 且亦由於需要較少原材料而降低製造成本。第三,可印刷 元件之表面積應大以捕獲大量入射光子。 包括利用旋塗摻雜劑方法(如,參看實例8)之可提供言 品質摻雜半導體材料之良好界定空間分佈之任一處理 將摻雜劑引人半導體材料中。將摻雜劑引人半導體 之例示性方法證明可控制摻雜劑在一、- ’ 一 4二維空間中 空間分佈(意即,植入深度及植入有摻雜劑之 面積)。圖34A及圖35A所示之製造途徑的顯著優二 雜劑植入與活化可在無塵室條件及高溫下分 1 96164.doc -102- 1284423 而,可印刷摻雜半導體元件及/或P-N接面之隨後製造及組 合可在低溫並在非無塵室條件下進行,藉此允許以高產出 率在各種基板材料上製造太陽能電池。 實例9:製造可拉伸電路及電子裝置
本發明提供當被拉伸、屈曲或變形時,可展現良好效能 之可拉伸電子電路、裝置及裝置陣列。與實例2中所述之 可拉伸半導體元件相似,本發明提供包含具有一支持表面 且與具有一曲線形内表面(諸如一展現一波形結構之曲線 形内表面)的裝置、裝置陣列或電路接觸之可撓性基板的 可拉伸電路及電子裝置。在此結構排列中,裝置、裝置陣 列或電路結構之曲線形内表面之至少—部分被黏結至可換 性基板之支持表面。然而,與實例2中之可拉伸半導體不 同’本發明之此態樣之裝置、裝置陣列或電路係—包含複 數個整合裝置組件(諸如半導體、介電f、電極、摻雜半 導體及導體)之多組件元件。在一例示性實施例中,淨厚 度小於約1G微米之可撓性電路、裝置及裝置陣列包含複數 個整合裝置組件,宜至少一部八 干/、至乂 °卩分具有一週期波形曲線形結 構0 在本發明之—有用實施例中,提供—包含複數個互連组 件之獨立電路或裝p該電路或裝置之内表面與—在伸展 :態:預應變彈性基板接觸並至少部分黏結至其上。預應 欠可藉由包括(但不限於)滾壓及/或預彎曲該彈性基板之此 已知的任一方式來達成,且該彈性基板可藉由沿 早個軸伸展或藉由沿複數個軸伸展而發生預應變。黏結 96164.doc -103- 1284423 可直接藉由該電路或裝置之至少一部分内表面與預應變彈 性基板之間之共價鍵結或凡得瓦爾力,或藉由利用黏接劑 或一中間黏結層來達成。黏結預應變彈性基板與電路或裝 置=後,允許該彈性基板至少部分鬆弛為一無張力狀態, 此f曲該可印刷半導體結構之内表面。電路或裝置之内表 • 自之變曲產生-曲線形内表面,其在某些有用實施例中具 有一週期或非週期波形組態。本發明包括其中包含電裝置 % 或電路之所有組件呈現一週期或非週期波形組態的實施 例0 可拉伸電子電路、裝置及裝置陣列之週期或非週期波形 ^態使其可適應拉伸或f曲組態,而在電路或裝置之個別 、且件上不會產生大的應變。本發明之此態樣可在可拉伸電 子電路、裝置及裝置陣列處於彎曲、拉伸或變形狀態時提 仏/、的有用電學行為。藉由本發明之方法形成之週期波形 組態的週期可隨下列條件而變化··⑴包含電路或裝置之整 鲁纟組件之總體的淨厚度及⑼包含整合裝置組件之材料的 機械性質,諸如楊氏模數及撓曲剛度。 圖36A展示一說明一種製造可拉伸薄膜電晶體陣列之例 示性方法的處理流程圖。如圖36A中所示,利用本發明之 技術提供獨立可印刷薄膜電晶體陣列。經由乾式轉印接觸 P刷方法以曝露電晶體之内表面之方式將薄膜電晶體陣列 轉印至_PDMS基板。接著,經曝露之内表面與一處於伸 展狀怨之至溫固化之預應變PDMS層接觸。隨後,預應變 MS層之疋全固化將電晶體之内表面黏結至預應變 96164.doc -104- 1284423 層。允許預應變PDMS層冷卻,且處於一至少部分為無張 力狀態。PDMS層之鬆弛將一週期波形結構引入陣列中之 電晶體,藉此使得其可拉伸。圖36A之插圖提供一藉由本 發明之方法製造之可拉伸薄膜電晶體陣列的原子力顯微 圖。該原子力顯微圖展示在拉伸或變形狀態提供良好電效 能之週期波形結構。 圖36B展示處於無張力及拉伸組態之可拉伸薄膜電晶體 陣列之光學顯微圖。以一在陣列上產生約2〇%淨應變之方 式拉伸該陣列不會斷裂或破壞該等薄膜電晶體。觀測到自 無張力組態轉變為一應變組態為一可逆過程。圖36B亦提 供一施加至閘極之若干電位之汲極電流對汲極電壓的曲 線,其展示可拉伸薄膜電晶體在無張力與拉伸組態均展現 良好效能。 實例10 :大面積、選擇性轉印可印刷微結構矽(叫_si广一 種製造支持於可撓性基板上之高效能薄膜電晶體 之基於印刷之方法 本發月之方法、裝置及裝置組件提供一種用於製造高效 能整合微電子裝置及裝置陣列之新型基於印刷之製造平 :£。關於宏觀電子及微電子技術之本發明之方法較習知的 處理方法之優勢包括適於廣泛基板材料、實體尺寸及表面 形態。此外,本發明之基於印刷之方法可以低成本、高效 率製造途徑在大面積基板上製造整合微電子裝置及裝置陣 列’且其與已存在之高產出率印刷設備及技術相容。 形成現代社會結構之S進資訊技術主要依賴微電子裝置 96164.doc 1284423 之使用,其涉及愈來愈高之整合密度。自二十世紀50年代 晚期之原始電路(1C),其可倂入少於4個電晶體,當前技術 水平之1C可將數百萬電晶體整合於一大體均等尺寸封裝 中。然而,吾人對開發新的裝置形狀因子愈來愈感興趣, 其中半導體裝置後入於涉及大面積及/或可挽性材料之结 構中之能力支持使用用來試圖降低成本,且同時保持高的 裝置效能級之製造方法。此等裝置技術可找到廣泛應用, 作為主動矩陣像素顯示驅動器及RJ7識別標籤之組件。最近 報告詳述了使用溶液處理方法建構特別是基於半導體奈米 線(NW)或網路化奈米管的此等電路之模型。儘管以此途 徑製備之功能裝置前景光明,但是其通常以比習知的高溫 半導體處理方法顯著低之裝置效能級為特徵。舉例而言, 對於利用溶液處理方法製備之薄膜電晶體(TFT)報告自約 2 cm2/Vs至約40 cm2/Vs變化之場效遷移率。 在一態樣中,本發明提供一”由上而下"製造策略,其使 用自用於超高效能TFT之絕緣物上矽晶圓獲得之微結構單 晶石夕__Si)帶。此製造技術可適於多種有用半導體材料, 且已成功適於其它卫業有用半導體材料,其包括_、— 及 GaAs 〇 在此實例中’說明了用於實施此技術之大量重要處理步 驟’其包括允許選擇性轉印及精確對準大基板區域上之石夕 帶之製造方法,及適用於剛性(意即,玻璃)及可撓性塑膠 土板之通用印刷程序^此處詳細報告可用以自⑽晶圓選 擇和除ps’Si,且隨後以圖案化形^將其轉印至—塑膠基 96164.doc -106-
