TW201826334A - 連續滲入合成裝置 - Google Patents

連續滲入合成裝置 Download PDF

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TW201826334A
TW201826334A TW106143566A TW106143566A TW201826334A TW 201826334 A TW201826334 A TW 201826334A TW 106143566 A TW106143566 A TW 106143566A TW 106143566 A TW106143566 A TW 106143566A TW 201826334 A TW201826334 A TW 201826334A
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珍 威廉 馬耶斯
維爾納 科納本
克日什托夫 卡米爾 卡赫爾
羅 大衛 庫爾特 狄
伯特 鍾布勒德
迪特 皮爾陸克斯
寶琳 卡爾卡
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荷蘭商Ａｓｍ智慧財產控股公司
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Abstract

一種連續滲入合成裝置，其包含：一反應室2，其經建構且配置成固持至少一第一基板12；一前驅體分佈及移除系統3、5，其向該反應室設置一經蒸發之第一或第二前驅體且自該反應室移除一經蒸發之第一或第二前驅體；以及一順序控制器40，其以可操作方式連接至該前驅體分佈及移除系統且包含設置有一程式之一記憶體M，該程式在該順序控制器40上運行時藉由以下來執行對設置於該基板12上之一可滲入材料之滲入：啟動該前驅體分佈及移除系統以將該第一前驅體設置且維持在該反應室中持續一第一時段T1；啟動該前驅體分佈及移除系統以自該反應室移除該第一前驅體之一部分持續一第二時段T2；以及啟動該前驅體分佈及移除系統以將該第二前驅體設置且維持在該反應室中持續一第三時段T3。

Description

連續滲入合成裝置
本發明大體上係關於製造電子元件之裝置及方法。更特定言之，本發明係關於用滲入裝置在基板上形成結構或層。
隨著趨勢已使半導體元件具有愈來愈小的尺寸，已出現了不同的圖案化技術。此等技術包括間隔物所界定的四倍圖案化、極遠紫外光刻(EUV)和與間隔物所界定的雙圖案化組合之EUV。另外，定向自組裝(DSA)已被視為將來微影應用之選擇方案。DSA涉及使用嵌段共聚物限定自組裝之圖案。所使用之嵌段共聚物可包括聚(甲基丙烯酸甲酯)(PMMA)、聚苯乙烯或聚(苯乙烯-嵌段-甲基丙烯酸甲酯)(PS-b-PMMA)。其他嵌段共聚物可包括新出現之「高χ」聚合物，其可潛在地實現較小尺寸。
上述圖案化技術可利用安置於基板上之可滲入材料，諸如EUV聚合物或DSA嵌段共聚物抗蝕劑，以實現基板的高解析度圖案化。為了滿足高解析度與線邊緣粗糙度兩者之需求，聚合物抗蝕劑可為薄層。然而，此類聚合物抗蝕劑薄層可具有若干缺點。特定言之，高解析度聚合物抗蝕劑可能具有低抗蝕刻性且可能遭受高線邊緣粗糙度。此低抗蝕刻性及高線邊緣粗糙度可使得至底層之轉移更困難。
因此，滲入可滲入材料(例如圖案化材料抗蝕劑)來改變可滲入材料特性可為有利的。為執行滲入，具有可調諧滲入製程之滲入裝置可為有利的。
根據本發明之至少一個具體例，提供一種包含連續滲入合成裝置之連續滲入裝置，該連續滲入合成裝置包含：反應室，其經建構且配置成固持至少一第一基板；前驅體分佈及移除系統，其向反應室設置氣態第一或第二前驅體且自反應室移除氣態第一或第二前驅體；以及順序控制器，其以可操作方式連接至前驅體分佈及移除系統且包含設置有一程式之記憶體，該程式在順序控制器上運行時藉由以下來執行對設置於該基板上之可滲入材料之滲入：啟動前驅體分佈及移除系統以將第一前驅體設置且維持在反應室中持續第一時段T1；啟動前驅體分佈及移除系統以自反應室移除第一前驅體之一部分持續第二時段T2；以及啟動前驅體分佈及移除系統以將第二前驅體設置且維持在反應室中持續第三時段T3。記憶體中之程式可以長於第二時段T2之第一時段T1來程式化。設置第一前驅體之第一時段T1可經程式化長於移除第一前驅體之一部分的第二時段T2以使得第一前驅體得到充足的時間以深度地滲入可滲入材料。
第二時段T2可經足夠長程式化以自反應室以及自可滲入材 料之表面移除第一前驅體以確保僅第一前驅體滲入可滲入材料且在可滲入材料上無明顯的沈積。
第二時段T2可經足夠長程式化以自反應室、自可滲入材料之表面，以及部分地自可滲入材料中之孔隙移除第一前驅體。以此方式可調諧滲入之深度。
根據另一具體例，提供一種連續滲入合成裝置，其包含：反應室，其經建構且配置成固持至少第一基板；前驅體分佈及移除系統，其向反應室設置經蒸發之第一或第二前驅體且自反應室移除經蒸發之第一或第二前驅體；以及順序控制器，其以可操作方式連接至前驅體分佈及移除系統且包含設置有一程式之記憶體，該程式在順序控制器上運行時藉由以下來執行對設置於該基板上之可滲入材料之滲入：啟動前驅體分佈及移除系統以將第一前驅體設置且維持在反應室中持續第一時段T1；啟動前驅體分佈及移除系統以自反應室移除第一前驅體之一部分持續第二時段T2；以及啟動前驅體分佈及移除系統以將第二前驅體設置且維持在反應室中持續第三時段T3。
記憶體中之程式經程式化以在第一時段T1期間執行：啟動前驅體分佈及移除系統以關閉氣體移除流動路徑，且將第一前驅體設置於反應室持續裝載時段LP；以及啟動前驅體分佈及移除系統以關閉第一前驅體流動路徑且將第一前驅 體維持在反應室中同時使移除流動路徑保持關閉持續浸泡時段SP。以此方式，可在滲入製程可必需之較長第一時段期間保證第一前驅體之經濟性使用。
根據另一具體例，提供一種用連續滲入合成裝置形成圖案化結構或層之方法，其中該方法包含：將具有圖案化可滲入材料之基板設置於反應室中之頂部上；以及在至少一個滲入循環中用滲入材料滲入圖案化可滲入材料。滲入循環包含：啟動前驅體分佈及移除系統以將第一前驅體設置且維持在反應室中持續第一時段T1；啟動前驅體分佈及移除系統以自反應室移除第一前驅體之一部分持續第二時段T2；以及啟動前驅體分佈及移除系統以將第二前驅體設置且維持在反應室中持續第三時段T3。第一時段T1長於第二時段T2。圖案化可滲入材料可為圖案化光致抗蝕劑或DSA材料。
第一時段T1可包含：關閉氣體移除流動路徑且將第一前驅體設置於反應室持續裝載時段LP；以及關閉第一前驅體流動路徑且將第一前驅體維持在反應室中同時使移除流動路徑保持關閉持續浸泡時段SP。
因此，連續滲入合成裝置包含：第一蒸發器，其經建構且配置成蒸發包含烴類之化合物； 第二蒸發器，其經建構且配置成蒸發包含金屬鹵化物之化合物；前驅體分佈及移除系統，其經建構且配置成為反應室設置來自第一或第二蒸發器中之一者的經蒸發之第一前驅體，及來自第一及第二蒸發器中之另一者的第二前驅體，且自反應室移除第一及第二前驅體；以及順序控制器，其以可操作方式連接至前驅體分佈及移除系統且包含設置有一程式之記憶體，該程式在順序控制器上運行時藉由以下來執行對可滲入材料之滲入：啟動前驅體分佈及移除系統以將第一前驅體設置於反應室中之基板上之可滲入材料持續第一時段T1；啟動前驅體分佈及移除系統以自反應室移除第一前驅體之一部分持續第二時段T2；以及啟動前驅體分佈及移除系統以將第二前驅體設置於反應室中之基板上之可滲入材料持續第三時段T3。第一蒸發器可經建構且配置成蒸發金屬烴類化合物。第二蒸發器可經建構且配置成蒸發金屬鹵化物化合物。可滲入材料、金屬烴類與金屬鹵化物之間的反應保證可滲入金屬中之金屬量可為最佳化的。所滲入之金屬量可設置所需的抗蝕刻性。
