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TWI749031B - 填充間隙的方法及儀器 - Google Patents

填充間隙的方法及儀器 Download PDF

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TWI749031B
TWI749031B TW106124129A TW106124129A TWI749031B TW I749031 B TWI749031 B TW I749031B TW 106124129 A TW106124129 A TW 106124129A TW 106124129 A TW106124129 A TW 106124129A TW I749031 B TWI749031 B TW I749031B
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維爾加米 波爾
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Abstract

本發明提供一種用於藉由以下填充在基板上製造構件期間所產生之一或多個間隙的方法及儀器：向該一或多個間隙之表面之底部區域提供第一反應物；將第二反應物提供至該基板；及，允許該第一反應物以一個分子之該第一反應物比多個分子之該等第二反應物的化學計量比引發在該表面之該底部區域中之該第二反應物之反應，保持未提供該第一反應物之該一或多個間隙之該表面之頂部區域最初實質上為空的。

Description

填充間隙的方法及儀器
本發明大體而言係關於用於製造電子器件之方法及儀器。
更特定言之，本發明係關於一種用於利用沉積方法填充在用於製造電子器件之基板上製造構件期間所產生之一或多個間隙的方法及儀器，該方法包含：向一或多個間隙之表面提供第一反應物；將第二反應物提供至基板；及，允許第一反應物引發第二反應物之反應。
在基板上製造積體電路期間，可在該基板上產生間隙(例如，溝槽)。根據特定應用，可採取多種形式再填充溝槽。
基礎溝槽填充方法可具有缺陷，包括在再填充期間在溝槽中形成空隙。在溝槽經完全填充之前，當再填充材料在溝槽頂部附近形成縮窄時，可形成空隙。此類空隙可損害積體電路(integrated circuit；IC)上之器件之器件隔離及IC之整體結構完整性。不幸地，在溝槽填充期間防止空隙形成可通常對該等溝槽發起尺寸限制，此可限制器件之器件裝填密度。
若溝槽經填充用於器件隔離，則在量測器件隔離之有效度中之關鍵參數可為場臨限電壓，亦即，產生連接相鄰隔離器件之寄生電流所 必需的電壓。場臨限電壓可受多個物理特性及材料特性影響，諸如溝槽寬度、溝槽填充材料之介電常數、基板摻雜、場植入劑量及基板偏壓。
可藉由減小溝槽深度及/或使溝槽側壁逐漸變窄來降低空隙形成以使得開口可在頂部比在底部更寬。減小溝槽深度之權衡可能為降低器件隔離之有效度，而具有逐漸變窄側壁之溝槽之較大頂部開口耗用額外的積體電路實際面積。
舉例而言，目的為提供一種改良之或至少替代性間隙填充方法。
因此，提供一種用於利用沉積方法填充在基板上製造構件期間所產生之一或多個間隙的方法，該方法包含：向一或多個間隙之表面之底部區域提供第一反應物；將第二反應物提供至表面；及，允許第一反應物以一個分子之第一反應物比多個分子之第二反應物的化學計量比引發表面之底部區域中之第二反應物之反應，保持未提供第一反應物之一或多個間隙之表面之頂部區域最初實質上為空的。
藉由使第一反應物以一個分子之第一反應物比多個分子之第二反應物的化學計量比引發表面之底部區域中之第二反應物的反應，保持未提供第一反應物之一或多個間隙之表面之頂部區域最初實質上為空的，可在間隙開口未變得縮窄之情況下非常快速地自底部向上填充間隙。
