TWI406338B - 半導體之膜形成方法與設備 - Google Patents

半導體之膜形成方法與設備 Download PDF

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TWI406338B
TWI406338B TW097128114A TW97128114A TWI406338B TW I406338 B TWI406338 B TW I406338B TW 097128114 A TW097128114 A TW 097128114A TW 97128114 A TW97128114 A TW 97128114A TW I406338 B TWI406338 B TW I406338B
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film
gas
plasma
semiconductor device
sicn film
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TW200913072A (en
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Takaaki Matsuoka
Kohei Kawamura
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Tokyo Electron Ltd
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Description

半導體之膜形成方法與設備 【相關申請案之交互參照】
本申請案主張美國臨時申請案第60/961942號的優先權，該臨時申請案申請於2007年7月25日，標題為「Method for Semiconductor Deposition」，其整體內容藉由參考文獻方式合併於此。
本發明係關於一種用以在基板上形成薄膜的方法。此方法可應用於半導體裝置、液晶顯示裝置、以及有機電激發光(EL，electro－luminescent)元件。
在例如半導體裝置、液晶顯示裝置、以及有機電激發光(EL，electro－luminescent)元件之電子裝置的製造程序中，執行薄膜形成程序以在基板的表面上形成導電膜或絕緣膜。用以在基板上使用電漿以形成薄膜的電漿薄膜形成程序被利用在此種薄膜形成程序上。當在薄膜形成程序中將CF膜形成於基板上並且進一步將絕緣膜形成於CF膜上的情況下，存在有下列問題：氟原子會擴散至絕緣膜內，因此CF膜與絕緣膜的可接觸性會降低。此外，存在有下列問題：當CF膜以及絕緣膜在後續薄膜形成程序被加熱處理時，絕緣膜會因為被擴散至絕緣膜內的氟原子所腐蝕而產生剝落。
順道一提，上述電漿薄膜形成程序通常係藉由電漿薄膜形成設備加以執行。近年來，藉由以微波場產生電漿而形成薄膜之微波電漿薄膜形成設備，在作為一種電漿薄膜形成設備上已引起注意。依照此種微波電漿薄膜形成設備，相較於習知薄膜形成設備，吾人可獲得高密度電漿，因此可在短時間內有效地對基板執行薄膜形成程序。
上述微波電漿薄膜形成設備可例如設有用以將基板放置在處 理容器內部的放置基座，並且將徑向線槽孔天線(slot antenna)以及噴淋板設置在處理容器的上部分，此噴淋板可使來自供應氣體之徑向線槽孔天線的微波通過。又，微波電漿薄膜形成設備利用來自於處理容器之壁表面的薄膜用供應材料氣體。
例如，作為使用微波電漿薄膜形成設備以形成薄膜的電漿處理方法已被知悉如下。舉例而言，日本公開專利公報第2005－093737號揭露一種用以在基板上形成薄膜的電漿處理方法，其能夠藉由將供應至基板之自由基以及離子的數量最佳化，而在短時間內以低溫形成高品質薄膜。此外，日本公開專利公報第2006－324023號揭露一種電漿薄膜形成裝置，其能夠藉由將噴淋板的溫度維持在期望的溫度，並且改善噴淋板之板內溫度的均勻性，而使噴淋板的變形或扭曲降至最低。
