TWI630281B - 沉積金屬合金膜之方法 - Google Patents
沉積金屬合金膜之方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
Abstract
茲提供沉積膜的方法,所述方法包含下列步驟:將基板的至少一部分暴露於金屬前驅物,以於基板上提供第一金屬,將基板的至少一部分暴露於有機金屬還原劑,以於基板上沉積第二金屬,以形成第一金屬與第二金屬的混合物或合金。可依序或同步暴露於金屬前驅物及有機金屬還原劑。
Description
一般而言,本發明的實施例與用於在基板表面上沉積膜的還原劑及方法有關。詳言之,本發明的實施例導向用於在基板上沉積鈦膜的還原劑及方法。
在基板表面上沉積薄膜為各種工業中之重要製程,該等工業包括半導體處理、擴散阻障塗層及用於磁性讀/寫頭之介電質。在半導體工業中,尤其,小型化要求對薄膜沉積之原子層級控制,以在高縱橫比結構上產生共形塗層。舉例而言,TiAl膜已被用於45nm至20nm節點(node)中的平坦高-k金屬閘中。
可藉由化學氣相沉積(CVD)製程或循環沉積製程來沉積金屬膜(例如,鈦)。舉例而言,可將基板暴露於鈦有機金屬前驅物及還原劑的混合物。鈦有機金屬前驅物與還原劑的反應可造成基板表面上的金屬鈦沉積。在循環製程(如原子層沉積(ALD))中,基板被暴露於,例如,鈦有機金屬前驅物,鈦有機金屬前驅物可吸附或化學吸附至基板的表面。可用合適的還原劑將鈦有機金屬複合物還原為金屬鈦。在ALD製程
中,金屬前驅物及還原劑各別對基板暴露,以避免用於CVD製程中的氣相反應。原子層沉積製程可導致具有已知厚度的膜之受控制沉積。
通常藉由以有機金屬還原劑來還原含鈦前驅物的氯化物,而完成鈦合金膜的沉積。用於沉積TiAl合金的一個慣用製程涉及四氯化鈦(TiCl4)與有機鋁前驅物的反應,以提供包含鈦及鋁的膜。然而,在相關技術領域中對用於沉積不同介金屬膜的前驅物及方法有所需求。
本發明的一或多個實施例導向在處理腔室中沉積合金膜的方法。基板被安置在處理腔室中。基板的至少一部分被暴露於金屬鹵化物前驅物,以於基板上提供第一金屬。從處理腔室清除未反應的金屬鹵化物前驅物。基板表面的該部分被暴露於包含第二金屬的有機金屬還原劑,第二金屬不同於第一金屬,以於基板上沉積第二金屬,產生第一金屬及第二金屬之合金。
在某些實施例中,金屬鹵化物包含四氯化鈦。
在一或多個實施例中,有機金屬還原劑包含第二金屬的烷類。在某些實施例中,第二金屬包含選自由Ge、In、Sn、Sb、Tl、Pb、Bi、Zn、Al、Ga及前述各者之混合物所組成之群組中之金屬。在一或多個實施例中,第二金屬的烷類包含二甲基-金屬氫化物、二乙基氫化-金屬(diethylhydrido-metal)、甲基二氫-金屬(methyldihydro-metal)及化學式為[(CxHy)z-aMHa]n之烷基金屬氫化物中之一或多
者,其中x的值為1至3,y的值為2x+2,z的值為2至5,a的值為1至2,且n的值為1至4。在一或多個實施例中,第二金屬的烷類包含胺類。在某些實施例中,有機金屬還原劑包含四乙基錫、三甲基銦及二乙基鋅中之一或多者。
在一或多個實施例中,基板對金屬鹵化物之暴露與基板對有機金屬還原劑之暴露至少部份重疊。
某些實施例進一步包含下列步驟:清除有機金屬還原劑。
在一或多個實施例中,基板依序暴露於金屬鹵化物及有機金屬還原劑。在某些實施例中,基板在暴露於有機金屬還原劑之前暴露於金屬鹵化物。在一或多個實施例中,基板在暴露於金屬鹵化物之前暴露於有機金屬還原劑。
