TWI538046B - 氣體輸送系統之塗覆方法 - Google Patents

氣體輸送系統之塗覆方法 Download PDF

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TWI538046B
TWI538046B TW100110182A TW100110182A TWI538046B TW I538046 B TWI538046 B TW I538046B TW 100110182 A TW100110182 A TW 100110182A TW 100110182 A TW100110182 A TW 100110182A TW I538046 B TWI538046 B TW I538046B
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意恩 肯沃西
道恩 奧特卡
郝芳莉
李奧納多 夏普勒斯
杜益君
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Description

氣體輸送系統之塗覆方法
本發明係關於氣體輸送系統之塗覆方法。
電漿常被使用於基板的處理中，此基板如：半導體基板或被使用於製造平面顯示器的玻璃面板。舉例來說，於部分的基板製程中(例如：電漿蝕刻、化學氣相沉積、電漿輔助化學氣相沉積、物理氣相沉積等)，基板會被分割成各將成為積體電路之數個晶粒或矩形區域。接著，為了在基板上形成電子元件，基板會以一連串將材料選擇性去除(蝕刻)和附加(沉積)的步驟進行處理。
在一個示範的電漿製程中，基板於蝕刻前被塗覆一層硬化乳劑薄膜(亦即光阻遮罩)，然後，硬化乳劑的區域會被選擇性去除，造成部分下層的基板暴露出來。接著，將基板放置於位在一基板支撐結構上的一電漿處理系統的腔室中，該基板支撐結構包含稱為夾盤之單極或雙極電極。接著使適當的製程氣體(例如：C4F8、C4F6、CHF3、CH2F2、CF4、CH3F、C2F4、N2、O2、HBr、Ar、Xe、He、H2、NH3、SF6、BCl3、Cl2等)經由氣體輸送系統的氣體通道流入腔室中，並電離而形成電漿，以蝕刻基板的暴露區域。含鹵素的製程氣體具有很高的腐蝕性且可能損壞氣體通道的內表面。
本發明揭示一氣體輸送系統之氣體通道內表面之塗覆方法，該氣體輸送系統被配置來輸送製程氣體進入電漿處理系統的腔室內，此方法包含：(a)使抗腐蝕材料的流體前驅物流過氣體通道，並沉積一層流體前驅物，以完全塗覆氣體通道內表面；(b)去除內表面上的過量流體前驅物；(c)使流體前驅物的沉積層固化，以形成抗腐蝕材料塗層。
圖1顯示電漿處理系統100的簡化橫剖面圖。一般來說，一或多種製程氣體會透過一進氣口108，從氣體輸送系統122流入腔室102。這些製程氣體接著會被電離以形成電漿110，以處理(例如：蝕刻或沉積)基板114的暴露區域，此基板如置於一靜電夾盤116上的半導體基板或玻璃面板。噴淋頭電極104以及襯管112有助於使電漿110最佳地聚焦於基板114上。
氣體輸送系統122可包括一或多個質流控制器，此質流控制器連接於裝有電漿製程氣體(例如：C4F8、C4F6、CHF3、CH2F3、CF4、HBr、CH3F、C2F4、N2、O2、Ar、Xe、He、H2、NH3、SF6、BCl3、Cl2、WF6等)的壓縮氣體鋼瓶124a-f。氣體鋼瓶124a-f被提供局部排氣的外殼128進一步的保護著。質流控制器126可以是在半導體產業中用來量測與調節氣體到電漿處理系統之質量流量的自含式(self-contained)裝置(由一轉換器、控制閥和控制與訊號處理電子元件所組成)。氣體輸送系統122包含供製程氣體流動的氣體通道。氣體輸送系統的各式各樣元件藉由允許某些元件(例如處理室門)移動的配管及風箱部而互相連接。
在半導體廠中，為了最大化生產率與良率，在電漿處理期間需要輸送超純製程氣體。然而，因為這類氣體的高腐蝕性與易反應性本質，使得這類氣體的輸送引起特別的挑戰。
