TWI582260B - 利用化學氣相沉積法在矽基板上製備鎳薄膜以及在矽基板上製備矽化鎳薄膜的方法 - Google Patents

利用化學氣相沉積法在矽基板上製備鎳薄膜以及在矽基板上製備矽化鎳薄膜的方法 Download PDF

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TWI582260B
TWI582260B TW105104568A TW105104568A TWI582260B TW I582260 B TWI582260 B TW I582260B TW 105104568 A TW105104568 A TW 105104568A TW 105104568 A TW105104568 A TW 105104568A TW I582260 B TWI582260 B TW I582260B
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鍋谷俊一
鈴木和治
原田了輔
曾根孝之
橫尾道弘
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田中貴金屬工業股份有限公司
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Description

利用化學氣相沉積法在矽基板上製備鎳薄膜以及在矽基板上製備矽化 鎳薄膜的方法
本發明係關於一種利用化學沉積法(化學氣相沉積法(CVD法)、原子層沉積法(ALD法)),直接在矽基板上製備高品質之鎳薄膜的方法。又關於一種使該鎳薄膜矽化,以製備矽化鎳薄膜的方法。
近年,為了謀求金屬氧化物半導體場效電晶體(MOSFET;metal-oxide-semiconductor field-effect transistor)等的半導體元件中的電極材料的低電阻化,而研究「使鎳薄膜矽化之矽化鎳膜(NiSi)」的應用。作為該NiSi膜的形成方法,一般係在矽基板上形成鎳薄膜,並藉由對其進行熱處理,使矽從矽基板擴散而矽化,進而產生NiSi。
如上所述,作為用於在矽基板上製備NiSi薄膜之鎳薄膜的製備方法,至今為止雖有很多應用濺鍍法等物理氣相沉積法(PVD)的例子,但化學氣相沉積法(CVD法)及原子層沉積法(ALD法)等化學氣相沉積法的應用逐漸引起矚目。近幾年來,半導體元件邁向三維積體化,因此所使用之電極亦變成立體結構。接著,因PVD法難以形成立體結構的薄膜,故宜應 用階梯覆蓋(step coverage)性能優異的化學氣相沉積法。
作為利用化學氣相沉積在矽基板上形成鎳膜的方法,例如,使用鎳脒(nickel amidinate)作為前驅物(原料化合物),並使用NH3作為反應氣體的方法,被認為係基本的方法(專利文獻1)。然而,使用鎳脒所產生的鎳膜,因為源自原料物質的氮(N)及源自反應氣體(即NH3)的N被導入膜中,而在膜中產生氮化鎳(NiNx)。這種雜質成為阻礙電極低電阻化的主要原因,專利文獻1中,在成膜後進行熱處理以去除N。以上的鎳薄膜的成膜及高純度化製程,最終可形成無N成分的高純度且低電阻的鎳薄膜。接著,亦可藉由在矽基板上形成這種高純度的鎳薄膜,來製備NiSi膜。
然而,這種經由形成NiNx膜的方法中,隨著去除N而產生膜密度降低及形態(粗糙度)變化的情況,更進一步,亦具有殘留N的疑慮。因此具有「形成電阻相對塊材鎳較高之鎳薄膜」這樣的問題。而且,即使將這種鎳薄膜矽化,亦無法形成較佳的電極。
此處,為了形成無雜質殘留之高品質的鎳薄膜,將作為前驅物及反應氣體之構成元素的可能殘留於鎳薄膜中的N等元素排除,可說是適當的應對方法。從此觀點來看,作為較佳條件,宜使用烴系的鎳錯合物作為前驅物,並使用氫氣作為反應氣體。這是因為,只要是烴系鎳錯合物,則錯合物成分係以烴的形態排出,進而減少雜質殘留於薄膜中的疑慮。