某些實施例進一步包含下列步驟:將合金膜浸入合金化劑(alloying agent),其中合金化劑包含SiH4、GeH4、三甲基鎵(trimethylgallium)及B2H6中之一或多者。
在一或多個實施例中,合金膜含有少於20%的碳。
本發明的額外實施例導向在處理腔室中,於基板上沉積合金膜的方法。基板被安置於處理腔室內。可提供第一金屬的金屬鹵化物前驅物以及包含第二金屬(第二金屬不同於第一金屬)的有機金屬還原劑被同步流入處理腔室,以沉積包含第一金屬及第二金屬的合金膜。
在某些實施例中,金屬鹵化物包含四氯化鈦。在一或多個實施例中,有機金屬還原劑包含第二金屬的烷類。在某些實施例中,第二金屬包含選自由Ge、In、Sn、Sb、Tl、
Pb、Bi、Zn、Al、Ga及前述各者之混合物所組成之群組中之金屬。在一或多個實施例中,合金膜含有少於20%的碳。
本發明的進一步實施例導向在處理腔室中,於基板上沉積合金膜的方法。基板被安置於處理腔室內。可提供第一金屬的金屬鹵化物前驅物被流入處理腔室,以接觸基板的一部分。包含第二金屬的有機金屬還原劑被流入處理腔室,以接觸基板的一部分,第二金屬不同於第一金屬。金屬鹵化物及有機金屬還原劑被同步流入處理腔室的不同區域,且由惰性氣體簾幕分隔,以防止金屬鹵化物與有機金屬還原劑之氣相反應。
如本文所用,「基板(substrate)」指的是任何基板或形成於基板上的材料表面或膜,在製造製程期間,可於所述基板、材料表面或膜上進行處理。舉例而言,依據應用,可於基板表面上進行處理的基板表面包括諸如矽、氧化矽、應變矽、絕緣體上矽(SOI)、碳摻雜之氧化矽、氮化矽、經摻雜之矽、鍺、砷化鎵、玻璃、藍寶石及任何其它材料(如金屬、金屬氮化物、金屬合金、介電質、高k介電質及其它導電材料)等材料。基板包括,但不限於,半導體晶圓。可將基板暴露於預處理製程,例如,以研磨、蝕刻、還原、氧化、羥基化、退火及/或烘烤基板表面。除了直接在基板本身的表面上進行的膜處理之外,所揭露的任何膜處理步驟也可於底層(底
層形成在基板上)上進行,細節揭露於下文,且當上下文指出時,術語「基板表面(substrate surface)」欲包括此類底層。術語「基板表面」可指整個基板表面或基板表面的一部分。
基板可具有各種尺寸(諸如,200mm或300mm直徑的晶圓),也可為矩形或正方形片。基板上可使用本發明之實施例的基板包括,但不限於,半導體晶圓,諸如結晶矽(如,Si<100>或Si<111>)、氧化矽、應變矽、矽鍺、經摻雜或無摻雜之多晶矽、經摻雜或無摻雜之矽晶圓、III-V族材料(如GaAs、GaN、InP,等等)以及經圖案化或未經圖案化之晶圓。可將基板暴露於預處理製程,以研磨、蝕刻、還原、氧化、羥基化、退火及/或烘烤基板表面。
根據本發明的各種實施例,所提供的是與沉積金屬合金有關的方法,所述金屬合金可適於作為N-金屬膜。在一或多個實施例中,合金膜具有可調整的工作函數。
膜沉積可由任何合適的技術進行,包括但不限於,化學氣相沉積(CVD)及原子層沉積(ALD)。在一或多個實施例中,所提供的膜包含具有低碳含量的HfAl、TiAl或TaAl中之一或多者。
在一或多個實施例中,可使用ALD、CVD或PVD製程來沉積膜。在與CVD製程有關的實施例中,可適當地將基板暴露於持續且同步的,或實質上同步的超過一種的前驅物。如本文所用,術語「實質上同步的(substantially simultaneously)」指的是一種成分流的大部分與另一種成分流重疊,儘管可能有些時候該等成分沒有一起流入。
