TW201331997A - 在基板上沉積矽鍺錫層的方法 - Google Patents

在基板上沉積矽鍺錫層的方法 Download PDF

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TW201331997A
TW201331997A TW102100949A TW102100949A TW201331997A TW 201331997 A TW201331997 A TW 201331997A TW 102100949 A TW102100949 A TW 102100949A TW 102100949 A TW102100949 A TW 102100949A TW 201331997 A TW201331997 A TW 201331997A
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tin
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Yi-Chiau Huang
Errol Antonio C Sanchez
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Applied Materials Inc
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Abstract

本文揭露在基板上沉積矽鍺錫(SiGeSn)層的方法。在某些實施例中，本發明之方法可包括下列步驟：在約450攝氏度或更低之溫度下，且在約100托耳或更低之壓力下，將矽源、鍺源及錫源共同流入製程腔室，以於基板之第一表面上沉積該SiGeSn層，其中該錫源包含錫鹵化物。在某些實施例中，該錫鹵化物包含四氯化錫(SnCl4)。

Description

在基板上沉積矽鍺錫層的方法
本發明之實施例一般關於在基板上沉積層的方法，且更特別關於在基板上沉積矽鍺錫(SiGeSn)層的方法。
如矽鍺錫(SiGeSn)之IV族元素的三元合金所具有的鍵結結構是依據合金的成分來決定。諸如鍺(Ge)或錫(Sn)等組成元素之成分的調和可容許對合金中之鍵結結構或應變(strain)的獨立調和。舉例而言，對合金中之鍵結結構或應變的調和可用來增進電子遷移率、調整接合電阻或與從半導體材料形成電子元件有關的其它合適的態樣。不幸地，用來形成SiGeSn合金的慣用錫源不是稀有就是不穩定或二者皆是。範例錫源可為氫化錫等。錫源的不穩定性可能導致不良的合金品質，如因從錫源併入錫(Sn)失敗之故而不具有適當的鍵結結構或應變，及/或缺乏製造再現性(manufacturing reproducibility)。
因此，本發明提供了在基板上沉積SiGeSn層的改良方法。
本文揭露了將矽鍺錫(SiGeSn)層沉積於基板上的方法。在某些實施例中，一種方法可包括下列步驟：在約450攝氏度或更低之溫度下，且在約100托耳或更低之壓力下，將矽源、鍺源及錫源共同流入製程腔室，以於基板之第一表面上沉積SiGeSn層。在某些實施例中，錫鹵化物包含四氯化錫(SnCl4)。
在某些實施例中，可提供電腦可讀取媒體，在該電腦可讀取媒體儲存有指令，當所述指令被執行時，可導致在製程腔室中進行將矽鍺錫(SiGeSn)層沉積於基板上的方法。該方法可包括本文所揭露之方法的任何實施例。
本發明的其它及進一步之實施例描述於下文。
100‧‧‧方法
102‧‧‧步驟
104‧‧‧步驟
202‧‧‧基板
204‧‧‧第一表面
206‧‧‧第二表面
208‧‧‧基板
210‧‧‧介電層
214‧‧‧SiGeSn層
216‧‧‧SiGeSn層的一部分
218‧‧‧蝕刻劑
300‧‧‧設備
302‧‧‧處理腔室