尤其，氣體輸送系統中的腐蝕現象實質上會降低基板的良率。舉例來說，在蝕刻基板的製程中，污染物可能由製程氣體的材料(例如：碳、氟、氫、氮、氧、矽、硼、氯等)、基板的材料(例如：光阻、矽、氧、氮、鋁、鈦等)、或電漿製程腔室或氣體輸送系統內部的結構材料(例如：不鏽鋼、鋁、石英等)所產生。
在半導體生產中，所製造之裝置特徵部的十分之一大小的微粒可能實質上損壞裝置。接著，為了儘量減少與消除系統污染物的可能來源，一般會精心設計與製程氣體接觸的元件。因為氣體輸送系統可能是重要的污染物來源，氣體通道通常由一組挑選的金屬所組成(例如：電拋光的不鏽鋼、銅、鋁、金屬合金等)。
舉例來說，不鏽鋼是一種鐵(Fe)基合金，具有重要合金添加物鉻(Cr)和鎳(Ni)，鉻能使金屬有『不鏽』和抗腐蝕的特性，而鎳可穩定奧斯田鐵(austenite)並讓金屬無磁性且堅韌。電拋光一般來說可改善零件的表面化學，藉以強化表面鈍態氧化膜並由表面去除任何游離鐵。
一般來說，不鏽鋼包含可進一步防止「氧化」或生鏽的「鈍態」膜塗層。此膜在暴露於氧氣時迅速地形成。一旦形成此膜，金屬就成鈍態，且氧化或『生鏽』速率將大大地減緩。
儘管努力減少來自於如同電拋光、鈍化層、鏡面光滑表面光度(Ra<5密耳(mil))的製程之腐蝕，但由於長期暴露於製程氣體，仍會發生腐蝕，尤其在會定期暴露於濕氣中的特定區域，例如：接近熔接接點的部分和不鏽鋼氣體通道的部分。
腐蝕的程度和污染物的量可依很多因素而定，例如：氣體濃度和純度、溼氣含量、溫度、氣體通道材料中的局部不均勻性、系統流速、暴露時間、暴露頻率。舉例來說：例如氯化氫或溴化氫之含鹵素氣體，於溼氣位準超過數個百萬分之一(ppm)時可以腐蝕不鏽鋼。
儘管溼氣可以減少，但其一般無法完全消除。舉例來說，雖然電漿製程氣體通常以純化形式而貯存於壓縮氣體鋼瓶中，當替換鋼瓶或維修處理腔室時，濕氣都可能被引進氣體輸送系統內。
儘管不鏽鋼的真正腐蝕量趨於微小，但從腐蝕區域釋放出來的鐵與鉻，可經由不鏽鋼氣體通道中之氣體流動，而被搬運到其中半導體基板正接受處理之電漿處理室。因此，在電漿處理室中接受處理之半導體基板會發生嚴重的污染。基板上的鐵與鉻污染物之標準容忍值小於5.0x1010原子/平方公分(atoms/cm2)。因此，期望有用以避免或有效地減少不鏽鋼氣體通道的腐蝕的方法。減少氣體輸送系統中的腐蝕之一方法為，防止不鏽鋼氣體通道(例如：配管和風箱)接觸腐蝕性氣體。
一種根據此策略的方法為使用抗腐蝕的配管(例如：聚乙烯配管、聚丙烯配管、彈性玻璃配管、金屬塗覆塑膠配管、陶瓷配 管、有導電遮屏夾在兩層塑膠或電鍍鋁之間的層板配管)。
藉由參考文獻方式併入於此之共同受讓的美國專利第7,234,222號，揭示了將塑膠套管結合或射出成形至不鏽鋼配管之內表面上的方法。
於此描述流動塗覆方法的實施例，其中一抗腐蝕材料的流體前驅物流經氣體輸送系統的氣體通道，以便沉積一層流體前驅物於氣體通道的內表面上；且使沉積的此層流體前驅物固化，以在氣體通道的內表面上形成一層抗腐蝕材料。氣體通道由熔接金屬(例如：不鏽鋼)配管、風箱、配件、凸緣、閥及其類似物等所形成。流動塗覆方法可有效地塗覆具有複雜的幾何形狀和/或小直徑的內表面(例如：風箱內表面或外徑為0.25英吋以下的配管內表面)。
一流動塗覆方法實施例包含以下步驟：(a)用適當的去污劑和/或適當的化學藥品(例如：使用10到20wt.%的硝酸3分鐘和用去離子水沖洗內表面至少5分鐘)來清除氣體輸送系統的氣體通道內表面；(b)乾燥內表面(例如：藉由吹入乾燥的氮氣或乾燥的空氣經過氣體通道，且在至少120℃溫度下的真空烤箱中烘烤氣體通道)；(c)使抗腐蝕材料的流體前驅物(例如：PERMABOND製造的HL126液態高分子前驅物或甲基丙烯酸酯)流過氣體通道，並沉積一層流體前驅物以塗覆氣體通道內表面；(d)去除內表面上的過量流體前驅物(例如：藉由吹入乾燥的氮氣或乾燥的空氣到氣體通道中)；(e)使流體前驅物的沉積層固化，以形成抗腐蝕材料塗層(例如：藉由在溫度至少100℃與壓力為1到10托耳(Torr)的真空烤箱內烘烤氣體通道，或將氣體通道保持在環境溫度或壓力下至少24小時)。