在其它實施例中,可使用原子層沉積(ALD)製程來沉積膜。因此,在一個實施例中,以兩種或更多種前驅物接觸基板表面是依序發生或實質上依序發生。如本文所用,「實質上依序(substantially sequentially)」意味著一種成分流的大部分不與另一種成分流重合,儘管可能有些重疊。
在ALD製程的示範實施例中,可在前半反應中將第一化學前驅物(「A」)(例如,TiCl4)脈衝或流動至基板表面。典型地可藉由排空-抽氣及/或藉由流入惰性淨化氣體,來移除過量的反應物及反應副產物。接著,可將「B」前驅物,例如鋁有機金屬複合物,遞送至表面,其中前半反應的前驅物與「B」前驅物反應,生成混合的金屬膜。「B」共反應物也與潛在的反應性物種形成自我飽和鍵(self-saturating bond),以提供飽和的後半反應。典型地可利用第二淨化期來移除未被使用的反應物及反應副產物。接著可流入「C」前驅物以與潛在的物種反應,並接著移除過量的「C」前驅物。可接著再次流入「A」、「B」及「C」前驅物及淨化氣體。
本發明的某些實施例導向沉積合金膜的方法。可將基板安置於處理腔室(例如,ALD或CVD腔室)內。可將基板的至少一部分暴露於金屬前驅物,或第一金屬前驅物,以於基板上提供第一金屬。提及「基板的一部分(a portion of substrate)」可意味著任何尺寸的部分,包括整個基板表面。可從處理腔室清除未反應的金屬前驅物,或第一金屬前驅物。被暴露於金屬前驅物的基板部分接著被暴露於有機金屬還原劑,以於基板上沉積第二金屬,導致金屬的混合物或合
金被沉積。金屬前驅物中的金屬與有機金屬還原劑中的金屬可為相同金屬或不同金屬。在某些實施例中,來自金屬前驅物的第一金屬與來自有機金屬還原劑的第二金屬不同,導致混合的金屬或合金膜之沉積。舉例而言,金屬前驅物可含有鈦,且有機金屬還原劑可含有鋁,導致鈦鋁合金膜的形成。在某些實施例中,可自處理腔室清除有機金屬還原劑,或更具體而言,未反應的有機金屬還原劑及反應副產物。
金屬前驅物可為任何合適的化合物,該化合物包括任何合適的金屬原子。合適的金屬原子包括,但不限於,過渡金屬、3族至6族過渡金屬。在某些實施例中,金屬前驅物的金屬為鈦、鉭、鎢及鋁中之一或多種金屬。在一或多個實施例中,金屬前驅物的金屬為鈦。金屬前驅物可為化合物,該化合物可被還原以在基板上沉積金屬。舉例而言,金屬前驅物可為金屬鹵化物。在一或多個實施例中,金屬鹵化物為氯化物、氟化物、溴化物、碘化物及該等鹵化物之混合物中的一或多者。在某些實施例中,金屬鹵化物包含四氯化鈦。合適的金屬鹵化物包括過渡金屬鹵化物、3族至6族過渡金屬鹵化物。對某些6族金屬鹵化物而言,金屬鹵化物前驅物可包含不飽和金屬鹵化物(例如,WCl5)。
有機金屬還原劑可為任何合適的化合物,該化合物能還原金屬前驅物,以沉積金屬。有機金屬還原劑中的金屬可為任何合適的金屬,該金屬包括與金屬前驅物之金屬相同的金屬。在某些實施例中,金屬前驅物具有第一金屬,且有機金屬還原劑具有第二金屬,其中第一金屬及第二金屬二者