又，日本公開專利公報第2005－150612號揭露一種電漿薄膜形成設備，此設備可防止用於電漿激發的氣體在其被供應至處理容器之前進行電漿化，並且適度地在高頻波供應側的區域(亦即，電漿產生區域)內產生電漿。又，國際公開專利公報(International Published Unexamined Patent Application)第2000－74127號揭露一種電漿處理設備，其能夠維持電漿的穩定度，不論用於此程序之氣體的類型為何，此係因為處理用氣體之解離或鍵結，而造成並無薄膜貼附在微波導入部分之介電噴淋板的表面上。
然而，根據使用以上文獻所述之方法的任何其中之一，吾人尚無法充分達到改善基板上所形成之薄膜的耐熱性，或防止薄膜的過度解離。因此，一直存在形成於基板上之薄膜間的可接觸性會劣化之問題。此外，關於形成於基板上的薄膜，向來需要能夠在各種不同條件下發揮功能之特性。又，關於製造成本，一直期望可省略製造步驟並且降低材料花費。
本發明之一實施樣態為一種半導體裝置，其包含：氟化絕緣 膜；以及SiCN膜，直接沉積在氟化絕緣膜上，其中SiCN膜的氮密度從氟化絕緣膜與SiCN膜之間的界面減少。
此氮密度可逐漸減少。SiCN膜可藉由使位在分隔成複數區域之容器內的電漿氣體產生反應而產生。SiCN膜可藉由調整位在複數區域內的氣體流量比例而產生。
形成SiCN膜內部的流量比例可不同於形成SiCN膜外部的流量比例。此容器可包含上區域以及下區域，而當形成SiCN膜的外部時，流入上區域的氣體量可大於流入下區域的氣體量。
此容器可包含上區域以及下區域，而當形成SiCN膜的內部時，流入下區域的氣體量可大於流入上區域的氣體量。添加氣體可流入上區域以及材料氣體可流入下區域。氣體流量比例可隨時間加以調整。
在本發明中，位於與CFx 膜之界面附近具有高耐氟性並且以整體而言具有低介電常數的SiCN膜可被形成以作為硬質遮罩。
在本發明之方法用於進一步將薄膜形成於基板上所形成之薄膜上的情況下，可防止薄膜的過度解離。當薄膜被過度解離時，其會變成蝕刻物質並且無法促成薄膜的形成。當薄膜的過度解離可被防止時，此薄膜會變成形成物質，因此可改善薄膜之間的可接觸性。同樣地，藉由使用本發明之方法所形成的薄膜可充分改善耐熱性(可容許溫度極限)。
又，根據使用本發明之方法，可形成具有各種不同特性的薄膜。同樣地，根據使用本發明之方法，可形成具有各種不同組成成分的薄膜。因此，吾人可控制薄膜的特性以及組成成分。
又，在相同類型氣體被用於本發明之方法的情況下，兩者可具有不同的解離條件。因此，假使利用不同類型的氣體時，氣體成分可共存於此區域。因此，低成本氣體可被利用，以替代高成本氣體。並且，具有類似於使用高成本氣體所形成之薄膜之構造的薄膜可被形成。
由於根據利用本發明之方法以時間調整氣體流量比例，所以 可形成具有更多特性的薄膜以及具有更多組成成分的薄膜。因此，可有效控制薄膜的特性以及薄膜的組成成分。同樣地，製造成本可藉由利用低成本材料替代高成本材料而降低。
根據使用本發明之方法改變氣體流量比例，可改變薄膜表面組成以及內部組成。例如，當薄膜表面結構具有高的介電常數以及機械強度時，然而，其可能被形成為具有相當低之機械強度以及低介電常數的結構。又，為了增加薄膜的機械強度或耐熱強度，通常會將稱為硬化的後薄膜形成程序用於低介電常數(Low K)材料，然而，此種程序可藉由使用本發明之方法而被省略。
以下將說明使用徑向線槽孔天線(RLSA，radial line slot antenna)以產生電漿的化學氣相沉積設備。圖1與圖2係顯示依照本發明之第一實施例之微波電漿處理設備10的構造圖。