為概述本發明之目的及相較於先前技術所達成之優點，本發明之某些目的及優點已描述於以上本文中。當然，應明瞭無須所有該等目的或優點皆可根據本發明之任何特定具體例來達成。因此，舉例來說，熟悉技藝人士當認知本發明可以達成或最佳化本文所教示或提出之一個優點或一組優點而無須達成本文中可能教示或提出之其他目的或優點的方式來具體化或實施。
所有此等具體例意欲在本文所揭示之本發明之範疇內。此等及其他具體例將自以下參考附圖的某些具體例之詳細描述而對熟習此項技術者變得顯而易見，但本發明並不受限於所揭示之任何特定具體例。
應瞭解，圖式中之構件係為簡單及清楚起見而展示且未必按比例繪製。舉例而言，可相對於其他構件將圖式中之一些構件之尺寸擴大以幫助改良對所說明之本發明之具體例的理解。
圖1描繪根據一具體例之連續滲入合成裝置。
圖2a及2b說明根據至少一個具體例之可由圖1之連續滲入裝置執行的滲入程式。
圖3描繪根據一具體例之連續滲入裝置之反應室。
圖4描繪根據另一具體例之連續滲入裝置之反應室。
圖5描繪根據一具體例之包含分批反應器之連續滲入裝置之反應室。
圖6說明根據至少一個具體例之可由具有額外前驅體供應系統的圖1之連續滲入裝置執行的滲入程式。
圖7a至7d展示在具有不同滲入配方之連續滲入裝置上滲入之層上的次級離子質譜分析(SIMS)量測。
圖8a及8b描繪在具有不同滲入配方之連續滲入裝置上滲入的圖案之橫剖面。
儘管在下文中揭示特定具體例及實施例，但彼等熟習此項技術者應理解，本發明延伸超出本發明所具體揭示之具體例及/或用途及其明 顯修改及等效物。因此，希望所揭示之本發明之範疇不應受下文所描述之具體揭示之具體例限制。
圖1描繪根據一具體例之連續滲入合成裝置。該裝置包含由適合材料(諸如鋼、鋁或石英)製成之反應室2。頂部設置有可滲入材料之基板12可藉由基板處置器、經由基板開口(未示出)置放於反應室2中之基板固持器10上。反應室2形成一端經凸緣封閉之腔室，氣體經由一或多個開口引入該反應室，該一或多個開口設置有至少一個(分佈)反應室閥門19以控制該等開口之打開及關閉。分佈反應室閥門19設置前驅體分佈及移除系統3、5之液體分佈部分接近於反應室2。
前驅體分佈及移除系統3、5可經由分佈反應室閥門19將第一前驅體28或第二前驅體29設置於反應室。可藉由利用第一前驅體加熱器32蒸發容器30中所含有之液體或固體以設置足夠的蒸氣壓以傳送至室2中而將第一前驅體28作為氣體引入至室2中。第一前驅體加熱器32可向容器30中之第一前驅體設置熱量。同樣地，可藉由利用第二前驅體加熱器33蒸發包含於容器31中之液體或固體以設置足夠的蒸氣壓以傳送至反應室2中而將第二前驅體29作為氣體引入至室2中。雖然第一及第二前驅體之經描繪流動路徑可部分共用，但其亦可部分地或完全地分離。在經分離之流動路徑之情況下，各流動路徑可設置有單獨的分佈反應室閥門19。
前驅體分佈及移除系統3、5可包含沖洗系統以經由沖洗閥門24及分佈反應室閥門19將沖洗氣體34設置於反應室2。沖洗氣體可為諸如氮氣之惰性氣體且可用於沖洗反應室2。如描繪之沖洗氣體之流動路徑，雖然第一及第二前驅體可部分地共用，但其亦可部分地或完全地分離。 在經分離之流動路徑之情況下，各流動路徑可設置有單獨的分佈反應室閥門19。
替代地或附加地，沖洗系統可經建構且配置成經由沖洗反應室閥門(未示出)將沖洗氣體直接設置於反應室2中，該沖洗反應室閥門直接將沖洗氣體設置於反應室2中。藉由將沖洗氣體直接設置於反應室中，使用前驅體分佈及移除系統以裝載前驅體同時沖洗反應室變得可能。以此方式有可能增加產出量。
選擇地，自前驅體管道18至泵39之單獨排氣(未描繪)可用於更有效地沖洗前驅體管道18同時關閉分佈反應室閥門19。
反應室可由凸緣在另一端封閉，該凸緣經由設置有一或多個反應室閥門36(諸如閘閥)之一或多個開口連接至前驅體分佈及移除系統之氣體移除部件。氣體移除泵39可為前驅體分佈及移除系統之氣體移除部分的一部分。
反應室2可設置有開口(未示出)以將基板設置於基板固持器10。門可被設置成關閉及打開開口以被基板處置器設置接近於基板固持器12。基板固持器亦可形成反應室2之一部分且可以向下方向移動以被基板處置器設置接近於基板固持器10。
第一前驅體28可為具有形成在基板12上之可滲入材料中的滲入材料之元素的化合物。第一前驅體28可通過第一前驅體閥門20及分佈反應室閥門19設置於反應室2中。圖1說明具有各自分別含有第一及第二前驅體28及29的兩個容器30及31之系統。然而，所形成之滲入材料類型將決定前驅體及容器之數目。舉例而言，若需要三元滲入材料，則裝 置可包括三種容器及三種前驅體閥門。容器30及31視需要可為前驅體之瓶子或其他來源。舉例而言，若前驅體中之一者可為固體，則可設置特別適合之容器以加速固體前驅體之昇華。容器30、31中之一者亦可設置氣態前驅體，使得無需加熱。
順序控制器40(例如，微控制器)以可操作方式連接至一或多個反應室閥門19、36，前驅體閥門20、22及沖洗閥門24。順序控制器40包含用於儲存程式之記憶體M以使裝置能夠執行用第一前驅體28及第二前驅體29滲入設置於反應室2中之基板12上之可滲入材料。溫度感測器26可監測反應室溫度。溫度傳感器26可同樣設置有壓力感測器。溫度傳感器以可操作方式與順序控制器40連接以最佳化滲入之製程條件。順序控制器40之記憶體M中之程式可經程式化以定序閥門19、20、22、24及36在適當的時間處之打開及關閉以將第一及第二前驅體設置且移除至反應室2。
裝置可設置有加熱系統，該加熱系統包含第一加熱構件14(例如加熱電阻絲)及加熱控制器16，且以可操作方式連接至溫度感測器26。溫度感測器26中之一或多者同樣可設置有壓力感測器。加熱控制器以可操作方式連接至順序控制器40。溫度感測器26可用於測量反應室2中之溫度且向加熱控制器16設置關於此溫度之反饋以調節加熱構件14之溫度，從而調節反應室2之溫度。可存在額外的溫度感測器以控制反應室2及/或前驅體分佈及移除系統中之溫度，從而在裝置中設置多區溫度控制。
溫度感測器26中之一或多者同樣可設置有壓力感測器。壓力感測器可以可操作方式連接至順序控制器40以在經量測壓力之基礎上調 節製程順序。
(分佈)反應室閥門19與反應室2之間的前驅體進料流管道可設置有加熱構件14的一部分。沿著前驅體進料流管道之加熱構件14的此部分可個別地用延伸於管道中的溫度感測器26及加熱控制器16控制，以調節前驅體進料流管道之溫度。
反應室2與(移除)反應室閥門36之間的前驅體移除流管道可設置有加熱構件14的一部分。沿著前驅體移除流管道之加熱構件14的此部分可個別地用延伸於前驅體移除流管道中的溫度感測器26及加熱控制器16控制。
以此方式可避免冷斑，該冷斑可導致反應室2、前驅體進料流管道及前驅體移除流管道中出現冷凝。前驅體冷凝可導致前驅體不能有效地及時脫離反應室，且因此冷凝物可與後續前驅體反應，從而形成可污染反應室及基板12之粒子。特別言之，傳送前驅體之流動路徑中的粒子可導致多種問題。
可將溫度設定為最佳化製程溫度。滲入製程之速度可用壓力及時間標度，在此期間使得第一或第二前驅體滲入基板上之可滲入材料：在較高溫度時滲入更快的進行。因此在較高壓力下之製程有利的減小製程時間且最大化產出量但增加了冷凝之風險。最佳化製程溫度在反應室2中之第一或第二前驅體之最大壓力下應高於第一或第二前驅體之沸點溫度以避免冷凝。藉由控制自反應室2直至反應室閥門19、36中之至少一者的溫度，能夠最小化冷凝風險。
