TW201704244A - 五氯二矽烷 - Google Patents

五氯二矽烷 Download PDF

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TW201704244A
TW201704244A TW105115713A TW105115713A TW201704244A TW 201704244 A TW201704244 A TW 201704244A TW 105115713 A TW105115713 A TW 105115713A TW 105115713 A TW105115713 A TW 105115713A TW 201704244 A TW201704244 A TW 201704244A
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ruthenium
film
precursor
nitrogen
substrate
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TW105115713A
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TWI773643B (zh
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周曉兵
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道康寧公司
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    • H01L21/02208Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
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Abstract

所揭示者係一種用於沉積的矽前驅物化合物,該矽前驅物化合物包含五氯二矽烷;一種用於成膜的組成物,該組成物包含該矽前驅物化合物,以及下列中之至少一者:惰性氣體、分子氫、碳前驅物、氮前驅物、以及氧前驅物;一種使用該矽前驅物化合物在一基材上形成一含矽膜的方法,以及藉此所形成的含矽膜。

Description

五氯二矽烷
一般而言,本發明關於一種用於成膜的前驅物化合物以及組成物、關於一種用於以該前驅物化合物或組成物經由一沉積設備形成一膜的方法、以及關於藉由該方法所形成的膜。
元素矽、及其他矽材料(諸如氧化矽、碳化矽、氮化矽、碳氮化矽、及氧碳氮化矽)具有各種已知的用途。例如,在用於電子或光伏元件的電子電路之製造中,矽膜可用來作為半導體、絕緣層或犧牲層。
已知製備矽材料的方法可以使用一或多種矽前驅物。這些矽前驅物的使用不限於製造用於電子或光伏半導體應用的矽。例如,矽前驅物可用於製備基於矽之潤滑劑、彈性體、及樹脂。
我們在電子和光伏產業中看到對於改良的矽前驅物之長久以來的需求。我們認為改良的前驅物會實現降低沉積溫度及/或製造出更精細的半導體特徵,以得到性能更好的電子和光伏元件。
【發明摘要】
我們已發現一種改良的矽前驅物。本發明提供下列實施例之各者:一種用於沉積的前驅物化合物,該前驅物化合物包含五氯二 矽烷(後文中,「矽前驅物化合物(Silicon Precursor Compound)」)。
一種用於成膜的組成物,該組成物包含該矽前驅物化合物,以及下列中之至少一者:惰性氣體、分子氫、碳前驅物、氮前驅物、以及氧前驅物。
一種在一基材上形成一含矽膜的方法,該方法包含在該基材存在下,使由五氯二矽烷所組成的矽前驅物的蒸氣經歷沉積條件,以在該基材上形成一含矽膜,其中該含矽膜係一矽氮膜或一矽氧膜,且該方法使用原子層沉積。
