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TWI534290B - 透過自由基化成份化學氣相沉積形成的共形層 - Google Patents

透過自由基化成份化學氣相沉積形成的共形層 Download PDF

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TWI534290B
TWI534290B TW100104616A TW100104616A TWI534290B TW I534290 B TWI534290 B TW I534290B TW 100104616 A TW100104616 A TW 100104616A TW 100104616 A TW100104616 A TW 100104616A TW I534290 B TWI534290 B TW I534290B
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conformal
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TW201142073A (en
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梁靜美
陳曉琳
李東擎
英戈爾尼廷Ｋ
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應用材料股份有限公司
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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
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    • 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
    • C23C16/22—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 inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • 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
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    • 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
    • C23C16/448—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/452—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
    • 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
    • C23C16/56—After-treatment
    • H10P14/6334—
    • H10P14/6522—
    • H10P14/69215—
    • H10W20/098—

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Description

透過自由基化成份化學氣相沉積形成的共形層
此申請案主張於西元2010年7月21日提出申請之名稱為「FORMATION OF SILICON OXIDE USING NON-CARBON FLOWABLE CVD PROCESSES」的美國專利申請第12/840,768號，以及於西元2010年3月5日提出申請之名稱為「CONFORMALS BY RADICAL-COMPONENT CVD」的美國臨時專利申請第61/311,061號的權益。就各方面而言，這些申請案的全文係以參照方式併入本文中。
本發明關於製造半導體裝置的方法。
自從數十年前引進了半導體裝置，半導體裝置幾何形態之尺寸已經顯著地減小。現代半導體製造設備常規地製造具有45 nm、32 nm與28 nm特徵尺寸之裝置，且正在發展並實現新設備以製造具有甚至更小幾何形態之裝置。減小的特徵尺寸致使裝置上之結構特徵具有減小的空間尺寸。元件上之間隙與溝槽的寬度限縮到一程度，其中間隙深度對其寬度之縱橫比變得高到足夠使以介電材料來填充間隙更富有挑戰性。沉積之介電材料傾向在間隙完全填滿之前於頂部堵塞，而在間隙中間產生空隙(void)或縫隙。
數年來，已經發展許多技術來避免使介電材料堵塞間隙的頂部，或「密封(heal)」已經形成的空隙或縫隙。一種方式以高度可流動的前驅物材料來開始，高度可流動的前驅物材料可形成於經圖案化基材表面上(例如，SOG沉積技術)。這些可流動的前驅物可流入並填充非常小的基材間隙，而不會形成空隙或弱的縫隙。
於某些應用中，基材間隙內部的表面可能不會被可流動的介電材料所潤濕。舉例而言，這傾向在下方材料於高溫下沉積時所發生。因此，需要有新的沉積製程以及材料，以在結構基材上形成介電材料，致使可流動的材料可更簡單地滲透基材表面中的間隙。本發明滿足了這種和其它需求。
茲揭露用以自無碳矽與氮前驅物與自由基-氮前驅物形成含有矽與氮的共形介電層(例如，矽-氮-氫(Si-N-H)膜)之方法、材料以及系統。無碳矽與氮前驅物主要藉由接觸自由基-氮前驅物而激發。因為矽與氮膜是在無碳情況下形成，因此可在較少孔洞形成及較低體積收縮率下完成膜至硬化的氧化矽之轉化。可將經沉積的含矽與氮膜完全或部分轉化為氧化矽，其容許共形介電層的光學特性成為可選擇的。可於低溫下進行含矽與氮薄膜的沉積，以於基材溝槽中形成襯墊層。已發現低溫襯墊層可增進濕潤特性，並容許可流動的膜更完整地填充溝槽。
本發明的具體實施例包括於基材處理腔室中之基材處理區域中的經圖案化基材上形成共形含矽與氮層的方法。這些方法包括將無碳含矽與氮前驅物與自由基-氮前驅物混合。藉由接觸自由基-氮前驅物而主要地激發無碳含矽與氮前驅物。這些方法進一步包括於經圖案化基材上沉積具有共形層厚度的共形含矽與氮層。
本發明的具體實施例進一步包括形成具降低的體積收縮率之含矽層的方法。這些方法包括移轉含有間隙之基材，以及於基材上沉積共形含矽與氮層。共形含矽與氮層具有共形性(conformality)。這些方法進一步包括於共形含矽與氮層上沉積可流動的含矽與氮層。含矽層包含共形含矽與氮層以及可流動的含矽與氮層二者。
額外之具體實施例與特徵係部分地揭示在以下說明中，且其部分地對於熟習此技藝之人士在參閱說明書時變得明顯，或可藉由實施本發明而瞭解。可藉由說明書中所描述之工具、組合和方法來瞭解並獲得本發明之特徵與優點。
茲描述用以自無碳矽與氮前驅物與自由基-氮前驅物形成含有矽與氮的共形介電層(例如，矽-氮-氫(Si-N-H)膜)之方法、材料以及系統。無碳矽與氮前驅物主要藉由接觸自由基-氮前驅物而激發。因為矽與氮膜是在無碳情況下形成，因此可在較少孔洞形成及較低體積收縮率下完成膜至硬化的氧化矽之轉化。可將經沉積的含矽與氮膜完全或部分轉化為氧化矽，其容許共形介電層的光學特性成為可選擇的。可於低溫下進行含矽與氮薄膜的沉積，以於基材溝槽中形成襯墊層。於多個具體實施例中，已發現低溫襯墊層可增進濕潤特性，並容許可流動的膜更完整地填充溝槽。在導入關於用以形成共形介電層的方法及系統之額外細節的過程中，本發明之具體實施例的多個態樣將被呈現在一個具體實施例的論述中，並可瞭解到，除非有相反的陳述，該等態樣也可被應用在其餘的具體實施例中。