舉例而言，若第一或第二前驅體為三甲基鋁(TMA)，則蒸氣 壓為：20℃~9托；40℃~25托；60℃~64托；80℃~149托；100℃~313托；128℃~760托。
自此等值可以看出，製程壓力能夠藉由提高反應室中之溫度而實質性增加。然而，若小部分存在於與前驅體接觸且具有略微地較低溫度之裝置中，則立刻存在非所需之前驅體冷凝風險。
TMA前驅體與可滲入材料之相互作用可主要經由吸附及擴散發生。由於吸附及擴散之速率以及吸附反應之平衡可受到溫度變化的影響，因此溫度會對滲入產生明顯的作用。
滲入製程在90℃下可為最佳的，而在120℃及150℃下，滲入不太適合於TMA。對於基於吸附之處理而言，此可預期。在較高溫度下，吸附反應之平衡可向單獨的TMA及聚合物物種轉移。因此在20℃與450℃之間、較佳在50℃與150℃之間、更佳在60℃與110℃之間且最佳在65℃與95℃之間的製程溫度為較佳的。
加熱系統可經建構且配置成將反應室及自反應室至至少其對應反應室閥門之管道的溫度控制在20℃與450℃之間，較佳在50℃與150℃之間，更佳在60℃與110℃之間且最佳在65℃與95℃之間。順序控制器可經建構且配置成達至及/或維持第一或第二前驅體在反應室中之壓力在滲 入期間在0.001與1000托之間，較佳在1與400托之間，更佳在5與100托之間且最佳在10與50托之間以避免冷凝。以此方式，吾等產生避免裝置中出現冷凝的足夠安全容許量，同時就使用前驅體TMA而言具有最佳製程溫度及壓力。
裝置可包含含有液體流動控制器之直接液體噴射器(DLI)及氣化器。液體流動控制器可控制液體流動至蒸發器以蒸發第一或第二前驅體。可不需要加熱在流動控制器與蒸發器之間流動的液體。蒸發器可經加熱以蒸發第一或第二前驅體。加熱系統16可經建構且配置成在第一或第二前驅體在反應室中之壓力下將反應室2至蒸發器之溫度控制至第一或第二前驅體之沸點溫度以避免冷凝。蒸發器可經建構且配置在反應室中以將經蒸發之前驅體直接設置於反應室中。蒸發器亦可經建構且配置在裝置之前驅體分佈及移除系統中。
前驅體分佈及移除系統可包含用於設置前驅體之鼓泡器。鼓泡器可設置具有0.1至200，較佳地1至3秒的第一前驅體之脈衝，與0.01至30，較佳地0.3至1秒的混合氣體之脈衝交替的非連續前驅體流。
參看圖1，在典型的操作期間，第一前驅體28藉由自容器30暴露於呈氣相之第一前驅體28而滲入基板上之可滲入材料中。第一前驅體28可與基板上之可滲入材料反應且變成滲入在基板上之可滲入材料中的經化學吸附或物理吸附之衍生物。隨後第二前驅體29藉由自容器31暴露於呈氣相之第二前驅體29而滲入基板上之可滲入材料中。第二前驅體29可與滲入在基板上之可滲入材料中的第一前驅體28之經化學吸附或物理吸附之衍生物反應以變成最終滲入材料。
用於儲存第一或第二前驅體之容器30、31可儲存金屬之烷基化合物或硼之烷基化合物。金屬可為鋁且烷基化合物可選自由以下組成之群：三甲基鋁(TMA)、三乙基鋁(TEA)及氫化二甲基鋁(DMAH)。
用於儲存第一或第二前驅體之容器30、31可儲存金屬鹵化物化合物，該金屬鹵化物化合物可為氯化鈦(IV)(TiCl)、氯化鉭(V)(TaCl5)及/或氯化鈮(NbCl5)。
為滲入鋯或鉿，容器30、31可經建構且配置成儲存Zr或Hf前驅體。Zr或Hf前驅體可包含金屬有機的前驅體、有機金屬前驅體或鹵化物前驅體。在一些具體例中，前驅體為鹵化物，諸如氯化鋯(IV)(ZrCl4)或HfCl4、氯化鉿(IV)。在一些其他具體例中，前驅體為Hf或Zr之烷基胺化合物，諸如TEMAZ或TEMAH。
用於儲存第一或第二前驅體之容器30、31可儲存選自包含氧、水或過氧化氫之群的氧化劑，或選自包含氨及肼之群的氮化物。氧O2及水可用供應管線來供應。臭氧O3可用氧O2供應管線及臭氧生成器來生成。
裝置可包含：第一容器31，其用於含有容納第一或第二前驅體，諸如較佳選自由以下組成之群的鋁或硼烴類化合物：三甲基鋁(TMA)、三乙基鋁(TEA)及氫化二甲基鋁(DMAH)二甲基乙基胺基鋁烷(DMEAA)、三甲基胺基鋁烷(TEAA)、N-甲基吡咯啶鋁烷(MPA)、三-異丁基鋁(TIBA)、三第三丁基鋁(TTBA)三甲基硼及三乙基硼；及第二容器，其用於容納第一及第二前驅體中之另一者，諸如較佳來自由以下組成之群的金屬鹵化物：氯化鈦(IV)(TiCl)、氯化鉭(V)(TaCl5)及氯化鈮(NbCl5)。後者可 較佳用於滲入金屬碳化材料。
圖2a及2b說明用於圖1之裝置中的根據本發明之至少一個具體例的滲入方法。該方法包括用基板處置器將基板設置於反應室中之第一步驟50，該基板在基板上具有至少一種可滲入材料。
可滲入材料可為多孔的。孔隙度可藉由將可滲入材料中之空隙空間量測為可滲入材料之總體積之分數來量測且可具有在0與1之間的值。若總體積內空隙空間之分數大於0.1，大於0.2，或甚至大於0.3，則可滲入材料可限定為多孔的。
在一具體例中，可滲入材料可為經圖案化層(例如圖案化抗蝕劑層)。抗蝕劑層可退火。退火步驟可具有自抗蝕劑脫去水分或其他污染物、硬化抗蝕劑、選擇性地自基板表面燒掉抗蝕劑之部分或產生所需的孔隙度的目的。
在一具體例中，經圖案化層可藉由具有嵌段共聚物薄膜且促進嵌段共聚物薄膜之定向自組裝以形成經圖案化層來設置。滲入此類經圖案化層可改良此類經圖案化層之品質。嵌段共聚物膜可例如具有較低抗蝕刻性且可藉由將圖案滲入共聚物中來改良圖案之抗蝕刻性。
在一具體例中，經圖案化層可藉由用微影裝置暴露光致抗蝕劑來設置。滲入此類經圖案化層可改良此類經圖案化層之品質。經圖案化光阻層可例如具有較低的抗蝕刻性且藉由滲入圖案化光致抗蝕劑可改良該圖案之抗蝕刻性。
在一具體例中，可滲入材料可為填充結構中之間隙或開口的聚合物，隨後其藉由滲入轉移至金屬氧化物或金屬中。聚合物可為已在基 板上之特定表面(例如間隙之底部)上區域選擇性生長的聚合物。聚合物層可退火。退火步驟可具有自聚合物脫去水分或其他污染物、硬化聚合物、自基板表面選擇性地燒掉聚合物之部分或產生所需的孔隙度的目的。
在圖2a中的步驟50期間，將基板安置於圖1中之反應室2中之後可藉由順序控制器40中之記憶體M知道程式來清潔反應室及基板，使移除泵39將反應室2抽空。可選擇地，沖洗氣體34可設置有沖洗系統以經由沖洗閥門24及分佈反應室閥門19沖洗反應室2及/或反應室2可經加熱以增強排氣。記憶體M中之程式可經程式化以啟動前驅體分佈及移除系統以自反應室2移除氣體且用沖洗系統設置沖洗氣體以使反應室在滲入開始之前被沖洗1至4000秒，較佳地100至2000秒。記憶體M中之程式可經程式化以啟動加熱器系統16以將反應室2加熱至在20℃與450℃之間、較佳地在50℃與150℃之間且最佳地在70℃與100℃之間的溫度以增強污染排氣。
隨後，順序控制器40之記憶體M可設置有一程式，該程式在順序控制器40之處理器上執行時，使滲入裝置執行滲入方法51，在該方法中，可滲入材料可在一或多個滲入循環期間被滲入材料滲入。各滲入循環可包含以下步驟： 步驟52包含將第一前驅體設置於反應室中之基板上之滲入材料持續第一時段T1。順序控制器40之記憶體M可設置有一程式，該程式在順序控制器40之處理器上執行時，使滲入裝置關閉沖洗閥門24及分佈反應室閥門19且藉由打開第一前驅體閥門20及利用使經啟動的第一前驅體溫度控制器32加熱容器32來蒸發來自第一容器30的第一前驅體28 而在分佈反應室閥門19之上游的前驅體分佈及移除系統之管道中積累第一前驅體。隨後順序控制器40之記憶體M中之程式可經程式化以打開閥門19持續更短的時段以將第一前驅體28傳送至反應室2。