一種根據該方法所形成的膜。
【發明詳述】
發明內容及摘要以引用方式併入本文中。上文概述之本發明實施例、用途及優點將在下文進一步描述。
本發明的態樣在本文使用各種常見慣例來描述。例如,所有的物質狀態都是在25℃和101.3kPa下測定,除非另有指明。所有的%均按重量計,除非另有說明或指明。除非另有指明,所有的%值都是以所有用以合成或製造該組合物的成分之總量計,所有用以合成或製造該組合物的成分加總為100%。任何包含一個屬及其次屬的馬庫西群組包括該屬中的次屬,例如在「R係烴基或烯基(R is hydrocarbyl or alkenyl)」中,R可以是烯基,或者R可以是烴基,而該烴基除了其他次屬之外還包括烯基。對於美國專利實務,茲以引用方式將本文中引用的所有美國專利申請公開案和專利、 或其一部分(若只引用該部分)在以併入的標的物不與本實施方式牴觸下併入本文中,若有任何這樣的牴觸則以本實施方式為準。
本發明的態樣在本文中使用各種專利用語來描述。例如,「替代地(alternatively)」指示不同且有區別的實施例。「比較例(comparative example)」意指非發明的實驗。「包含(comprises)」及其變型(包含(comprising)、由…組成(comprised of))是開放式的。「由……所組成(consists of)」及其變型(由…組成(consisting of))是封閉式的。「接觸(contacting)」表示使進行物理接觸。「可(may)」代表有選擇性,而非必要性。「可選(地)(optionally)」代表可存在或不存在。
本發明的態樣在本文中使用各種化學用語來描述。該等用語之涵義相對應於其由IUPAC發布之定義,除非本文另有定義。為了方便起見,對某些化學用語加以定義。
用語「沉積(deposition)」是在特定位置上產生冷凝物質的製程。冷凝物質在尺寸上可以或可不受到限制。沉積的實例為形成膜、形成棒、以及形成粒子的沉積。
用語「膜(film)」意指在一個維度受到限制的材料。受限的維度可以特徵化為「厚度(thickness)」,並作為在所有其他條件相同之下,隨著沉積該材料以形成膜的過程之時間長度增加而增加的維度。
用語「鹵素(halogen)」是指氟、氯、溴或碘,除非另有定義。
用語「IUPAC」是指國際純化學暨應用化學聯合會。
用語「缺乏(lack)」是指不含或完全不存在。
「元素週期表(Periodic Table of the Elements)」是指由IUPAC 在2011年公布的版本。
用語「前驅物(precursor)」意指含有所指元素的原子並且有用於作為在藉由沉積方法所形成的膜中之元素來源的物質或分子。
用語「分離(seperate)」意指造成實體上分開,並因此不再直接接觸。
用語「基材(substrate)」意指具有至少一個表面的物理支撐,另一材料可配置於該至少一個表面上。
本發明提供用於成膜的矽前驅物化合物以及組成物。儘管矽前驅物化合物不限於此等應用,但矽前驅物化合物特別適合用於形成含矽膜之沉積製程。例如,可在其他應用中利用矽前驅物化合物,如作為用於製備矽氧烷或矽氮烷材料的反應物。本發明進一步提供形成一種膜的方法,以及根據該方法所形成的膜。
矽前驅物化合物具有化學名稱:五氯二矽烷,該化學名稱具有通式HSiCl2SiCl3。當矽前驅物化合物係用於本發明之組成物及方法中時,矽前驅物化合物可具有自99面積%(GC)至99.9999999面積%(GC)的純度。