第1圖為流程圖，其繪示根據本發明之具體實施例的用以製作共形介電層之方法100中的經選擇步驟。。方法100包括提供無碳矽前驅物至反應腔室(步驟102)。無碳矽前驅物可以是，舉例而言，矽與氮前驅物、矽與氫前驅物或含矽-氮-與-氫前驅物，還有其它類型的矽前驅物。這些前驅物的特殊實例可包括矽烷基胺(silyl-amine)，如H2N(SiH3)、HN(SiH3)2及N(SiH3)3，還有其它矽烷基胺。這些矽烷基胺可與可作為載氣、反應性氣體或兩者皆可的額外氣體混合。額外氣體的實例可包括H2、N2、NH3、He以及Ar，還有其它氣體。無碳矽前驅物的實例也可包含單獨存在或與其它含矽氣體(例如，N(SiH3)3)、含氫氣體(例如，H2)及/或含氮氣體(例如，N2、NH3)混合之矽烷(SiH4)。無碳矽前驅物也可包括二矽烷、三矽烷、高階矽烷以及氯化矽烷，其可單獨存在或與另一個或前述無碳矽前驅物結合。
除了無碳以外，矽前驅物還可為無氧。氧的缺乏可於自前驅物形成的矽與氮層中造成較低的矽醇(Si-OH)基團濃度。沉積膜中存在過多的矽醇部分，可於自沉積層移除羥基(-OH)部分的後沉積步驟期間造成增加的孔隙率以及收縮率。在其它具體實施例中，矽前驅物含有氧，其可併入共形含矽與氮膜中。為了調整沉積膜的沉積特性及/或光學特性，含有氧可能是理想的。可如單獨的前驅物般導入含氧前驅物，且可同時將無碳矽前驅物及含氧前驅物流入基材處理區域。
另外可將自由基-氮前驅物提供至反應腔室(步驟104)。自由基-氮前驅物為含氮-自由基物種，其於反應腔室外部自更穩定的氮前驅物形成。舉例而言，如NH3等穩定的氮前驅物可於反應腔室外部的電漿單元中活化，以形成自由基-氮前驅物，其接著輸送進入反應腔室。在不同的具體實施例中，穩定的氮前驅物也可為包含NH3與N2、NH3與H2、NH3與N2與H2以及N2與H2的混合物。在與N2以及H2的混合物中，也可用胼來取代NH3或與NH3組合。穩定的氮前驅物(以及自由基-氮前驅物)也可伴隨著載氣，如氬(Ar)、氫(H2)、氮(N2)、氦等等。所產生的自由基-氮前驅物可為．N、．NH、．NH2中之一或多種，且也可能伴隨著於電漿中所形成的離子化物種。
一般而言，不包括氮的自由基前驅物也將容許形成含矽與氮層。若包括氮的話，自由基前驅物可為自由基-氮前驅物，其與前述之前驅物一起提供至遠端電漿區域。自由基前驅物於反應腔室中與沉積區域分隔的一個區段中產生，而前驅物於沉積區域混合並反應，以沉積矽與氮層於沉積基材(例如，半導體晶圓)上。於自由基前驅物為自由基-氮前驅物的具體實施例中，穩定的氮前驅物流入遠端電漿區域並由電漿激發。穩定的氮前驅物(以及自由基-氮前驅物)也可伴隨著載氣，如氫(H2)、氮(N2)、氬、氦等等。另外也於所揭露的具體實施例中發現，自輸入氣體形成的基本上由氮(N2)所組成(可有或沒有額外惰性載氣)之自由基-氮前驅物可產生有利的膜。於含矽前驅物包含氮的具體實施例中，自由基-氮前驅物也可由基本上由氫(H2)(及視情況而定的惰性載氣)所組成的輸入氣體所形成的自由基前驅物所取代。
於多個具體實施例中，自由基-氮前驅物於反應腔室中藉由篩具或噴灑頭與基材處理區域分隔的一個區段中產生。於基材處理區域中，無碳矽前驅物及自由基-氮前驅物混合並反應(步驟106)，以於沉積基材上沉積共形含矽與氮膜(步驟108)。自由基-氮前驅物對無碳矽前驅物提供主要的激發反應。於多個具體實施例中，自由基-氮前驅物對無碳矽前驅物提供僅有的激發反應。於沉積其間，沒有或基本上沒有電漿功率被施加至基材處理區域。
於不同的具體實施例中，基材處理區域中的壓力低於200mTorr(毫托)、150mTorr、100mTorr、75mTorr或50mTorr中之一。於不同的具體實施例中，共形含矽與氮膜的厚度可低於30nm、20nm、15nm、10nm及5nm中之一。於不同的具體實施例中，共形含矽與氮膜的生長速率可低於30nm/min、20nm/min、15nm/min、10nm/min及5nm/min中之一。如前所述，參照第1圖所描述的數值界限也可應用於本文他處所描述的其它具體實施例。前驅物的流速可夠低以在基材處理區域中構成相對低的壓力。或者，可增加抽取速度。於不同的具體實施例中，共形含矽與氮膜沉積期間的基材溫度可低於200℃、150℃、100℃、75℃及50℃中之一。隨著沉積之後，可硬化及/或退火所沉積之層，以增加膜的氧含量，將參照第2圖而更詳細地於本文中討論。