根據一另一具體實例，提供一種半導體處理儀器以提供一種改良之或至少替代性間隙填充方法。該儀器包含： 一或多個反應室，其用於容納基板，該基板具有在基板上製造構件期間所產生的間隙；第一反應物之一第一源，其經由第一閥與該等反應室中之一者氣體連通；及，第二反應物之一第二源，其經由第二閥與該等反應室中之一者氣體連通；其中該儀器包含：電漿氣體之一電漿氣體源，其經由電漿氣體閥與該等反應室中之一者氣體連通；一射頻電源，其經建構且經佈置以產生電漿氣體之電漿；一加熱器，其經建構且經佈置以加熱該等反應室中之一者中的基板，及一控制器，其可操作地連接至第一氣體閥、第二氣體閥及電漿氣體閥、射頻電源及加熱器且經組態並程式化以控制：該第一源、該電漿氣體源及該射頻源之時序及量以使用該第一源、該電漿氣體源及該射頻電源將第一反應物實質上提供於間隙之表面之底部區域中；及該第二反應物及該加熱器之時序及量以在降低的溫度下以一個分子之該第一反應物比多個分子之該等第二反應物的化學計量比沉積，從而在間隙中引起反應，保持未提供該第一反應物之一或多個間隙之表面之頂部區域最初實質上為空的。
出於概述本發明及所達成的優於先前技術之優點的目的，已在上文中對本發明之某些目標及優點加以描述。當然，應理解，未必所有 的此類目的或優點均可根據本發明之任何特定具體實例來達成。
因此，舉例而言，熟習此項技術者將認識到，可以如本文中所教示或建議來達成或最佳化一個優點或一組優點而不一定達成如本文中可能教示或建議的其他目標或優點的方式來實施或進行本發明。
所有此等具體實例意欲在本文所揭示之本發明範圍內。此等及其他具體實例將自參考附圖之以下某些具體實例之詳細描述而對熟習此項技術者變得顯而易見，本發明並不受限於所揭示之任何特定具體實例。
1:基板
2:導電性平板電極
3:反應室
4:導電性平板電極
5:轉移室
6:排氣管線
7:排氣管線
11:反應區
12:接地
13:循環導管
14:隔離板
16:轉移區
20:HRF功率
21:氣體管線
22:氣體管線
24:氣體管線
100:沉積方法
110:步驟
120:步驟
130:步驟
101:步驟
102:步驟
103:步驟
104:步驟
105:步驟
106:步驟
107:步驟
參考某些具體實例之圖式在下文中描述本文中所揭示的本發明之此等及其他特徵、態樣及優點，該等圖式意欲說明而非限制本發明。
圖1A為可用於本發明之一具體實例中的用於填充間隙之電漿增強型原子層沉積(plasma-enhanced atomic layer deposition；PEALD)儀器之示意性表示。
圖1B說明可用於本發明之一具體實例中的使用流通系統(flow-pass system；FPS)之前體供應系統之示意性表示。
圖2為用於根據一第一具體實例填充間隙之方法之流程圖。
圖3為與圖2之方法一起使用的用於向一或多個間隙之表面之底部區域提供第一反應物的第一方法的流程圖。
圖4為與圖2之方法一起使用的用於向一或多個間隙之表面之底部區域提供第一反應物的第二方法的流程圖。
圖5為與圖2之方法一起使用的用於向一或多個間隙之表面之底部區域提供第一反應物的第三方法的流程圖。
儘管在下文中揭示某些具體實例及實例，但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實例及/或用途及其明顯修改及等效物。因此，意欲所揭示之本發明之範圍不應受下文所描述之特定所揭示具體實例限制。
圖2為根據本發明之至少一個具體實例的方法之流程圖，其中在基板上製造構件期間所產生之一或多個間隙可利用沉積方法100填充。間隙可小於40nm或甚至20nm寬。間隙可超過40nm、100nm、200nm或甚至400nm深。