【先前技術文獻】 【專利文獻】
【專利文獻1】WO2011/040385國際公開案。
然而,至今為止尚無可使用烴系鎳錯合物直接在矽上製備鎳薄膜的研討例。根據本案發明人等的研究,作為以往使用烴系鎳錯合物形成鎳薄膜的例子,有幾個關於形成有氧化膜(SiO2)之矽基板的報告例,可以此形成較佳的鎳膜。然而,無氧化膜的矽材表面難以形成連續性的鎳薄膜,在本案發明人等的實際試驗之中,亦確認了此現象。
接著,在具有氧化膜的矽基板上形成鎳膜的情況,並無法將其矽化而成為NiSi。因為矽化係藉由使矽擴散到鎳膜而進行,若鎳膜與矽基板之間具有氧化膜,則其變成障壁而阻礙矽往鎳膜擴散。因此,為了形成NiSi薄膜,必須在矽材表面形成鎳薄膜。
因此,本發明為了形成NiSi薄膜,提供一種可直接在矽基板上形成鎳薄膜,且在形成之鎳薄膜中無殘留雜質的方法。又,亦提出將形成之鎳薄膜確切地進行矽化以製備NiSi薄膜的方法。
本案發明人等,為了解決上述課題,而研究「一方面使用烴系鎳錯合物作為前驅物,一方面直接在矽基板上使鎳成膜」的條件。在該研究中,首先,摸索在烴系鎳錯合物中,可直接在矽上成膜的範圍(鎳錯合物的種類),同時對各種成膜條件進行研究。又,在此研究中必需留意,即使是烴系鎳錯合物,亦無法斷言在鎳薄膜中殘留雜質的情形不常發生。亦即,雖相較於鎳脒,烴系鎳錯合物殘留雜質的疑慮較低,但因其構成元素,可能使碳(C)被導入鎳膜之中。本案發明人等的研究中,亦具有根據成膜條件的設定,而在鎳膜(基板與鎳膜的交界部)殘留碳的疑慮。接著,本案發明 人等進行深入研究的結果,發現在矽基板上形成較佳之鎳薄膜的成膜條件,從而完成本發明。
亦即,本發明係一種製備鎳薄膜之方法,其係利用化學氣相沉積法在矽基板上製備鎳薄膜之方法,其特徵為:使用如下式所示之結構中不含碳與氫以外之元素的烴系鎳錯合物作為原料化合物,該鎳錯合物係將環戊二烯基(Cp)或其衍生物,及由3~9個的碳原子所形成之鏈狀或環狀的烯基或其衍生物配位於鎳的鎳錯合物;使用氫氣作為反應氣體;更進一步,以成膜壓力1~150torr、成膜溫度80~250℃作為成膜條件。
(式中,X為3~9個的碳原子所形成之鏈狀或環狀的烯基或其衍生物;環戊二烯基的取代基R1~R5為CnH2n+1;n為0~6之整數)。
以下對本發明進行進一步詳細說明。本發明之鎳薄膜之製備方法,基本步驟係以一般的化學氣相沉積法為基準。以化學氣相沉積法所進行的薄膜製備步驟,係使成為前驅物的金屬錯合物氣化,並將其與反應氣體一併輸送至基板表面,以在基板表面從金屬錯合物析出金屬。本發明之鎳薄膜的製備方法亦係按照該步驟進行,但其特徵係規定使用之前驅物 的種類與成膜條件(成膜壓力、成膜溫度)。在以下的說明中對該特徵部分進行詳細說明。
本發明中用於製備鎳薄膜的前驅物,係結構中除了碳與氫以外不包含其他元素的烴系鎳錯合物。如上所述,係用於抑制雜質殘留於已成膜的鎳之中。接著,本發明所使用之烴系鎳錯合物,係上述之特定的烴系鎳錯合物。在烴系鎳錯合物中使用該鎳錯合物,係因為其與氫氣具有適當的反應性以及具有優異的氣化特性。
該烴系鎳錯合物,係配位有環戊二烯基或其衍生物,及鏈狀或環狀的烯基或其衍生物的鎳錯合物。使烯基的碳數為3~9,係因為考慮到鎳錯合物的氣化、分解特性。宜為環狀的烯基(環烯基),特別宜為下式所示之化合物或該等衍生物中的任一種:環丁烯基、環戊烯基、環己烯基、環庚烯基、環辛烯基、環壬烯基。配位有該等基團的鎳錯合物,在氣化階段中穩定氣化,且在成膜階段中易於低溫分解,適合作為化學沉積用原料。
(R6~R65為CnH2n+1,n=0~6;n為整數)。