為相同金屬。舉例而言,兩種金屬都是鈦,而導致基本上純的鈦膜之沉積。如此說明書及隨附申請專利範圍所使用,術語「基本上純的(substantially pure)」意味著在原子基礎(atomic basis)上低於約5%的雜質,或在原子基礎上低於約2%的雜質,或在原子基礎上低於約1%的雜質。在某些實施例中,金屬前驅物具有第一金屬,且有機金屬還原劑具有第二金屬,第二金屬不同於第一金屬。舉例而言,第一金屬可為鈦,且第二金屬可為鋁,導致混合的鈦-鋁膜或鈦-鋁合金之沉積。
有機金屬前驅物中的金屬,也稱作第二金屬,可為任何合適的金屬。合適的金屬包括,但不限於,鍺、銦、錫、銻、鉈、鉛、鉍、鋅、鋁、鎵及前述金屬的混合物。
有機金屬還原劑的有機成分對於,例如,還原劑的還原潛力及與第一金屬的反應速率具有顯著影響。在某些實施例中,有機金屬還原劑可包含金屬烷類。在一或多個實施例中,第二金屬的烷類可包括二甲基-金屬氫化物、二乙基氫化-金屬、甲基二氫-金屬及化學式為[(CxHy)z-aMHa]n之烷基金屬氫化物中之一或多者,其中x的值為1至3,y的值為2x+2,z的值為2至5,a的值為1至2,且n的值為1至4。在某些實施例中,第二金屬的烷類包含胺類。有機金屬還原劑可為任何合適的有機金屬還原劑。某些實施例的有機金屬還原劑可包含四乙基錫、三甲基銦、三甲基鎵、三甲基鋁、鋁烷(alane)、金屬鋁烷(例如,鋁鋁烷(aluminum alane))及二乙基鋅中之一或多者。
可分開進行或同時進行基板對第一金屬(例如,金屬
鹵化物)的暴露與基板對有機金屬還原劑的暴露。在某些實施例中,對第一金屬前驅物的暴露與基板對有機金屬還原劑的暴露至少部份重疊。如此說明書及隨附申請專利範圍所使用,術語「至少部份重疊(at least partially overlap)」指的是,在處理週期的至少某部分同時將金屬前驅物及有機金屬還原劑二者流入處理腔室至基板表面。舉例而言,在傳統CVD製程中,可以同步將金屬前驅物及有機金屬還原劑二者流入處理腔室,並容許金屬前驅物及有機金屬還原劑在沉積於基板表面上之前以氣相進行混合/反應。在較不傳統的方法中,可將金屬前驅物及有機金屬還原劑各別流入處理腔室,使得在一時段只有該等氣體中的一種氣體接觸基板,且這兩種氣體在各別時段混合或接觸基板。
在某些實施例中,可依序將基板暴露於金屬前驅物(例如,金屬鹵化物)及有機金屬還原劑。依序暴露意味著在任何給定的時間中,基板的特定部分僅暴露於金屬前驅物及有機金屬還原劑中之一者。接著在不同的時間中,將基板的特定部分暴露於金屬前驅物及有機金屬還原劑中之另一者。舉例而言,在空間式原子層沉積(spatial ALD)製程中,基板表面之各別部分被暴露於金屬前驅物流及有機金屬還原劑流。可相對於氣體分配組裝移動基板(反之亦可),使得基板的各獨立部分被暴露於兩種氣體流。在某些實施例中,可將金屬前驅物及有機金屬還原劑同步流入處理腔室的不同區域。可藉由惰性氣體簾幕分隔這些各別的氣流,以防止金屬前驅物及有機金屬還原劑的氣相反應。惰性氣體簾幕可為任何合適的氣
流、真空流(vacuum flow)或氣流與真空流的組合,以保持反應性氣體分離。舉例而言,氣體簾幕可包含真空流、淨化氣體流及第二真空流,以確保氣體簾幕兩側的反應性氣體不會在氣相下發生反應。
可依據特定製程來改變對金屬前驅物及有機金屬還原劑暴露的順序。在某些實施例中,基板,或基板的部分,可在暴露於有機金屬還原劑之前先暴露於金屬前驅物。在一或多個實施例中,基板,或基板的部分,可在暴露於金屬前驅物之前先暴露於有機金屬還原劑。在一或多個實施例中,基板,或基板的部分,可同時暴露於金屬前驅物及有機金屬還原劑。