(I 1284423 板上之兩種方法。為方便起見,稱為方法I(圖3 7A)及方法 Π(圖37B)之該等方法使用不同之黏接劑黏結機制以影響 μδ-Si之基於印刷之圖案轉印。方法I利用模製之Sylgard 3600聚二甲基矽氧烷(pDMS)戳記(由D〇w c〇rning c〇rp•提 供之一新的實驗性、高模數PDMS產品)與卜^以物件之間之 物理黏結。方法Π使用一最近開發之無人控制之軟微影技 術以將ps_Si化學黏結至經PDMS塗覆之基板。 鲁圖37A提供一展示一種用於將gS_Si元件圖案化至一塑膠 基板上之本發明之處理方法(方法的示意圖。在本實例 中’塑膠基板包含一聚對苯二甲酸乙二酯(ΡΕτ)薄片。利 用標準光微影技術於一 SOI基板頂部上顯影一花生形光阻 圖案。電漿蝕刻之後光阻剝離產生支持於一内埋式氧化物 層之頂部上的ps-Si"花生"。隨後,利用HF不完全蝕刻樣 本以給出僅由存在於ps-Si啞鈐末端之剩餘氧化物層固持之 底切花生。隨後,利用一模製成具有對應於所要圖案轉印 φ 之潛像之特徵的硬3600 PDMS戳記層壓s〇I晶圓。歸因於 PDMS之強自黏性,戳記之凸起特徵對應於自s〇I表 面選擇性移除之區域。將戳記自SOI晶圓剝離之後,接著 將其置放為與塗覆有聚胺基甲酸酉旨(PU)之聚對苯二甲酸乙 二酯(PET)薄片接觸,PU已利用UV燈部分固化。將條形塗 覆技術用以沈積PU黏接階層以確保整個大面積(6〇〇 cm2) 塑膠基板上之均一塗層厚度。隨後,將戳記上之置放 為與塑膠薄片之經PU塗覆側接觸,接著,由夾層之pet側 預形成一第二UV/Ozone曝露以完全固化且增強其至 96164.doc -107- 1284423 9
Si之黏結。自塑膠基板剝離戳記使得微結構矽與pdms分 離,且因此完成了轉印至經PU塗覆之基板。 圖3 7B提供一說明一種用於將y_Si元件圖案化至一塑膠 基板上之本發明之替代性處理方法(方法叫之示意圖。在 - 本實例中,塑膠基板包含一聚對苯二甲酸乙二酯(PET)薄 • 片。此最近報告之貼花轉印微影(DTL)技術利用一經光化 學處理以提供空間調變黏接強度之平的、未模製pDMS厚 φ 片來實現圖案轉印。利用一微反應器光罩在習知的Sylgard 184 PDMS之厚片的表面上圖案化uv/〇z〇ne(uv〇)處理從 而以高空間解析度圖案化UV0改質。曝露之後,將經光化 學改質之PDMS塗覆之PET置放為與呈現花生狀之s〇I晶圓 • 接觸,且加熱至7〇°C持續30分鐘。S0I晶圓上之花生形狀 的製造遵循與方法ι(參看圖37A)相同之程序,新增7HF蝕 刻步驟之後將Si〇2薄膜(5 nm)蒸鍍至表面上之步驟。此層 • 便於強化學黏結至PDMS。加熱之後,自s〇I剝離pDMS, φ 使得Ks-Sl圖案化轉印至PDMS之UVO改質區域。 圖38A展示用於本發明之方法中之所謂花生狀叩_si物件 之設計。圖38A中之插入光學影像展示最佳^^蝕刻條件, 其中移除通道下之内埋式氧化物,而保留犧牲Si〇2部分。 因為花生形狀之末端較該結構之本體稍寬,所以該花生形 狀尤其有益。一旦在HF溶液中蝕刻下方氧化物層,則可最 佳化時序以使得完全移除中央下方之氧化物層而仍然將 si〇2之犧牲部分保留於任一末端處(圖38a之插入影像中 所見之啞鈴區域)。正是此剩餘Μ%層將叩固持於其原 96164.doc -108- 1284423 始位置。在無此氧化物橋層的情況下,藉由光微影在S0I 晶圓上產生之ps-Si的規則(order)不易於保持。圖38B展示 當在HF溶液中過度蝕刻Si物件時失去此規則之實例。如圖 38B所示’當在HF溶液中過度蝕刻該樣本時,si物件開始 漂浮於HF溶液中。當藉由方法I或方法η自s〇i晶圓移除pS_si 時,犧牲區域之邊緣發生斷裂。 圖38C、圖38D、圖38E及圖38F展示一系列顯微圖,其 描繪利用方法I所實現之ps-Si轉印之每一步驟的進展。圖 38C展示在最佳底切HF蝕刻之後,SOI晶圓上之pS-Si。圖 3 8D展示在PDMS戳記移除一部分pS-Si後之SOI晶圓。如圖 38D所示,PDMS戳記移除一部分pS-Si,藉此使得SOI上之 鄰近區域完好。因為SOI晶圓上之未使用之微結構矽物件 保留於其原始位置,所以其可藉由一戳記拾取並在隨後印 刷步驟中轉印(如下文所述)。圖38E展示轉印至PDMS戳記 上之ps·Si結構。ps-Si帶每一末端之缺少之中心揭示在將 微結構矽自SOI轉印至PDMS戳記上的過程中發生斷裂之圖 案。圖38F展示ps-Si之第二轉印(此次自PDMS戳記至經PU 塗覆之塑膠基板)之一代表性結果,其中黏附至PU之pS_si 支持於該塑膠上。 可進行自一小型PDMS戳記至一較大塑膠表面之多次轉 印。圖39A及圖39B提供藉由3600 PDMS戳記將ps-Si選擇 性轉印至PU/PET薄片之光學影像。如圖39A所示,其中藉 由利用8x8 cm戳記多次轉印而將ps-Si稀疏地轉印至一塑膠 基板上之大面積(15x15 cm)轉印。影像中之每一像素具有 96164.doc •109- 1284423 與圖38F中所不之組態相同之組態,且遵循對圖至%e 描述之相同之協定。圖39B之插圖展示一更複雜之模製型 式’一’’DARPA macroE,,文字,其包含在大小上比圖則至 圖38E中加凴之叩-以物件小之花生狀pS-Si物件。如圖39B 所示之物件界定字母”A”(環繞插圖影像)之品質說明了轉 •印之高圖案保真度。此等資料表明僅戳記直接接觸之彼等 區域最終轉印至塑膠基板。應注意,此轉印更難以利用習 φ 知的Sylgard PDMS有兩個原因。第一,當特徵之間之 分離距離超過特徵高度之二十倍時,Sylgard 184會下陷。 此處所不之此等實例包含此等設計規則,因此排除利用較 低模數之聚合物來進行高保真轉印。第二,吾人亦發現 ί
Sylgard 184有時並不具有足夠黏接力以自s〇I晶圓拾取每 一 gs-Si花生,且在利用由此聚合物製備之戳記之某些應用 中,觀測到缺陷。購自Dow Corning之3 600 PDMS即使在 縱比為1 ·· 2 0 0的情況下亦不會明顯下陷,且更重要的在 • 於’其與^^-以物件之黏接力比184 PDMS之黏接力強。 一利用方法II進行ps-Si轉印之實例展示於圖39C及圖39D 中。圖39C為已化學黏結有gS-Si,且pS-Si隨後被轉印至其 上之塗覆有Sylgard 184之PET基板之一區段的光學顯微 圖。圖39D展示一以此方式轉印之叩-以的較高倍放大影 像。應注意,用於此說明中之花生尺寸相對較小,帶寬為 25 μηι。有趣的是,吾人發現當此等較小特徵自s〇i晶圓移 除時,該等較小特徵具有一不同破裂點。在圖39D之放大 ·· 圖中,吾人亦注意到PDMS表面亦不再平坦。此之原因在 96164.doc -110- rc 1284423 於以下事實:PDMS區段實際上互相關聯轉印至SOI,被扯 出與藉由圖案化UVO處理活化之區域接觸之塊,該等區域 為PDMS下陷且與花生之間之晶圓表面接觸之區域。 圖40A說明一利用花生形狀基於利用方法I之轉印製 造之一裝置之例示性裝置幾何形狀。為建構此等裝置,將