304‧‧‧可選的噴淋頭
306‧‧‧熱源
308‧‧‧基板支撐件
310‧‧‧化學輸送系統
312‧‧‧前驅物接觸腔室
314‧‧‧導管
316‧‧‧第一交叉流氣體導管
318‧‧‧第二交叉流氣體導管
320‧‧‧側進入點
322‧‧‧第一導管
324‧‧‧第二導管
326‧‧‧清潔氣體管線
328‧‧‧供給系統
330‧‧‧排放系統
332‧‧‧排放蓋
334‧‧‧活性源
336‧‧‧凝結阱
338‧‧‧閥
340‧‧‧排放導管
350‧‧‧入口
352‧‧‧真空泵
354‧‧‧減量導管
356‧‧‧減量系統
358‧‧‧被清潔之氣體排放處
360‧‧‧側壁
362‧‧‧氣體供給導管
364‧‧‧氣體供給導管
366‧‧‧節流閥
368‧‧‧護套
370‧‧‧控制器
372‧‧‧中央處理單元
374‧‧‧記憶體
376‧‧‧支援電路
可藉由參照描繪於隨附圖式中之本發明的說明性實施例，而瞭解以上所簡述且更詳細於下文中討論之本發明的實施例。然而，應注意的是，隨附圖式僅為說明本發明之典型實施例，而非用於限制其範疇，本發明亦允許其它等效實施例。
第1圖描繪根據本發明的某些實施例的將矽鍺錫(SiGeSn)層沉積於基板上之方法的流程圖。
第2A至2D圖分別描繪根據本發明的某些實施例的於基板上製造矽鍺錫(SiGeSn)層的階段。
第3圖描繪根據本發明的某些實施例的用於在基板上沉積層的設備。
為方便瞭解，在可能情況下已使用相同元件符號以 指出諸圖所共有之相同元件。圖式並非按比例繪製，且可能為了清晰之故而加以簡化。可考慮將一個實施例之元件及特徵有利地併入其它實施例，而無需進一步記載。
本文揭露了將矽鍺錫(SiGeSn)層沉積於基板上的方法。本發明之方法有利地增進層品質，如達到期望的鍵結結構或層應變，及改進的製造再現性。以下將討論本發明之方法的其它及進一步優點。
第1圖描繪根據本發明的某些實施例的將SiGeSn層沉積於基板上之方法100的流程圖。以下根據在基板上製造SiGeSn層的階段來描述方法100，根據本發明的某些實施例的於基板上製造SiGeSn層的各階段圖示於第2A至2D圖中。如第2A圖所圖示，基板202可包括第一表面204及第二表面206。在某些實施例中，第一表面204可如圖所示為基板208的被暴露表面。舉例而言，基板208可包括矽(Si)、鍺(Ge)、錫(Sn)中之一或多者，或可包括其它合適的基板材料。舉例而言，基板可為矽基板、鍺基板、矽-鍺(SiGe)基板、鍺-錫基板(GeSn)等等。在某些實施例中，第二表面206可為介電層(如設置於基板208上之介電層210)的一部分。舉例而言，介電層可包含二氧化矽(SiO2)、氮化矽(Si3N4)或可用來形成介電層的其它合適材料中之一或多者。
圖示於第2A圖之基板202的實施例僅為範例，且基板202可能有其它合適的配置。舉例而言，如第2A圖所圖示，基板202可為部份形成之元件的一部分，所述元件如金 氧半導體場效電晶體(metal-oxide-semiconductor field effects transistor；MOSFET)。然而，本文所揭露的本發明之方法也可用於其它元件，如鰭式場效電晶體(fin field effects transistors；FinFETs)或類似者。在互補金氧半導體(CMOS)等應用中，本文所形成的SiGeSn層可作為光電能帶隙(opto-electronic bandgap)材料而被用於源極/汲極區域或通道區域中。