本文所述之方法也可包括額外的子製程。在一或多個實施例中,所述方法進一步包含:將經沉積的膜浸入合金化劑。舉例而言,可將包含第一金屬及第二金屬之混合金屬膜暴露於合金化劑,以形成合金。如本文所用,「浸入(soak)」或「浸入(soaking)」及類似術語指的是某種製程,在該製程中基板或基板的部分暴露於反應氣體,且氣體與表面反應,但不沉積層。某些實施例進一步包含將合金膜浸入合金化劑,此舉中合金化劑包含SiH4、GeH4、三甲基鎵及B2H6中之一或多者。
相較於藉由其它方法所沉積的類似膜而言,藉由本文所述之方法所沉積的膜可具有較低的碳汙染。舉例而言,由本案所主張的方法所沉積的合金膜含有少於約20%的碳。
可持續使表面交替暴露於反應物,直到達成期望的
膜厚度為止,對大多數的預期應用而言,期望的膜厚度可將近在5Å至100Å的範圍內,更特定而言為自約15Å、20Å、25Å或30Å至約45Å、50Å、55Å或60Å。可瞭解到,可同步流入反應物及淨化氣體,且基板及/或氣流噴嘴可振動,使得基板如期望般依序暴露於反應物及淨化氣體。當然,以上提及的ALD周期僅為各式各樣的ALD製程周期之範例,在彼等ALD製程周期中,可藉由前驅物及/或共反應物的交替層形成沉積層。
應注意到這些順序僅為範例,且可有許多如上文所討論的變化。淨化步驟可移除處理腔室內的任何過量前驅物、副產物及其它汙染。載氣、淨化氣體或其它製程氣體可含有氮、氫、氬、氖、氦或前述氣體之組合。
前驅物及/或反應物可處於氣態或蒸氣態,或對氣相沉積製程有利的其它狀態。在淨化期間,典型地可將惰性氣體導入處理腔室,以淨化反應區或者從反應區移除任何殘留的反應性化合物或副產物。替代地,在整個沉積製程期間可持續流入淨化氣體,使得在介於前驅物與共反應物的脈衝之間的時間延遲期間僅有淨化氣體流入。
如本文所使用的沉積氣體或製程氣體指的是單一氣體、多種氣體、含有電漿的氣體、(多種)氣體及/或(多種)電漿的組合。沉積氣體可含有用於氣相沉積製程的至少一種反應性化合物。在氣相沉積製程期間,反應性化合物可處於氣態、電漿態、蒸氣態。並且,製程可含有淨化氣體或載氣而不含反應性化合物。
在某些實施例中,可在電漿增進原子層沉積(plasma enhanced atomic layer deposition,PEALD)製程期間形成一或多層。在某些製程中,使用電漿可提供足夠的能量,以促進物種進入激發態,在激發態中可使表面反應變得更好且更有可能發生。把電漿導入製程可為連續式或脈衝式。在某些實施例中,前驅物(或反應性氣體)的序列脈衝及電漿被用來處理層。在某些實施例中,可在本地(即,在處理區內)或遠端(即,在處理區外部)離子化反應物。在某些實施例中,遠端離子化可發生於沉積腔室的上游,使得離子或其它高能物種或發光物種不會直接接觸沉積膜。在某些PEALD製程中,電漿在處理腔室外部產生,如藉由遠端電漿產生器系統產生。可透過習知技藝者所知的任何合適的電漿產生製程或技術來產生電漿。舉例而言,可藉由微波(MW)頻率產生器或射頻(RF)產生器中之一或多者來產生電漿。可依據將使用的特定反應性物種來調整電漿的頻率。合適的頻率包括,但不限於,2MHz、13.56MHz、40MHz、60MHz及100MHz。儘管可在本文所揭露的沉積製程期間使用電漿,但應注意到電漿並非必要。
根據一或多個實施例,可在形成層之前及/或之後使基板受到處理。可在相同腔室或在一或多個獨立處理腔室中進行此處理。在某些實施例中,可從第一腔室將基板移動至獨立的第二腔室,以進行進一步處理。可從第一腔室將基板直接移動至獨立的處理腔室,或可從第一腔室將基板移動至一或多個傳遞腔室,並接著將基板移動至期望之獨立的處理腔室。因此,處理設備可包含多個腔室,所述多個腔室與傳