又,該鎳錯合物中,配位於鎳的另一個配位子、即環戊二烯 (Cp),除了取代基(R1~R5)皆為氫原子以外,亦可為經烷基取代的衍生物。作為環戊二烯衍生物,宜為「在取代基(R1~R5)之中,一個為烷基,剩餘4個取代基為氫原子」之衍生物。又,作為取代基(R1~R5),碳數可為0~6,宜為4以下。若環戊二烯的取代基過長,則具有下述傾向:有機鎳化合物的熔點上升,蒸氣壓隨著分子量增加而降低,導致難以蒸發而在成膜時,膜中混入雜質等,而難以維持適合作為化學沉積用原料的特性。
利用化學氣相沉積法進行鎳成膜時,使上述前驅物氣化並供給至矽基板。此時,將氣化之前驅物與反應氣體一併輸送至基板上。為了不在鎳膜中殘留雜質,該反應氣體係使用氫氣。
基板係使用矽基板,其可為單晶矽、多晶矽中的任一種,宜使用高純度者。對於矽基板,使用在鎳成膜前已去除氧化膜者。
又,根據本案發明人等的研究,使用在矽基板的表面摻入適量的B、P、As中任一種的情況中,可快速地形成連續性的鎳薄膜。藉由摻入B、P或As來提高鎳的成膜速度的理由並不明確,但本案發明人等發現,基板表面狀態的變化促進鎳化合物的吸附與分解。使B、P或As的最大劑量為1018atms/cm3。因為即使超過1018atms/cm3,成膜速度亦不會變化。較宜為1013~1016atms/cm3。於矽基板摻入B、P或As的方法並無特別限定,可使用離子注入法、熱擴散法等。
關於本發明中以烴系鎳錯合物所進行之鎳成膜的條件,係規定成膜壓力與成膜溫度。該等成膜條件,成為直接在矽上使鎳成膜的重要條件。
成膜壓力係為了成膜所需之前驅物的供給量而規定。若成膜 壓力超過150torr,則前驅物難以氣化而變得供給不足。又,低於1torr的情況,供給量亦為不足。較佳成膜壓力為50~120torr,易於得到膜的連續性與平滑性。
又,根據本案發明人等的研究,可確認利用烴系鎳錯合物之鎳薄膜,殘留雜質的可能性雖低,但具有因成膜溫度變為高溫而殘留碳的疑慮。接著,因成膜溫度超過250℃,則增大碳殘留量。因此,本發明中使成膜溫度為80~250℃。若未滿80℃,則難以進行成膜反應而難以得到必要的膜厚。較佳成膜溫度為100~220℃。另外,成膜溫度係指基板的加熱溫度。
接著,對本發明之矽化鎳(NiSi)薄膜之製備方法進行說明。上述鎳薄膜的製備步驟中,在成膜之後的階段,純度高且形態性亦為優異。而且因為直接接觸矽,故亦易於藉由矽化而形成NiSi膜。可藉由在惰性氣體(宜為氮氣、氬氣)或氫氣環境下,加熱基板並以300~600℃加熱鎳膜,以進行矽化。
根據本發明,可在直接接觸成為基板之矽的狀態下製備鎳薄膜。以本發明所形成之鎳薄膜,不含C、N、O等雜質,並易於藉由適當的熱處理進行矽化而形成NiSi膜。
第一圖係顯示因矽基板有無氧化膜而能否進行鎳成膜及矽化(第一實施形態)的結果的影像。
第二圖係顯示鎳在摻入B之矽基板上的成膜速度之測定結果(第二實施形態)的圖。
第三圖係確認利用熱處理對在第二實施形態中成膜之鎳薄膜進行矽化的影像。
第四圖係顯示矽化後之薄膜剖面的X射線光電子能譜(XPS;x-ray photoelectron spectroscopy)分析結果的圖。
以下,就本發明中的最佳實施形態進行說明。
第一實施形態:此實施形態係為了研究可否以烴系鎳錯合物在矽基板上形成鎳成膜及其矽化而進行。此處,準備多片高純度矽基板,並分別對其進行成膜試驗。準備「藉由酸洗去除氧化膜之矽基板」和「不進行酸洗而保留氧化膜之矽基板」兩種矽基板。酸洗係將基板浸漬於稀釋氫氟酸(DHF;dilute hydrofluoric acid)(0.5%)5分鐘,以去除表面的氧化膜。
成膜試驗使用(η3-環己烯基)(η5-環戊二烯)鎳(II)作為前驅物。接著,使用冷壁(Cold Wall)式的成膜裝置,藉由CVD法形成鎳薄膜。成膜試驗後,對基板表面進行電子顯微鏡(SEM;scanning electron microscope)觀察,並評估鎳成膜的優劣。成膜條件如下所述。
前驅物加熱溫度:90℃