方法100通常藉由將矽源、鍺源及錫源共同流入而使於102，其中錫源包含錫鹵化物。舉例而言，矽源可包括一或多種矽烷(SixHy)，其中，例如，y=2x+2，如二矽烷(Si2H6)、三矽烷(Si3H8)、新戊矽烷(Si5H12)或其它合適的較高階矽烷。矽源可包括氯化矽烷，例如，具有通式SixHyClz的氯化矽烷，其中y+z=2x+2，且x=1、2、…。範例氯化矽烷可包括二氯矽烷(SiH2Cl2)、四氯矽烷(SiCl4)等等。在某些實施例中，諸如在約450攝氏度或更低(例如，範圍自約300至約450攝氏度)的溫度下，及在期望SiGeSn層中有較高的錫濃度(例如，約百分之8至約百分之9的錫)的情況下，可能需要以諸如三矽烷及/或新戊矽烷等較高階矽烷作為矽源。舉例而言，鍺源可包括諸如二鍺烷(Ge2H6)、三鍺烷(Ge3H8)等一或多種鍺烷(GexHy)，其中，舉例來說，y=2x+2，以及較高階的氫化鍺等等。鍺源可為氯化鍺烷，例如具有通式GexHyClz的氯化鍺烷，其中y+z=2x+2，x=1、2、…。範例氯化鍺烷可包括四氯化鍺(GeCl4)等。錫源可包括錫鹵化物，如一或多種氯化錫(SnCl1-4)。在某些實施例中，錫源可包含四氯化錫 (SnCl4)。相較於如上所述的稀有且不穩定之錫源而言，使用錫鹵化物作為錫源可提供如上所討論之增進的層品質、可製造性等。
錫鹵化物可為如上所討論的錫鹵化物氣體，或具有化學式RxSnCly的有機金屬氯化物，其中R為甲基或第三丁基，x為1或2，且y為2或3。可在任何合適的流速下將錫鹵化物提供至處理腔室，合適的流速可例如，如介於約0.1 sccm與約300 sccm之間，如介於約1 sccm與約200 sccm之間，或約10 sccm的流速。錫鹵化物也可與載氣混合，以在處理腔室中達到期望的空間速度及/或混合效率。錫鹵化物可源自於錫鹵化物結晶的固態或液態源，或昇華進入流動載氣流內的固體，或蒸發進入流動載氣流內的液體，所述載氣流可如包括氮(N2)、氫(H2)、氬(Ar)或氦(He)中之一或多者的載氣流，或者可藉由在接觸腔室中使鹵素氣體(視情況伴隨著上述載氣中之一)通過固態錫上來進行反應Sn+2Cl2→SnCl4，以產生錫鹵化物。於下文根據設備300討論接觸腔室，且接觸腔室可與處理腔室相鄰，並藉由導管耦接處理腔室，較佳地使用短導管以降低錫鹵化物顆粒沉積於導管中的可能性。
在某些實施例中，第二氣體(如氫(H2)、氮(N2)、氦(He)、氬(Ar)等氣體中之一或多者)可與矽源、鍺源及錫源中之任何一或多者共同流入。在某些實施例中，第二氣體可用來自矽、鍺及/或錫源中釋放矽、鍺及/或錫，以進行沉積。在某些實施例中，可使用第二氣體作為載氣，以達到矽、鍺及/或錫源之期望流動速度。舉例而言，可使用較高的流動速度 來增進正在形成之矽-鍺-錫(SiGeSn)層的均勻度。
矽源、鍺源及錫源可在任何合適的比例下共同流入，以產生具有Si(1-x-y)GexSny之通常化學劑量比例的SiGeSn層(如，下文所討論之SiGeSn層214)，其中0<x、y<1且0<x+y<1。x及y的調和可使SiGeSn層中的鍵結結構或應變能被調和而不影響其它性質。可在約450攝氏度或更低的溫度(例如範圍自約300至約450攝氏度)下共同流入矽源、鍺源及錫源。可在約100托耳或更低的壓力(例如範圍自約5至約100托耳)下共同流入矽源、鍺源及錫源。可在前述溫度範圍中之較低溫度下達成在SiGeSn層中之較高的錫濃度。如上所討論，在前述溫度範圍中之較低溫度下，可能需要較高階的矽烷。舉例而言，在前述溫度範圍中之較高溫度下，且當錫的期望濃度為約百分之1至約百分之2時，可利用諸如二矽烷等較低階的矽烷。
視情況，可與矽源、鍺源及錫源共同流入額外材料源，例如，摻質源。典型的摻質可包括硼(B)、磷(P)、砷(As)等中之一或多者。舉例而言，摻職源可包括二硼烷(B2H6)、膦(PH3)、胂(AsH3)等。也可利用額外的摻質及/或摻質源。
於104，可如上文所討論般，藉由共同流入矽源、鍺源及錫源，而在基板208的第一表面204上沉積SiGeSn層214。舉例而言，可藉由任何合適的沉積方法來沉積SiGeSn層214，如減壓化學氣相沉積(CVD)或任何其它合適的沉積方法。SiGeSn層214可被沉積達任何期望的厚度，如約0.001至約10微米。