此可隨著移除反應室閥門36打開且移除泵啟動持續沖洗時段FP以用第一前驅體沖洗反應室2來進行，但亦可省去此。當反應室2經建構且配置成容納單一基板時，則記憶體中之程式可經程式化以啟動前驅體分佈及移除系統持續在1至60，較佳地在2與30秒之間的沖洗時段FP。當反應室經建構且配置成容納2至25個基板時，記憶體中之程式可經程式化以具有在1至100之間，較佳地在2與50秒之間的沖洗時段。當反應室經建構且配置成容納26至200個基板時，記憶體中之程式經程式化以具有在1至100之間，較佳地在5與50秒之間的沖洗時段FP。
第一前驅體亦可由前驅體分佈及移除系統設置於反應室2同時藉由利用安裝在順序控制器40之記憶體M中的程式來關閉移除反應室閥門36而不使用移除泵39移除任何前驅體持續裝載時段LP。此導致第一前驅體在反應室2中之壓力積聚。當第一或第二前驅體在反應室2中之壓力達至所期望的製程壓力(較佳地在0.001與1000托之間，較佳地在1與400托之間，更佳地在5與100托之間且最佳地在10與50托之間)時，此積聚可藉由順序控制器40來終止。替代地，當反應室中之壓力增加超過預定之期望製程壓力(其亦可結束裝載時段LP)時，可存在打開的壓力釋放閥門。
隨後，第一前驅體可維持靜止滯留在反應室2中，同時使前驅體分佈及移除系統於浸泡時段SP不設置或移除任何前驅體。此可藉由順序控制器40根據儲存在順序控制器40之記憶體M中的程式關閉反應室閥 門19及36來進行。當反應室12經建構且配置成容納單一基板時，記憶體M中之程式可經程式化以啟動第一前驅體流動控制器持續1至3000秒之間，較佳地3與1000秒之間，更佳地5至500秒之間的裝載時段LP；以及10至9000秒之間，較佳地50與5000秒之間且更佳地100與1000秒之間的浸泡時段SP。當反應室12經建構且配置成容納2至25個基板時，順序控制器之記憶體中之程式可以1至3000秒之間，較佳地3與1000秒之間，更佳地5至500秒之間的裝載時段LP；及10至12000秒之間，較佳地15與6000秒之間且更佳地20與1000秒之間的浸泡時段SP來程式化。當反應室12經建構且配置成容納26至200個基板時，記憶體M中之程式可經程式化以具有1至3000秒之間，較佳地3與1000秒之間，更佳地5至500秒的裝載時段LP；及10至14000秒之間，較佳地50與9000秒之間，更佳地100與5000秒之間且最佳地100與800秒之間的浸泡時段SP。
因此第一時段T1可包含沖洗時段FP、裝載時段LP及/或浸泡時段SP。在整個時段T1期間，第一前驅體可滲入且吸收在可滲入材料中。在步驟52中，順序控制器40之記憶體M可由一程式來程式化，該程式在順序控制器之處理器上執行時，其將使滲入裝置設置第一前驅體持續1至20000之間，較佳地在20至6000之間，更佳地在50與4000之間，且最佳地在100與2000秒之間的第一時段T1。以此方式保證第一前驅體在可滲入材料中之深度滲入。
在步驟53中，移除第一前驅體之一部分持續第二時段T2。順序控制器40之記憶體M中之程式可打開移除反應室閥門36以用真空泵38自反應室2移除第一前驅體。附加地或替代地，可用沖洗系統設置沖洗 氣體34以藉由利用順序控制器40打開沖洗閥門24及分佈反應室閥門19來沖洗反應室2。
順序流動控制器40之記憶體M中之程式可由一程式來程式化，該程式在順序控制器40之處理器上執行時使滲入裝置具有比移除第一前驅體之部分的第二時段T2更長的將第一前驅體設置於可滲入材料的時段T1。記憶體M中之程式可以比第二時段T2長2至10000倍之間，較佳地5至2000倍之間，更佳地10至1000倍之間的第一時段T1來程式化。記憶體M中之程式可以在0.1至3000秒之間，較佳地在3至100秒之間，更佳地在6至50秒之間，甚至更佳在8至30秒之間且最佳地在10至25秒之間的第二時段T2來程式化。
在步驟53中，第二時段T2可僅足以自反應室移除第一前驅體，例如0.1至50秒，較佳1至10秒。以此方式可滲入材料存在滲入，且可滲入材料上存在沈積。
替代地，第二時段T2可經選擇僅夠長以自反應室以及自可滲入材料之表面移除第一前驅體。舉例而言，在1至1000秒，較佳8至100秒之T2下，可僅存在第一前驅體在靜置可滲入材料中之滲入且在完成步驟53之後無明顯沈積留存於可滲入材料之表面上。
替代地，在步驟53中，第二時段T2可選擇足夠長(例如2至3000秒，較佳30至100秒)以自反應室、自可滲入材料之表面以及自可滲入材料中之經滲入第一前驅體的部分移除第一前驅體。以此方式可調諧滲入之深度，從而影響線寬減小。
反應室2可經建構且配置成容納單一基板且記憶體M中之 程式可以比第二時段T2長2至6000之間，較佳地4至100之間且最佳地8至50倍之間的第一時段T1來程式化。此類反應室之第一時段T1可在1至20000秒之間，較佳地在20至4000秒之間，更佳地在30與1000秒之間。
反應室2可經建構且配置成容納2至25個基板且記憶體M中之程式可以比第二時段T2長2至8000倍之間，較佳地10至500倍之間且最佳地20至200倍之間的第一時段T1來程式化。此類反應室之第一時段T1可在1至16000秒之間，較佳地在20至7000秒之間，更佳地在30與1500秒之間。
反應室2可經建構且配置成容納26至200個基板且記憶體M中之程式可以比第二時段T2長2至10000倍之間，較佳地10至2000倍之間，更佳地20至1000倍之間的第一時段T1來程式化。此類反應室12之第一時段T1可在1至20000秒之間，較佳地在100至10000秒之間，更佳地在200與6000秒之間且最佳地在300與4000秒之間。
在步驟54中，藉由順序控制器40啟動前驅體分佈及移除系統以將第二前驅體設置且維持在反應室中持續第三時段T3來將第二前驅體設置於反應室2。記憶體M中之程式可以1至20000秒之間，較佳地5與5000之間且最佳地10與2000秒之間的第三時段T3來程式化。
順序控制器40之記憶體可經程式化以關閉沖洗閥門24及分佈反應室閥門19且藉由打開第二前驅體閥門22及利用加熱第二容器31來蒸發來自第二容器31之第二前驅體29而將第二前驅體積聚在分佈反應室閥門19之上游的前驅體分佈及移除系統之管道中。隨後順序控制器40之記憶體M中之程式可經程式化以打開閥門19持續一段時間以將第二前驅體 28傳送至反應室2。
已結合第一前驅體描述沖洗時段FP、裝載時段LP及浸泡時段SP。順序控制器之記憶體可設置有一程式，該程式在順序控制器40之處理器上執行時，其將使滲入裝置同樣運行具有沖洗時段FP、裝載時段LP及或浸泡時段SP之第三時段T3。在整個第三時段T3期間，第二前驅體可滲入可滲入材料且與可滲入材料中之經吸收之第一前驅體衍生物反應，從而導致具有經滲入材料之可滲入材料的強化。
可選擇地，滲入循環可具有步驟55，其中可移除第二前驅體之一部分持續第四時段T4。順序控制器40可打開移除反應室閥門36以用真空泵38自反應室2移除第二前驅體。附加地或替代地，可用沖洗系統設置沖洗氣體34以藉由利用順序控制器40打開沖洗閥門24及分佈反應室閥門19來沖洗反應室2。第四時段T4可在0.1至3000秒之間，較佳地在10至500秒之間，更佳地在30至250秒之間且最佳地在60至200秒之間。
程式M可經程式化以使得當該程式在滲入裝置之順序控制器40之處理器上執行時，滲入順序可在環路56中重複N次，其中N在1至60，較佳地3至20之間，且最佳地在5至12之間。
前驅體28及29可經選擇以使得該等前驅體在可滲入材料中形成金屬或介電質滲入材料。前驅體在滲入期間經蒸發且較佳地為氣態。