沉積方法可包含在第一步驟110中向一或多個間隙之表面之底部區域提供第一反應物。一或多個間隙之表面之底部區域可經界定為包括底部本身之間隙之總高度的下部75%、50%、25%或甚至10%。沉積方法可包含在第一步驟110中向一或多個間隙之表面之底部區域提供第一反應物，而可能不向一或多個間隙之表面之頂部區域提供該第一反應物。而一或多個間隙之表面之頂部區域可經界定為間隙之總高度的頂部90%、75%、50%或甚至25%。
在第二步驟120中，可將第二反應物提供至表面；且在第三步驟130中，第一反應物可以一個分子之第一反應物比多個分子之第二反應物的化學計量比引起在表面之底部區域中之第二反應物的反應的引發，保持未提供第一反應物之一或多個間隙之表面之頂部區域最初實質上為空的。
第一反應物可包含路易斯酸(Lewis acid)金屬或類金屬。 路易斯酸金屬或類金屬係選自由以下組成之群：鋁、硼、鎂、鈧、鑭、釔、鋯或鉿。第一反應物可為例如三甲基鋁(TMA)。
第二反應物可包含矽烷醇蒸氣以在與TMA反應中形成氧化矽層，如Dennis Hausmann等人之論文「Rapid Vapor Deposition of Highly Conformal Silica Nanolaminates」，Science第298卷，2002年10月11日，第402-405頁中所描述，該論文以引用之方式併入本文中。第二反應物可為參(第三戊氧基)矽烷醇或參(第三丁氧基)矽烷醇。TMA與矽烷醇可快速反應成大於2奈米(例如，10奈米)/循環的氧化矽層。
可在提供第一反應物及/或第二反應物之後移除過量反應物及副產物以防止在其他處發生反應。沉積方法可重複多個循環以自底部區域填充間隙至頂部區域使得再填充材料在間隙經完全填充之前將不在間隙之頂部附近形成縮窄。
第二反應物可以相比於可提供第一反應物之劑量相對較大的劑量引入以適應一個分子之第一反應物比多個分子之第二反應物的化學計量比。
圖3描繪圖2中之向一或多個間隙之表面之底部區域提供第一反應物的步驟110之方法。步驟110可包含將第一反應物提供至表面之頂部區域及底部區域的步驟101。
第一反應物可包含路易斯酸金屬或類金屬。路易斯酸金屬或類金屬係選自由以下組成之群：鋁、硼、鎂、鈧、鑭、釔、鋯或鉿。第一反應物可為例如三甲基鋁(TMA)。TMA可在步驟101中與間隙之表面之頂部區域及底部區域中存在之OH結合。
隨後在步驟102中，第一反應物可在頂部區域中經鈍化。鈍化在一或多個間隙之頂部區域中之第一反應物可藉由提供電漿進行以鈍化在頂部區域中之第一反應物，而第一反應物在底部區域中保留活性，此係因為電漿隨著向下進入較小溝槽而變得愈來愈弱。電漿可為鈍化頂部區域中之TMA的氮電漿，而活性TMA保留在底部區域中。咸信，電漿可使頂部區域中之吸附TMA氮化，從而使其在後續反應步驟中不反應。
可使用半導體處理儀器執行具有電漿之程序循環，該儀器包含：一或多個反應室，其用於容納基板，該基板具有在基板上製造構件期間所產生的間隙；第一反應物之一第一源，其經由第一閥與該等反應室中之一者氣體連通；及，第二反應物之一第二源，其經由第二閥與該等反應室中之一者氣體連通；其中該儀器包含：電漿氣體之一電漿氣體源，其經由電漿氣體閥與該等反應室中之一者氣體連通；一射頻電源，其經建構且經佈置以產生電漿氣體之電漿；一加熱器，其經建構且經佈置以加熱該等反應室中之一者中的基板，及一控制器，其可操作地連接至第一氣體閥、第二氣體閥及電漿氣體閥、射頻電源及加熱器且經組態並程式化以控制：該第一源、該電漿氣體源及該射頻源之時序及量以使用該第一源、該 電漿氣體源及該射頻電源將第一反應物實質上提供於間隙之表面之底部區域中；及該第二反應物及該加熱器之時序及量以在降低的溫度下以一個分子之該第一反應物比多個分子之該等第二反應物的化學計量比沉積，從而在間隙中引起反應，保持未提供該第一反應物之一或多個間隙之表面之頂部區域最初實質上為空的。