現請參見第2圖，其顯示另一流程圖，繪示了根據本發明之具體實施例的用以在經圖案化基材上形成共形介電膜之方法200中的經選擇步驟。方法200可包括移轉經圖案化基材(步驟202)。基材可具有在生產基材上的電子組件(例如，電晶體)以及內連線的過程期間所存在的溝槽、間隙及其它垂直特徵結構。可用已於描述第1圖的過程中所呈現之方法，將共形含矽與氮層沉積於基材上(步驟204)。
於含矽與氮膜沉積之後，可於含氧氣氛206中或簡單暴露至含氧氣氛206加熱經圖案化基材。當導入含氧氣氛時，基材可維持於反應腔室中，或者可將基材轉移至導入含氧氣氛的不同腔室。含氧氣氛可包括一或多種含氧氣體，如分子氧(O2)、臭氧(O3)、水蒸汽(H2O)及氧化氮(NO、NO2等等)，以及其它含氧氣體。含氧氣氛也可包括自由基氧以及羥基物種，如原子氧(O)、氫氧化物(OH)等，其可於遠端產生，並傳輸進入基材腔室。含氧物種的離子也可存在。
含氧氣氛提供了氧氣，以將含矽與氮膜部分或完全轉化為氧化矽(SiO2)膜。含矽與氮膜缺少碳導致最終氧化矽膜中形成顯著較少的孔洞。其也導致在轉化為氧化矽期間，膜的較少體積縮小(即，收縮率)。舉例而言，當轉化為氧化矽時，自含碳之矽前驅物形成的矽-氮-碳層可能有40體積%或更高的收縮率，而實質上無碳的矽與氮膜的收縮率可能約15體積%或更低。
於多個具體實施例中，在暴露至含氧氣氛期間，可加熱經圖案化基材至高於50℃、100℃、150℃、200℃、250℃、300℃、400℃、500℃、600℃、800℃及1000℃中之一者。於多個具體實施例中，在暴露至含氧氣氛期間，基材溫度可低於100℃、200℃、300℃、400℃、500℃、600℃、800℃、1000℃或1100℃中之一者。在不同的具體實施例中，該等上限中之任一者可結合該等下限中之任一者，以形成額外的基材溫度範圍。
具體實施例可包含具不同溫度及氣氛的多個加熱階段。舉例而言，可於較低的第一溫度下，在包括水蒸汽(H2O)的氣氛中進行第一加熱階段，而可在較高的第二溫度下，在本質上缺乏水蒸汽的乾燥含氧氣氛中進行第二加熱階段。也可在非含氧氣氛(例如，乾燥的N2、He、Ar等等)中進行第三加熱階段。在其它具體實施例中，於高溫氧氣(O2)退火(例如，高於800℃)之前，可於低溫(例如，介於200℃與400℃之間)下進行臭氧硬化。於不同的具體實施例中，含氧氣氛硬化及/或退火可降低折射率(於193nm下測量)的實部(real portion)至低於1.8、1.75、1.7或1.65中之一。於不同的具體實施例中，硬化及/或退火可降低消光係數(折射率的虛部(imaginary portion)量；同樣於193 nm下測量)至低於0.15、0.10、0.075、0.050或0.025中之一。於不同的具體實施例中，轉化為氧化矽是不完全的，且轉化後的消光係數高於0.010、0.025、0.050、0.075以及0.10中之一。在額外的具體實施例中，該等上限中之任一者可結合該等下限中之任一者，以形成額外的消光係數範圍。
第3圖為流程圖，其繪示根據本發明的具體實施例的用以於基材上的間隙中形成介電層的方法300中之經選擇步驟。方法300可包括移轉經圖案化基材進入基材處理區域(步驟302)。基材可具有複數個間隙，供形成於基材上之裝置組件(例如，電晶體)的間隔與結構所用。間隙可具有高度及寬度，其定義高度對寬度(即，H/W)的縱橫比(aspect ratio，AR)，其顯著大於1：1(例如，5：1或更大、6：1或更大、7：1或更大、8：1或更大、9：1或更大、10：1或更大、11：1或更大、12：1或更大，等等)。於許多例子中，高AR是因小的間隙寬度之故，該間隙寬度之範圍介於約90 nm至約22 nm或更小(例如，約90 nm、65 nm、45 nm、32 nm、22 nm、16 nm等等)。