矽前驅物化合物可以任何方式提供。例如,矽前驅物化合物可經合成或以其他方式獲得以用於該方法中。在一實施例中,矽前驅物化合物係藉由三氯矽烷(HSiCl3)的熱分解(在600℃至800℃加熱)合成。用於合成矽前驅物化合物的額外實施例包括在矽存在或不存在下之四氯化矽與氫的還原性偶合;四氯化矽與三氯矽烷間之去氫氯化(dehydrochlorinative)偶合;矽或金屬矽化物的氫氯化,該等金屬矽化物係諸如矽化鎂及矽化銅;較高矽數之氯矽烷的氫氯化,諸如過氯新戊矽烷;以金屬氫化物部分還原 六氯二矽烷,該等金屬氫化物係諸如LiH、LiAlH4、NaH、NaAlH4、LiAl(OBu-t)3H、LiAl(Bu-i)2(OBu-t)H、二異丁基氫化鋁、紅鋁(Vitride)、NaBH4、Mg(BH4)2、(CH3)4N(BH4)、KB(C2H5)3H、三(第二丁基)硼氫化鈉(N-Selectride)、三(第二丁基)硼氫化鋁(L-Selectride)、三(第二丁基)硼氫化鉀(K-Selectride)、以及三(2-異戊基)硼氫化鉀(KS-Seiectride);以及二矽烷的氯化。矽前驅物化合物可經由蒸發或汽提而分離。
如上所述,用於成膜的組成物包含矽前驅物化合物,以及下列中之至少一者:惰性氣體、分子氫、碳前驅物、氮前驅物、以及氧前驅物;替代地下列中之至少一者:惰性氣體、氮前驅物、以及氧前驅物。在用於形成元素矽膜及單晶膜之組成物中,分子氫可與矽前驅物化合物一起使用,該元素矽膜包括非晶矽、多晶矽。於本文中一般而言,分子氫、碳前驅物、氮前驅物、或氧前驅物的蒸氣或氣體狀態可稱作額外反應物氣體。
在用於根據本方法的實施例形成矽碳膜之組成物中,碳前驅物可與矽前驅物化合物一起使用。矽碳膜含有Si以及C原子且可包含碳化矽。碳前驅物可包含下列、替代地基本上由下列所組成、替代地由下列所組成:C、H、及可選地Si原子。當碳前驅物係在用於形成碳氮化矽膜或氧碳化矽膜之方法中使用時,包含C、H、及可選地Si原子的碳前驅物可進一步分別包含N或O原子,或當碳前驅物係在用於形成氧碳氮化矽膜之方法中使用時,該包含C、H、及可選地Si原子的碳前驅物可進一步包含N及O原子。基本上由C、H、及可選地Si原子所組成之碳前驅物缺乏N及O原子,但可以可選地具有一或更多個鹵素原子(如,Cl)。由C及H原子所組成之碳前驅物的實例係烴,諸如烷。由C、H、及Si原子所組成之碳前驅物 的實例係烴基矽烷,諸如丁基二矽烷或四甲基矽烷。
在用於根據本方法的實施例形成矽氮膜之組成物中,氮前驅物可與矽前驅物化合物一起使用。矽氮膜含有Si及N原子以及可選地C及/或O原子,且可包含氮化矽、氧氮化矽、或氧碳氮化矽。氮化矽可以是SixNy,其中下標x係1、2、或3,而下標y係一自1至5之整數。氮前驅物可包含N原子以及可選地H原子;替代地氮前驅物可基本上由N原子以及可選地H原子所組成;替代地氮前驅物可由N以及可選地H原子所組成。當氮前驅物係在用於形成碳氮化矽膜或氧氮化矽膜之方法中使用時,包含N以及可選地H原子的氮前驅物可進一步分別包含C或O原子,或當氮前驅物係在用於形成氧碳氮化矽膜之方法中使用時,該包含N以及可選地H原子的氮前驅物可進一步包含C及O原子。基本上由N原子以及可選地H原子所組成之氮前驅物缺乏C及O原子,但可選地可具有一或更多個鹵素原子(如,Cl)。由N原子所組成之氮前驅物的一實例係分子氮。由N及H原子所組成之氮前驅物的實例係氨以及胼。由O及N原子所組成之氮前驅物的一實例係一氧化氮(N2O)及二氧化氮(NO2)。
在用於根據本方法的一實施例形成矽氧膜之組成物中,氧前驅物可與矽前驅物化合物一起使用。矽氧膜含有Si及O原子以及可選地C及/或N原子,且可包含氧化矽、氧碳化矽、氧氮化矽、或氧碳氮化矽。氧化矽可以是SiO或SiO2。氧前驅物可包含O原子以及可選地H原子;替代地可基本上由O原子以及可選地H原子所組成;替代地可由O原子以及可選地H原子所組成。當氧前驅物係在用於形成氧碳化矽膜或氧氮化矽膜之方法中使用時,包含O原子以及可選地H原子的氧前驅物可進一步分別包 含C或N原子,或當該氧前驅物係在用於形成氧碳氮化矽膜之方法中使用時,該包含O原子以及可選地H原子的氧前驅物可進一步包含C及N原子。由O原子所組成之氧前驅物的實例係分子氧及臭氧。臭氧可以用在空氣中至高5% v/v或於分子氧中至高14% v/v之形式遞送。由O及H原子所組成之氧前驅物的實例係水及過氧化氫。由O及N原子所組成之氧前驅物的一實例係一氧化氮及二氧化氮。