如第2B圖所繪示，SiGeSn層214的一部分216可被沉積於介電層210的第二表面206上。在某些實施例中，如第2C圖所繪示，可使用蝕刻劑218來蝕刻SiGeSn層214，以選擇性移除已被沉積於介電層210的第二表面206上之SiGeSn層214的該部分216。舉例而言，可同步或交替進行SiGeSn層214的沉積及蝕刻。蝕刻劑218可包含氯(Cl)或溴(Br)中之至少一者，且可視情況包含氫(H)。舉例而言，在某些實施例中，蝕刻劑可為氯化氫(HCl)、溴化氫(HBr)、氯(Cl2)或溴(Br2)中之至少一者。
第2D圖繪示生長達到期望厚度的SiGeSn層214，其中在如上所述的選擇性蝕刻製程之後，該SiGeSn層214不存在於介電層210的第二表面206上。
第3圖為根據另一個實施例的設備300之概要圖。設備300有利於實現本文所述之用於形成SiGeSn層的方法。處理腔室302具有基板支撐件308，基板支撐件308可為設置於處理腔室302內部的旋轉基板支撐件。熱源306經設置而面向基板支撐件308的一側。或者，熱源可埋入基板支撐件308。如於2007年2月6日核准，名稱為「Method for forming a high quality low temperature silicon nitride film」的共同讓與之美國專利第7,172,792號所述的具有經加熱之基板支撐件的腔室，可適用於實現本文所述之方法。如於2008年3月27日公開，名稱為「Modular CVD Epi 300 mm Reactor」的共同讓與之美國專利公開第2008/0072820號所述的具有燈泡加熱模組的腔室，也可適用於實現本文所述之方法。皆可購自加 州聖大克勞拉市的應用材料股份有限公司的EpiTM 300 mm反應器或300 mm xGenTM腔室可適用於完成並使用本文所述之實施例。處理腔室302可具有噴淋頭304供氣體進入腔室。替代或組合，氣體可經由側進口320提供至處理腔室，側進口320耦接腔室302的側壁360。
供給系統328，包括化學輸送系統310及金屬前驅物接觸腔室312，可經由多個導管耦接至腔室302。第一導管322及第二導管324可將供給系統328耦接至可選的噴淋頭304。噴淋頭304可為雙路徑(dual-pathway)噴淋頭，以防止材料源(如，矽源、鍺源及/或錫源)在進入腔室302之前混合。範例雙路徑噴淋頭描述於2006年1月10日核准，名稱為「Gas distribution showerhead for semiconductor processing」的共同讓與之美國專利第6,983,892號中。
替代地或額外地，可藉由提供第一及第二交叉流(cross-flow)氣體導管316及318至側進入點320，來實現交叉流氣體注射(cross-flow gas injection)。交叉流注射配置的一個實例描述於美國專利第6,500,734號中。設備300可含有噴淋頭配置及交叉流注射配置二者(視情況具有可調和之二者間的氣流比例)，或僅含有其中一種或另一種配置。
化學輸送系統310可視情況以諸如氮(N2)及/或氫(H2)等載氣將矽源、鍺源或錫源輸送至腔室302。化學輸送系統310也可將沉積或選擇性控制物種輸送至腔室302。化學輸送系統310可包括液態或氣態源及控制件(未繪示)，液態或氣態源及控制件可被配置於氣體分配板中。