此類儀器可在(例如)圖1A中所說明。圖1A為可用於本發明之一些具體實例中的適宜結合程式化控制以實施本文中所描述之程序的PEALD儀器之示意圖。在此圖式中，藉由將一對平行且彼此面對的導電性平板電極4、2提供在反應室3之內部11(反應區)中，將HRF功率(13.56MHz或27MHz)20施加於一側，且將另一側12電接地，在該等電極之間激發電漿。溫度調節器提供於較低段2(下部電極)中，且位於其上之基板1之溫度在既定溫度下保持恆定。上部電極4亦用作噴淋板，且將反應物氣體(及惰性氣體)及前驅氣體分別經由氣體管線21及氣體管線22，且經由噴淋板4引入至反應室3。
此外，在反應室3中，提供具有排氣管線7之循環導管13，經由該排氣管線排放反應室3之內部11中之氣體。此外，安置於反應室3下方之轉移室5具有密封氣體管線24以將密封氣體經由轉移室5之內部16(轉移區)引入至反應室3之內部11中，其中提供有用於隔離反應區與轉移區之隔離板14(晶圓轉移至轉移室5或自該轉移室轉移所經由之閘閥在此圖示中被省去)。轉移室亦具有排氣管線6。在一些具體實例中，多元素膜之沉積及表面處理在相同的反應空間中執行，使得全部步驟可在不暴露 基板於空氣或其他含氧氣氛圍的情況下連續地實施。在一些具體實例中，遠端電漿單元可用於激發氣體。
在一些具體實例中，在圖1A中描繪之儀器中，圖1B中所說明之(先前描述之)交換非活性氣體流與前驅氣體流之系統可用於以脈衝形式引入前驅氣體而實質上不波動反應室之壓力。
在一些具體實例中，可使用雙室反應器(用於處理彼此緊密安置之晶圓的兩個區段或隔室)，其中反應氣體及惰性氣體可經由共用管線供應而前驅氣體經由非共用管線供應。
儀器可具有加熱器以藉由升高基板、第一反應物、第二反應物及第三反應物中之一或多者的溫度來活化該等反應物。經專門設計以執行ALD程序之例示性單一晶圓反應器可以商標名Pulsar®、Emerald®、Dragon®及Eagle®購自ASM International NV(Almere,The Netherlands)。經專門設計以執行ALD程序之例示性分批ALD反應器亦可以商標名A400TM及A412TM購自ASM International N.V。
儀器可具有可操作地與控制器連接之射頻源，其經建構且經佈置以產生第一反應物、第二反應物或第三反應物之電漿。電漿增強型原子層沉積PEALD可在購自荷蘭，阿爾梅勒之ASM International N.V.的Eagle® XP8 PEALD反應器中執行，該儀器包含電漿源以活化該等反應物中之一或多者。
熟習此項技術者將瞭解，儀器包括經程式化或以其他方式經組態以使得本文中其他處所描述之沉積及反應器淨化程序得以實施之一或多個控制器(圖中未示)。如熟習此項技術者將瞭解，該等控制器與多個電 源、加熱系統、泵、機器人，及反應器之氣流控制器或閥連通。
圖4描繪圖2中之向一或多個間隙之表面之底部區域提供第一反應物的步驟110之替代性方法。在步驟103中，可鈍化表面之頂部區域中所存在之反應性位點。隨後，步驟104可包含將第一反應物提供至表面之頂部區域及底部區域以與底表面上之其餘活性位點反應。
第一反應物可包含路易斯酸金屬或類金屬。路易斯酸金屬或類金屬係選自由以下組成之群：鋁、硼、鎂、鈧、鑭、釔、鋯或鉿。第一反應物可為例如三甲基鋁(TMA)。
在步驟103中鈍化表面之頂部區域之反應性位點可包含提供電漿以鈍化存在於頂部區域中之活性位點，而底部區域中之活性位點可由於該電漿而保留且從而電漿之作用隨著向下進入較小溝槽中而變得愈來愈弱。電漿可為氮電漿或氬電漿。TMA可與底部區域中之活性位點反應，而其將不在經鈍化之頂部區域中反應，僅保留底部區域中之TMA。更特定言之，在步驟104中，TMA可與間隙之表面之底部區域中之OH基團結合。如相對於圖3所提及之相同儀器可用於此方法。
圖5描繪圖2中之向一或多個間隙之表面之底部區域提供第一反應物的步驟110之另一替代性方法。另一替代性方法包含：在步驟105中，將聚合物材料提供於表面之底部區域中；在步驟106中，藉由第一反應物浸潤聚合物材料；及在步驟107中，自底部區域移除聚合物材料同時允許第一反應物保留。