惰性氣體可與前述前驅物之任一者以及組成物或方法的任一實施例組合使用。惰性氣體的實例係氦、氬、及其混合物。例如,在其中所形成之含矽膜係元素矽膜之方法的實施例中,氦可與矽前驅物化合物及分子氫組合使用。替代地,在其中所形成之含矽膜分別係矽碳膜、矽氮膜、或矽氧膜之方法的實施例中,氦可與矽前驅物化合物及碳前驅物、氮前驅物、及氧前驅物之任一者一起使用。
本方法所形成之膜係含有Si的材料,且在一個維度受到限制,該維度可稱作該材料的厚度。含矽膜可以是元素矽膜、矽碳膜、矽氮膜、或矽氧膜(如氮化矽、碳氮化矽、氧氮化矽、或氧碳氮化矽膜)、替代地矽氮膜或矽氧膜(如氮化矽、氧化矽)。本方法所形成之元素矽膜缺乏C、N、及O原子,且可以是非晶形或結晶Si材料。本方法所形成之矽碳膜含有Si及C原子以及可選地N及/或O原子。本方法所形成之矽氮膜含有Si及N原子以及可選地C及/或O原子。本方法所形成之矽氧膜含有Si及O原子以及可選地C及/或N原子。
該膜可有用於電子或光伏應用。如,氮化矽膜可作為絕緣層、鈍化層、或在電容器中之多晶矽層之間的介電層而形成。
形成膜的方法使用原子層沉積設備。本方法中所利用之沉積設備一般係基於所欲之形成膜之方法而選擇,且可以是任何所屬技術領域中具有通常知識者已知之沉積設備。
在某些實施例中,沉積設備包含物理氣相沉積設備。在這些實施例中,沉積設備一般選自濺鍍設備、原子層沉積設備(包括電漿增強原子層沉積設備以及熱原子層沉積設備)、以及直流電(DC)磁控濺鍍設備,替代地沉積設備係原子層沉積設備。這些物理氣相沉積設備之各者的最佳操作參數係基於該方法中所利用之矽前驅物化合物,及在其中利用了經由沉積設備所形成之膜的所欲應用而定。在某些實施例中,沉積設備包含濺鍍設備。濺鍍設備可以是例如離子束濺鍍設備、反應性濺鍍設備、或離子輔助濺鍍設備。
然而,較佳的是沉積設備包含原子層沉積設備。在使用原子層沉積設備之實施例中,形成膜之方法可稱作原子層沉積方法,且包括電漿增強原子層沉積(PEALD)、空間原子層沉積(SALD)、以及熱原子層沉積(TALD)。一般而言,原子層沉積方法係所屬技術領域中眾所周知的。
在使用化學氣相沉積設備之方法的實施例中,化學氣相沉積設備可以選自,例如可流動化學氣相沉積設備、熱化學氣相沉積設備、電漿增強化學氣相沉積設備、光化學氣相沉積設備、電子迴旋共振設備、感應耦合電漿設備、磁約束電漿設備、低壓化學氣相沉積設備、以及噴射氣相沉積設備。這些化學氣相沉積設備之各者的最佳操作參數係基於該方法中所利用之矽前驅物化合物,及在其中利用了經由沉積設備所形成之膜的所欲應用而定。在某些實施例中,沉積設備包含電漿增強化學氣相沉積設 備。在其他實施例中,沉積設備包含低壓化學氣相沉積設備。
在化學氣相沉積中,用於形成膜之氣體一般係在沉積艙中混合與反應。該反應形成蒸氣狀態之適當膜元素或分子。然後元素或分子沉積在一基材(或晶圓)上且積累以形成膜。一般而言,化學氣相沉積需要對系統添加能量,諸如加熱沉積艙及基材。
一般而言氣體物種之反應係所屬技術領域中眾所周知的,且可經由本發明之方法實行任何習知化學氣相沉積(CVD)技術。例如,可使用方法諸如簡單熱氣相沉積、電漿增強化學氣相沉積(PECVD)、電子迴旋共振(ECRCVD)、大氣壓化學氣相沉積(APCVD)、低壓化學氣相沉積(LPCVD)、超高真空化學氣相沉積(UHVCVD)、氣溶膠輔助化學氣相沉積(AACVD)、直接液體注入化學氣相沉積(DLICVD)、微波電漿輔助化學氣相沉積(MPCVD)、遠端電漿增強化學氣相沉積(RPECVD)、原子層化學氣相沉積(ALCVD)、熱絲化學氣相沉積(HWCVD)、混合物理化學氣相沉積(HPCVD)、快速熱化學汽相沉積(RTCVD)、及氣相磊晶化學氣相沉積(vapor-phase epitaxy chemical vapor,VPECVD)、光輔助化學氣相沉積(vapor-phase epitaxy chemical vapor deposition,PACVD)、火焰輔助化學氣相沉積(FACVD)、或任何相似的技術。