接觸腔室312可藉由導管314耦接至側進入點320或噴淋頭304，導管314經設置以將金屬前驅物攜至腔室302。可將導管314、316及322加熱至介於約50℃與約200°C之間的溫度，以控制或避免金屬前驅物於導管中凝結。接觸腔室312典型含有固態金屬或金屬鹵化物結晶的床。金屬鹵化物結晶(如，錫鹵化物)可被昇華為載氣並透過氣體供給導管362及364中之一或二者提供。固態金屬可與透過氣體供給導管362及364中之一或二者所提供的鹵素氣體源接觸。在一個實施例中，可透過第一氣體供給導管362提供鹵素氣體源，而可透過第二氣體供給導管364提供載氣。無論是用於昇華或反應的氣體皆可能流經粉末化的金屬或金屬鹵化物流體化床，以增進接觸。可使用篩網粗濾器(mesh strainer)或過濾器來避免粒子被挾帶進入腔室302。或者，氣體可流過固定的固態金屬或金屬鹵化物床。
排放系統330耦接腔室302。排放系統330可在任何合宜位置處耦接腔室，合宜位置可取決於氣體進入腔室的位置。就氣體透過噴淋頭304進入的情況而言，排放系統可例如，藉由一或多個進口(portal)或透過環形開口耦接腔室的底壁，並位在熱源306周圍。於某些實施例中，可將環狀岐管設置在接近基板支撐件的邊緣處，並耦接排放系統330。就交叉流實施例而言，排放系統330可耦接與側進入點320相對之腔室側壁。
排放導管340經由節流閥366將排放蓋332耦接至真空泵352。護套368可自排放蓋332至真空泵352的入口 350環繞排放導管340及節流閥366。護套368容許對排放導管340的熱控制，以避免排放物種於管線中凝結。任何加熱介質，如蒸氣、或熱空氣、水、或其它熱流體可被用於將排放導管維持在排放氣體的露點以上之溫度。或者，護套可包括阻抗式加熱元件(如，電毯)。若有需要的話，可藉由閥338將凝結阱(condensation trap)336耦接至排放導管340，以進一步增進對排放系統330中之任何凝結物的捕捉。真空泵352透過減量導管(abatement conduit)354佈線(pay off)至減量系統356，通常不會加熱減量導管354或為減量導管354設置護套，且被清潔之氣體於358排放。為了近一步減少排放導管340中的潮濕及成核反應，可以石英或以惰性聚合物材料塗佈排放導管340。
可藉由活性源334將電漿或紫外線活化的清潔劑耦接進入排放系統330，活性源334可耦接微波或RF腔室，以產生活性清潔物種。清潔氣體管線326可自化學輸送系統310將清潔氣體提供至排放導管340，且若需要的話透過活性源334進行。用於清潔之活性物種的使用使清潔能在降低的溫度下進行。
用於清潔進行本文所述之方法的腔室(如腔室302)的方法可包括：將鹵素氣體提供至腔室，將殘留物轉化成揮發性鹵化物。於清潔期間，腔室的溫度典型維持在低於約600℃，且金屬沉積物被轉化為MClx。鹵素氣體可為氯氣、氟氣、HCl或HF。可加熱腔室達到不需要單獨加熱排放導管的程度，特別是若排放導管被絕緣時。或者，若需要的話，可將 腔室溫度維持在低於約400℃，並加熱排放導管340以避免凝結。
可提供控制器370並將控制器370耦接設備300的多個部件，以控制該等部件的運作。控制器370包括中央處理單元(CPU)372、記憶體374以及支援電路376。控制器370可直接控制設備300，或透過與特定製程腔室及/或支撐系統部件相關的電腦(或控制器)來控制設備300。控制器370可為任何形式的通用電腦處理器之一，通用電腦處理器可用於供控制多種腔室及次處理器所用之工業設定中。控制器370的記憶體或電腦可讀取媒體374可為諸如本地或遠端之隨機存取記憶體(random access memory；RAM)、唯讀記憶體(read only memory；ROM)、軟碟、硬碟、光學儲存媒體(如，光碟(compact disc)或數位影音碟(digital video disc))、快閃記憶碟(flash drive)或任何其它形式的數位儲存器等容易獲得的記憶體中之一或多者。支援電路376耦接CPU 372，並以習用的方式支援處理器。這類電路包括快取記憶體、電源供應、時脈電路、輸入/輸出電路及次系統等。如本文所述之本發明的方法可儲存於記憶體374中作為軟體例行程序，軟體例行程序可被執行或呼叫以用本文所述的方式控制製程腔室300的運作。也可由第二CPU(未繪示)儲存及/或執行軟體例行程序，第二CPU可位在受CPU 372控制之硬體的遠端。