一經氧化銦錫(ΙΤΟ)塗覆之PET薄片用作基板。該ΙΤΟ充當 閘極’且將稀SU-8 5(量測之電容=5.77 nF/cm2)用作閘極介 電質。圖40B提供在閘極電壓範圍(Vg=_25 乂至2〇 v)内之 ps-Si TFT之I-V曲線。如圖4〇b所示,此等塑膠支持、花生 形狀之ps-Si TFT展示一積累模式之n型通道電晶體行為。 如圖40C之插入影像中所示,該裝置之通道長度為丨⑽ 且該裝置之寬度為400 μηι。圖4〇c展示在一恆定之源極-汲 極電壓(VsdM V)下量測之轉印特徵曲線,其指示有效遷 移率為1 73 cm /Vs。圖40C中之插圖展示本發明之實際裝 置之光學顯微圖。該轉印特徵曲線指示臨限電壓為· 2.5 V且有效遷移率為173 em2/Vs。此等值與對此類型⑽咖 厚之底部閘極結構所期望之效能特徵一致。 此實例中所述之選握柯Μ 1 , 擇f生轉印方法提供一將微結構矽自 SOI晶圓轉印至一可撓性、 / 在觀電子糸統之有效途徑。利 用此等技術且對比習知的 的液澆鑄方法,微結構矽物件可 在精確對準下自S0I母晶圓 、 轉p ’且用最小化浪費之方法 加以利用。此工作中猫办 九之新型3600 PDMS的機械性質表 明與商業Sylgard 184 PDMs MS^脂相比,該新型3600 PDMS ,、有夕種重要優勢,尤盆是 八疋其尺寸穩定性及較高表面黏接 96164.doc -111. 1284423 性質。亦證實印刷技術適於建構倂入高效能ps-Si薄膜電晶 體之宏觀電子系統。
實驗 方法I
利用一商業SOI晶圓(SOITEC、P型、頂部Si厚度=100 111]1、電阻率=13.5至22.5〇]1111-(:111、145 11111内埋式氧化物 層)製造ps-Si物件。利用光微影(Shipley 1805抗蝕劑)將 SOI晶圓圖案化為所要花生形狀之幾何形狀(中部區段長 度:200 μιη,寬度·· 25 μιη,花生直徑·· 50 μηι)。隨後, 乾式 I虫刻(Plasmatherm RIE 系統、SF6 流、40 seem、50 mTorr、RF功率=100 W、45 sec)用以移除曝露石夕。接著, 在HF(49%)溶液中蝕刻下方Si02進行80秒。對於方法I之 3600 PDMS 戳記而言,一特定 PDMS(Dow Corning、 3600、彈性模數=8 MPa)與 Sylgard 1 84 (Dow Corning、彈 性模數= 1.8 Mpa)以1:1之比混合,且利用標準軟微影圖案 化方法固化。UV源(臭氧活性汞燈、173 pW/cm2)用以固化 PU薄膜黏接層(Norland光學黏接劑73號)。利用條形塗覆 程序(Meyer bar、RD specialties)將此等後面的薄膜塗覆於 PET基板上(厚度為1 80 μιη、Mylar薄膜、Southwall技術)。 方法II 對於方法II而言,所使用之花生形狀之大小係比方法I中 所使用之花生形狀小(中部區段長度:10 μηι、寬度:2 μηι ;末端直徑:5 μιη)。除了將RIE蝕刻時間減少為25秒 (以最小化側壁蝕刻)及將内埋式氧化物層在濃(49%)HF溶 96164.doc -112- 1284423 • 液中蝕刻30秒之外,一相似之製造協定可用以產生此等結 構。在HF溶液蝕刻步驟之後,將樣本在水浴中沖洗,且在 一爐中於70°C下乾燥5分鐘。隨後,將50 A 8丨02層蒸鍍於 該樣本之頂部上(Temescal FC-1800電子束蒸鍍機)。為了 將一 PDMS薄層黏結至PET基板上,首先藉由以1000 rpm旋 -塗30秒而將PU層澆鑄於PET上,並且將其曝露至UVO(173 W/cm2)4分鐘。隨後,以1000 rpm進行30秒將PDMS薄膜旋 塗澆鑄於在65°C下熱固化3小時之PU上。 ® 選擇性區域軟微影圖案化程序包含將經塗覆之PET基板
之未圖案化PDMS側置放為與UVO光罩之圖案化側接觸。 製造此微反應器遮罩遵循Childs等人所述之程序。該圖案 ’ 由兩個聯鎖矩形陣列(1.2x0.6 mm)組成。隨後,經由UVO 光罩在自汞球(UVOCS TlOxlO/OES)約3 cm距離處照射 PDMS 3分鐘。曝露之後,自UVO光罩剝離PDMS戳記,且 ’ 將曝露之PDMS面置放為與花生狀SOI晶圓接觸。在70°C下 φ 加熱30分鐘後之後,使用鑷夾緩慢剝離PDMS,且移除與 照射區域對準之ps-Si段。 裝置之製造 在3000 rpm下將66%(v) SU_8 2000稀釋劑稀釋之SU-8 5 旋塗於經塗覆之PET樣本之ITO側進行30秒。隨後,將SU-8環氧樹脂在60°C下約1分鐘内預固化一熱板上。接著,在 其表面上具有ps-Si之PDMS戳記(方法I)達成與環氧樹脂層 接觸30秒,且將PDMS戳記剝離以將ps-Si轉印至環氧樹 > 脂。接著,SU-8介電質在115°C下2分鐘内完全固化,曝露 96164.doc -113 - 1284423 至UV下ίο秒,且在115°c下後烘焙2分鐘。隨後,藉由電 子束蒸鑛添加用於鈦接點之金屬(4〇 nm),且利用標準光 微影方法與利用1% HF溶液蝕刻協同圖案化源極-汲極區 域。 實例11 :利用印刷GaAs線陣列於塑膠基板上形成之可弩 曲GaAs金屬半導體場效電晶體 本發明之製造方法相對於可組合及整合於有用功能裝置 鲁 及裝置組件中之材料為通用的。詳言之,本發明之方法適 用於利用包括非矽材料之多種高品質半導體材料製造基於 半導體之微電子及宏觀電子裝置。為表明本發明之方法之 此能力,藉由本發明之方法製造具有GaAs微線之可彎曲金 屬半導體場效電晶體(MESFET),且估計其電及機械屬 性。 利用尚品質、單晶半導體奈米結構及微結構於大面積、 機械可撓性塑膠基板上形成場效電晶體對於廣泛應用於顯 φ 示器、感應器、醫療裝置及其它系統非常有益。大量方法 已表明可將高品質半導體材料(諸如,Si奈米線、微帶、片 狀等)轉印至用於機械可撓性金屬氧化物半導體場效電晶 體(MOSFET)之塑膠基板上。本發明之方法可用於利用具 有整合歐姆源極/汲極接點之GaAs微線(被稱作微結構GaAs 或ps-GaAs之一類材料)在塑膠基板上製造可彎曲金屬半導 體場效電晶體(MESFET)。在此等方法中,高品質塊GaAs 晶圓提供用於”由上而下"製造程序之初始材料以形成微/奈 \ 米線。此外,利用彈性體戳記之轉印印刷技術將此等線之 96164.doc -114- 1284423 良好排序陣列與塑膠基板整合。以此方法形成之mesfet 之電學及機械量測結果表明利用本發明之方法可達成良好 效能及優良可彎曲性。 圖41提供一於可撓性塑膠基板(聚對苯二甲酸乙二酯 (PET))上製造MESFET之主要步驟的示意性說明,該等 MESFET利用具有蠢晶!!型通道層,及經整合AuGe/Ni/Au 之歐姆接點之單晶GaAs線陣列。具有一磊晶si摻雜η型 • GaAs層(濃度為 4.0xl〇17/cm3、iqe inc·,Bethlehem,ΡΑ)之 (100)半絕緣GaAs(SI-GaAs)晶圓提供用於產生微線之源材 料。經由電子束(及/或熱)蒸鍍之光微影及金屬化產生包含 用於歐姆接點之習知的多層堆疊,意即AuGe( 120 nm)/Ni(20 nm)/Au(120 nm)之窄金屬條陣列(寬度為2 μηι且 間隔為13 μηι)。