參考圖1，微波電漿處理設備10包含處理容器11以及設置在處理容器11內的台階13，此台階以靜電夾頭固持待處理的基板12，其中台階13較佳係以AlN或Al2 O3 經由熱等壓製(HIP，hot isostatic pressing)處理而形成。在處理容器11中，於台階13周圍的空間11A中以相等距離形成有至少兩個或較佳係兩個以上或等於三個的排氣口111A，並因此具有相對於位在台階13上之基板12的軸向對稱。待稍後進行說明，吾人經由排氣口111A以漸次導螺桿幫浦(gradational lead screw pump)將處理容器11排空至低壓。
處理容器11較佳由含Al的沃斯田鐵(austenite)不銹鋼所形成，並經由氧化製程而在內壁表面上形成氧化鋁的保護膜。又，在處理容器11對應於基板12的一部分外壁中，形成有經由熱等壓製(HIP)處理所形成之緻密Al2 O3 的盤狀噴淋板14，以作為部分的外壁，其中噴淋板14包含大量的電漿通路14A。如此藉由熱等壓製方式所形成的Al2 O3 噴淋板14係利用Y2 O3 添加劑來形成，並 具有0.03%以下的孔隙度。此意謂著Al2 O3 噴淋板實質上不具有孔洞或針孔，並且具有非常大但不如AlN之30W/mK的陶瓷導熱係數。
噴淋板14係隔著密封環111S而被安裝在處理容器11上，以及同樣由熱等壓製處理所形成之緻密Al2 O3 的覆蓋板15係隔著密封環111T而被設置在噴淋板14上。在此噴淋板與覆蓋板15接觸的一側，噴淋板14被形成具有電漿通路14B，此電漿通路與作為電漿通路的各噴嘴孔相連通，其中電漿通路14B亦與形成在噴淋板14之內部的另一個電漿通路14C相連通，此噴淋板的內部係與形成在處理容器11之外壁上的電漿入口111P相連通。
噴淋板14係被處理容器11之內壁上所形成之延伸部分的嵌接末端所固持，其中延伸部分111B在用以固持噴淋板14的部分被形成具有圓弧面，俾能抑制放電。
因此，供應至電漿入口111P之例如Ar或Kr的電漿在通過位於噴淋板14內的通路14C與14B之後，會經由電漿通路14A而被均勻地供應至噴淋板14正下方的空間11B。
在覆蓋板15上，設有由盤狀狹縫板16、固持狹縫板16的盤狀天線本體17、以及介設在狹縫板16與天線本體17之間的低損耗介電材料(例如Al2 O3 、SiO2 或Si3 N4 )的減速板18所形成的徑向線槽孔天線20，該狹縫板16形成有圖2所示之與覆蓋板15緊密接觸之若干狹縫16A與16B。徑向線槽孔天線20透過密封環111U而被安裝在處理容器11上，並且從外部微波源(無圖示)經由同軸波導器21將2.45GHz或8.3GHz頻率的微波饋送至徑向線槽孔天線20。以此種方式所供應的微波從位於狹縫板16上的狹縫16A與16B經由覆蓋板15以及噴淋板14而被發射進入處理容器的內部。因此，微波可使得在由噴淋板14正下方之空間11B內的電漿通路14A所供應之電漿中產生電漿激發。吾人應可注意到覆蓋板15以及噴淋板14係由Al2 O3 所形成，並且作為有效的微波透射窗。為了避免在電漿通路14A－14C中產生電漿激發，在上述通路 14A－14C中，電漿被保持在約6666 Pa－13332 Pa(約50－100 Torr)的壓力下。
為了改善徑向線槽孔天線20與覆蓋板15之間的緊密接觸，本發明之微波電漿處理設備10在一部分的處理容器11上具有環狀溝槽，俾能與狹縫板16相嚙合。透過與溝槽相連通的排氣口11G對溝槽抽氣，降低了形成在狹縫板16與覆蓋板15之間之間隙內的壓力，且徑向線槽孔天線20因大氣壓力而被穩固地推往覆蓋板15上。吾人應注意：此種間隙不僅包含在狹縫板16內所形成的狹縫16A與16B，而且亦包含其他不同原因所形成的間隙。吾人應進一步注意到：此種間隙被設置在徑向線槽孔天線20與處理容器11之間的密封環111U所密封。