第一前驅體及第二前驅體可根據圖2a及2b之程式在圖1之裝置中與以下各者一起用於滲入可滲入材料：氧化鋁(Al2O3)、氧化矽(SiO2)、氮化矽(SiN)、氮氧化矽(SiON)、碳氮化矽(SiCN)、碳化矽(SiC)、碳化鈦(TiC)、氮化鋁(AlN)、氮化鈦(TiN)、氮化鉭(TaN)、鎢(W)、鈷(Co)、氧 化鈦(TiO2)、氧化鉭(Ta2O5)、氧化鋯(ZrO2)或氧化鉿(HfO2)。
可選擇地，滲入材料(諸如金屬或介電質)同樣可用滲入裝置沈積在可滲入材料之整個容積的頂部上。舉例而言，若可滲入材料經圖案化，則可進行此以使得圖案更寬且更抗蝕刻。
圖案化結構可用圖1之連續滲入合成裝置藉由將具有圖案化可滲入材料之基板設置於反應室12之頂部上且在至少一個滲入循環中滲入具有滲入材料之圖案化可滲入材料來產生。圖案化可滲入材料可為圖案化光致抗蝕劑或DSA材料。基板在基板與圖案化可滲入材料之間可具有硬質遮罩。硬質遮罩可為旋塗式玻璃、旋塗碳、氮化矽層、抗反射塗層、非晶碳及/或化學氣相沈積(CVD)層(例如，SIOC或非晶碳層)。
雖然基板保持在連續滲入合成裝置中，但可移除可滲入材料同時允許滲入材料保留在該基板上。可滲入材料可藉由將可滲入材料加熱至在80℃與600℃，較佳地100℃至400℃且最佳地在120℃與300℃之間的溫度來移除。此使得滲入材料之圖案化結構相對於圖案化可滲入材料的線寬或線寬粗糙度減小。
可滲入材料亦可藉由設置電漿以移除反應室中之可滲入材料來移除。含有氧氣或氫之電漿可用於移除可滲入材料之一部分且可利用電漿生成器以激發氧物種以用於有效移除可滲入材料之部分。電漿生成器可供應氧氣(O2)或氫氣(H2)，或替代地氫氣(H2)或氧氣(O2)及氮氣(N2)之氣體混合物。用於移除可滲入材料之一部分之蝕刻劑可因此包含氧氣激發物種及氮氣激發物種中之至少一者。
圖3描繪根據另一具體例之連續滲入裝置。前驅體分佈及移 除系統經由進入端口66設置來自反應室2之一側的第一或第二前驅體。進入端口可用閥門19來關閉。離開端口67經設置至分佈及移除系統以自反應室2移除前驅體。
用於固持基板12之基板固持器10可上下移動。基板固持器10可在反應室2之頂部之邊緣68下方移動以允許基板處置器(未描繪)設置基板或自基板固持器10移除基板。藉由將其向上移動，可再次關閉反應室。基板固持器10可包含用於加熱基板12之第三加熱構件。
根據圖3之具體例之優勢為對於單一基板反應室2，反應室2可具有0.5-1公升之較小容積。較小容積使其有可能具有較低的前驅體使用率。基板與反應室之頂部之間的空間可因此小於1公分，較佳地小於5mm且最佳地小於3mm。
圖4描繪根據另一具體例之連續滲入裝置。反應室2包含噴淋頭69。噴淋頭69可設置在反應室2之頂部中。噴淋頭61可與前驅體分佈及移除系統連接以向基板12之表面設置第一前驅體28或第二前驅體29。前驅體分佈及移除系統可藉由開口67移除第一前驅體28或第二前驅體29。沖洗系統亦可連接至噴淋頭69以沖洗反應室2。
噴淋頭69亦可與前驅體分佈及移除系統連接以自反應室2移除第一或第二前驅體。在此情況下，開口67可連接至沖洗系統以沖洗反應室2。
用於固持基板12之基板固持器10可上下移動。基板固持器10可包含用於加熱基板12之第三加熱構件(未示出)。此具體例之優勢為噴淋頭快速地設置前驅體且自基板之表面移除前驅體同時容積仍可接受的在 2至5公升，較佳地3至4公升之間。
圖5描繪根據另一具體例之連續滲入裝置。裝置包含具有50至200公升之容積的25至250個基板之分批反應室70。基板可裝載於設置有基板固持器之舟皿71中以用基板處置器容納25至250個基板。具有基板之舟皿71可以一種裝載操作，藉由通過在反應室之下部末端處的開口將舟皿升高至反應室中而移動至反應室70中。舟皿70之底部部分71A可密封反應室70。加熱構件40可經設置以控制反應室70之溫度。第一及第二前驅體可利用入口72設置且可經由前驅體分佈及移除系統之出口73移除。閥門可用於控制氣流且應注意確保將經蒸發之前驅體保持在超過其在反應室70中之沸點溫度的溫度下。此可藉由使加熱構件控制入口72及出口73以及直至閥門(例如，反應室閥門36)之溫度來進行。
在裝置設置有包含液體流動控制器及蒸發器的直接液體噴射系統(DLI)之情況下，液體流動控制器可控制液體流動至蒸發第一或第二前驅體之蒸發器。可不需要加熱在流動控制器與蒸發器之間流動的液體。蒸發器可經加熱以直接蒸發第一或第二前驅體。
蒸發器可設置在分批反應室中以將第一或第二前驅體直接設置於該室中。分批反應器使得滲入大量基板的同時提高裝置之產出量係有可能的。
高解析度聚合物抗蝕劑在暴露之後可具有較低的抗蝕刻性且可遭受較高的線邊緣粗糙度。此較低抗蝕刻性及較高的線邊緣粗糙度可使至底層之轉移更困難。因此可有利的係滲入圖案化抗蝕劑以改變抗蝕劑之特性。為執行滲入，可有利的係具有可最佳化滲入抗蝕劑中之金屬量的 滲入裝置。
因此，提供一種連續滲入合成裝置，其包含：反應室2(參見圖1)，其經建構且配置成固持設置有可滲入材料(例如，圖案化抗蝕劑)之至少第一基板12；第一蒸發器，其經建構且配置成蒸發包含烴類之化合物；第二蒸發器，其經建構且配置成蒸發包含金屬鹵化物之化合物；前驅體分佈及移除系統3、5，其經建構且配置成為反應室設置來自第一或第二蒸發器中之一者中的經蒸發之第一前驅體及來自第一及第二蒸發器中之另一者的第二前驅體以及自反應室移除第一及第二前驅體；以及順序控制器40，其以可操作方式連接至前驅體分佈及移除系統且包含設置有一程式之記憶體M，該程式在順序控制器上運行時藉由以下執行對可滲入材料之滲入：啟動前驅體分佈及移除系統以將第一前驅體設置於反應室中之基板上之可滲入材料持續第一時段T1；啟動前驅體分佈及移除系統以自反應室移除第一前驅體之一部分持續第二時段T2；以及啟動前驅體分佈及移除系統以將第二前驅體設置於反應室中之基板上之可滲入材料持續第三時段T3。第一蒸發器可經建構且配置成蒸發金屬烴類化合物。第二蒸發器可經建構且配置成蒸發金屬鹵化物化合物。
第一及第二蒸發器可為前驅體分佈及移除系統3、5之一部分，其可經由分佈反應室閥門19將第一前驅體28及/或第二前驅體29設置於反應室。可藉由利用第一前驅體加熱器32蒸發容器30中所含有之液體 或固體以設置足夠的蒸氣壓以傳送至室2中而將第一前驅體28作為氣體引入至室2中。第一前驅體加熱器32可向容器30中之第一前驅體設置熱量。同樣地，可藉由利用第二前驅體加熱器33蒸發容器31中所含有之液體或固體以設置足夠的蒸氣壓以傳送至反應室2中而將第二前驅體29作為氣體引入至室2中。
在隨後將第一及第二前驅體傳送至反應室2之後，可滲入材料、金屬烴類及金屬鹵化物之間的反應可確保可滲入金屬中之金屬量可為最佳化的。所滲入之金屬量可設置所需的抗蝕刻性。
在設置第一及第二前驅體之間自反應室移除第一前驅體之一部分持續第二時段T2可藉由例如用惰性氣體(氮氣)沖洗第一前驅體及/或用前驅體分佈及移除系統3、5自反應室泵抽第一前驅體來完成。此可為必需的，因為否則第一及第二前驅體可在反應室內部的表面上反應且形成粒子及/或污染物。
第一蒸發器可經建構且配置成將鋁烴類化合物蒸發為金屬烴類化合物。鋁烴類化合物可選自由以下組成之群：三甲基鋁(TMA)、三乙基鋁(TEA)、三-異丁基鋁(TIBA)、三第三丁基鋁(TTBA)二甲基乙基胺基鋁烷(DMEAA)、氫化二甲基鋁(DMAH)、三甲基胺基鋁烷(TEAA)及N-甲基吡咯啶鋁烷(MPA)。金屬烴類化合物可包含氮原子。
