TWI828871B - 用於腔室部件保護的含氧氟化合物 - Google Patents
用於腔室部件保護的含氧氟化合物 Download PDFInfo
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Abstract
本文描述的實施例提供形成氟化金屬膜的方法。該方法包括:將物體定位在具有處理區域的原子層沉積(ALD)腔室中;使用原子層沉積(ALD)製程在物體上沉積含金屬氧化物層;使用活化氟化製程在含金屬氧化物層上沉積金屬氟層;及重複沉積含金屬氧化物層和沉積金屬氟層,直到形成具有預定膜厚度的氟化金屬膜為止。活化氟化製程包括將氟前驅物(FP)的第一流引入處理區域。FP包括至少一種有機氟試劑或至少一種氟化氣體。
Description
本案揭示內容的實施例大致上關於形成氟化金屬膜的方法。更特定而言,本案揭示內容的實施例關於以形成氟化金屬膜的方法塗佈部件。
在清潔或製造半導體、OLED和平板裝置(諸如基板、腔室部件、腔室工具、腔室、和腔室主機)時,經常期望在該等裝置上形成氟化塗層。若缺少氟化塗層,則在半導體、OLED和平板處理期間鹵化電漿可能會腐蝕半導體、OLED和平板裝置的表面。可能存在的表面腐蝕能夠影響半導體、OLED和平板的性能,並且衝擊產品良率、腔室上線時間、及客戶成本。
大多數當前的氟化塗佈技術是利用諸如HF-吡啶及氟之類的材料,上述材料無法提供對氟化塗層之性質的精確控制。因此,該技術中需要一種形成氟化塗層的改良方法。
在一個實施例中,提供一種形成氟化金屬膜的方法。該方法包括:將物體定位在具有處理區域的原子層沉積(ALD)腔室中;使用原子層沉積(ALD)製程在物體
上沉積含金屬氧化物(metal-oxide containing)層;使用活化氟化(activated fluorination)製程在含金屬氧化物層上沉積金屬氟層;及重複沉積含金屬氧化物層和沉積金屬氟層,直到形成具有預定膜厚度的氟化金屬膜為止。活化氟化製程包括將氟前驅物(FP)的第一流引入處理區域。FP包括至少一種有機氟試劑或至少一種氟化氣體。
在另一實施例中,提供一種形成氟化金屬膜的方法。該方法包括:使用含金屬氧化物層原子層沉積(ALD)製程在物體上沉積含金屬氧化物層;使用活化氟化製程在含金屬氧化物層上沉積金屬氟層;以及重複沉積含金屬氧化物層和沉積金屬氟層,直到形成具有預定膜厚度的氟化金屬膜為止。ALD製程包括:將物體定位在具有處理區域的ALD腔室中;將含氧前驅物的第一流引入處理區域;將含金屬前驅物的第二流引入處理區域;以及重複引入含氧的前驅物的第一流和含金屬的前驅物的第二流,直到形成具有預定層厚度的含金屬氧化物層為止。活化氟化製程包括:將氟前驅物(FP)的第三流引入處理區域;以及將氟化活化前驅物(FAP)的第四流引入處理區域。FP包括至少一種有機氟試劑或至少一種氟化氣體。
在又一實施例中,提供一種形成氟化金屬膜的方法。該方法包括:使用含金屬氧化物層原子層沉積(ALD)製程在物體上沉積含金屬氧化物層;使用活化氟化製程在含金屬氧化物層上沉積金屬氟層;以及重複沉積含金屬氧
化物層和沉積金屬氟層,直到形成具有預定膜厚度的氟化金屬膜為止。ALD製程包括:將物體定位在具有處理區域的ALD腔室中;將含釔前驅物的第一流引入處理區域;將含氧前驅物的第二流引入處理區域;以及重複引入含釔前驅物的第一流和引入含氧前驅物的第二流,直到形成具有預定層厚度的含金屬氧化物層為止。活化氟化製程包括:將氟前驅物(FP)的第三流引入處理區域;以及將氟化活化前驅物(FAP)的第四流引入處理區域。FP包括至少一種有機氟試劑或至少一種氟化氣體。
100:腔室
101:腔室主體
102:主體部分
104:蓋部分
108:入口