遞站聯繫。此類設備可稱作「叢集工具(cluster tool)」或「叢集的系統(clustered system)」等等。
一般而言,叢集工具為包含多個腔室的模組系統,該多個腔室可進行多種功能,該等功能包括基板中心尋找(substrate center-finding)及定向、去氣(degas)、退火、沉積及/或蝕刻。根據一或多個實施例,叢集工具包括至少一第一腔室及中心傳遞腔室。中心傳遞腔室可容置機械手臂,機械手臂可使基板往返於處理腔室及負載鎖定腔室之間。傳遞腔室典型地維持在真空狀態下,並且傳遞腔室提供中介階段(intermediate stage)用以自一個腔室將基板輸送至另一個腔室,及/或輸送至位於叢集工具前端的負載鎖定腔室。可適用於本發明的兩個已知叢集工具為Centura®及Endura®,兩者皆可購自加州聖大克勞拉市的應用材料公司。一個此類階段式真空基板處理設備的細節揭露於名稱為「Staged-Vacuum Wafer Processing Apparatus and Method」的美國專利第5,186,718號中,該專利於1993年2月16日授予Tepman等人。然而,為了進行本文所描述之製程的特定步驟之目的,可改變腔室的確切布置與組合。可使用的其它處理腔室包括,但不限於,循環層沉積(cyclical layer deposition,CLD)、原子層沉積(ALD)、化學氣相沉積(CVD)、物理氣相沉積(PVD)、蝕刻、預清潔、化學清潔、諸如RTP等熱處理、電漿氮化、去氣、定位、羥化及其它基板處理腔室。藉由在叢集工具上的腔室中執行製程,可避免環境雜質對基板造成表面汙染,而不會在沉積後續膜之前發生氧化。
根據一或多個實施例,基板持續處於真空或「負載鎖定(load lock)」條件下,且當基板從一個腔室被移動至下一個腔室時不被暴露於周圍空氣。因此傳遞腔室處於真空下,且在真空壓力下傳遞腔室被「抽氣(pump down)」。惰性氣體可存在於處理腔室或傳遞腔室中。在某些實施例中,惰性氣體被用作淨化氣體,以在基板的表面上形成層之後,移除部分或所有反應物。根據一或多個實施例,可於沉積腔室的出口處注入淨化氣體,以防止反應物自沉積腔室移動到傳遞腔室及/或附加的處理腔室。因此,惰性氣體流可在腔室出口形成簾幕。
可在單一基板沉積腔室中處理基板,其中單一基板在處理另一個基板前被載入、處理並卸載。也可以連續方式處理基板,例如輸送帶系統,其中多個基板被個別載入腔室的第一部分內,移動通過該腔室並從該腔室的第二部分卸載。腔室的形狀及相關的輸送帶系統可形成筆直路徑或彎曲路徑。此外,處理腔室可為旋轉料架(carousel),其中多個基板沿著中心軸移動並在整個旋轉料架路徑中暴露於沉積、蝕刻、退火、清潔等製程。
在處理期間,可加熱或冷卻基板。可藉由任何合適的手段完成此類加熱或冷卻,合適的手段包括,但不限於,改變基板支撐件的溫度並使加熱或冷卻的氣體流到基板表面。在某些實施例中,基板支撐件包括可受控制的加熱器/冷卻器,以用傳導方式改變基板溫度。在一或多個實施例中,可加熱或冷卻所利用的氣體(無論反應性氣體或惰性氣體),以
局部改變基板溫度。在某些實施例中,可將加熱器/冷卻器安置於腔室內靠近基板表面處,以用對流方式改變基板溫度。