用流動&在石英管中於高溫下退火晶圓 (意即’ 450°C下1分鐘)形成至n_GaAs之歐姆接點。 沿GaAS之(0 Ϊ i)結晶方向界定金屬條使得利用一由上 春 而下製造方法產生微線(具有整合歐姆接點)。如圖41中處 理步驟i所示,將一光阻圖案界定於金屬條之頂部(3 μιη 覓),此等線之間之開口位於相鄰金屬條之間。此等開口 允許餘刻劑(在體積上Η3Ρ〇4(85重量❶/g):h2O2(30重量 %):H2〇=l :13:12)擴散至GaAs表面以各向異性蝕刻GaAs。 光阻保護歐姆條與GaAs之間之介面免於曝露。各向異性蝕 刻沿GaAs表面產生反向凸台及底切,其使得形成自母晶圓釋 放之具有三角形截面及窄的寬度之GaAs線。藉由控制光阻 之幾何形狀及蝕刻時間,底切產生具有小至微米及/或奈米 96164.doc -115- 1284423 長度級之寬度的GaAs線。每一線具有由一界定所得 MESFET之通道長度之間隙分離之兩歐姆條。如圖41中之 處理步驟ii所示,聚二曱基矽氧烷(PDMS)之一平的、彈性 體戳記與塗覆有光阻之GaAs線之接觸於PDMS之疏水表面 與光阻之間形成一凡得瓦爾力。如圖41中之處理步驟iii所 示,此相互作用可使得當自母晶圓剝離戳記時,所有GaAs 線自晶圓移除至PDMS之表面。此轉印處理保持該等線之 微影界定之空間組織(意即對準陣列)。隨後,層壓具有 GaAs線之PDMS戳記抵靠覆蓋有為一種可光固化之聚合物 之液體聚胺基甲酸酯的PET薄片(PU,ΝΕΑ 121,Norland Products Inc” Cranbury,NJ) 〇 如圖41中之處理步驟iv所示,固化PU、剝離PDMS戳記 及藉由〇2反應性離子蝕刻(RIE,Uniaxis 790,電漿-熱反應 離子蝕刻系統)移除光阻使得具有經曝露歐姆條之有序 GaAs線嵌入於PU/PET基板之表面上。在轉印印刷處理 中,光阻不僅可充當一黏接層,而且可充當保護膜以保護 GaAs線之表面及歐姆接點被污染。如圖41之處理步驟v所 示,PU/PET基板上之進一步微影處理界定電極(250 mm Au),其連接歐姆條以形成源極及汲極,且用於閘極 (Ti(150 nm)/Au(150 nm))。歸因於PU/PET薄片(厚度約為 200 μιη)及GaAs線(寬度及厚度均小於5 μιη)之可彎曲性, 該所得MESFET陣列具有機械可撓性。 圖42A呈現一展示一塑膠基板(PU/PET)上基於GaAs線之 MESFET之幾何形狀的截面圖的示意圖。源極/汲極形成至 96164.doc -116- 1284423 «•GaAs層之歐姆接點。閘極形成一至此層之蕭特基接點。 固化PU與GaAs線之側壁之間之強的相互作用將該等線黏 結至PU/PET基板上。以此幾何形狀且利用先前所述之處 理方法,活性π-GaAs層(意即,電晶體通道)從不接觸除了 光阻外之任意聚合材料。Ti/Au閘極形成一與心GaAs表面 之蕭特基接點,障壁允許施加一相對負電壓(意即,小於 0·5 V)以調變源極與汲極之間之電流,其如習知的 _ MESFET。圖42B展示一根據圖41之處理流程圖製造之塑 膠上之兩個基於GaAs線之MESFET的代表性影像,其每一 者使用 h個GaAs線之陣列。該等線具有經良好對準之方 向及約1·8 μηι之均一寬度。150 μηι寬及250 μιη長之Au襯墊 將十個GaAs線上之歐姆條連接起來以形成用於每一個別 MESFET之源極及汲極。15 μηι寬且沈積於源極與汲極之 間之50 μιη之間隙(電晶體通道)中之Ti/Au條提供閘極。此 等條連接至一用於探測之較大金屬襯墊。該等線上之金屬 _ 與塑膠基板上之金屬之間之對比差異主要歸因於餃刻 光阻過程中產生之PU上之表面粗糙度。圖42c展示具有數 百個電晶體之2 cmx2 cm PET薄片之影像,該影像清晰表 明該薄片具有可撓性。多個印刷步驟及/或線製造流程可 用以產生圖案化於塑膠基板上整個大面積之大量線。諸如 GaAs線寬度、源極/汲極寬度、通道及閘極長度之各種參 數易於經調適以產生具有多種所要輸出特徵之旭^”^丁。 電晶體之DC效能係特徵化以估計其電及機械性質。圖 • 43A、圖43B及圖43C呈現由一具有5〇 長之通道、15 96164.doc -117- 1284423 長之閘極之GaAs MESFET屋生之結果,其與圖42B所示之 結果相似。圖4 3 A展示閘極電壓在〇 · 5 v至-2 · Ο V之間且以 0·5 V為步長時之電流-電壓(在汲極與源極之間)曲線。該 /ds-心8特徵曲線與利用n型GaAs層及標準技術建構之基於 習知的晶圓之MESFET相當,意即,/DS在高厂ds區域飽 和’且/DS隨閘極電壓減小而減小。在線性區域,在vgs=0 V處之通道電阻為及通道=6.4 kQ。圖43B展示在不同rDS量 I 測之本發明之GaAs MESFET之轉印特徵曲線(意即,jds_ 厂gs)。所有曲線在相同閘極電壓(意即,_2·65 V)處具有最 小值。在高的正閘極電壓下/DS下降係歸因於藉由在此區域 中之蕭特基接點所產生之自閘極至源極之漏電流。圖43c 展示在VDS=4 V處之轉印曲線,其繪製為(jrDs)i/2-FGs,且 清晰展示對於MESFET所預期之線性關係。在jds = 〇19 mA及KDS = 4 V處之夾斷電壓與轉導分別為^ = 2·65 v及 = 168 pS。此等特徵曲線指示在pet基板上製造之電晶 • 體之行為與藉由傳統方法於晶圓上製造之典型GaAs MESFET之行為相似。 對於正考慮之多種目標應用而言,機械可撓性表示塑膠 基板上裝置之一重要參數。吾人藉由彎曲支持ΡΕτ薄片來 測试電晶體。圖44A及圖44B展示在可撓性pe丁基板在(A) 聲曲之則,(B)彎曲至一彎曲半徑為8·4 mm後上其上之基 於GaAs線之MESFET之閘極調變電流-電壓特徵曲線。此 等圖將電晶體在基板被彎曲至半徑為8·4 mm之前與之後的 效能進行比較,彎曲至半徑為84 mm意即,對於2〇〇 μπι* 96164.doc 1284423 基板而言,相應表面應變為1.2%(在此情況下為拉伸)。此 等結果指示電晶體可經受此等高的應變而不會失效。實際 上’在此情況下在Fgs = Ο V飽和電流增長了約20%。圖 44C展示在鬆弛彎曲基板至其平坦、未彎曲狀態之後,基 於GaAs線之MESFET之閘極調變的電流電壓特徵曲線。 對比圖44C與圖44A指示在釋放應變(意即,使得基板再次 變平)之後電晶體恢復其初始狀態之效能。圖44D展示根據 彎曲(具有不同表面應變)/未彎曲之3個循環中在厂DS = 4 v 及厂gs = 〇 V處/DS之變化,其指示此等MesfET可經受在裴 置處引起於0%至1.2%之間變化之拉伸應變之多次彎曲循 環,而其效能不會顯著變化(小於2〇%)。藉由應變觀測之 系統變化可與機械應變引起GaAs線之晶格及其能量級分佈 之轉移的事實相關。 此實例描述一種方法,其涉及⑴藉由GaAs晶圓之高溫 退火產生歐姆接點,(ii)藉由各向異性化學蝕刻產生具有 此等經整合之歐姆接點之GaAs微線,(iii)利用一彈性體戮 記將此等線乾式轉印印刷至塑膠基板上,及(iv)藉由低温 處理塑膠上之此專線製造高品質MESFET,以在塑膠基板 上產生可撓性GaAs MESFET。GaAs之本質形狀(如,高遷 移率)、製造具有短的閘極長度之MESFET之能力及用於將 此等裝置整合於複雜電路(潛在地具有利用相似方法但用 其它半導體建構之其它電晶體)中之直截了當的途徑指示 可用於達成對先進通信、空間遙測(Space)及其它系統之高 頻回應。此等優勢以及此等裝置之顯著良好機械可撓性使 96164.doc -119- 1284423 得GaAs線MESFET有益於可撓性宏觀電子系統。