當採用電漿增強原子層沉積方法時,電漿包含合成氣體電漿、氮電漿、或於作為載體之氮或氬氣中之氨電漿、或氧電漿。合成氣體包含氮及氫。所屬技術領域中具有通常知識者將了解合成氣體的組成。
可利用化學氣相沉積來形成具有多種厚度之膜,該等厚度係視膜的最終用途而定。舉例來說,膜可具有數奈米之厚度或數微米之厚度、 或更大或更小之厚度(或落在這些值之間的厚度)。這些膜可以可選地被塗層覆蓋,諸如SiO2塗層、SiO2/改質陶瓷氧化物層、含矽塗層、含矽碳塗層、含碳化矽塗層、含矽氮塗層、含氮化矽塗層、含矽氮碳塗層、含矽氧氮塗層、及/或類鑽石碳塗層。一般而言,此等塗層及其沉積方法係所屬技術領域中已知的。
該方法中所利用之基材係不受限的。在某些實施例中,基材僅受限於在該溫度以及在沉積艙的環境中之熱及化學安定性的需求。因此,基材可以是,例如玻璃、金屬、塑膠、陶瓷、半導體,包括但不限於矽(如單晶矽、多晶矽、非晶矽等)。
基材可具有平坦或經圖案化表面。經圖案化表面具有帶有在以下範圍之寬高比的特徵:自1至500、替代地自1至50、替代地自10至50。CVD或ALD膜可在平坦或經圖案化基材上都適形。
本發明之方法的實施例可包括包含一氧化氮(N2O)之反應性環境。一般而言,此等反應性環境係所屬技術領域中已知的。一般而言在這些實施例中,該方法涉及在一氧化氮的存在下分解矽前驅物化合物。此一方法的一實例描述於美國專利第US 5,310,583號中。利用一氧化氮可修飾在化學氣相沉積方法中形成之所得膜之組成。
一般而言,化學氣相沉積設備,以及因此所利用之化學氣相沉積方法係藉由平衡若干因子而選擇,該等因子包括但不限於矽前驅物化合物、所欲的膜純度、基材的幾何組態、以及經濟考量。
化學氣相沉積以及原子層沉積中所控制之主要操作變數包括但不限於反應器溫度、基材溫度、壓力、在矽前驅物化合物之氣相中的 濃度、任何額外的反應物氣體濃度(例如,任何碳前驅物、氮前驅物、及/或氧前驅物之氣體的濃度)、總氣體流、以及基材。化學氣相沉積以及原子層沉積係自包括但不限於熱解、氧化、還原、水解、及其組合之化學反應而產生。選擇化學氣相沉積以及原子層沉積之最佳溫度需要有對矽前驅物化合物以及所選化學反應之動力學與熱力學之了解。
一般而言,習知化學氣相沉積及原子層沉積方法需要顯著地高反應器溫度,諸如大於600℃,如600℃至1000℃。然而,咸信矽前驅物化合物可以大幅較低的反應器溫度在化學氣相沉積以及原子層沉積中利用。例如,本方法可在自100℃至700℃、替代地自200℃至700℃、替代地自200℃至600℃、替代地自200℃至500℃、替代地自200℃至400℃、替代地自100℃至300℃的反應器溫度實行。實行該方法之反應器溫度可以是恆溫的或動態的。
一般而言,化學氣相及原子層沉積製程以自0.01托至100托、替代地0.01托至10托、替代地自0.1至10托、替代地自1至10托的壓力實施。
化學氣相沉積以及原子層沉積製程一般涉及產生前驅物、運輸前驅物至反應艙中、以及將前驅物吸收至經加熱基材上,或前驅物之化學反應且後續吸收至基材上。以下列舉化學氣相沉積方法的粗略調查以說明大量可用選項中的一些。所屬技術領域中具有通常知識者可調整這些方法以用於原子層沉積。
化學氣相及原子層沉積製程沉積以下厚度的膜:自0.01奈米至1微米、替代地自0.1至100奈米、替代地自1至100奈米、替代地自 10至100nm。