如參照第2至3圖所描述，共形含矽與氮層可沉積於基材上(步驟304)。如本文中所使用，共形層指的是表面上之大體上一致的材料層與該表面具有相同外形，亦即，層的表面以及欲覆蓋之表面大體上為平行的。本發明所屬技術領域中具有通常知識者將可理解，所沉積的材料可能不會100%共形，且因此術語「大體上(generally)」容許可接受的公差。本文將共形性量化為在兩個不同位置處所測量之共形層的兩個厚度的比例：其中一個厚度是在間隙的側壁上，且另一個厚度是在間隙底部。在跨越晶圓或跨越晶粒之厚度有顯著變化的例子中，可合理使用來自多個取樣點的平均測量值。請注意，間隙填充膜之沉積期間所發生的各種效應使壁厚度或底部厚度皆有可能成為較小者。可將兩個厚度中的較小者除以較大者之比例轉換為百分比。於不同的具體實施例中，依此方式所測量之含矽與氮層的共形性可大於70%、80%、90%及95%中之一者。
藉由增加基材處理區域中的壓力，將可流動的含矽與氮層沉積於共形層上(步驟306)。可藉由增加該等前驅物(自由基氮前驅物及/或無碳含矽前驅物)中之一或二者的流速來完成此步驟。交替或結合，可藉由部分關閉閥門或降低真空泵的實際抽取速度，來降低抽取速度。於不同的具體實施例中，當可流動的層形成時，基材處理區域中的壓力大於500mTorr、750mTorr、1Torr或2Torr中之一者。共形層的濕潤特性協助可流動層滲透進入間隙。因為該層可流動，其可填充具高縱橫比的間隙，而不會在填充材料的中央周圍產生空隙或弱接縫。舉例而言，在完全填充間隙之前，沉積可流動的材料較不會過早阻塞間隙的頂部而在間隙中間留下空隙。
流動性(flowability)可能成因於將自由基-氮前驅物與無碳矽前驅物混合所造成的多種性質。這些性質可包括在沉積的膜中有顯著的氫成分及/或短鏈聚矽氮烷(polysilazane)聚合物的存在。在膜形成期間及之後，這些短鏈成長並網路化以形成更密集的介電材料。舉例而言，沉積的膜可具有矽氮烷類，Si-NH-Si骨幹(即，Si-N-H膜)。當矽前驅物及自由基-氮前驅物兩者為無碳時，所沉積的含矽與氮膜本質上也為無碳。當然，「無碳」不必然表示膜內甚至缺乏微量的碳。碳污染物可存在於前驅物材料中而構成它們進入經沉積的矽與氮前驅物之方式。然而，這些碳雜質的量遠小於可能在具有碳部分的矽前驅物(例如，TEOS、TMDSO等等)中發現的量。
相似於第1至2圖之先前具體實施例，共形且可流動的含矽與氮膜之沉積後可跟隨著硬化及/或退火(步驟308)。可部分或完全轉化至氧化矽，並可能影響可流動的膜及共形沉積的膜二者。含氧氣氛可包括分子氧、臭氧及水蒸汽還有其它氣體。於某些例子中，可自包括含氧氣體的混合物擊發電漿，然而在其它例子中，不從氣體形成電漿。
進入CVD腔室之含氧氣體可包括一或多種化合物，其在進入腔室前被活化(例如，激化(radicalize)、離子化等等)。舉例而言，含氧氣體可包括自由基氧物種、自由基羥物種等等，其藉由透過遠端電漿源暴露更穩定的前驅物化合物而活化。更穩定的前驅物可包括產生羥(OH)自由基與離子之水蒸氣及過氧化氫(H2O2)，以及產生原子氧(O)自由基與離子之分子氧及/或臭氧。
示範性氧化矽沉積系統
可執行本發明的具體實施例之沉積腔室可包括高密度電漿化學氣相沉積(HDP-CVD)腔室、電漿增進化學氣相沉積(PECVD)腔室、次大氣壓化學氣相沉積(SACVD)腔室以及熱化學氣相沉積腔室，還有其它類型的腔室。可執行本發明的具體實施例之CVD系統的特定實例包括可購自加州聖大克勞拉市(Santa Clara)的Applied Material,Inc.的CENTURA ULTIMA HDP-CVD腔室/系統，以及PRODUCER PECVD腔室/系統。