110:出口
112:支撐組件
114:基座
116:心柱
118:支撐表面
120:開口
122:處理區域
124:泵
126:RF源
128:電極
200:方法
201~203:操作
300:氟化金屬膜
301:物體
302a~302n:含金屬氧化物層
304a~304n:金屬氟層
306:預定層厚度
310:預定膜厚度
為了可以詳細了解本案揭示內容的上述特徵,可透過參考實施例(其中一些在附圖中說明)而得到對上文簡要概述的本案揭示內容進行更特定的敘述。然而,應注意,附圖僅說明示範性實施例,因此不應被認為是對本案之範疇的限制,並且可容許其他等效實施例。
圖1是根據一實施例的原子層沉積腔室的示意圖。
圖2是流程圖,說明根據一實施例的形成氟化金屬膜的方法的操作。
圖3A至圖3C是根據一實施例的在形成氟化金屬膜的方法期間的基板的示意性剖面圖。
圖4是根據一實施例的形成氟化金屬膜的方法的活化氟化製程的示意圖。
為有助理解,如可能則使用相同的元件符號指定圖中共通的相同元件。考量一個實施例的元件和特徵可有益地併入其他實施例中,而無需贅述。
本文描述的實施例關於一種形成氟化金屬膜的方法。該方法包括:使用原子層沉積(ALD)製程在物體上沉積含金屬氧化物層;使用活化氟化製程在含金屬氧化物層上沉積金屬氟層;以及重複沉積含金屬氧化物層及沉積金屬氟層,直到形成具有預定膜厚度的氟化金屬膜為止。
圖1是原子層沉積(ALD)腔室100的示意圖。應了解下文描述的腔室是示範性腔室,並且其他腔室(包括來自其他製造商的腔室)可以與本案揭示內容的態樣一併使用,或經修改而完成本案揭示內容的態樣,該態樣諸如形成氟化金屬膜300的方法200。
ALD腔室100包括腔室主體101。腔室主體包括主體部分102、及蓋部分104、以及支撐組件112。入口108和出口110配置在腔室主體101的主體部分102和蓋部分104之間。支撐組件112至少部分地配置在腔室主體101的主體部分102內。支撐組件112包括基座114,該基座114藉由心柱116可移動地配置在腔室主體101中。基座114包括支撐表面118,該支撐表面118設置成支撐物體301,在此進一步詳細描述。心柱116延伸穿過腔室主體101,並且連接升舉系統(未示出),該升舉系統使基座114在處理位置(如圖所示)和移送位置之間移動。移送
位置有助於將物體301移送通過形成在主體部分102的側壁中的開口120,以提供對ALD腔室100內部的進出。
在處理位置,支撐組件112的基座114接觸主體部分102,而形成由支撐表面118、主體部分102的上表面、和蓋部分114的下表面所界定的處理區域122。當處於處理位置的支撐組件112接觸主體部分102而形成處理區域122時,入口108和出口110與處理區域122流體連通。以此方式,使氣體透過入口108提供至處理區域122。氣體在處理區域122中流動遍及物體301,並且藉由泵124透過出口110排出。RF(射頻)源126耦接蓋部分104的電極128。RF源126供能給電極128,以助於從處理區域122中的氣體生成電漿。當基座114連接到RF源126時,基座114接地或基座114可以用作陰極,以在蓋部分104的下表面和基座114之間生成電容式電場,而使電漿物種朝向物體301加速。
圖2是流程圖,說明如圖3A至圖3C所示的形成氟化金屬膜300的方法200的操作。為了有助於解釋,將參考圖1、圖3A至圖3C、及圖4描述圖1,圖4為在方法200中所利用的活化氟化製程的示意圖。然而,注意可協同方法200利用除了圖1之ALD腔室100之外的ALD腔室。
在操作201,利用ALD製程將第一含金屬氧化物層302a沉積在物體301上。物體301可以是基板、腔室部件、腔室工具、腔室、和腔室主機。在能與本文所述的其他實施例結合的實施例中,第一含金屬氧化物層的金屬包