可以施加相同的第二塗層。合成的塗層可具有0.0014到0.0034英吋的厚度且不容易碎。
然而，如圖2所示，如果氣體通道包含被熔接於氣體通道的 其他元件(例如：配管、配件、閥、凸緣等)之風箱201，流體前驅物會積聚在風箱201之內表面的迴旋段202，並可能在迴旋段202處固化成過量的抗腐蝕材料，其可能剝落並造成微粒污染。
在延長暴露於腐蝕性氣體之後檢驗氣體輸送系統中之未塗覆不鏽鋼風箱，顯示出風箱的迴旋段沒有任何腐蝕的跡象，而其他元件及在此氣體輸送系統的元件之間的熔接接點則顯示出嚴重的腐蝕。因此，選擇性的塗覆方法，其中在氣體輸送系統的氣體通道的所有內表面上塗覆抗腐蝕物質，同時留下其中之風箱的內表面不塗覆，可以消除抗腐蝕材料積聚於風箱迴旋段中的問題。
選擇性塗覆方法的一實施例包含以下步驟：
(a)在將風箱熔接至其餘氣體通道之前，以可避免流體前驅物附著之遮蔽劑(如：光阻、油、矽烷和/或烷氧矽烷(矽烷和/或烷氧矽烷可在風箱的內表面上提供一矽烷化層))塗覆風箱的內表面；
(b)將風箱熔接至其他元件上；
(c)使流體前驅物(例如：HL126液態高分子前驅物或甲基丙烯酸酯)流過氣體通道，並沉積一層流體前驅物，以塗覆氣體通道中除了風箱內表面以外的內表面；
(d)去除過量流體前驅物(例如：藉由吹入乾燥的氮氣或乾燥的空氣到氣體通道中)；
(e)使流體前驅物的沉積層固化(例如：藉由在溫度至少100℃、壓力為1到10托耳(Torr)的真空烤箱內烘烤氣體通道，或將氣體通道保持在環境溫度和壓力下至少24小時)。
(f)非必要地，去除風箱內表面的遮蔽劑。
遮蔽劑可以是光阻、油、矽烷、烷氧矽烷或其他合適的物質。流體前驅物可以是高分子HL126或甲基丙烯酸酯或其他合適的物質。遮蔽劑可以用丙酮、光阻去除劑或其他合適的材料加以去除(例如：溶解、蝕刻等)。
雖然氣體輸送系統的氣體通道內表面塗覆方法已參照具體的實施例詳細描述，熟悉本技藝者將明瞭：在不離開隨附之申請專 利範圍之情況下，可進行各種變化與修改、且可使用等效物。
100‧‧‧電漿處理系統
102‧‧‧腔室
104‧‧‧噴淋頭電極
108‧‧‧進氣口
110‧‧‧電漿
112‧‧‧襯管
114‧‧‧基板
116‧‧‧夾盤
122‧‧‧氣體輸送系統
124a、124f‧‧‧氣體鋼瓶
126‧‧‧質流控制器
128‧‧‧外殼
201‧‧‧風箱
202‧‧‧迴旋段
圖1顯示電漿處理系統的簡化橫剖面圖。
圖2顯示抗腐蝕材料之流體前驅物積聚在風箱迴旋段內。
100‧‧‧電漿處理系統
102‧‧‧腔室
104‧‧‧噴淋頭電極
108‧‧‧進氣口
110‧‧‧電漿
112‧‧‧襯管
114‧‧‧基板
116‧‧‧夾盤
122‧‧‧氣體輸送系統
124a、124f‧‧‧氣體鋼瓶
126‧‧‧質流控制器
128‧‧‧外殼

Claims (17)

  1. 一種氣體輸送系統之氣體通道之內表面的塗覆方法，該氣體輸送系統被配置來輸送製程氣體到於其中對半導體基板進行處理的電漿處理系統的腔室，該方法包含：(a)使抗腐蝕材料的流體前驅物流過該氣體通道，並沉積一層該流體前驅物，以塗覆該氣體通道之該內表面；(b)去除該內表面上的過量流體前驅物；及(c)使該流體前驅物沉積層固化，以形成抗腐蝕材料塗層，其中該氣體通道將製程氣體輸送到該電漿處理系統的該腔室，且其中該流體前驅物為液體。
  2. 如申請專利範圍第1項之氣體輸送系統之氣體通道之內表面的塗覆方法，更包含在使該流體前驅物流入之前，先清理該內表面與乾燥該內表面。
  3. 如申請專利範圍第2項之氣體輸送系統之氣體通道之內表面的塗覆方法，其中：藉由接觸10到20wt.%的硝酸3分鐘和用去離子水沖洗至少5分鐘，來清除氣體通道內表面；及藉由吹入乾燥的氮氣或乾燥的空氣經過該氣體通道，且在至少120℃溫度下的真空烤箱中烘烤該氣體通道，以使該內表面乾燥。