總之’具有經整合之歐姆接點之GaAs微/奈米線已藉由 金屬沈積及圖案化、高溫退火及各向異性化學钱刻由塊晶 圓製備。此等線提供用於高效能裝置之唯一類型材料,其 可直接建構於諸如塑膠或紙之不經常使用之裝置基板上。 詳言之,在低溫下將此等線之經組織陣列轉印印刷至塑膠 基板上產生高品質、可彎曲金屬半導體場效電晶體 (MESFET)。聚對苯二甲酸乙二酯上之裝置之電及機械特 徵說明可達成之級效能。此等結果指示此方法應用於製造 消費型及軍事電子系統中之新興應用中的高速可撓性電路 前景光明。 實例12利用可印刷半導體元件之裝置組態 圖45提供一說明一用於塑膠基板上p型底部閘極薄膜電 晶體之本發明之例示性裝置組態的示意圖。如圖45所示, P型底部閘極薄膜電晶體包含一具有摻雜接觸區域之矽可 印刷半導體元件、一氧化銦錫底部閘極、一環氧樹脂介電 質層及源極與汲極。塑膠基板係一聚對苯二甲酸乙二酯 (PET)薄片。圖45亦提供此等裝置對於多種閘極電壓之典 型的電流-電壓特徵曲線。 ’、 圖46提供-說明-用於塑膠基板上互補邏輯閑之本發明 之例示性裝置組態的示意圖。如圖46所示,該互補邏輯深 包含-P型薄膜電晶體及-N型薄膜電晶體,每一者
可印刷半導體元件’且提供於聚對苯二甲酸乙 薄片上。 V 96164.doc -120- 1284423 圖47提供一說明一用於塑膠基板上頂部閘極薄膜電晶體 之本發明之例示性裝置組態的示意圖。如圖45所示,頂部 閘極薄膜電晶體包含一具有摻雜接觸區域之矽可印刷半導 體元件、一 Si〇2介電層及閘極、源極與汲極。塑膠基板係 具有環氧樹脂薄層之聚對苯二甲酸乙二酯(PET)薄片以便 於該等薄膜電晶體及其組件之轉印及組合。圖47亦提供此 等裝置對於多種閘極電壓之典型的電流-電壓特徵曲線。 ^ 【圖式簡單說明】 圖1不意性說明一種用於產生及組合包含單晶矽帶之可 印刷半導體元件之本發明之例示性方法。 圖2提供一說明一種用於將可印刷半導體元件組合於一 基板之一接收表面上之選擇性乾式轉印接觸印刷方法的示 意圖。 圖3A至圖3C係展示用於本發明之選擇性乾式轉印接觸 印刷方法之裝置、裝置組態及裝置組件的示意圖。 • 圖4A1及圖4A2展示一用於利用乾式轉印接觸印刷之本 發明之組合方法之可印刷半導體元件的較佳形狀。圖4幻 提供一透視圖,且圖4A2提供一俯視圖。圖4B1及圖4B2展 不一用於利用乾式轉印接觸印刷之本發明之組合方法之可 印刷半導體元件的較佳形狀。圖4B1提供一透視圖,且圖 4B2提供一俯視圖。 圖5A至圖5C呈現包含具有選定實體尺寸之單晶矽微帶 之多種可印刷半導體元件的光學及掃描電子顯微圖。 圖6呈現一塗覆有PDMS之聚醯亞胺薄片上之包含單晶矽 96164.doc -121 - 1284423 微帶之經轉印可印刷半導體元件的影像。 圖7呈現一具有一可印刷半導體元件之一薄膜電晶體之 光學顯微圖影像。 圖8提供一展示一在一預氧化矽晶圓上製造之襞置之電 流-電壓(IV)特徵的曲線。 圖9提供一展示一在塗覆有IT〇閘極及聚合物介電質之
Mylar薄片上製造之裝置在Vds=〇1 ν下量測之轉印特徵的 曲線。 圖l〇A至圖10H提供說明一種用於製造具有複合可印刷 半導體元件之薄膜電晶體陣列之本發明之方法的示意圖。 圖11A至圖11D提供說明一種用於製造一包含經整合之 閘極、閘極介電質、半導體、源極及汲極之可印刷裝置之 本發明之方法的圖。 圖12提供一展示一本發明之可拉伸可印刷半導體元件之 原子力顯微圖。 圖13展示一提供一具有曲線形内表面之半導體結構之展 開圖之原子力顯微圖。 圖14展示一本發明之可拉伸可印刷半導體元件陣列之原 子力顯微圖。 圖15展示本發明之可拉伸可㈣何體元件之光學顯微 圖0 圖16展示本發明之可拉伸可印刷半導體元件之—原子力 顯微圖,該可拉伸可印刷半導體元件具有—黏結至一在其 支持表面上具有一二維凸起圖案之可撓性基板的半導體結 96l64.doc -122- 1284423 構。 圖17展不一說明一種本發明之製造可拉伸半導體元件之 例示性方法的流程圖。 圖18A展示一種由一 Si-Ge磊晶基板製造可印刷半導體元 件之例示性方法。 圖 展卞種用於由塊梦基板,較佳為一單晶碎基板 製造可印刷半導體元件之例示性方法。 圖18C展示由塊矽基板,較佳為一單晶矽基板製造可印 刷半導體元件之另一例示性方法。 圖1 8D展示由塊矽基板,較佳為一單晶矽基板製造可印 刷半導體元件之另一例示性方法。 圖18E展示一種由一超薄矽基板製造可印刷半導體元件 之例示性方法。 圖18F展不一種由一支持基板上之多晶矽薄膜製造可印 刷半導體元件之例示性方法。 圖18G展示一種由一 si〇2基板上之多晶矽薄膜製造可印 刷半導體元件之例示性方法。 圖18H(1)及圖i8H(2)說明一種用於利用本發明之可印刷 半導體元件製造單晶半導體薄膜之方法。 圖181展示一種由GaAs基板製造包含微線之可印刷半導 體元件之例示性方法。 圖18J展示一種用於製造包含單晶矽帶之可印刷半導體 元件之替代性方法。 圖18K展示一種用於製造包含單晶石夕帶之町印刷半導體 96164.doc -123- 1284423 元件之替代性方法。 圖19提供一說明產生GaAs奈米線陣列且將其轉印至一 基板之例不性方法之步驟的示意圖,該基板諸如包含塗覆 有固化聚胺基甲酸酯(PU)薄層之聚對苯二甲酸乙二酯 (PET)薄片之塑膠基板。 圖20A提供一由利用孤立Si〇2線圖案化之GaAs晶圓所獲 得之獨立GaAs線之掃描電子顯微圖。圖2〇]3至圖2盹展示 由#刻利用2 μηι寬之Si〇2線圖案化之(jaAs晶圓所獲得之個 別線之掃描電子顯微圖影像。圖2〇F提供一展示藉由本發 明之方法製造之線的頂表面之平均寬度5線對蝕刻時間之 依賴性的曲線。 圖21A至圖21G展示印刷於PDMS及PU/PET基板上之多種 GaAs線陣列之影像。 圖22A至圖22C展示PMDS及PU/PET基板上之inp線陣列 之掃描電子顯微圖影像。 圖23 A提供一包含GaAs線陣列之例示性兩端子二極體裝 置之示忍圖及影像。圖2 3 B展示在不同彎曲半徑記錄之兩 端子二極體裝置之電流-電壓(/-F)曲線,其指示包含GaAs 線陣列之兩端子二極體裝置展現了預期之二極體特徵。