藉由透過排氣口11G以及溝槽111G，以小分子量的惰性氣體填充位於狹縫板16與覆蓋板15之間的間隙，可促進從覆蓋板15至狹縫板16的熱傳遞。因此，考慮到大熱傳導以及大游離能，較佳係使用He作為此種惰性氣體。在以He填充間隙的情況下，較佳係將壓力設定成約0.8atm。在圖1的構造中，在排氣口11G上設有閥11V，其用以對溝槽111G抽氣以及將惰性氣體填充入溝槽111G中。
吾人應注意：同軸波導器21A的外波導管係連接至盤狀天線本體17，而中央導線21B係經由形成在減速板18內的開口而連接至狹縫板16。因此，饋送至同軸波導器21A的微波在天線本體17與狹縫板16之間的徑向(radial direction)進行傳播，並且從狹縫16A與16B發射。
圖2顯示形成在狹縫板16上的狹縫16A與16B。參考圖2，狹縫16A以同心圓的方式加以排列，以對每一狹縫16A設置狹縫16B，而使狹縫16B與狹縫16A垂直交叉，並且使狹縫16B與狹縫16A進行同心圓對正。狹縫16A與16B形成有對應於在狹縫板16之徑向經由減速板18所壓縮之微波波長的間隔，因此，微波會以近平面波(near plane wave)的形式從狹縫板16加以發射。因為狹 縫16A與狹縫16B互相形成垂直關係，以此種方式所發射的微波會形成包含兩個垂直極化成分的圓極化波(circularly polarized wave)。
在圖1之電漿處理設備10中，設有冷媒區塊19，此冷媒區塊在天線本體17上形成有冷媒水通路19A，以及吾人可藉由冷媒水通路19A內的冷媒水冷卻冷媒區塊19而經由徑向線槽孔天線20吸收在噴淋板14所累積的熱量。冷媒水通路19A係以螺旋狀的形式被形成在冷媒區塊19上，而具有受控之氧化還原電位的冷媒水被供應至此冷媒水通路，其中氧化還原電位的控制可藉由通入H2 氣體以消除溶解在冷媒水中的氧而實現。
在圖1之微波電漿處理設備10中，在噴淋板14與台階13上的基板12之間的處理容器11中更設有處理氣體供應機構31，其中處理氣體供應機構31具有排列成網格狀的氣體通路31A，並透過大量處理氣體噴嘴孔來釋出由處理氣體入口111R所供應的處理氣體，此處理氣體入口係設置在處理容器11的外壁上。因此，吾人可在處理氣體供應機構31與基板12之間的空間11C內實現期望的均勻基板處理。此種基板處理包含：電漿氧化處理、電漿氮化處理、電漿氧氮化處理、以及電漿化學氣相沉積(CVD，chemical vapor deposition)處理。又，吾人可藉由供應易於分解的氟碳化合物氣體，例如C4 F8 、C5 F8 或C4 F6 ，或含F或Cl的蝕刻氣體，並且進一步藉由從高頻電源13A將高頻電壓施加至台階13，而實施基板12的反應性離子蝕刻。
在本實施例之微波電漿處理設備10中，吾人可避免因將處理容器11之外壁加熱至約150℃的溫度，而使反應副產物沉積在處理容器的內壁上。因此，微波電漿處理設備10能夠固定並可靠地進行僅大約一天一次的乾式清理程序。
圖3係顯示圖1之處理氣體供應機構31之結構的立體圖。參考圖3，吾人以盤狀導電構件311與312的堆疊物，例如含Mg的Al合金或添加Al的不銹鋼，形成處理氣體供應機構31。設有配 置成矩陣形式的氣體通路31A，以作為電漿通路。例如，氣體通路31A具有19mm×19mm的尺寸，並且同時在列(row)方向與排(column)方向重複以24mm的間隔加以設置。處理氣體供應機構31具有約8.5mm的總厚度，並且典型上被安裝離基板12的表面大約16mm。
圖4係顯示圖3之盤狀導電構件311之結構的底視圖。參考圖4，在盤狀導電構件311中，設有與處理氣體供應通路31C連通的網格狀處理氣體通路31B，此處理氣體供應通路係沿著圖4之虛線所表示之盤狀導電構件311的外圍而形成。處理氣體供應通路31C被連接至處理氣體入口111R。在盤狀導電構件311的反面，形成有與處理氣體通路31B連通的大量處理氣體噴嘴孔31D。處理氣體從處理氣體噴嘴孔31D被釋出至盤狀導電構件312。