括下述之至少一者:釔(Y)、鋁(Al)、鈣(Ca)、鎂(Mg)、鍶(Sr)、鋇(Ba)、鈧(Sc)、鋅(Zn)、錫(Sn)、鎵(Ga)、銦(In)、釩(V)、錳(Mn)、鈰(Ce)、鏑(Dy)、鉺(Er)、銪(Eu)、釓(Gd)、鈥(Ho)、鑭(La)、鎦(Lu)、釹(Nd)、鐠(Pr)、鉕(Pm)、釤(Sm)、鈧(Sc)、鋱(Tb)、釷(Tm)、鐿(Yb)、鋯(Zr)、或鉿(Hf)。ALD製程包括將物體301移送到ALD腔室100中並且將物體301定位在基座114上。利用ALD製程沉積的第一含金屬氧化物層302a具有預定層厚度306。
在能夠與本文描述的其他實施例結合的一個實施例中,沉積Y2O3的第一含金屬氧化物層302a的ALD製程包括將含釔前驅物流引入處理區域122中。遍及處理區域122流動的含釔前驅物流動遍及物體301,並且在物體301上形成含釔層。將含氧前驅物流提供到處理區域122。在能夠與本文所述的其他實施例結合的一個實施例中,含氧前驅物包括H2O、O3或O2。在能夠與本文所述的其他實施例結合的一個實施例中,流動遍及處理區域122的含氧前驅物流動遍及物體301,並且活化成電漿而形成氧自由基。在能夠與本文描述的其他實施例結合的另一實施例中,氧自由基可在遠端電漿源中形成,該遠端電漿源將氧自由基提供至處理區域122。在其中形成氧自由基的實施例中,氧自由基與在物體301上的釔層反應,而在該物體301上形成Y2O3層。重複流動含釔前驅物、流動含氧前驅
物、以及(在某些實施例中)將含氧前驅物活化成為電漿,持續上述的重複直到形成具有預定層厚度306的Y2O3的第一含金屬氧化物層302a為止。
在能夠與本文描述的其他實施例結合的另一實施例中,沉積Al2O3的第一含金屬氧化物層302a的ALD製程包括將含氧前驅物流引入處理區域122中。在能夠與本文所述的其他實施例結合的一個實施例中,該含氧前驅物包括O2。流動遍及處理區域122的含氧前驅物流動遍及物體301,並且活化成電漿而形成氧自由基。在能夠與本文描述的其他實施例結合的另一實施例中,氧自由基可在遠端電漿源中形成,該遠端電漿源將氧自由基提供給處理區域122。在其中形成氧自由基的實施例中,氧自由基反應且在物體301上沉積氧層。諸如三甲基鋁(CH3)3Al(TMA)之類的含鋁前驅物流被提供至處理區域122。流動遍及處理區域122的含鋁前驅物流動遍及物體301、與物體301上的該氧層反應,並且在物體301上形成Al2O3層。重複流動含氧前驅物、(在一些實施例中)將含氧前驅物活化成電漿、及流動含鋁前驅物,持續該重複直到形成具有預定層厚度306的Al2O3的第一含金屬氧化物層302a為止。
在操作202,利用活化氟化製程在第一含金屬氧化物層302a上沉積第一金屬氟層304a。如圖4所示,操作202的活化氟化製程包括將氟前驅物(FP)流引入處理區域122。流動遍及處理區域122的FP流動遍及物體301。FP與第一金屬氟層304a的末端羥基或其他表面基團反
應,且與第一含金屬氧化物層302a的金屬鍵結。在能夠與本文描述的其他實施例結合的多個實施例中,FP包括至少一種有機氟試劑。有機氟試劑的實例包括(但不限於)下述至少一者:六氟乙醯丙酮(hexafluoro-acetylacetonate,HHFAC)、四氟丙醇(TFP)、六氟丙醇(HFP)、或1,1,1,2-四氟乙烷(HFC-134)。在能夠與本文描述的其他實施例結合的多個實施例中,FP包括至少一種氟化氣體。氟化氣體的實例包括(但不限於)下述至少一者:三氟化氮(NF3)、五氟化磷(PF5)、或六氟化硫(SF6)。