基板加熱溫度:200℃
載體氣體:氬氣60sccm
反應氣體:氫氣100ccm
壓力:100torr
成膜時間:20分鐘
接著,對成膜之鎳薄膜,進行熱處理以使其矽化。熱處理條件係使基板溫度為500℃,並在10sccm氫氣+10sccm氬氣的氣體環境中加熱 基板。加熱時間皆為10分鐘。
第一圖係各基板中鎳薄膜及熱處理後之薄膜的SEM影像。由第一圖可知,藉由本實施形態所使用之前驅物及成膜條件,直接在矽基板上使鎳成膜。接著,可確認藉由將其進行熱處理以進行矽化,進而在矽基板上形成SiNi薄膜。另一方面,具有氧化膜(SiO2)的矽基板亦可形成鎳薄膜。然而,即使對其進行熱處理,亦不會變化成SiNi薄膜。這被認為係因為鎳薄膜與矽基板之交界的SiO2層成為屏障層,阻礙矽的擴散而沒有進行矽化。
第二實施形態:此處,以使矽基板表面摻入B的狀態,製備鎳薄膜。在基板上摻入B,係在注入離子之後以900℃進行30分鐘的退火處理,藉此摻入1015atms/cm3 B,並與上述相同地,在成膜前進行酸洗。本實施形態的成膜試驗中,使用與第一實施形態相同的前驅物((η3-環己烯基)(η5-環戊二烯)鎳(II))進行鎳成膜,並評估成膜速度。成膜條件如下所述,測定成膜時間1分鐘、2分鐘、5分鐘、15分鐘的情況中鎳薄膜的膜厚。
前驅物加熱溫度:90℃
基板加熱溫度:175℃
載體氣體:氬氣100sccm
反應氣體:氫氣100ccm
壓力:100torr
成膜時間:1分鐘、2分鐘、5分鐘、15分鐘
第二圖係顯示該成膜試驗的結果。由第二圖可知,摻入B的矽基板中,在鎳薄膜的成膜過程中幾乎沒有醞釀時間(incubation time),從成膜開始即開始迅速成長。又,相對於成膜時間,膜厚線性地增大。本實 施形態中,顯示8.2nm/min的較為良好的成膜速度。
又,對以本實施形態的成膜時間1分鐘、2分鐘製備鎳薄膜之基板,進行熱處理以使鎳薄膜矽化成NiSi薄膜。熱處理條件係使基板溫度為500℃,並在10sccm氫氣+10sccm氬氣的氣體環境中加熱基板。加熱時間皆為10分鐘。
第三圖係各鎳薄膜的熱處理前後的SEM影像。每個鎳薄膜都藉由熱處理在其上部形成NiSi薄膜。可確認到即使是鎳薄膜較薄的情況(成膜時間1分鐘),亦可均勻地矽化。
又,第四圖中顯示NiSi薄膜(Ni的成膜時間為2分鐘)的X射線光電子能譜分析的結果。本實施形態所形成的NiSi薄膜中,並無測量到C、N、O中任一種雜質。又,可確認到Ni與Si的組成比亦幾乎為1:1,可得到良好品質的矽化鎳薄膜。
【產業上的可利用性】
本發明之方法,可直接在矽基板上製備鎳薄膜,並可得到無殘留C、N、O等雜質的高品質鎳薄膜。又,可藉由熱處理直接使該鎳薄膜成為NiSi膜。本發明之方法,係以化學氣相沉積法這種段差被覆性能優異的薄膜製程為基礎,適合製造各種半導體元件中具有三維結構的立體電極。

Claims (2)

  1. 一種製備鎳薄膜之方法,係利用化學氣相沉積法在沒有氧化膜的矽基板上直接製備鎳薄膜之方法,其特徵為:使用表面摻入B、P、As中任一種的矽基板,作為矽基板;使用如下式所示之結構中不含碳與氫以外之元素的烴系鎳錯合物作為原料化合物,該鎳錯合物係將環戊二烯基(Cp)或其衍生物,及由3~9個的碳原子所形成之鏈狀或環狀的烯基或其衍生物配位於鎳的鎳錯合物;使用氫氣作為反應氣體;更進一步,以成膜壓力1~150torr、成膜溫度80~250℃作為成膜條件; (式中,X為3~9個的碳原子所形成之鏈狀或環狀的烯基或其衍生物)。
  2. 一種矽化鎳薄膜之製備方法,其特徵為:利用申請專利範圍第1項之方法製備鎳薄膜後,藉由在惰性氣體或氫氣體環境下以300~600℃加熱基板,以使鎳薄膜矽化。
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