僅以特定範例為例，而對於其中依照本發明之微波電漿處理設備10用以在基板上形成薄膜的實施例進行說明。在本發明中，由於改變待導入微波電漿處理設備10之空間11B與11C之氣體的流量比例，所以可層疊具有不同分子組成比例的薄膜。例如，假使三甲基矽烷與氮氣被同時導入空間11B與空間11C時，SiCN硬質遮罩可被形成在基板上；然而，在此種情況下，假使空間11B與空間11C中的流量比例在界面區域的薄膜形成期間與薄膜區域的薄膜形成期間之間被改變時，可形成在界面與薄膜區域之間具有不同分子組成比例的SiCN膜。
典型上，CFx 膜等等被層疊於基板上，於其上再層疊SiCN膜；然而，例如開始將SiCN膜層疊於CFx 膜上時(在界面區域的薄膜形成期間)，使通往空間11B的流量比例大於通往空間11C的流量比例，而在薄膜區域的薄膜形成期間，使通往空間11C的流量比例大於通往空間11B的流量比例。相較於流量比例1：1之薄膜形成的情況，以此種方式設置可分別使界面附近以及薄膜內之Si－N鍵以及Si－C鍵的百分比增加。在CFx 膜的界面附近，為了增加CFx 與SiCN膜之間的附著性，具有高耐氟性的SiCN膜係較佳的。具 有高百分比Si－N鍵的SiCN膜為高耐氟性膜，因此較佳係透過上述處理來形成此薄膜。另一方面，相較於具有高百分比Si－C鍵的SiCN膜，具有高百分比Si－N鍵的SiCN會具有較大的介電常數。因此，在除了界面區域附近以外的區域內，即在薄膜區域內，較佳為具有高百分比Si－C鍵的SiCN膜，因此，較佳之情況係透過上述處理來形成此薄膜。由於利用此種方法，所以在與CFx 膜之界面附近有高耐氟性並且以整體而言具有低介電常數的SiCN膜可被形成作為硬質遮罩。
待通入上述空間11B以及空間11C的氣體並沒有被特別限制於如上所述的氣體，而吾人可通入任何類型的氣體。典型上，吾人可將例如氬(Ar)、氮氣(N2 )、氨氣(NH3 )、或氫氣的氣體通入空間11B，而將三甲基矽烷與氮氣、矽烷、二矽烷、甲基矽烷(例如單甲基矽烷、二甲基矽烷、三甲基矽烷、或四甲基矽烷)、矽氮烷(例如甲基矽氮烷或乙基矽氮烷)等等的氣體混合物通入空間11C。假使期望在基板上形成SiCN膜時，較佳係分別將氬氣以及三甲基矽烷與氮氣的氣體混合物導入空間11B以及空間11C。另一方面，假使期望在基板上形成SiC膜時，較佳係分別將氬氣以及三甲基矽烷導入空間11B以及空間11C。又，假使期望在基板上形成SiN膜時，較佳係分別將氬氣、以及矽烷或二矽烷導入空間11B以及空間11C。同樣地，即使分別將氮氣以及三甲基矽烷導入空間11B以及空間11C，亦可形成SiCN膜。
即使SiCN、SiC、或SiN係基於對應上述方法其中之一，而藉由改變空間11B以及空間11C內的氣體流量比例加以形成，吾人亦可形成具有不同分子組成比例的薄膜。吾人可注意到以上使用「解離」一詞，然而，此並非意謂在成形膜內的薄膜組成被分離，而係意謂已被導入空間11B或空間11C的氣體在氣體反應之後呈現解離狀態，薄膜係在此種狀態下基於此反應而形成。
以上說明本發明之一實施例，然而，本發明並不限於上述特定範例。例如，薄膜被形成在基板上，然而，用以形成依照本發 明之薄膜的方法可被應用在形成其他的薄膜，例如電極膜。同樣地，例如氙氣、或氪氣的其他氣體可被利用作為從噴淋板14所供應的氣體。又，用以形成依照本發明之薄膜的方法不僅可被應用在半導體裝置的基板，而且可例如應用在用以製造液晶顯示裝置或有機電激發光(EL，electro－luminescent)元件的基板。