將氟化活化前驅物(FAP)流提供給處理區域122。流動遍及處理區域122的FAP流動遍及物體301,與在物體301上鍵結到第一含金屬氧化物層302a的金屬的FP反應,並且在第一含金屬氧化物層302a上形成第一金屬氟層304a。第一金屬氟層304a具有與第一含金屬氧化物層302a的末端金屬鍵結的氟。在能夠與本文所述的其他實施例結合的一個實施例中,FAP包括至少一種含氧前驅物。含氧前驅物的實例包括但不限於H2O、臭氧(O3)。在能夠與本文描述的其他實施例結合的另一實施例中,FAP包括含氧電漿。形成該含氧電漿可透過:使含氧前驅物流動遍及處理區域122,並且將含氧前驅物活化成含氧電漿。可在遠端電漿源中形成含氧電漿,該遠端電漿源將含氧電漿的自由基提供至處理區域122。在本文所述的實施例中,FAP包括但不限於下述至少一者:H2O、O3、O2
或含氧自由基的電漿,該電漿是由微波、RF、遠端電漿、熱絲、電子束、及氧化或還原電漿源之其中一者形成。
在操作203,重複操作201和202以形成複數個含金屬氧化物的層和金屬氟層302a、304a、302b、304b、302c、304c、……、302n、304n,直到形成具有預定膜厚度310的氟化金屬膜300為止。在能夠與本文描述的其他實施例結合的實施例中,含金屬氧化物層302a、302b、302c、302n之其中一者具有不同的預定層厚度306。每一含金屬氧化物層302a、302b、302c、302n的預定層厚度306供以控制氟化金屬膜300中的氟對氧(O:F)的比和氧原子百分比。在直接氟化製程中,將氟前驅物(例如HF或氟(F2))直接用作氟化劑,這可能導致不受控制的氟擴散。在活化氟化製程中,FP與含金屬氧化物層反應而形成表面加成物(adduct)。FAP與加成物反應,並且以受控方式從FP釋放氟原子。加成物的反應和氟原子的釋放有助於控制氟化金屬膜300的O:F比和氧原子百分比。控制O:F比和氧原子百分比提供調整氟化金屬膜300的抗腐蝕性及應用的能力。在一些實施例中,O:F比小於1:1,諸如小於1:6。在一些實施例中,氧的原子百分比小於20%,例如小於10%。在能夠與本文描述的其他實施例結合的一個實施例中,含金屬氧化物層302a、302b、302c、302n具有一氧原子百分比,使得氟化金屬膜300是由純金屬氟化物組成,具有小於5%的氧含量,即,氟化金屬膜300的氧原子百分比小於5%。在能夠以與本文描述的其他實施例
結合的另一個實施例中,含金屬氧化物層302a、302b、302c、302n具有一氧原子百分比,使得氟化金屬膜300是由純金屬氟化物組成,具有小於2%的氧含量,即,氟化金屬膜300的氧原子百分比小於2%。
在能夠與本文描述的其他實施例結合的一個實施例中,在方法200期間,處理區域122中的溫度為約150℃至400℃,並且處理區域122中的壓力為約0.01毫巴至100毫巴。在能夠與本文描述的其他實施例結合的一個實施例中,處理區域122中的溫度控制O:F比和氧原子百分比。例如,介於約250℃至300℃之間的處理區域122中的溫度造成O:F比小於1:2、氧原子百分比小於20%、且氟原子百分比大於50%。在方法200的示範性實施例中(該實施例能夠與本文所述的其他實施例結合),操作201包括:將含釔前驅物流引入處理區域122達約1毫秒(msec)至約100秒(sec)、將淨化氣體流引入處理區域122達約1毫秒至約1000秒以淨化處理區域122、使處理區域中的包括H2O、O3、O2電漿和O2中的至少一者的前驅物流動且活化達約1毫秒至約100秒、及將淨化氣體流引入處理區域122達約1毫秒至約1000秒。操作202包括:將FP引入處理區域122達約1毫秒至約100秒、將淨化氣體流引入處理區域122達約1毫秒至約1000秒、將FAP引入處理區域122達約1毫秒至約100秒、及將淨化氣體流引入處理區域122達約1毫秒至約1000秒。重複操作201和202,直到具有預定膜厚度310的氟化金屬膜300形成為止。