在熱CVD中,膜係藉由使矽前驅物化合物之經蒸氣化形式的氣流通過經加熱基材上而沉積。當矽前驅物化合物之經蒸氣化形式接觸經加熱基材,矽前驅物化合物一般會反應及/或分解以形成膜。
在PECVD中,矽前驅物化合物之經蒸氣化形式係藉由使該矽前驅物化合物通過電漿域而反應,以形成反應性物種。然後反應性物種會集中並沉積在基材上以形成膜。一般而言,PECVD優於熱CVD的優點是可以使用較低的基材溫度。PECVD中所利用之電漿包含衍生自各種來源之能量,該等來源係諸如:放電;在無線電頻率、或微波範圍的電磁場;雷射;或粒子束。儘管可修改這些變數的任一者,但通常PECVD利用於中等功率密度(每平方公分0.1至5瓦特(W/cm2))之無線電頻率(10千赫茲(kHz)至102百萬赫茲(MHz))或微波能量(0.1至10千兆赫茲(GHz))。然而,一般而言具體頻率、功率、以及壓力係依沉積設備而量身打造。
在AACVD中,矽前驅物化合物係溶解在化學介質中以形成混合物。將包含矽前驅物化合物與化學介質之混合物封裝於傳統氣溶膠中。氣溶膠將矽前驅物化合物原子化並引入至經加熱艙中,在該經加熱艙中,矽前驅物化合物經歷分解及/或化學反應。AACVD的一個優點係無需真空就能形成膜之能力。
所選沉積製程以及操作參數將對膜之結構與性質有所影響。通常,控制膜結構的定向、膜聚結之方式、膜的均勻性、以及膜的結晶/非結晶結構係可能的。
應注意的是,也可在沉積艙中使用促進所欲沉積之環境。舉 例來說,於本文中,諸如空氣、氧、氧電漿、氨、胺、胼等之反應性環境或惰性環境皆可使用。
額外地,本發明提供一種根據本方法所形成之膜。膜的組成及結構不僅隨沉積設備及其參數而變動,亦隨所利用的矽前驅物化合物以及於本方法期間存在或不存在任何反應性環境而變動。矽前驅物化合物可與任何其他已知前驅物化合物組合利用,或可在沒有任何其他前驅物化合物之本方法中利用。
因為矽前驅物化合物缺乏至少一個Si-N鍵及Si-C鍵以及Si-O鍵,所以可利用矽前驅物化合物以形成元素矽膜。
替代地,矽前驅物化合物可與傳統上用來形成包括結晶矽或氮化矽之矽膜的其他基於矽之前驅物化合物一起用。在此等實施例中,膜可以是例如結晶的或磊晶的。視在本方法期間反應性環境的存在而定,除了包含矽及氮外,膜可進一步包含氧及/或碳。
矽前驅物化合物之純度可以藉由29Si-NMR、反相液相層析術、或更可能的是藉由如後所述的氣相層析術(GC)而測定。例如,由GC測定的純度可以係自60面積%至100面積%(GC)、替代地自70面積%至100面積%(GC)、替代地自80面積%至100面積%(GC)、替代地自90面積%至100面積%(GC)、替代地自93面積%至100面積%(GC)、替代地自95面積%至100面積%(GC)、替代地自97面積%至100面積%(GC)、替代地自99.0面積%至100面積%(GC)。各100面積%(GC)可獨立地如先前所定義。
藉由以下的非限制性實例來進一步說明本發明,並且本發明實施例可以包括以下限制性實例之特徵和限制的任意組合。環境溫度係約 23℃,除非另有指明。下表包括實例中所用之縮寫。
氣相層析術熱導偵檢器(GC-TCD)條件:具有30公尺之長度、0.32mm之內徑的毛細管柱,且在該毛細管柱的內表面上含有塗層形式的0.25μm厚之固定相,其中該固定相係由苯基甲基矽氧烷所組成。載氣係使用每分鐘105mL的流量之氦氣。GC儀器是Agilent型號7890A氣相層析儀。入口溫度係150℃。GC實驗溫度曲線係由下列所組成:在50℃持溫(保持)2分鐘、以15℃/分鐘的速率升溫到250℃、然後在250℃持溫(保持)10分鐘。