基板也可在處理期間靜止或轉動。轉動的基板可以連續方式轉動或以多個斷續的步驟轉動。舉例而言,基板可在整個製程期間被轉動,或基板可在暴露於不同的反應性氣體或淨化氣體之間小量地轉動。在處理期間轉動基板(無論是以連續方式或以多個步驟轉動)可藉由最小化例如,氣流幾何學中的局部變異性的效應,而有助於產生更均勻的沉積或蝕刻。
在原子層沉積型腔室中,可以空間上或時間上分隔的製程將基板暴露於第一前驅物及第二前驅物。時域ALD為傳統製程,其中第一前驅物流入腔室以與表面反應。在流入第二前驅物之前,從腔室清除第一前驅物。在空間式ALD中,同步將第一前驅物及第二前驅物二者流入腔室,但在空間上分隔所述兩個前驅物流,使得兩個前驅物流之間存在防止該等前驅物混合的一區域。在空間式ALD中,基板須相對於氣體分配板移動,反之亦可。
在整篇說明書中對「一個實施例(embodiment)」、「某些實施例」、「一或多個實施例」或「一實施例」之參考意指與實施例結合而描述之特定特徵、結構、材料或特性包括於本發明之至少一個實施例中。因此,諸如「在一或多個實施例中」、「在某些實施例中」、「在一個實施例中」或「在一實施例中」之用語出現於整篇說明書之不同位置並非必然指代本發明之相同實施例。此外,可以任何適合方式
將特定特徵、結構、材料或特性組合於一或多個實施例中。
儘管已參閱特定實施例描述本文之本發明,但是應理解到,此等實施例僅說明本發明之原理及應用。對於熟習此項技術者將為顯而易見的是,在不脫離本發明之精神及範疇之情況下,可對本發明之方法及設備進行各種修改及變化。因此,希望本發明包括在隨附申請專利範圍及該等隨附申請專利範圍之等效物之範疇內的修改及變化。
Claims (14)
- 一種在一處理腔室中沉積一合金膜的方法,該方法包含下列步驟:在該處理腔室內安置一基板;將該基板的至少一部分暴露於一金屬鹵化物前驅物,以於該基板上提供一第一金屬;從該處理腔室清除未反應的金屬鹵化物前驅物;將該基板表面之該部分暴露於一有機金屬還原劑,該有機金屬還原劑包含一第二金屬,該第二金屬不同於該第一金屬,以於該基板上沉積該第二金屬,產生該第一金屬及該第二金屬之一合金,該有機金屬還原劑包含該第二金屬之一烷類,該第二金屬係選自由In、Sb、Tl、Pb、Bi及前述各者之混合物所組成之群組中,該第二金屬之該烷類包含二甲基-金屬氫化物、二乙基氫化-金屬(diethylhydrido-metal)、甲基二氫-金屬(methyldihydro-metal)及化學式為[(CxHy)z-aMHa]n之烷基金屬氫化物中之一或多者,其中x的值為1至3,y的值為2x+2,z的值為2至5,a的值為1至2,且n的值為1至4。
- 如請求項1所述之方法,其中該金屬鹵化物包含四氯化鈦。
- 如請求項1所述之方法,其中該第二金屬之該烷類包含一胺類。
- 如請求項1所述之方法,其中該基板對該金屬鹵化物之暴露與該基板對該有機金屬還原劑之暴露至少部份重疊。
- 如請求項1所述之方法,進一步包含下列步驟:清除該有機金屬還原劑。
- 如請求項1所述之方法,其中該基板依序暴露於金屬鹵化物及該有機金屬還原劑。
- 如請求項6所述之方法,其中該基板係在暴露於該有機金屬還原劑之前暴露於該金屬鹵化物。
- 如請求項6所述之方法,其中該基板係在暴露於該金屬鹵化物之前暴露於該有機金屬還原劑。
- 如請求項1所述之方法,進一步包含下列步驟:將該合金膜浸入一合金化劑(alloying agent),其中該合金化劑包含SiH4、GeH4、三甲基鎵(trimethylgallium)及B2H6中之一或多者。