可與本發明的示範性方法一起使用之基材處理腔室的實例可包含那些在Lubomirsky等人於2006年5月30日提申且名稱為「PROCESS CHAMBER FOR DIELECTRIC GAPFILL」的共同讓渡美國臨時專利申請案第60/803,499號中所顯示及描述者，其整體內容以為一切目的參照之方式併入本文中。額外的示範性系統可包括那些在美國專利第6,387,207及6,830,624號中所示及描述者，其也以為一切目的參照之方式併入本文中。
沉積系統的具體實施例可併入較大製造系統內，以生產積體電路晶片。第4圖顯示根據所揭露之具體實施例的一個此類沉積系統400、烘烤及硬化腔室。於此圖中，一對前開式晶圓盒(front opening unified pod，FOUP) 402供應基材，基材(例如，300 mm直徑之晶圓)由機器人手臂404承接，並在置入晶圓處理腔室408a-f中之一者以前先置入低壓保持區406內。可用第二機器人手臂410以自保持區406向處理腔室408a-f來回移轉基材晶圓。
處理腔室408a-f可包括一或多個系統組件，用以在基材晶圓上沉積、退火、硬化及/或蝕刻可流動的介電膜。於一種配置中，兩對處理腔室(例如，408c-d及408e-f)可用以在基材上沉積可流動的介電材料，且第三對處理腔室(例如，408a-b)可用來退火經沉積的介電材料。於另一種配置中，相同的兩對處理腔室(例如，408c-d及408e-f)可用以在基材上沉積並退火可流動的介電膜，而第三對腔室(例如，408a-b)可用來進行經沉積的膜之UV或E-光束硬化。於再一種配置中，全部三對腔室(例如，408a-f)可用以在基材上沉積並硬化可流動的介電膜。於又一種配置中，兩對處理腔室(例如，408c-d及408e-f)可用來進行可流動的介電膜之沉積及UV或E-光束硬化兩者，而第三對處理腔室(例如，408a-b)可用以退火介電膜。所述製程中的任一或多者可在與不同具體實施例所顯示的製造系統分離之(複數)腔室上進行。
此外，處理腔室408a-f中的一或多者可如濕式處理腔室般進行配置。這些處理腔室包括在含有濕氣的氣氛中加熱可流動的介電膜。因此，系統400的具體實施例可包括濕式處理腔室408a-b以及退火處理腔室408c-d，以在沉積的介電膜上進行濕式及乾式退火二者。
第5A圖為根據所揭露之具體實施例的基材處理腔室500。遠端電漿系統(RPS)510可處理氣體，其接著透過氣體入口總成511行進。氣體入口總成511內可見到兩個顯著不同的氣體供應通道。第一通道512承載通過遠端電漿系統(RPS)510的氣體，而第二通道513則避開RPS 500。於所揭露的具體實施例中，第一通道512可供製程氣體所用，而第二通道513可供處理氣體所用。所示的蓋體(或導電頂部區域)521以及開孔隔板553之間間設有絕緣環524，其容許AC電位施加至相對於開孔隔板553的蓋體521。製程氣體行進通過第一通道512進入腔室電漿區域520，且可在腔室電漿區域520中由電漿單獨激發或與RPS 510聯合激發。於本文中，腔室電漿區域520及/或RPS 510的組合稱為遠端電漿系統。開孔隔板(又稱為噴灑頭) 553隔離腔室電漿區域520以及噴灑頭553下方的基材處理區域570。噴灑頭553容許電漿存在腔室電漿區域520中，以避免直接於基材處理區域570中激發氣體，而仍可容許被激發的物種自腔室電漿區域520行進至基材處理區域570。
接附至基材處理區域的排放系統之抽取速度可經選擇並配置，以使基材處理區域中的壓力維持在200 mTorr、150 mTorr、100 mTorr、75 mTorr或50 mTorr中之一者以下，以促進共形含矽與氮膜的沉積。