第二蒸發器可經建構且配置成蒸發包含鈦、鉿、鈮及/或鋯之金屬鹵化物化合物。鹵化物可為氯化物。金屬鹵化物可選自由以下組成之群：氯化鈦(IV)(TiCl4)、氯化鉭(V)(TaCl5)、氯化鋯(IV)(ZrCl4)、氯化鉿(IV)(HfCl4)及氯化鈮(NbCl5)。
三甲基鋁(TMA)及氯化鈦(IV)(TiCl4)之滲入可設置於可滲入材料中令人滿意的金屬濃度，特定言之此係由於將氯化鈦(IV)(TiCl4)完全滲入可滲入材料中可為困難的。
連續滲入合成裝置之記憶體中之程式可經程式化以啟動前驅體分佈及移除系統以在第三時段T3之後自反應室移除第二前驅體之至少一部分持續第四時段T4。在設置第二前驅體之後自反應室移除第二前驅體之一部分持續第四時段T4可藉由例如用惰性氣體(氮氣)沖洗第二前驅體及/或用前驅體分佈及移除系統自反應室泵抽第二前驅體來完成。此可為必需的，因為否則第一及第二前驅體可在後續製程步驟中在反應室內部的表面上反應且形成粒子及/或污染物。若第二前驅體在不保留剩餘在反應室中之任何前驅體的情況下完全反應及/或當剩餘第一前驅體可允許在反應室之環境中時，可省去移除。
在順序控制器上運行時執行對可滲入材料之滲入的程式可經程式化以重複滲入循環之至少一部分N次。N可在1至60，較佳地1至10之間且最佳地在1至5之間(例如1、2、3或4)。舉例而言，設置第一前驅體持續第一時段T1、第一次移除持續第二時段T2，第二前驅體持續第三時段T3及第二次移除持續第四時段T4的整個循環可重複N次。替代地，可重複滲入循環之一部分，例如設置第一前驅體持續第一時段T1、第一次移除持續第二時段T2，隨後N次設置第二前驅體持續第三時段T3及第二次移除持續第四時段T4。在此情況下，第一前驅體僅經滲入一次而第二前驅體經設置多次。但其亦可為相反，其中第一前驅體經滲入多次而第二前驅體僅經滲入一次。
連續滲入合成裝置可設置有用於設置額外前驅體之額外前驅體供應器且前驅體分佈及移除系統可經建構且配置成為反應室設置來自額外前驅體供應器之額外前驅體以及自反應室移除該額外前驅體。以與可藉由利用第一前驅體加熱器32蒸發容器30中所包含之液體或固體以設置足夠傳送至室2中的蒸氣壓而將第一前驅體28作為氣體引入至室2中相同的方式，額外前驅體供應器可經由圖1中之分佈反應室閥門19向反應室設置額外前驅體。額外前驅體供應器可因此設置有額外容器及額外前驅體加熱器以設置足夠的蒸氣壓以用於額外前驅體傳送至室2中。替代地，額外前驅體可設置為氣體以使得不需要加熱及蒸發。
圖6說明根據至少一個具體例之滲入程式，該滲入程式可由具有額外前驅體供應器系統的圖1之連續滲入裝置執行。在圖6中，物件50至56與圖2a中具有相同編號之物件相同。圖1中之記憶體M可設置有一程式，該程式在順序控制器上運行時藉由在步驟55的第四時段T4之後，在步驟57處，啟動前驅體分佈及移除系統以將額外前驅體設置於反應室中之基板上之可滲入材料持續第五時段T5而執行對可滲入材料之滲入。額外前驅體供應器可包含用於儲存選自包含以下之群的氧化劑之額外容器：氧氣、水、臭氧或過氧化氫。氧氣(O2)及水可用供應管線來供應。臭氧(O3)可用額外前驅體供應器中之氧氣供應管線及臭氧生成器來生成。
在步驟58處，記憶體可啟動前驅體分佈及移除系統以自反應室移除額外前驅體之至少一部分持續第六時段T6。若第二前驅體在不保留剩餘在反應室中之任何前驅體的情況下完全反應及/或當剩餘第一前驅體可允許在反應室之環境中時，可省去移除。若例如水、氮氣或氧氣用作額 外前驅體，則可為後者情況。
在順序控制器上運行時執行對可滲入材料之滲入的程式可經程式化以經由56亦相對於額外前驅體重複滲入循環之至少一部分N次。N可在1至60，較佳地1至10之間且最佳地在1至5之間(例如1、2、3或4)。舉例而言，設置第一前驅體持續第一時段T1、第一次移除持續第二時段T2，設置第二前驅體持續第三時段T3、第二次移除持續第四時段T4、設置額外前驅體持續第五時段T5及第三次移除持續第六時段T6的整個循環可重複N次。
替代地，可重複滲入循環之一部分，例如設置第一前驅體持續第一時段T1、及第一次移除持續第二時段T2、隨後N次設置第二前驅體持續第三時段T3、第二次移除持續第四時段T4、設置額外前驅體持續第五時段T5及第三次移除持續第六時段T6。在此情況下，第一前驅體僅經滲入一次而第二前驅體及額外前驅體經由可選擇的捷徑59設置多次。舉例而言，TMA可經滲入一次而TiCl4及水經滲入多次。其亦可為相反，其中第一前驅體經滲入多次而第二前驅體及額外前驅體僅經滲入一次。此外同樣第一前驅體及第二前驅體可經由可選的捷徑60滲入多次而額外前驅體僅經滲入一次。
連續滲入合成裝置之記憶體中之程式可以在0.1至20000秒之間的第一時段T1、在0.1至3000秒之間的第二時段T2，及/或在0.1至20000秒之間的第三時段T3來程式化。連續滲入合成裝置之記憶體中之程式可以在0.1至3000秒之間的第四時段T4來程式化。第五時段T5可在0.1至20000秒之間經程式化。第六時段T6可在0.1至3000秒之間經程式化。
連續滲入合成裝置可包含經建構且配置成將反應室之溫度控制至在0與450℃之間的製程溫度的溫度控制系統。裝置中之壓力控制系統可經建構且配置成將反應室中之壓力控制至在0.001與1000托之間的製程壓力。
第一及第二蒸發器中之一者或兩者可包含用於加熱第一或第二前驅體之加熱器。第一及第二蒸發器中之一者或兩者可包含用於自液體蒸發第一或第二前驅體之蒸發器。第一及第二蒸發器中之一者或兩者可包含用於自固體昇華第一或第二前驅體之昇華器。緩衝容積可設置在反應室於該等蒸發器中之至少一者之間以緩衝蒸發前驅體。
實施例TMA及TiCl 4
在壓力約8托下，在三甲基鋁(TMA)之單一晶圓反應室中之滲入可藉由滲入第一前驅體持續範圍在1至2000秒之間，較佳地在2至600秒之間，更佳地在4與400秒之間，且最佳地在6與200秒之間的第一時段T1來完成。在壓力約8托下，例如記憶體中之程式可經程式化以藉由以下來執行50秒的第一時段T1：啟動前驅體分佈及移除系統以打開第一前驅體流動路徑且關閉氣體移除流動路徑以及將第一前驅體設置於反應室持續30秒的裝載時段LP；以及啟動前驅體分佈及移除系統以關閉第一前驅體流動路徑且將第一前驅體維持在反應室中同時使移除流動路徑保持關閉持續20秒的浸泡時段SP。必須理解此等時段視第一前驅體之(部分)壓力而定且藉由增加壓力可縮短該等時段，以及其視反應室之大小而定且減少反應室之大小可縮短該等時段。
第二時段T2可經選擇在0.01至10000秒之間，較佳地在1至6000秒之間，更佳地在5與4000秒之間，且最佳地在20與2000秒之間。移除及/或沖洗可有必要自反應器之壁移除第一前驅體以便能夠使得反應室無粒子。在一最佳化反應器中，可藉由其他方式預防第一前驅體黏附至壁以使得更短的移除/沖洗時段為可能的。因此在此實施例中，吾等使用4分鐘沖洗，但用最佳化系統20至30秒亦為可能的。
在壓力約8托下在氯化鈦(IV)(TiCl4)之單一晶圓反應室中的滲入可藉由滲入第二前驅體持續範圍自1至2000，較佳地在2至600之間，更佳地在4與400之間，且最佳地在6與200秒之間的第三時段T3來完成。在壓力約8托下，例如記憶體中之程式可經程式化以藉由以下來執行50秒的第三時段T3：啟動前驅體分佈及移除系統以打開第二前驅體流動路徑且關閉氣體移除流動路徑且將第二前驅體設置於反應室持續30秒的裝載時段LP；以及啟動前驅體分佈及移除系統以關閉第二前驅體流動路徑且將第二前驅體維持在反應室中同時使得移除流動路徑保持關閉持續20秒的浸泡時段SP。必須理解此等時段視第二前驅體之(部分)壓力而定且藉由增加壓力可縮短該等時段，以及其視反應室之大小而定且減少反應室之大小可縮短該等時段。