GC-MS儀器和條件:藉由電子撞擊離子化及化學離子化氣相層析-質譜法(EI GC-MS及CI GC-MS)分析樣本。Agilent 6890 GC條件包括一具有30公尺(m)×0.25毫米(mm)×0.50微米(μm)膜組態的DB-1管柱。烘箱程式為在50℃持溫2分鐘、以15℃/分鐘升溫至250℃、且在250℃持溫10分鐘。氦載氣流量為70mL/分鐘的恆定流速和50:1的分離噴射。Agilent 5973 MSD條件包括自15至800道耳頓的MS掃描範圍、EI離子化作用及使用5%的NH3及95%的CH4的客製化CI氣體混合物之CI離子化作用。
29Si-NMR儀器及溶劑:使用Varian 400MHz汞光譜儀。使用C6D6做為溶劑。
1H-NMR儀器及溶劑:使用Varian 400MHz汞光譜儀。使用C6D6做為溶劑。
實例(Ex)A(預示):五氯二矽烷之合成:在700℃溫度加熱三氯矽烷以產出五氯二矽烷,且從所得反應混合物中蒸餾出五氯二矽烷,以給出經純化之五氯二矽烷。
Ex.1(預示):使用矽前驅物化合物以LPCVD形成元素矽膜:使用LPCVD反應器、及含有矽前驅物化合物且與LPCVD反應器流體連通之鼓泡器;加熱含有矽前驅物化合物之鼓泡器至40℃以增加該矽前驅物化合物之蒸氣壓。然後使氫載氣流過鼓泡器,以攜帶矽前驅物化合物的蒸氣進入LPCVD反應器,其中LPCVD反應器含有經加熱到700℃的複數個垂直定向並間隔開的矽晶圓,所以在晶圓上形成適形之元素矽膜。
Ex.2:使用矽前驅物化合物以原子層沉積(ALD)形成氮化矽膜。使用ALD反應器、以含有矽前驅物化合物且與ALD反應器流體連通之 罐(亦即「鼓泡器(bubbler)」)。將含有矽前驅物化合物之鼓泡器維持在室溫(亦即,約23℃)。然後以氬吹掃ALD反應器,其中ALD反應器含有經加熱到500℃或600℃(如下表中所註明)的複數個水平定向並間隔開的矽晶圓。然後使矽前驅物化合物的蒸氣流入ALD反應器中持續10秒。然後再次以氬吹掃ALD反應器,以移除任何殘留的矽前驅物化合物的蒸氣。接下來,使氨流入ALD反應器中持續10秒。然後重複前述步驟順序(矽前驅物、吹掃、氨)直到在晶圓上形成具有所欲厚度之適形氮化矽膜。該表中的一個循環等同十秒前驅物用量、接著十秒Ar吹掃、接著十秒氨用量、以及接著十秒Ar吹掃的一順序。
Ex.3(預示):使用矽前驅物化合物與氨(NH3)以LPCVD形成氮化矽膜:使用LPCVD反應器、及含有矽前驅物化合物且與LPCVD反應器流體連通之鼓泡器;加熱含有矽前驅物化合物之鼓泡器至40℃以增加該矽前驅物化合物蒸氣壓。然後使He載氣流過鼓泡器,以攜帶矽前驅物化合物的蒸氣進入LPCVD反應器,其中LPCVD反應器含有蒸氣氨及經加熱 到500℃的複數個垂直定向並間隔開的矽晶圓,以在晶圓上形成適形氮化矽膜。
Ex.4(預示):使用矽前驅物化合物以氨與PECVD形成氮化矽膜:使用PECVD反應器、及與PECVD反應器流體連通之鼓泡器;加熱含有矽前驅物化合物之鼓泡器至40℃以增加矽前驅物化合物蒸氣壓。然後使He載氣流過鼓泡器,以攜帶矽前驅物化合物的蒸氣進入PECVD反應器,其中PECVD反應器具有衍生自氨的電漿並含有經加熱到500℃的複數個水平定向並間隔開之矽晶圓,從而在晶圓上形成適形氮化矽膜。
Ex.5:使用矽前驅物化合物以含氮原子氣體物種PEALD形成氮化矽膜。使用PEALD反應器以及含有矽前驅物化合物且與PEALD反應器流體連通之罐(「鼓泡器(bubbler)」)。將含有矽前驅物化合物之鼓泡器維持在室溫。以氮吹掃PEALD反應器,其中PEALD反應器含有經加熱到自350至500℃之溫度(如表中各運轉所指明者)的複數個水平定向並間隔開的矽晶圓。然後使矽前驅物化合物的蒸氣流入ALD反應器中。然後再次以氮吹掃ALD反應器,以移除任何殘留的矽前驅物化合物的蒸氣。接下來,在電漿電源打開之狀態,使含氮原子物種(如氨、氮、氮與氫的混合物)流入ALD反應器中。然後再次以氮吹掃ALD反應器,以移除任何殘留的電漿所產生的反應性物種。然後重複前述步驟順序直到在晶圓上形成具有所欲厚度之適形氮化矽膜。下表中的一個循環等同一秒前驅物用量、接著30秒氮吹掃、接著十五秒電漿處理、以及接著30秒氮吹掃的一順序。