- 如請求項1所述之方法,其中該合金膜含有少於20%的碳。
- 一種在一處理腔室中,於一基板上沉積一合金膜的方法,該方法包含下列步驟:在該處理腔室內安置該基板;以及將一金屬鹵化物前驅物及一有機金屬還原劑同步流入該處理腔室,該金屬鹵化物前驅物提供一第一金屬且該有機金屬還原劑包含一第二金屬,該第二金屬不同於該第一金屬,以沉積一合金膜,該合金膜包含該第一金屬及該第二金屬,該有機金屬還原劑包含該第二金屬之一烷類,該第二金屬係選自由In、Sb、Tl、Pb、Bi及前述各者之混合物所組成之群組中,該第二金屬之該烷類包含二甲基-金屬氫化物、二乙基氫化-金屬(diethylhydrido-metal)、甲基二氫-金屬(methyldihydro-metal)及化學式為[(CxHy)z-aMHa]n之烷基金屬氫化物中之一或多者,其中x的值為1至3,y的值為2x+2,z的值為2至5,a的值為1至2,且n的值為1至4。
- 如請求項11所述之方法,其中該金屬鹵化物包含四氯化鈦。
- 如請求項11所述之方法,其中該合金膜含有少於20%的碳。
- 一種在一處理腔室中,於一基板上沉積一合金膜的方法,該方法包含下列步驟:在該處理腔室內安置該基板;以及將一金屬鹵化物前驅物流入該處理腔室以接觸該基板的一部分,該金屬鹵化物前驅物提供一第一金屬,該第一金屬包含鈦、鉭、鎢、鋁中之一或多者;以及將一有機金屬還原劑流入該處理腔室以接觸該基板的一部分,該有機金屬還原劑包含一第二金屬,該第二金屬不同於該第一金屬,該有機金屬還原劑包含該第二金屬之一烷類,該第二金屬係選自由In、Sb、Tl、Pb、Bi及前述各者之混合物所組成之群組中,該第二金屬之該烷類包含二甲基-金屬氫化物、二乙基氫化-金屬(diethylhydrido-metal)、甲基二氫-金屬(methyldihydro-metal)及化學式為[(CxHy)z-aMHa]n之烷基金屬氫化物中之一或多者,其中x的值為1至3,y的值為2x+2,z的值為2至5,a的值為1至2,且n的值為1至4,其中該金屬鹵化物及有機金屬還原劑係同步流入該處理腔室的不同區域,且係由一惰性氣體簾幕分隔,以防止該金屬鹵化物與有機金屬還原劑之氣相反應,且其中該合金膜為基本上純的,且在原子基礎上具有低於約1%的雜質。
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US10036089B2 (en) | 2018-07-31 |
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EP3014651B8 (en) | 2018-12-26 |
EP3014651A4 (en) | 2016-11-23 |
TW201504468A (zh) | 2015-02-01 |
CN110592554A (zh) | 2019-12-20 |
KR102298038B1 (ko) | 2021-09-02 |
US20150004316A1 (en) | 2015-01-01 |
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WO2014210328A1 (en) | 2014-12-31 |
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