圖7a至7d展示在用不同滲入配方所滲入之光阻劑層上的次級離子質譜分析(SIMS)量測。SIMS為用於藉由用聚焦初級離子束濺射樣品之表面，及收集且分析經射出次級離子來分析固體表面及薄膜之組成的技術。
圖7a描繪在用100秒TMA及100秒TiCl4且無H2O且N 為5個循環所滲入之光阻劑層上的SIMS量測。在滲入期間重量增加的量測值為△m=2.9毫克/約706cm2晶圓表面。圖7a描繪已滲入大量鋁及鈦。
圖7b描繪在用100秒TMA及100秒TiCl4且無H2O且N為1個循環所滲入之光阻劑層上的SIMS量測。在滲入期間重量增加量測值為△m=1.6毫克/約706cm2晶圓表面。圖7b描繪已滲入大量鋁及一些鈦。
圖7c描繪在用100秒TiCl4及100秒TMA且無H2O且N為1個循環所滲入之光阻劑層上的SIMS量測。在滲入期間經量測的重量增加為△m=0.92毫克/約706cm2晶圓表面。圖7c描繪已滲入大量鋁及一些鈦。
圖7d描繪在用50秒TMA及20秒H2O且N為1個循環所滲入之參考光阻劑層上的SIMS量測。在滲入期間經量測之重量增加為△m=0.6毫克/約706cm2晶圓表面。
如圖7a至7d中所示，在以上使用TMA之製程下，將大量TiCl4滲入至基板上之可滲入材料(諸如光阻劑)中可為有可能的。藉由首先滲入TMA及其次TiCl4，可完成較高的質量攝入。藉由首先滲入TiCl4且其次TMA可完成約30%的較低質量攝入。首先滲入TMA且其次H2O的質量攝入可具有比首先TMA且其次TiCl4低約50%的質量增加。
金屬可均一地滲入可滲入層之整個深度且當使用TMA及TiCl4時可能在經滲入材料上未明顯形成外皮。若包含聚合物之經圖案化層滲入，則此可為有利的。之後可用氧電漿輕輕地蝕刻經圖案化層。軟蝕刻可導致經圖案化層之一定收縮。在軟蝕刻步驟中，經圖案化層之聚合物可經部分移除，從而將金屬保留在該層中。輕輕地蝕刻經圖案化層可導致線在經圖案化層中之一定收縮且亦可改良該等線之線邊緣粗糙度(LER)。軟邊 緣之一個或兩個功效可為想要的。
圖8a描繪與圖7a類似的用100秒TMA及100秒TiCl4且無H2O且N為5個循環所滲入之圖案的橫剖面。圖8a之頂部部分T展示在軟蝕刻之前的圖案且底部B部分展示在軟蝕刻之後的圖案。展示的係圖案化收縮了一點，其可能為想要的。
連續滲入合成裝置可設置有用於設置額外前驅體(例如水)之額外前驅體供應器，且前驅體分佈及移除系統可經建構且配置成為反應室設置水。水可導致在可滲入材料上形成外皮。若包含聚合物之經圖案化層滲入，則此可為有利的。之後可輕輕地蝕刻經圖案化層。軟蝕刻步驟可導致經圖案化層之一定收縮。外皮可防止經圖案化層收縮且與其對應的若不需要收縮，則用額外前驅體(例如，水)形成之外皮可為有益的且亦可藉由該外皮改良線之線邊緣粗糙度(LER)。
圖8b描繪用100秒TMA及100秒TiCl4及20秒H2O且N為5個循環所滲入之圖案的橫剖面。圖8b之頂部部分T展示軟蝕刻之前的圖案且底部B部分展示軟蝕刻之後的圖案。展示的係當包括額外水前驅體時圖案確實不收縮，其可為想要的。
額外前驅體可自反應室移除持續第六時段T6。若額外前驅體在不保留剩餘在反應室中之任何前驅體的情況下完全反應及/或當剩餘額外前驅體可允許在反應室之環境中時，可省去移除。若使用例如水，則可為後者情況。
所展示且描述之特定實施方案係對本發明及其最佳模式之說明且並不意欲以任何方式另外限制態樣及實施之範圍。實際上，出於簡 潔起見，系統之習知製造、連接、製備及其他功能性態樣可不加以詳細描述。此外，各種圖中展示之連接線意欲表示各種構件之間的例示性功能性關係及/或物理耦合。許多替代或附加功能關係或實體連接可存在於實際系統中，及/或在一些具體例中可不存在。
應理解，本文中所述之組態及/或方法本質上為例示性的，且此等特定具體例或實施例不視為具有限制意義，原因在於可能存在諸多變化。本文所述之特定程序或方法可表示任何數目的處理策略中之一或多者。因此，所說明之各種動作可以所說明之順序、以其他順序進行，或在一些情況下被省去。
本發明之主題包括各種製程、系統及組態，及本文中所揭示之其他特徵、動作、作用及/或特性，以及其任何及所有等效者的所有新穎的且非顯而易見的組合及子組合。

Claims (36)

  1. 一種連續滲入合成裝置，其包含：一反應室，其經建構且配置成固持至少一第一基板；一前驅體分佈及移除系統，其向該反應室設置一經蒸發之第一或第二前驅體且自該反應室移除一經蒸發之第一或第二前驅體；以及一順序控制器，其以可操作方式連接至該前驅體分佈及移除系統且包含設置有一程式之一記憶體，該程式在該順序控制器上運行時藉由以下來執行對設置於該基板上之一可滲入材料之滲入：啟動該前驅體分佈及移除系統以將該第一前驅體設置且維持在該反應室中持續一第一時段T1；啟動該前驅體分佈及移除系統以自該反應室移除該第一前驅體之一部分持續一第二時段T2；以及啟動該前驅體分佈及移除系統以將該第二前驅體設置且維持在該反應室中持續一第三時段T3，其中該記憶體中之該程式以長於該第二時段T2之該第一時段T1來程式化。
  2. 如請求項1之裝置，其中，該記憶體中之該程式以比該第二時段T2長2至10000倍之間的該第一時段T1來程式化。
  3. 如請求項1之裝置，其中，該記憶體中之該程式以1至20000秒之間的該第一時段T1來程式化。
  4. 如請求項1之裝置，其中，該記憶體中之該程式以0.1至3000秒之間的該第二時段T2來程式化。
  5. 如請求項1之裝置，其中，該裝置包含經建構且配置成將該反應室 之溫度控制至在20℃與450℃之間的一製程溫度的一加熱系統及經建構且配置成將該反應室中之一壓力控制至在0.001與1000托之間的一製程壓力的一壓力控制系統。
  6. 如請求項1之裝置，其中，該反應室經建構且配置成容納一單一基板且該記憶體中之該程式以比該第二時段T2長2至6000之間的該第一時段T1來程式化。
  7. 如請求項1之裝置，其中，該反應室經建構且配置成容納2至25個基板且該記憶體中之該程式以比該第二時段T2長2至8000之間的該第一時段T1來程式化。
  8. 如請求項1之裝置，其中，該反應室經建構且配置成容納26至200個基板且該記憶體中之該程式以比該第二時段T2長2至10000之間的該第一時段T1來程式化。
  9. 如請求項1之裝置，其中，該記憶體中之該程式以在1至20000秒之間的該第一時段T3來程式化。
  10. 如請求項1之裝置，其中，該記憶體中之該程式經程式化以：啟動該前驅體分佈及移除系統以在滲入循環之末端處的第三時段T3之後自該反應室移除該第二前驅體之一部分持續第四時段T4；且，重複該滲入循環N次，其中N在1至60之間。
  11. 如請求項10之裝置，其中，該記憶體中之該程式經程式化以啟動該前驅體分佈及移除系統持續在0.1至3000秒之間的第四時段T4。
  12. 如請求項1之裝置，其中，該等第一及第二前驅體中的一者或兩者為一液體前驅體且該裝置包含： 直接液體噴射器(DLI)蒸發器系統，其以可操作方式連接至該順序控制器以給予且蒸發該第一或第二前驅體。
  13. 如請求項1之裝置，其中，該裝置包含用於儲存一第一或第二前驅體之一容器且該容器經建構且配置成含有選自由以下組成之群的一烷基鋁化合物：三甲基鋁(TMA)、三乙基鋁(TEA)，及氫化二甲基鋁(DMAH)。
  14. 如請求項1之裝置，其中，該裝置包含用於儲存一第一或第二前驅體之一容器且該容器經建構且配置成含有一金屬鹵化物化合物，諸如氯化鈦(IV)(TiCl 4)、氯化鉭(V)(TaCl 5)、氯化鋯(IV)(ZrCl 4)、氯化鉿(IV)(HfCl 4)及/或氯化鈮(NbCl 5)。