  4. 如申請專利範圍第1項之氣體輸送系統之氣體通道之內表面的塗覆方法，其中該氣體通道為不鏽鋼配管之形式，其具有0.25英吋以下的外徑。
  5. 如申請專利範圍第1項之氣體輸送系統之氣體通道之內表面的塗覆方法，其中重複步驟(a)到(c)。
  6. 如申請專利範圍第1項之氣體輸送系統之氣體通道之內表面的塗覆方法，其中該塗層為抗含鹵素製程氣體者。
  7. 如申請專利範圍第1項之氣體輸送系統之氣體通道內表面的塗覆方法，其中該抗腐蝕材料塗層之厚度為0.0014到0.0034英吋。
  8. 一種氣體輸送系統之氣體通道之內表面的塗覆方法，該氣體輸送系統被配置來輸送製程氣體到電漿處理系統的腔室，該方法包含：(a)使抗腐蝕材料的流體前驅物流過該氣體通道，並沉積一層該流體前驅物，以塗覆該氣體通道之該內表面；(b)去除該內表面上的過量流體前驅物；及(c)使該流體前驅物沉積層固化，以形成抗腐蝕材料塗層，其中：該流體前驅物包含一或多個甲基丙烯酸酯；藉由吹入乾燥的氮氣或乾燥的空氣到該氣體通道中，以去除過量流體前驅物；及藉由在溫度為至少100℃及壓力為1到10托耳(Torr)的真空烤箱內烘烤該氣體通道，或者藉由將該氣體通道保持在環境溫度及壓力下至少24小時，以使該流體前驅物沉積層固化。
  9. 一種氣體輸送系統之氣體通道之內表面的塗覆方法，該氣體輸送系統被配置來輸送製程氣體到電漿處理系統的腔室，該方法包含：(a)使抗腐蝕材料的流體前驅物流過該氣體通道，並沉積一層該流體前驅物，以塗覆該氣體通道之該內表面；(b)去除該內表面上的過量流體前驅物；及(c)使該流體前驅物沉積層固化，以形成抗腐蝕材料塗層，其中該氣體通道為不鏽鋼配管之形式，其具有0.25英吋以下的外徑，且其中將至少一不鏽鋼風箱熔接至該不鏽鋼配管。
  10. 如申請專利範圍第9項之氣體輸送系統之氣體通道之內表面的塗覆方法，更包含：在將該風箱熔接至該配管之前，以防止該流體前驅物之附著的遮蔽劑塗覆該風箱的內表面；及非必要的，在該固化步驟之後，去除該風箱之該內表面的該遮蔽劑。
  11. 如申請專利範圍第10項之氣體輸送系統之氣體通道之內表面的塗覆方法，其中該遮蔽劑為光阻、油、矽烷和/或烷氧矽烷。
  12. 一種氣體輸送系統，被配置來輸送製程氣體進入於其中對半導體基板進行處理的電漿處理系統的腔室內，該氣體輸送系統包含其內表面塗覆有一層抗腐蝕材料塗層的氣體通道，該塗層為藉由將沉積於該內表面上的一層流體前驅物加以固化所形成，其中該流體前驅物為液體。
  13. 如申請專利範圍第12項之氣體輸送系統，其中該氣體通道為不鏽鋼配管之形式，其具有0.25英吋以下的外徑。
  14. 如申請專利範圍第12項之氣體輸送系統，其中該塗層為抗含鹵素製程氣體者。
  15. 一種氣體輸送系統，被配置來輸送製程氣體進入電漿處理系統的腔室內，該氣體輸送系統包含其內表面塗覆有一抗腐蝕材料塗層的氣體通道，該抗腐蝕材料塗層為藉由將沉積於該內表面上的一層流體前驅物加以固化所形成，該氣體輸送系統更包含至少一個熔接至不鏽鋼配管上之不鏽鋼風箱，該不鏽鋼配管中具有有該氣體通道，且該風箱之內表面並未由該塗層加以塗覆。
  16. 一種電漿處理系統，包含一氣體輸送系統，該氣體輸送系統被配置來輸送製程氣體進入該電漿處理系統的腔室內，該氣體輸送系統包含其內表面塗覆有一抗腐蝕材料塗層的氣體通道，該抗腐蝕材料塗層為藉由將沉積於該內表面上的一層流體前驅物加以固化所形成，其中該氣體輸送系統輸送含鹵素製程氣體進入電漿處理系統的腔室中，且將該製程氣體激發成電漿，以處理被支撐於該腔室中之各半導體基板。
  17. 如申請專利範圍第16項之電漿處理系統，其中該基板係藉由電漿加以蝕刻。
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