表面之底部區域中之聚合物材料可藉由在步驟105中之提供聚合物材料於頂部區域及底部區域中來提供。聚合物材料可為聚醯亞胺 或聚醯胺酸聚合物或定向自組裝聚合物。隨後，可提供電漿以自頂部區域移除聚合物材料，而底部區域中之聚合物可由於電漿而保留，且從而電漿之蝕刻作用隨著向下進入較小溝槽中而變得愈來愈弱。電漿可為氮電漿、氧電漿、氫電漿、氟電漿或氬電漿或其任何組合。
在步驟106中，可藉由第一反應物浸潤聚合物材料。第一反應物可包含路易斯酸金屬或類金屬。路易斯酸金屬或類金屬係選自由以下組成之群：鋁、硼、鎂、鈧、鑭、釔、鋯或鉿。第一反應物可為例如三甲基鋁(TMA)。
在步驟107中，可藉由使材料在含氧氛圍中退火而自底部區域移除聚合物材料，同時允許第一反應物保留。此退火可例如在550℃下在空氣中進行15分鐘。聚合物材料可為例如聚醯亞胺或聚醯胺酸聚合物或定向自組裝聚合物。
下表展示進行以下之六個實例：將聚合物材料聚醯亞胺(PI)提供於表面上之膜中；藉由第一反應物TMA浸潤聚合物材料；及藉由在氧環境中退火來移除聚合物材料同時允許第一反應物保留。
Figure 106124129-A0305-02-0013-1
具有TMA之實例的第四及第五行展示TMA之厚度在550℃下在空氣中15分鐘之後保留於表面上。不具有TMA之實例展示可藉由在空氣中退火來幾乎完全地移除PI。如相對於圖3所提及之相同儀器可用於此方法。
在圖3至圖5之方法之後，TMA層保留於底部區域中。該方法可進一步包含在圖2之步驟120中加熱基板(例如，在100℃與300℃之間)且提供包含矽烷醇蒸氣之第二反應物以在與TMA反應中形成氧化矽層。
步驟120之矽烷醇可為參(第三戊氧基)矽烷醇或參(第三丁氧基)矽烷醇。TMA與矽烷醇可快速地反應成大於2奈米(例如10奈米)/循環的層。
可以足以使一或多個間隙之表面飽和的量引入矽烷醇蒸氣。矽烷醇蒸氣可與路易斯酸金屬或類金屬反應。路易斯酸金屬或類金屬可作為催化矽烷醇分子與正在增長的矽氧烷鏈之間的反應的催化劑反應。
應理解，本文中所描述之組態及/或方法本質上為例示性的，且此等特定具體實例或實例不應視為具有限制意義，原因在於可能存在諸多變化。本文所描述之特定常式或方法可表示任何數目之處理策略中之一或多者。因此，所說明之各種操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。
本發明之主題包括本文中所揭示之各種程序、系統及組態，及其他特徵、功能、作用及/或特性，及其任何及所有等效物的所有新穎但非顯而易見之組合及子組合。
1‧‧‧基板
2‧‧‧導電性平板電極
3‧‧‧反應室
4‧‧‧導電性平板電極
5‧‧‧轉移室
6‧‧‧排氣管線
7‧‧‧排氣管線
11‧‧‧反應區
12‧‧‧接地
13‧‧‧循環導管
14‧‧‧隔離板
16‧‧‧轉移區
20‧‧‧HRF功率
21‧‧‧氣體管線
22‧‧‧氣體管線
24‧‧‧氣體管線

Claims (20)

  1. 一種利用沉積方法來填充在基板上製造構件期間所產生之一或多個間隙的方法，該方法包含：向該一或多個間隙之表面之底部區域提供第一反應物；將第二反應物提供至該基板；及，允許該第一反應物以一個分子之該第一反應物比多個分子之該等第二反應物的化學計量比引發該表面之該底部區域中之該第二反應物的反應，保持未提供該第一反應物之該一或多個間隙之該表面之頂部區域最初實質上為空的，其中向該一或多個間隙之該表面之該底部區域提供該第一反應物包含：將聚合物材料提供於該表面之該底部區域中；藉由該第一反應物浸潤該聚合物材料；以及自該底部區域移除該聚合物材料同時使得該第一反應物保留在該底部區域中。
  2. 如申請專利範圍第1項之方法，其中該方法包含在提供第一反應物及/或第二反應物之後移除過量反應物及副產物。