圖 23C展示在以不同彎曲半徑彎曲後再進行鬆弛之後對兩端 子二極體裝置量測之電流-電壓(/_厂)曲線。 圖24提供一說明一種用於溶液印刷具有包含磁性接頭之 操縱元件的可印刷半導體元件之本發明之例示性方法的示 意圖。 96164.doc -124- 1284423 圖25提供說明將本發明之溶液印刷方法用以產生具有包 含薄鎳層之操縱元件之微結構的良好排序障列之若干光學 影像。 圖26A說明用以製造本發明之例示性可彎曲薄膜電晶體 裝置之步驟。圖26B呈現薄膜電晶體之底部閘極裝置組態 及部分裝置陣列之高倍放大及低倍放大光學影像之示意性 說明。 _ 圖27A呈現本發明之可彎曲薄膜電晶體之電流電壓特徵 曲線,其展示一如藉由應用忽略接點影響之標準場效電晶 體模型估什之在飽和區域為140 cm2/Vs,在線性區域為260 cm2/Vs之有效裴置遷移率。圖27B呈現若干裝置之轉印特 徵曲線,其以線性刻度(左侧軸)及對數刻度(右側軸)繪 製。圖27C展示藉由本發明之方法製造之若干可彎曲薄膜 電晶體之線性有效遷移率之分佈。 圖28A呈現一說明可印刷單晶矽半導體元件之顯著可撓 φ 性之溶液澆鑄帶之高解析度掃描電子顯微圖(左側插圖)。 圖28A之右側插圖展示一用以彎曲在此研究中估計之可彎 曲薄膜電晶體之實驗配置的圖片。圖28B展示當經受拉伸 及壓縮應變時,環氧樹脂介電電容之小(約小於1%)的線性 變化(參看頂部插圖)。圖28B之下部插圖呈現在閘極及汲 極偏壓均為4 V時量測之裝置之飽和電流的變化。 圖9A呈現用於在一 pET基板上產生包含可印刷異質 半導體元件之電晶體之製造方法的示意性表示。圖綱展 不具有利用本發明之技術製造之異質可印刷半導體元件之 96164.doc -125- 1284423 若干裝置的光學影像。 圖30A展示一作為L之函數的標準化電阻w的曲線, 其用於一用以特徵化接觸電阻之可印刷異質半導體元件與 接觸襯墊的排列(參看插圖)。圖3〇B展示飛行時間二次離 子質谱儀(TOF-SIMS)量測結果,其展示將圖案化s〇G用作 一擴散障壁(參看,圖29A之示意圖)將摻雜劑定位至矽中 之所要區域。在圖30B所示之影像中,亮的紅顏色指示磷 • 濃度較南。 圖31A至31D展示對應一環氧樹脂/ΙΤ〇/ρ]ΕΤ基板上之包 含可印刷接觸摻雜矽半導體元件之電晶體之量測結果。圖 31Α提供ΡΕ 丁基板上之具有摻雜接點之單晶矽電晶體之典 型的電流-電壓特徵曲線,其中L=7微米且w=2〇〇微米。自 底部至頂部,VGi -2 V變化至6 V。圖31B提供裝置之轉印 曲線(VfO.i V),該等裝置之通道長度自頂部至底部為” 微米、72微米、47微米、22微米、7微米及2微米。在每種 • 情況下之通道寬度為2〇〇微米。圖31C展示裝置在接通狀態 且在不同閘極電壓下作為通道長度L之函數之寬度標準化 電阻(R#itW)。實線表示線性擬合。尺度(scaling)與對於此 通道長度範圍之裝置效能具有可忽略影響之接點一致。圖 31C之插圖展示薄片傳導性[妙接通w)/ALrl,其作為閑極 電壓之函數由圖3 1C中之線性擬合之斜率的倒數來判定。 圖31D展示對具有未摻雜(三角形)及摻雜(方形)接點之裝置 在線性區域中估計之作為通道長度之函數的有效遷㈣。 . 圖32A展示作為應變(或彎曲半徑)之函數之有效裝置遷 96164.doc -126- 1284423 移率的變化,其藉由在未彎曲狀態下之值gGeff來標準化。 圖32B呈現在裝置處引起自〇與〇·98%之間之壓縮應變之幾 百次彎曲循環(使得半徑為9.2 mm)後的標準化有效遷移率
Keff/p〇eff0 圖33展示一利用本發明之一異質整合方法製造之包含直 接黏結於矽晶圓(1 〇 〇)上之氮化鎵微結構之複合半導體結 構的實例。 $ 圖34A提供一示意性說明用於製造一包含一可印刷 接面之太陽能電池之製造途徑中處理步驟的處理流程圖。 圖34B展示一藉由圖34A中所說明之製造途徑產生之一太 陽能電池裝置組態的示意圖。圖34C展示在照明具有圖 34B所示之組態之一太陽能電池裝置時觀測之光電二極體 之回應。 圖35A提供一示意性說明用於製造一包含可印刷p型及N 型摻雜半導體層之太陽能電池之一替代製造途徑中處理步 _ 驟的處理流程圖。圖35B展示一利用圖35A中說明之製造 途徑產生之一太陽能電池裝置的示意圖。圖35C展示圖 35B中示意性描繪之太陽能電池之一俯視圖的SEM影像。 圖35D提供一電流對偏壓的曲線,其說明了圖35(:中所示 之太陽能電池之光電二極體回應。圖3沾展示對應於若干 不同照明強度之電流對偏壓的曲線’其說明圖3 5 C中所干 之太陽能電池之光電二極體回應。 圖36A展示一說明一種製造可拉伸薄膜電晶體陣列之例 示性方法的處理流程圖。圖36B展示處於無張力與拉伸狀 96164.doc -127- 1284423 態之可拉伸薄膜電晶體陣列之光學顯微圖。 圖37A提供一展示一種用於將元件圖案化至一塑膠 基板上之本發明之處理方法(方法〗)的示意圖。圖37B提供 一說明一種用於將pS-Si元件圖案化至一塑膠基板上之本發 明之替代性處理方法(方法Π)之示意圖。 圖38A展示用於本發明之方法中之所謂花生狀物件 之設計。圖38Α中之插入光學影像展示最佳1117蝕刻條件, 其中移除通道下之内埋式氧化物而保留犧牲Si〇2部分。圖 3 8B展示當在HF溶液中過度蝕刻以物件時失去此規則之實 例。圖38C、圖38D、圖38E及圖38F展示一系列顯微圖, 其描繪利用方法I所實現之pS_si轉印之每一步驟的進展。 圖39A及圖39B提供藉由3600叩燃戳記將選擇性 轉印至PU/PET薄片上之光學影像。圖39C為已化學黏結有 gs-Si,且ps-Si隨後被轉印至其上之塗覆有Sylgard 184之 PET基板之一區段的光學顯微圖。圖39D展示一以此方式 轉印之ps-Si之較高倍放大影像。 圖40A說明一利用花生形狀μ。%基於利用方法〗之轉印製 造之一裝置之例示性裝置幾何形狀。圖4〇B提供在閘極電 壓範圍(Vg=-2.5 V至20 V)内之TF丁之][_v曲線。圖 40C展示在一恆定之源極_汲極電壓(Vsd=1 V)下量測之轉 印特徵曲線’其指示有效遷移率為173 cm2/Vs。圖4〇c中 之插圖展示本發明之實際裝置之光學顯微圖。 圖41提供一描繪在聚對苯二甲酸乙二酯(pET)基板上製 造Hs-GaAs MESFET之過程所涉及的步驟之示意性處理流 1284423 程圖。各向異性化學蝕刻可由標準(lOO)GaAs晶圓產生 線。使用一彈性體戳記之印刷技術戳記以保持空間組織 (意即,經排序陣列)之方式將此等線自晶圓轉印至塑膠裝 置基板。PR指示光阻。 圖42A呈現一展示一塑膠基板(PU/PET)上基於GaAs線之 MESFET之幾何形狀的截面圖的示意圖。源極/汲極形成至 π-GaAs層之歐姆接點。圖42B展示一根據圖41之處理流程 圖製造之塑膠上之兩個基於GaAs線之MESFET的代表性影 像,其每一者使用一十個GaAs線之陣列。