噴灑頭553位於腔室電漿區域520及基材處理區域570之間，且容許腔室電漿區域520內所生成的電漿流出物(前驅物或其它氣體的激發衍生物)通過貫穿板厚度的複數個穿孔556。噴灑頭553也具有一或多個凹陷容積551，其可填充以蒸氣或氣體形式的前驅物(如含矽前驅物)，並通過小孔555進入基材處理區域570，而非直接進入腔室電漿區域520。於此揭露的具體實施例中，噴灑頭553的厚度大於穿孔556的最小直徑550之長度。為了維持顯著濃度的激發物種自腔室電漿區域520滲透至基材處理區域570，可藉由形成部分通過噴灑頭553之穿孔556的較大直徑部份來限縮穿孔的最小直徑550之長度526。於所揭露的具體實施例中，穿孔556的最小直徑550之長度的數量級，可相等於或小於穿孔556之最小直徑的數量級。
於所示的具體實施例中，噴灑頭553可(經由穿孔556)散佈含有氧、氫及/或氮的製程氣體，及/或由腔室電漿區域520中的電漿所激發之此類製程氣體的電漿流出物。於多個具體實施例中，透過第一通道512導入RPS 510及/或腔室電漿區域520的製程氣體可含有氧(O2)、臭氧(O3)、N2O、NO、NO2、NH3、NxHy(包括N2H4、矽烷、二矽烷、TSA以及DSA)中的一或多者。製程氣體也可包含載氣，如氦、氬、氮(N2)等等。第二通道513也可散佈製程氣體及/或載氣，及/或用以自生長的膜或沉積的膜移除非所欲成分之膜-硬化氣體。電漿流出物可包括製程氣體的離子化或中性衍生物，且在本文中也可代表有關於導入之製程氣體的原子構成要素之自由基-氧前驅物及/或自由基-氮前驅物。
於多個具體實施例中，穿孔556的數量可介於約60至約2000之間。穿孔556可具有多種形狀，但最容易製作成圓形。於所揭露的具體實施例中，穿孔556的最小直徑550可介於約0.5 mm及約20 mm之間，或介於約1 mm及約6 mm之間。還可自由選擇穿孔的截面形狀，其可被製作成圓錐狀、圓柱狀或兩種形狀的組合。在不同的具體實施例中，使用來將氣體導入基材處理區域570之小孔555的數量可介於約100及約5000之間，或介於約500及約2000之間。小孔555的直徑可介於約0.1 mm及約2 mm之間。
第5B圖為根據所揭露之具體實施例的與處理腔室一起使用之噴灑頭553的底部視圖。噴灑頭553相當於第5A圖中所繪示的噴灑頭。所描繪的穿孔556於噴灑頭553底部具有較大的內徑(inner-diameter，ID)，而在噴灑頭553頂部具有較小ID。小孔555基本上平均散佈於噴灑頭表面上，甚至在穿孔556周圍，相較於本文所描述的其它具體實施例而言，這樣可協助提供更平均的混合。
當透過噴灑頭553中的穿孔556抵達之電漿流出物，與源自凹陷容積551並透過小孔555抵達之含矽前驅物結合時，示範性膜生成於基材處理區域570內之基座(未繪示)所支撐的基材上。雖然基材處理區域570也可經配備以維持供諸如硬化等其它製程所用之電漿，但在示範性膜生長期間，沒有電漿存在。
可在噴灑頭553上的腔室電漿區域520中或在噴灑頭553下的基材處理區域570中點燃電漿。電漿存在於腔室電漿區域520中，以自含氮與氫氣體流入物產生自由基氮前驅物。將典型在射頻(radio frequency，RF)範圍內的AC電壓施加於處理腔室的導電頂部份521以及噴灑頭553之間，以於沉積期間點燃腔室電漿區域520中的電漿。RF功率供應器產生13.56 MHz的高RF頻率，但也可單獨或結合13.56 MHz頻率而產生其它頻率。
當開啟基材處理區域570中的底部電漿，以硬化膜或清潔基材處理區域570邊界的內表面時，可讓頂部電漿處於低功率或無功率狀態。可藉由在噴灑頭553及基座或腔室底部之間施加AC電壓來點燃基材處理區域570中的電漿。當電漿存在時，可將清潔氣體導入基材處理區域570。
基座可具有供熱交換流體流動的熱交換通道，以控制基材的溫度。此配置容許冷卻或加熱基材之溫度，以維持相對低的溫度(自0℃到約120℃)。熱交換流體可包含乙二醇及水。也可使用配置來做平行同心圓形式的兩個完整匝數之埋入式單一迴圈埋入加熱器元件，以電阻加熱基座的晶圓支撐盤(較佳為鋁、陶瓷或其組合)達到相對高溫(自約120℃一直到約1100℃)。加熱器元件的外側部份可鄰近支撐盤的邊緣，而其內側部份可圍繞具有較小半徑的同心圓之路線。連接加熱器元件的線路通過基座的座腳。