  3. 如申請專利範圍第1項之方法，其中該沉積方法經多次重複以自該底部區域填充該間隙至該頂部區域。
  4. 如申請專利範圍第1項之方法，其中該第二反應物以與提供該第一反應物之劑量相比相對更大的劑量引入。
  5. 如申請專利範圍第1項之方法，其中向該一或多個間隙之該表面之該底部區域提供該第一反應物包含： 將該第一反應物提供至該一或多個間隙之該表面之該頂部區域及該底部區域；及，自該一或多個間隙之該頂部區域鈍化該第一反應物。
  6. 如申請專利範圍第5項之方法，其中鈍化該一或多個間隙之該頂部區域中之該第一反應物包含提供電漿以鈍化該間隙之該頂部區域中之該第一反應物。
  7. 如申請專利範圍第6項之方法，其中該電漿包含氮電漿。
  8. 如申請專利範圍第1項之方法，其中向該一或多個間隙之該表面之該底部區域提供該第一反應物包含：鈍化該表面之該頂部區域上之反應性位點；及，將該第一反應物提供至該表面之該頂部區域及該底部區域以與該表面上之其餘活性位點反應。
  9. 如申請專利範圍第8項之方法，其中鈍化該表面之該頂部區域之反應性位點包含提供電漿以自該頂部區域鈍化該等活性位點。
  10. 如申請專利範圍第9項之方法，其中該電漿為氮電漿及/或氬電漿。
  11. 如申請專利範圍第1項之方法，其中將聚合物材料提供於該表面之該底部區域中包含將聚合物材料提供於該頂部區域及該底部區域且提供電漿以自該頂部區域移除該聚合物材料。
  12. 如申請專利範圍第11項之方法，其中該電漿包含氮、氧、氫、氟及/或氬。
  13. 如申請專利範圍第1項之方法，其中自該底部區域移除該聚合物材料同時使得該第一反應物保留在該底部區域中包含在包含氧之氛圍下使 該材料退火。
  14. 如申請專利範圍第1項之方法，其中該聚合物材料包含聚醯亞胺或聚醯胺酸聚合物或定向自組裝聚合物。
  15. 如申請專利範圍第1項之方法，其中該第一反應物包含路易斯酸(Lewis acid)金屬或類金屬。
  16. 如申請專利範圍第15項之方法，其中該路易斯酸金屬或類金屬係選自由以下組成之群：鋁、硼、鎂、鈧、鑭、釔、鋯或鉿。
  17. 如申請專利範圍第16項之方法，其中該第一反應物包含三甲基鋁(TMA)。
  18. 如申請專利範圍第1項之方法，其中該方法包含加熱該基板在100℃與300℃之間且該第二反應物包含矽烷醇蒸氣以形成氧化矽層。
  19. 如申請專利範圍第18項之方法，其中該矽烷醇包含參(第三戊氧基)矽烷醇或參(第三丁氧基)矽烷醇。
  20. 一種半導體處理儀器，其包含：一或多個反應室，其用於容納基板，該基板具有在該基板上製造構件期間所產生的間隙；第一反應物之第一源，其經由第一閥與該等反應室中之一者氣體連通；及，第二反應物之第二源，其經由第二閥與該等反應室中之一者氣體連通；其中該儀器包含：電漿氣體之電漿氣體源，其經由電漿氣體閥與該等反應室中之一者氣體連通； 射頻電源，其經建構且經佈置以產生該電漿氣體之電漿；加熱器，其經建構且經佈置以加熱該等反應室中之一者中的該基板，及控制器，其可操作地連接至該第一閥、該第二閥及該電漿氣體閥、該射頻電源及該加熱器且經組態並程式化以控制：該第一源、該電漿氣體源及該射頻電源之時序及量以使用該第一源、該電漿氣體源及該射頻電源將該第一反應物實質上提供於該間隙之表面之底部區域中；該第二反應物及該加熱器之時序及量以在升高的溫度下以一個分子之該第一反應物比多個分子之該等第二反應物的化學計量比沉積，從而在該間隙中引起反應，保持未提供該第一反應物之該間隙之該表面之頂部區域最初實質上為空的；且該控制器進一步經組態並程式化以使聚合物材料自該底部區域被移除同時使得該第一反應物保留在該底部區域中。
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