Ex.6(預示):使用矽前驅物化合物以LPCVD形成氧化矽膜:使用LPCVD反應器、及與LPCVD反應器流體連通之鼓泡器;加熱含有矽前驅物化合物之鼓泡器至40℃以增加矽前驅物化合物蒸氣壓。然後使He載氣流過鼓泡器,以攜帶矽前驅物化合物的蒸氣進入LPCVD反應器,其中LPCVD反應器具有氧氣氛並含有經加熱到500℃的複數個垂直定向並間隔開的矽晶圓,從而在晶圓上形成適形氧化矽膜。
Ex.7:使用矽前驅物化合物以原子層沉積(ALD)形成氧化矽膜。使用ALD反應器、及含有矽前驅物化合物且與ALD反應器流體連通之鼓泡器。將含有矽前驅物化合物之鼓泡器維持在室溫。以Ar吹掃ALD反應器,其中ALD反應器含有經加熱到400℃至600℃(具體運轉之確切溫度係於下表中指明)的複數個水平定向並間隔開的矽晶圓。然後使矽前驅物化合物的蒸氣流入ALD反應器中。然後再次以Ar吹掃ALD反應器,以移除任何殘留的矽前驅物化合物的蒸氣。然後使臭氧流入ALD反應器中。重複前述步驟順序直到在晶圓上形成具有所欲厚度之適形氧化矽膜。下表中 的一個循環等同三秒前驅物用量、接著10秒氬吹掃、接著10秒臭氧處理、以及接著10秒氬吹掃的一順序。
Ex.7(預示):使用矽前驅物化合物以甲烷及PECVD形成碳化矽膜:使用PECVD反應器、及與PECVD反應器流體連通之鼓泡器;加熱含有矽前驅物化合物之鼓泡器至40℃以增加矽前驅物化合物蒸氣壓。然後使He載氣流過鼓泡器,以攜帶矽前驅物化合物的蒸氣進入PECVD反應器,其中PECVD反應器具有衍生自甲烷的電漿並含有經加熱到500℃的複數個水平定向並間隔開之矽晶圓,從而在晶圓上形成適形的碳化矽膜。
以下的申請專利範圍係以引用方式併入本文中,並且用語「請求項(claim)」可以用語「態樣(aspect)」取代。本發明之實施例也包括這些產生的有編號態樣。

Claims (9)

  1. 一種在一基材上形成一含矽膜的方法,該方法包含在該基材存在下,使由五氯二矽烷所組成的矽前驅物的蒸氣經歷沉積條件,以在該基材上形成一含矽膜,其中該含矽膜係一矽氮膜或一矽氧膜,且該方法使用原子層沉積。
  2. 如請求項1之方法,其包含在該基材存在下,使該矽前驅物的第一蒸氣與包含分子氮、氨、胺、胼、或其之任二或三者的組合的氮前驅物的第二蒸氣經歷沉積條件,以在該基材上形成該含矽膜,其中該含矽膜係該矽氮膜。
  3. 如請求項1之方法,其包含在該基材存在下,使該矽前驅物的第一蒸氣與包含分子氧、臭氧、一氧化氮、二氧化氮、水、過氧化氫、或其之任二或三者的組合的氧前驅物的第二蒸氣經歷沉積條件,以在該基材上形成該含矽膜,其中該含矽膜係該矽氧膜。
  4. 如請求項2至4中任一項之方法,其中該基材係在一經組態以用於原子層沉積的沉積反應器中加熱與沉積,該方法包含重覆地饋送該矽前驅物的該第一蒸氣;以惰性氣體吹掃;饋送該第二蒸氣至該沉積反應器中;以及以惰性氣體吹掃,以在該經加熱基材上形成該含矽膜,其中饋料可相同或不同。
  5. 如請求項1之方法,其中該原子層沉積係電漿增強原子層沉積,且其中該電漿係於氮或氬中之氨電漿或其中該電漿係合成氣體電漿、氮電漿、或氧電漿。
  6. 如請求項3之方法,其中該氣相沉積條件缺乏碳與氧,且該矽氮膜包 含一氮化矽膜。
  7. 如前述請求項中任一項之方法,其中該基材係半導體材料。
  8. 一種用於形成一矽氮膜的組成物,該組成物包含:由五氯二矽烷所組成的矽前驅物、以及氮前驅物。
  9. 一種於一矽氮膜的形成的一方法中之如請求項9之組成物的用途。
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