儘管前述內容指向本發明的實施例，但在不悖離本發明的基本範疇下可發想出本發明的其它及進一步實施例。
100‧‧‧方法
102、104‧‧‧步驟

Claims (20)

  1. 一種於一基板上沉積矽鍺錫(SiGeSn)層的方法，包含下列步驟：在約450攝氏度或更低之一溫度下，且在約100托耳或更低之一壓力下，將一矽源、一鍺源及一錫源共同流入一製程腔室，以於該基板之一第一表面上沉積該SiGeSn層，其中該錫源包含一錫鹵化物。
  2. 如請求項1所述之方法，其中該鹵化物包含四氯化錫(SnCl4)。
  3. 如請求項1所述之方法，進一步包含下列步驟：將該矽源、該鍺源及該錫源中之一或多者與一第二氣體共同流入。
  4. 如請求項3所述之方法，其中該第二氣體包含氫(H2)、氮(N2)、氬(Ar)或氦(He)中之至少一者。
  5. 如請求項1至4中任一項所述之方法，其中該矽源包含矽烷或氯化矽烷中之一或多者。
  6. 如請求項1至4中任一項所述之方法，其中該鍺源包含鍺 烷或氯化鍺烷中之一或多者。
  7. 如請求項1至4中任一項所述之方法，進一步包含下列步驟：蝕刻該SiGeSn層，以自一介電層之一第二表面選擇性移除該SiGeSn層的一部分，該介電層設置於該基板上鄰近該基板之該第一表面。
  8. 如請求項7所述之方法，其中沉積該SiGeSn層及蝕刻該SiGeSn層係同步進行。
  9. 如請求項1至4中任一項所述之方法，進一步包含下列步驟：將該矽源、該鍺源及該錫源中之一或多者與一摻質源共同流入。
  10. 如請求項9所述之方法，其中該摻質源係二硼烷(B2H6)、膦(PH3)或胂(AsH3)中之一或多者。
  11. 如請求項1至4中任一項所述之方法，其中該SiGeSn層中之錫(Sn)的一濃度為約8至約9%，且其中該矽源氣體包含矽烷或氯化矽烷中之一或多者。
  12. 如請求項1至4中任一項所述之方法，其中該矽鍺錫(SiGeSn)層係沉積達約0.001至約10微米之一厚度。
  13. 如請求項1至4中任一項所述之方法，其中在約300至約450攝氏度之一溫度下將該矽源、該鍺源及該錫源共同流入。
  14. 如請求項1至4中任一項所述之方法，其中在約5至約100托耳之一壓力下將該矽源、該鍺源及該錫源共同流入。
  15. 一種電腦可讀取媒體具有多個指令儲存於該電腦可讀取媒體上，當執行該等指令時能導致在一製程腔室中進行如請求項1至4中任一項所述之將矽鍺錫(SiGeSn)層沉積於一基板的一方法。
  16. 如請求項15所述之電腦可讀取媒體，其中該矽源包含矽烷或氯化矽烷中之一或多者，且其中該鍺源包含鍺烷或氯化鍺烷中之一或多者。
  17. 如請求項15所述之電腦可讀取媒體，其中該方法進一步包含下列步驟：蝕刻該SiGeSn層，以自一介電層之一第二表面選擇性移 除該SiGeSn層的一部分，該介電層設置於該基板上鄰近該基板之該第一表面。
  18. 如請求項15所述之電腦可讀取媒體，其中該方法進一步包含下列步驟：將該矽源、該鍺源及該錫源中之一或多者與一摻質源共同流入。
  19. 如請求項15所述之電腦可讀取媒體，其中該方法使該SiGeSn層中之錫(Sn)的一濃度為約8至約9%，且其中該矽源氣體包含矽烷或氯化矽烷中之一或多者。
  20. 如請求項15所述之電腦可讀取媒體，其中該方法進一步包含下列步驟：在約300至約450攝氏度之一溫度下，且在約5至約100托耳之一壓力下，將該矽源、該鍺源及該錫源共同流入。
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