圖42C展示具有 數百個電晶體之2 cmx2 cm PET薄片之影像,該影像清晰 表明該薄片具有可撓性。 圖43A、圖43B及圖43C呈現由一具有50 μπι長之通道、 15 μπι長之閘極之GaAs MESFET產生之結果,其與圖42Β 所示之結果相似。圖43 A展示閘極電壓在0.5 V至_2.0 V之 間且以0·5 V為步長時之電流-電壓(在汲極與源極之間)曲 線。圖43B展示在不同KDS量測之本發明之GaAs MESFET 之轉印特徵曲線(意即,/DS - FGS)。圖43C展示在VDS=4 V 處之轉印曲線,其繪製為(/DS)1/2 -厂GS,且清晰展示對於 MESFET所預期之線性關係。 圖44A及圖44B展示在可撓性PET基板在(A)彎曲之前; (B)彎曲至一彎曲半徑為8.4 mm後其上之基於GaAs線之 MESFET之閘極調變電流-電壓特徵曲線。圖44C展示在鬆 弛彎曲基板至其平坦、未彎曲狀態之後,基於GaAs線之 MESFET之閘極調變的電流-電壓特徵曲線。圖44D展示根 96164.doc -129- 1284423 據彎曲(具有不同表面應變)/未彎曲之3個循環中在厂DS == 4 V及Kgs = 〇 V處/ds之變化,其指不此等MESFET可經受在 裝置處引起於0%至I·2%之間變化之拉伸應變之多次彎曲 循環,而其效能不會顯著變化(小於2〇°/〇。 圖45提供一說明一用於塑膠基板上P型底部閘極薄膜電 晶體之本發明之例示性裝置組態的示意圖。 圖46提供一說明一用於塑膠基板上互補邏輯閘之本發明 之例示性裝置組態的示意圖。
圖47提供一說明一用於塑膠基板上頂部閘極薄膜電晶體 之本發明之例示性裝置組態的示意圖。 【主要元件符號說明】 100 SOI基板 105 單晶矽層 107 Si02 層 108 矽操縱層 120 遮罩元件 125 遮蔽區域 127 曝露表面區域 140 凸起特徵 141 侧壁 147 厚度 150 可印刷半導體元件 160 基板表面 162 金襯墊 96164.doc … 1284423
165 箭頭 166 箭頭 170 接觸表面 175 一致轉印裝置 190 懸浮液 300 可印刷半導體元件 305 母基板 310 第一圖案 315 一致轉印裝置 320 接觸表面 325 黏結區域 330 接收表面 335 基板 340 第二圖案 345 第三圖案 350 黏接塗層 360 凸起特徵 500 帶 502 軸 505 第一末端 510 中央區域 515 第二末端 520 母基板 525 犧牲層 96164.doc 131 - 1284423 527 帶 528 軸 529 母基板 530 對準保持元件 531 電晶體 532 源極 533 汲極 534 可印刷半導體元件
547 閘極 548 表面、基板 550 複合可印刷半導體元件 551 軸 552 選定長度 553 選定厚度 555 單晶矽結構 560 介電元件 561 光阻 562 下側 700 可拉伸可印刷半導體元件 705 可撓性基板 710 支持表面 715 彎曲半導體結構 720 曲線形内表面 730 變形軸 96164.doc -132· 1284423 D 汲極 G 閘極 S 源極
96164.doc -133 -
Claims (1)
1284423 十、申請專利範圍: L 一種電氣裝置,其包含: 一第一電極; 一第二電極;及 可印刷半導體元件,其定位為與該第-電極及該第 二電極電接觸’該可印刷半導體元件包含—整體無機半 v體、”。構’且其中該可印刷半導體元件於該第—電極與 該第二電極之間提供—大於或等於約50%之填充因子Γ 2·如5月求項1之電氣裝置,其中該可印刷半導體元件於該 第-電極與該第二電極之間提供一大於或等於約8〇%之 填充因子。 3· —種電氣裝置,其包含: 一第一電極; 一第二電極;及 一可印刷半導體元件,其定位A /、疋位為與该第一電極及該第 二電極電接觸’該可印刷半導體元件包含—整體鱼機半 導體結構,且其中該可印刷半導體元件具有至少一大於 或荨於約500奈米之截面尺寸。 4·如請求項1或3之電氣裝置,1中兮 七丄 、亥可印刷半導體元件具 有大於或等於約10奈米之厚度,— 大於或等於約100奈 水之見度,及一大於或等於約i微米之長产 5·如請求項丨或3之電氣裝置,其中 ° . 丨刷+導體元件具 有一選自約10奈米至約100微米範 <厚度 ,一 3登白的 1 〇〇奈米至約1毫米範圍之寬度,— 、" &自約1微米至約1 96164.doc 1284423 毫米範圍之長度。
如請求項1或3之電氣裝置,其中該可印刷半導體元件具 有一等於或小於約1〇之長度與寬度之比。 如請求項1或3之電氣裝置,其中該可印刷半導體元件具 有一等於或小於約1.5之長度與寬度之比。 如叫求項1或3之電氣裝置,其中該可印刷半導體元件具 有一等於或小於約之厚度與寬度之比。 如凊求項1或3之電氣裝置,其中該可印刷半導體元件包 3祕、纟°構可印刷半導體元件或一奈米結構可印刷半導 體元件。 1〇·如請求項1或3之電氣裝置,其中該第-電極與該第二電 極間隔一大於該可印刷半導體元件之該長度的5〇%之距 離。
如喷求項1或3之電氣裝置,其中該可印刷半導體元件延 伸一長度,其終止於第—末端及第二末端,其中該可印 刷半導體元件之該第一末端定位於該第一電極之5微米 内,且其中該可印刷半導體元件之該第二末端定位於該 第二電極之5微米内。 1如請求項…之電氣裝置,其中該可印刷半導體元件具 有一自由如下形狀組成之群中選擇之形狀: 一帶狀; 一片狀; 一柱狀; 一圓柱體; 96164.doc 1284423 一圓盤;及 一塊狀。 13.如請求項丨或3之電氣裝置,其進一步包含至少一額外可 印刷半導體元件’其中額外可印刷半導體元件係與 —電極及該第二電極電接觸。 μ 14· 一種電氣裝置陣列,其包含·· 一第一電極;
一第二電極;及 硬數個可印刷半導體元件,其中該等可印刷半導體元 件之每-衫位為與該第—電極及該第二電極電接觸, 其中該等可印刷半導體元件之每—者均包含—整體無機 半導體結構。 15.如請求項14之電氣裝置陣列,其中該等可印刷半導體元 件於該第-電極與該第二電極之間提供一大於或等於約 50%之填充因子。 ♦ 16.如請求項14之電氣裝置陣列,其中該等可印刷半導體元 件係相對於一選定對準軸大體縱向定向。 17.如請求項14之電氣裝置陣列,其中該等可印刷半導體元 件之e亥等相對位置係選擇為在小於或等於約$微米内。 A如請求項14之電氣裝置陣列,其中該等可印刷半導體元 件之每一者延伸一長度,其終止於第—末端及第二 端’其中該等可印刷半導體元件之該等第—末端之每一 者定位於該第一電極之5微米内,且其中該等可印刷半 冷體7G件之該等第二末端之每一者定位於該第二電極之 96164.doc 1284423 5微米内。 該等可印刷半導體元 米結構可印刷半導體 19·如請求項14之電氣裝置陣列,其中 件係微結構可印刷半導體元件、奈 元件或兩者。 -種用於將—可印料導體元件組合於—基板之一接收 表面上之方法,該方法包含以下步驟: 提供包含-整體無機半導體結構之該可印刷半導體元