與本發明相關的基板處理例如包含：電漿氧化處理、電漿氮化處理、電漿氧氮化處理、電漿化學氣相沉積處理等等。依照本實施例之微波電漿處理設備10，可藉由在約150℃的溫度下加熱處理容器的外壁，而避免使反應副產物等等沉積在上述處理容器11的內壁上，並且可藉由大約一天一次的乾式清理而持續穩定地加以操作。
10‧‧‧微波電漿處理設備
11‧‧‧處理容器
11A‧‧‧空間
11B‧‧‧空間
11C‧‧‧空間
11G‧‧‧排氣口
11V‧‧‧閥
12‧‧‧基板
13‧‧‧台階
13A‧‧‧高頻電源
14‧‧‧噴淋板
14A‧‧‧電漿通路
14B‧‧‧電漿通路
14C‧‧‧電漿通路
15‧‧‧覆蓋板
16‧‧‧狹縫板
16A‧‧‧狹縫
16B‧‧‧狹縫
17‧‧‧天線本體
18‧‧‧減速板
19‧‧‧冷媒區塊
19A‧‧‧冷媒水通路
20‧‧‧徑向線槽孔天線
21‧‧‧同軸波導器
21A‧‧‧同軸波導器
21B‧‧‧中央導線
31‧‧‧處理氣體供應機構
31A‧‧‧氣體通路
31B‧‧‧處理氣體通路
31C‧‧‧處理氣體供應通路
31D‧‧‧處理氣體噴嘴孔
111A‧‧‧排氣口
111B‧‧‧延伸部分
111G‧‧‧溝槽
111P‧‧‧電漿入口
111R‧‧‧處理氣體入口
111S‧‧‧密封環
111T‧‧‧密封環
111U‧‧‧密封環
311‧‧‧導電構件
312‧‧‧導電構件
圖1與圖2係顯示依照本發明之第一實施例之微波電漿處理設備之結構的圖；圖3係顯示圖1與圖2之微波電漿處理設備之處理氣體供應機構之結構的立體圖；及圖4係顯示構成圖3之一部分處理氣體供應機構之盤狀導電體的底視圖。
10‧‧‧微波電漿處理設備
11‧‧‧處理容器
11A‧‧‧空間
11B‧‧‧空間
11C‧‧‧空間
11G‧‧‧排氣口
11V‧‧‧閥
12‧‧‧基板
13‧‧‧台階
13A‧‧‧高頻電源
14‧‧‧噴淋板
14A‧‧‧電漿通路
14B‧‧‧電漿通路
14C‧‧‧電漿通路
15‧‧‧覆蓋板
16‧‧‧狹縫板
17‧‧‧天線本體
18‧‧‧減速板
19‧‧‧冷媒區塊
19A‧‧‧冷媒水通路
20‧‧‧徑向線槽孔天線
21‧‧‧同軸波導器
21A‧‧‧同軸波導器
21B‧‧‧中央導線
31‧‧‧處理氣體供應機構
31A‧‧‧氣體通路
111A‧‧‧排氣口
111B‧‧‧延伸部分
111G‧‧‧溝槽
111P‧‧‧電漿入口
111R‧‧‧處理氣體入口
111S‧‧‧密封環
111T‧‧‧密封環
111U‧‧‧密封環

Claims (9)

  1. 一種半導體裝置，包含：一氟化絕緣膜；及一SiCN膜，直接沉積在該氟化絕緣膜上，其中在該SiCN膜內的氮密度從該氟化絕緣膜與該SiCN膜之間的界面減少。
  2. 如申請專利範圍第1項之半導體裝置，其中該氮密度逐漸減少。
  3. 如申請專利範圍第1項之半導體裝置，其中該SiCN膜係藉由使位在分隔成複數區域之一容器內的電漿氣體發生反應而產生。
  4. 如申請專利範圍第3項之半導體裝置，其中該SiCN膜係藉由調整位在該複數區域內的氣體流量比例而產生。
  5. 如申請專利範圍第4項之半導體裝置，其中形成該SiCN膜之內部的流量比例係不同於形成該SiCN膜之外部的流量比例。
  6. 如申請專利範圍第5項之半導體裝置，其中該容器包含一上區域以及一下區域，而當形成該SiCN膜的外部時，流入該上區域的氣體量大於流入該下區域的氣體量。
  7. 如申請專利範圍第5項之半導體裝置，其中該容器包含一上區域以及一下區域，而當形成該SiCN膜的內部時，流入該下區域的氣體量大於流入該上區域的氣體量。
  8. 如申請專利範圍第6項之半導體裝置，其中使一添加氣體流入該上區域，並且使一材料氣體流入該下區域。
  9. 如申請專利範圍第4項之半導體裝置，其中該氣體流量比例係隨著時間加以調整。
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