總結而言,提供一種形成氟化金屬膜的方法。利用ALD製程和活化氟化製程提供了由重複ALD製程和活化氟化製程所形成的氟化金屬膜的精確的原子控制。例如,每一含金屬氧化物層的預定層厚度控制氟化金屬膜的O:F比和預定膜厚度。
儘管前述內容針對本案揭示內容的實例,但是在不脫離本案揭示內容的基本範疇的情況下,可以設計本案揭示內容的其他和進一步的實例,並且本案揭示內容的範疇由下文的申請專利範圍決定。
300:氟化金屬膜
301:物體
302a~302n:含金屬氧化物層
304a~304n:金屬氟層
306:預定層厚度
310:預定膜厚度
Claims (19)
- 一種形成氟化金屬膜的方法,包括:將一物體定位在具有一處理區域的一原子層沉積(ALD)腔室中;於該ALD腔室中使用一ALD製程在該物體上沉積一含金屬氧化物(metal-oxide containing)層;於該ALD腔室中使用一活化氟化(activated fluorination)製程在該含金屬氧化物層上沉積一金屬氟(metal-fluorine)層,該活化氟化製程包括:將一氟前驅物(FP)的一第一流引入該處理區域,該FP包括至少一種有機氟試劑或至少一種氟化氣體;及在該第一流中斷之後,將一氟化活化前驅物(FAP)的一第二流引入該處理區域;及重複沉積該含金屬氧化物層和沉積該金屬氟層,直到形成具有一預定膜厚度且具有小於1:1的O:F比的該氟化金屬膜為止。
- 如請求項1所述之方法,其中該ALD製程包括:將一含氧前驅物的一第一流引入該處理區域;將一含金屬前驅物的一第二流引入該處理區域;及重複引入該含氧前驅物的該第一流及引入該含金屬前驅物的該第二流,直到形成具有一預定層厚度的該含金屬氧化物層為止。
- 如請求項2所述之方法,其中該含金屬前驅物是一含鋁前驅物。
- 如請求項1所述之方法,其中該FAP包括下述至少一者:H2O、O3、O2或含氧自由基的電漿,該電漿是由微波、RF、遠端電漿、熱絲、電子束、及氧化或還原電漿源之其中一者形成。
- 如請求項1所述之方法,其中該含金屬氧化物層具有一預定層厚度。
- 如請求項1所述之方法,其中該含金屬氧化物層包括下述至少一者:釔(Y)、鋁(Al)、鈣(Ca)、鎂(Mg)、鍶(Sr)、鋇(Ba)、鈧(Sc)、鋅(Zn)、錫(Sn)、鎵(Ga)、銦(In)、釩(V)、錳(Mn)、鈰(Ce)、鏑(Dy)、鉺(Er)、銪(Eu)、釓(Gd)、鈥(Ho)、鑭(La)、鎦(Lu)、釹(Nd)、鐠(Pr)、鉕(Pm)、釤(Sm)、鋱(Tb)、釷(Tm)、鐿(Yb)、鋯(Zr)、或鉿(Hf)。
- 如請求項1所述之方法,其中該ALD製程包括:將一含釔前驅物的一第一流引入該處理區域;將一含氧前驅物的一第二流引入該處理區域;及重複引入該含釔前驅物的該第一流及引入該含氧前驅物的該第二流,直到形成具有一預定層厚度的該含金屬氧化物層為止。
- 如請求項1所述之方法,其中該至少一種有 機氟試劑包括下述一或多者:六氟乙醯丙酮(hexafluoro-acetylacetonate,HHFAC)、四氟丙醇(TFP)、六氟丙醇(HFP)、或1,1,1,2-四氟乙烷(HFC-134)。
- 如請求項1所述之方法,其中該至少一種氟化氣體包括下述一或多者:三氟化氮(NF3)、五氟化磷(PF5)、或六氟化硫(SF6)。