將該可印刷半導體元件與一具有一接觸表面之一致轉 p裝置接觸’其中該接觸表面與該可印刷半導體元件之 間之接觸將該可印刷半導體元件黏結至該接觸表面,藉 此形^上方安置有該可㈣半導體元件之該接觸表面; 將安置於該接觸表面上之該可印刷半導體元件與該基 板之該接收表面接觸,·及 將該-致轉印裝i之該接縣面與訪印刷半導體元 件分離’其中將該可印刷半導體元件轉印至該接收表面 藉此將及了印刷半導體元件組合於該基板之該接收 表面上0 21·如請求項20之方法,其中安置於該接觸表面上之該半導 體兀件與該接收表面之一選定區域接觸,且在一等於約 5 cm之接收表面積上一置放精確度大於或等於約h微 米。 22.如請求項20之方法,其進一步包含以下步驟: 提供額外可印刷半導體元件,其每一者包含一整體無 96164.doc 1284423 機半導體結構; 將該等可印刷半導體元件與一具有_接觸表 轉印裝置接觸,其中該接觸矣 致 :間之接觸將該等可印刷半導體元件黏結牛 面’且在包含該等可印射導體元件之—選定圖案2 對方向上產生上方安置有該 ’、 觸表面; p料導體疋件之該接 將安置於該觸表面上之料可印射導體元件心 基板之該接收表面接觸;及 〃 μ 一將該致轉印裝置之該接觸表面與該等可印刷半導體 23 24. 2分離’其中將料可印刷半導體元件於包含該選定 圖案之該等相對方L卩至該接收表面上。 •”求項22之方法,其中該等可印刷半導體於包含該選 定圖案之該等相對方向上提供於一母基板上,且其中在 轉印至該接收表面之過程中保持該等相對方向。 -種用於將一可印刷半導體元件組合於一基板之一接收 表面上之方法,該方法包含以下步驟·· 提供包含一整體無機半導體結構之該可印刷半導體元 件,其中該可印刷半導體元件具有纟少一大於或等於Ζ 500奈米之截面尺寸; 將邊半導體元件分散於一溶劑中,藉此產生一在該溶 劑中包含該半導體元件之懸浮液;及 藉由將該懸浮液溶液印刷至該接收表面上而將該半導 體兀件傳送至該基板,藉此將該半導體元件組合至該接 96164.doc 1284423 收表面上。 25·如請求項24之方法,其中藉由將該懸浮液溶液印刷至該 接收表面上而將該半導體元件傳送至該基板之該步驟使 用一自由如下技術組成之群中選擇之印刷技術·· 噴墨印刷; 熱轉印印刷; 毛細管作用印刷;及 絲網印刷。 26.如請求項24之方法,其進一步包含將該半導體元件導向 至該接收表面之一選定區域上及導向於一選定方向上之 步驟,其中利用靜電力、靜磁力或聲波將該半導體元件 導向至該接收表面之該選定區域上及導向於一選定方向 上。 27·如請求項24之方法,其進一步包含以下步驟: 提供額外可印刷半導體元件,其中該等額外可印刷半 導體元件之每一者具有至少一大於或等於約5 〇〇奈米之 截面尺寸; 將該等半導體元件分散於該溶劑中,藉此產生一在該 溶劑中包含該等半導體元件之懸浮液;及 藉由將該懸浮液溶液印刷至該接收表面上而將該等半 導體元件傳送至該基板,藉此將該等半導體元件組合至 該接收表面上。 28. —種用於製造一可印刷半導體元件之方法,該方法包含 以下步驟: 96164.doc 1284423 提供一具有一外表面之晶圓,該晶圓包含一無機半導 體材料; 藉由應用一遮罩遮蔽該外表面之一選定區域; 各向異性蝕刻該晶圓之該外表面,藉此產生一凸起結 構及該晶圓之至少一曝露表面,其中該凸起結構具有一 遮蔽側及一或多個未遮蔽側; 將一遮罩應用至該凸起結構之該等未遮蔽侧之至少一 部分;及 餘刻該晶圓之該等曝露表面,藉此製造該可印刷半導 體元件。 29. —種用於製造一可印刷半導體元件之方法,該方法包含 以下步驟: 提供一具有一外表面之晶圓,該晶圓包含一無機半導 體; 藉由應用一第一遮罩遮蔽該外表面之選定區域; 各向異性蝕刻該晶圓之該外表面,藉此產生複數個凸 起結構; 退火該晶圓,藉此產生一經退火之外表面; 藉由應用一第二遮罩遮蔽該經退火外表面之選定區 域;及 各向異性敍刻該經退火外表面,藉此產生該可印刷半 導體元件。 30. 種用於製造一可印刷半導體元件之方法,該方法勹人 以下步驟: 3 96164.doc 1284423 、,提仏具有-外表面之超薄晶圓,該晶圓包含一無機 半導體且具有一沿一垂直該外表面之軸的選定厚度; 藉由應用一遮罩遮蔽該外表面之選定區域,· 各向異性蝕刻該晶圓之該外表面,其中蝕刻該晶圓貫 穿該沿垂直該外表面之該軸之厚度,藉此產生該可印刷 半導體元件。 31· —種可拉伸半導體元件,其包含: φ 一具有一支持表面之可撓性基板;及 一具有-曲線形内表面之半導體結構,其中該曲線形 内表面之至少一部分黏結至該可撓性基板之該支持表 面。 32·如μ求項31之可拉伸半導體元件,其中該半導體結構處 於一彎曲構形。 认如請求項31之可拉伸半導體元件,其中具有該曲線形内 表面之該半導體結構係在經受應變。 # 34.如請求項31之可拉伸半導體元件,其中該曲線形内表面 有以週期波或一非週期波為特徵之輪廓外形。 35· -種用於製造一可拉伸半導體元件之方法,該方法包含 以下步驟·· 提供一具有一内表面之可印刷半導體結構; 提供一在一伸展狀態之預應變彈性基板,其中該彈性 基板具有一外表面;及 將該可印刷半導體結構之該内表面之至少一部分黏結 至在一伸展狀態之該預應變彈性基板之該外表面;及 96164.doc 1284423 ^許該彈性基板至少部分祕至—無張力狀態,其中 該彈性基板之鬆他f曲該可印刷半導體結構之該内表 面’藉此產生具有一曲線形内表面之該可拉伸半導體元 件。 36.如睛求項35之方法,其中該預應變彈性基板係沿一第一 軸、Λ —垂直於該第一軸之第二轴或沿第一軸與第二轴 兩者伸展。 37· —種可拉伸電子電路,其包含·· 一具有一支持表面之可撓性基板;及 具有一曲線形内表面之電子電路,其中該曲線形内 表面之至少一部分黏結至該可撓性基板之該支持表面。 3 8·如切求項37之可拉伸電子電路,其中該電子電路包含自 由以下元件組成之群中選擇之複數個整合裝置組件: 一半導體元件; 一介電元件; 一電極; 一導體元件;及 一摻雜半導體元件。 39· —種用於製造一可拉伸電子電路之方法,該方法包含以 下步驟: 提供一具有一内表面之可印刷電子電路; 提供一在一伸展狀態之預應變彈性基板,其中該彈性 基板具有一外表面;及 將該可印刷電子電路之該内表面之至少一部分黏結至 96164.doc 1284423 在一伸展狀態之該預應變彈性基板之該外表面;及 允許該彈性基板至少部分鬆弛至一無張力狀態,其中 該彈性基板之鬆弛彎曲該可印刷電子電路之該内表面, 其產生該内表面之至少一曲線,藉此製造該可拉伸電子 電路。 40.如請求項39之方法,其中在一伸展狀態之該預應變彈性 基板係藉由彎曲或滾動該彈性基板形成。
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