  15. 如請求項1之裝置，其中，該裝置包含用於儲存一第一或第二前驅體之一容器且該容器經建構且配置成含有選自包含以下之群的一氧化劑：水、臭氧、過氧化氫，或選自包含以下之群的氮化物：氨及肼。
    14.如請求項1之裝置，其中，該裝置包含：第一容器，其含有該第一或第二前驅體，諸如較佳地選自由以下組成之群的一鋁或硼烴類化合物：三甲基鋁(TMA)、三乙基鋁(TEA)及氫化二甲基鋁(DMAH)、二甲基乙基胺基鋁烷(DMEAA)、三甲基胺基鋁烷(TEAA)、N-甲基吡咯啶鋁烷(MPA)、三-異丁基鋁(TIBA)、三第三丁基鋁(TTBA)、三甲基硼及三乙基硼；及第二容器，其含有該等第一及第二前驅體中之另一者，諸如較佳來自由以下組成之群的一金屬鹵化物：氯化鈦(IV)(TiCl 4)、氯化鉭(V)(TaCl 5)、氯化鋯(IV)(ZrCl 4)、氯化鉿(IV)(HfCl 4)及氯化鈮(NbCl 5)。
    15.一種連續滲入合成裝置，其包含：一反應室，其經建構且配置成固持至少一第一基板； 一前驅體分佈及移除系統，其向該反應室設置一經蒸發之第一或第二前驅體且自該反應室移除一經蒸發之第一或第二前驅體；以及一順序控制器，其以可操作方式連接至該前驅體分佈及移除系統且包含設置有一程式之一記憶體，該程式在該順序控制器上運行時藉由以下來執行對設置於該基板上之一可滲入材料之滲入：啟動該前驅體分佈及移除系統以將該第一前驅體設置且維持在該反應室中持續一第一時段T1；啟動該前驅體分佈及移除系統以自該反應室移除該第一前驅體之一部分持續一第二時段T2；以及啟動該前驅體分佈及移除系統以將該第二前驅體設置且維持在該反應室中持續一第三時段T3，其中該記憶體中之該程式經程式化以在該第一時段T1或第三時段T3期間執行：啟動該前驅體分佈及移除系統以打開一第一前驅體流動路徑且關閉一氣體移除流動路徑且將該第一前驅體設置於該反應室持續一裝載時段LP；以及啟動該前驅體分佈及移除系統以關閉該第一前驅體流動路徑且將該第一前驅體維持在該反應室中同時使該移除流動路徑保持關閉持續一浸泡時段SP。
  16. 如請求項15之裝置，其中，該記憶體中之該程式經程式化以：啟動該前驅體分佈及移除系統以打開一氣體移除流動路徑且將該第一前驅體設置於該反應室同時在該裝載時段LP之前沖洗遍及該反應器之該第一前驅體持續一沖洗時段FP。
  17. 如請求項15之裝置，其中，該裝置設置有一壓力感測器，其經建構且配置成量測該反應室中之壓力且以可操作方式連接至該順序流動控制器且該記憶體中之該程式經程式化以：在該反應室中之該壓力達到所需之製程壓力時終止該裝載時段LP。
  18. 一種以請求項1之連續滲入合成裝置形成一圖案化結構之方法，其中，該方法包含：將具有一圖案化可滲入材料之一基板設置於該反應室中；以及在至少一個滲入循環中用滲入材料滲入該圖案化可滲入材料。
  19. 一種連續滲入合成裝置，其包含：一反應室，其經建構且配置成固持具有一可滲入材料之至少一第一基板；一第一蒸發器，其經建構且配置成蒸發一包含烴類之化合物；一第二蒸發器，其經建構且配置成蒸發包含一金屬鹵化物之化合物；一前驅體分佈及移除系統，其經建構且配置成為該反應室設置來自該第一或第二蒸發器中之一者的該蒸發之第一前驅體，及來自該第一及第二蒸發器中之另一者的一第二前驅體，且自該反應室移除該第一及第二前驅體；以及一順序控制器，其以可操作方式連接至該前驅體分佈及移除系統且包含設置有一程式之一記憶體，該程式在該順序控制器上運行時藉由以下來執行對該可滲入材料之滲入：啟動該前驅體分佈及移除系統以將該第一前驅體設置於該反應室 中之該基板上之該可滲入材料持續一第一時段T1；啟動該前驅體分佈及移除系統以自該反應室移除該第一前驅體之一部分持續一第二時段T2；以及啟動該前驅體分佈及移除系統以將該第二前驅體設置於該反應室中之該基板上之可滲入材料持續一第三時段T3。
  20. 如請求項19之裝置，其中，該第一蒸發器經建構且配置成蒸發一金屬烴類化合物。
  21. 如請求項20之裝置，其中，該第一蒸發器經建構且配置成蒸發一鋁烴類化合物。
  22. 如請求項21之裝置，其中，該第一蒸發器經建構且配置成蒸發選自由以下組成之群的一鋁烴類化合物：三甲基鋁(TMA)、三乙基鋁(TEA)、及氫化二甲基鋁(DMAH)、二甲基乙基胺基鋁烷(DMEAA)、三甲基胺基鋁烷(TEAA)、N-甲基吡咯啶鋁烷(MPA)、三-異丁基鋁(TIBA)、三第三丁基鋁(TTBA)。
  23. 如請求項19之裝置，其中，該第二蒸發器經建構且配置成蒸發一金屬鹵化物化合物。
  24. 如請求項19之裝置，其中，該第二蒸發器經建構且配置成蒸發選自由以下組成之群的一金屬鹵化物化合物：氯化鈦(IV)(TiCl 4)、氯化鉭(V)(TaCl 5)、氯化鋯(IV)(ZrCl 4)、氯化鉿(IV)(HfCl 4)及氯化鈮(NbCl 5)。
  25. 如請求項19之裝置，其中，該記憶體中之該程式經程式化以：啟動該前驅體分佈及移除系統以在該第三時段T3之後自該反應室移除該第二前驅體之一部分持續一第四時段T4。
  26. 如請求項25之裝置，其中，該裝置設置有用於設置一額外前驅體之一額外前驅體供應器且該前驅體分佈及移除系統經建構且配置成為該反應室設置來自該額外前驅體供應器之該額外前驅體且自該反應室移除該額外前驅體；且該記憶體設置有一程式，該程式在該順序控制器上運行時藉由以下來執行對該可滲入材料之滲入：啟動該前驅體分佈及移除系統以在該第四時段T4之後將該額外前驅體設置於該反應室中之該基板上之該可滲入材料持續一第五時段T5。
  27. 如請求項26之裝置，其中，該記憶體設置有一程式以啟動該前驅體分佈及移除系統以自該反應室移除該額外前驅體之一部分持續一第六時段T6。
  28. 如請求項26之裝置，其中，該額外前驅體供應器包含用於儲存一氧化劑之一容器，該氧化劑選自包含以下之群：氧、水、臭氧或過氧化氫。
  29. 如請求項19之裝置，其中，該記憶體中之該程式以在0.1至20000秒之間的該第一時段T1、在0.1至3000秒之間的該第二時段T2及在0.1至20000秒之間的該第三時段T3來程式化。
  30. 如請求項25之裝置，其中，該記憶體中之該程式經程式化以啟動該前驅體分佈及移除系統持續在0.1至3000秒之間的第四時段T4。
  31. 如請求項19之裝置，其中，在該順序控制器上運行時執行對可滲入材料之滲入的該程式經程式化以重複該滲入循環之至少一部分N次，其中N在1至60之間。
  32. 如請求項19之裝置，其中，該裝置包含經建構且配置成將該反應室之溫度控制至在0與450℃之間的一製程溫度的一溫度控制系統及經建構 且配置成將該反應室中之壓力控制至在0.001與1000托之間的一製程壓力的一壓力控制系統。
  33. 如請求項19之裝置，其中，該第一及第二蒸發器中之一者或兩者包含用於加熱該第一或第二前驅體之一加熱器。
  34. 如請求項19之裝置，其中，該等第一及第二蒸發器中之一者或兩者包含用於自一液體蒸發該第一或第二前驅體之一蒸發器。
  35. 如請求項19之裝置，其中，該等第一及第二蒸發器中之一者或兩者包含用於自一固體昇華該第一或第二前驅體之一昇華器。
  36. 如請求項19之裝置，其中，將一緩衝液容量設置於該反應室與該等蒸發器中之至少一者之間以緩衝經蒸發之前驅體。
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