- 一種形成氟化金屬膜的方法,包括:使用一含金屬氧化物層原子層沉積(ALD)製程在一物體上沉積一含金屬氧化物層,該ALD製程包括:將該物體定位在具有一處理區域的一ALD腔室中;將一含氧前驅物的一第一流引入該處理區域;將一含金屬前驅物的一第二流引入該處理區域;及重複引入該含氧前驅物的該第一流和該含金屬前驅物的該第二流,直到形成具有一預定層厚度的該含金屬氧化物層為止;於該ALD腔室中使用一活化氟化製程在該含金屬氧化物層上沉積一金屬氟層,該活化氟化製程包括:將一氟前驅物(FP)的一第三流引入該處理區域,該FP包括至少一種有機氟試劑或至少一種氟化氣體;及在該第三流中斷之後,將一氟化活化前驅物(FAP)的一第四流引入該處理區域;及 重複沉積該含金屬氧化物層和沉積該金屬氟層,直到形成具有一預定膜厚度且具有小於1:1的O:F比的該氟化金屬膜為止。
- 如請求項10所述之方法,其中該含金屬前驅物是一含鋁前驅物。
- 如請求項10所述之方法,其中該含金屬氧化物層包括下述至少一者:釔(Y)、鋁(Al)、鈣(Ca)、鎂(Mg)、鍶(Sr)、鋇(Ba)、鈧(Sc)、鋅(Zn)、錫(Sn)、鎵(Ga)、銦(In)、釩(V)、錳(Mn)、鈰(Ce)、鏑(Dy)、鉺(Er)、銪(Eu)、釓(Gd)、鈥(Ho)、鑭(La)、鎦(Lu)、釹(Nd)、鐠(Pr)、鉕(Pm)、釤(Sm)、鋱(Tb)、釷(Tm)、鐿(Yb)、鋯(Zr)、或鉿(Hf)。
- 如請求項10所述之方法,其中該FAP包括下述至少一者:H2O、O3、O2或含氧自由基的電漿,該電漿是由微波、RF、遠端電漿、熱絲、電子束、及氧化或還原電漿源之其中一者形成。
- 如請求項10所述之方法,其中該至少一種有機氟試劑包括下述一或多者:六氟乙醯丙酮(HHFAC)、四氟丙醇(TFP)、六氟丙醇(HFP)、或1,1,1,2-四氟乙烷(HFC-134)。
- 如請求項10所述之方法,其中該至少一種氟化氣體包括下述一或多者:三氟化氮(NF3)、五氟化磷(PF5)、或六氟化硫(SF6)。
- 一種形成氟化金屬膜的方法,包括:使用一含金屬氧化物層原子層沉積(ALD)製程在一物體上沉積一含金屬氧化物層,該ALD製程包括:將該物體定位在具有一處理區域的一ALD腔室中;將一含釔前驅物的一第一流引入該處理區域;將一含氧前驅物的一第二流引入該處理區域;及重複引入該含釔前驅物的該第一流和引入該含氧前驅物的第二流,直到形成具有一預定層厚度的該含金屬氧化物層為止;於該ALD腔室中使用一活化氟化製程在該含金屬氧化物層上沉積一金屬氟層,該活化氟化製程包括:將一氟前驅物(FP)的一第三流引入該處理區域,該FP包括至少一種有機氟試劑或至少一種氟化氣體;及在該第三流中斷之後,將一氟化活化前驅物(FAP)的一第四流引入該處理區域;及重複沉積該含金屬氧化物層和沉積該金屬氟層,直到形成具有一預定膜厚度且具有小於20%的氧原子百分比的該氟化金屬膜為止。
- 如請求項16所述之方法,其中該FAP包括下述至少一者:H2O、O3、O2或含氧自由基的電漿,該電漿是由微波、RF、遠端電漿、熱絲、電子束、及氧化或還原電漿源之其中一者形成。
- 如請求項16所述之方法,其中該含金屬氧化物層包括下述至少一者:釔(Y)、鋁(Al)、鈣(Ca)、鎂(Mg)、鍶(Sr)、鋇(Ba)、鈧(Sc)、鋅(Zn)、錫(Sn)、鎵(Ga)、銦(In)、釩(V)、錳(Mn)、鈰(Ce)、鏑(Dy)、鉺(Er)、銪(Eu)、釓(Gd)、鈥(Ho)、鑭(La)、鎦(Lu)、釹(Nd)、鐠(Pr)、鉕(Pm)、釤(Sm)、鋱(Tb)、釷(Tm)、鐿(Yb)、鋯(Zr)、或鉿(Hf)。
- 如請求項16所述之方法,其中該至少一種有機氟試劑包括下述一或多者:六氟乙醯丙酮(HHFAC)、四氟丙醇(TFP)、六氟丙醇(HFP)、或1,1,1,2-四氟乙烷(HFC-134)。
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