基材處理系統由系統控制器所控制。於一示範性具體實施例中，系統控制器包括硬碟機、軟碟機以及處理機。處理機含有單板電腦(single-board computer，SBC)、類比及數位輸入/輸出板、介面板以及步進馬達控制器板。CVD系統的各種部件符合Versa Modular European(VME)標準，該標準定義板、卡片機架以及連接器尺寸及類型。VME標準亦定義具有16位元資料匯流排及24位元位址匯流排之匯流排結構。
系統控制器控制CVD機器的全部活動。系統控制器執行系統控制軟體，其為儲存在電腦可讀取媒體中的電腦程式。較佳地，該媒體為硬碟機，但該媒體也可為其它類型的記憶體。電腦程式包含多組指令，其支配特定製程的時點、氣體之混合、腔室壓力、腔室溫度、RF功率等級、晶座位置以及其它參數。也可使用儲存於其它記憶體裝置(包含如軟碟或另一適當的磁碟機)的其它電腦程式來命令系統控制器。
可使用由系統控制器所執行的電腦程式產品來實施於基材上沉積膜堆疊的製程，或清潔腔室的製程。電腦程式碼可以任何慣用的電腦可讀取程式語言來撰寫：例如，68000組合語言、C、C++、Pascal、Fortran或其它程式語言。可以慣用的文字編輯器將合適的程式碼輸入單一檔案或多個檔案中，並儲存或體現於電腦可使用媒體中，如電腦的記憶體系統。若輸入的程式碼文字係以高階語言撰寫，則編譯該程式碼，並接著將所產生的編譯器碼連結預先編譯的Microsoft Windows常式庫(library routine)之目標碼(object code)。為了執行連結的、編譯的目標碼，系統使用者援引目標碼，致使電腦系統載入記憶體中的程式碼。CPU接著讀取並執行程式碼以進行程式中所指示的任務。
透過平面面板觸控螢幕作為使用者與控制器之間的介面。於較佳的具體實施例中，使用了兩個螢幕，其中一個安裝於清潔室壁供操作員所用，而另一個安裝於壁後供服務技師所用。在一次只接受一個輸入的例子中，這兩個螢幕可同步顯示相同的資訊。為了選擇特定畫面或功能，操作員觸碰觸控螢幕的指定區塊。被碰觸的區塊改變其標記顏色，或者顯示一個新的選單或畫面，以確認操作員與觸控螢幕之間的溝通。其它裝置，如鍵盤、滑鼠或其它指示或溝通裝置可取代或附加至觸控螢幕，以容許使用者與系統控制器溝通。
腔室電漿區域或RPS中之一區域可稱作遠端電漿區域。於多個具體實施例中，自由基氮前驅物於遠端電漿區域中生成，並行進至基材處理區域內，其中無碳含矽前驅物藉由自由基氮前驅物激發。於多個具體實施例中，無碳含矽前驅物僅由自由基氮前驅物激發。於多個具體實施例中，電漿功率基本上可僅施加至遠端電漿區域，以確保自由基氮前驅物對無碳含矽前驅物提供主要的激發反應。
於本文中，於含矽與氮層成長期間或於某些其它步驟進行期間，可將基材處理區域描述為「無電漿(plasma-free)」。「無電漿」並不必然意味著該區域完全沒有電漿。於電漿區域生成的離子化物種可行進至基材處理區域內，但無碳含矽前驅物本質上不會被施加到電漿區域的電漿功率所激發。很難界定腔室電漿區域中之電漿的邊界，且其可能透過噴灑頭中的通孔侵入基材處理區域上方。在感應耦合電漿的例子中，少量離子化可直接於基材處理區域中施行。進一步，低強度電漿可生成於基材處理區域中，而不需消除形成膜的可流動本性。於自由激氮前驅物生成期間，具有較腔室電漿區域低得多的強度之電漿的所有成因，皆不偏離本文中所用的「無電漿」之範疇。
本文使用之「基材(substrate)」可為在其上有或無層形成之支撐基材。支撐基材可為各種摻雜濃度及輪廓之絕緣體或半導體，且可為，例如在積體電路製造中所使用之類型的半導體基材。「氧化矽(silicon oxide)」之層用以作為含矽與氧材料的簡寫，且可與含矽與氧材料交換使用。就其本身而論，氧化矽可包括其它基礎構成要素，如氮、氫、碳等等的含量。於某些具體實施例中，氧化矽基本上由矽與氧組成。術語「前驅物(precursor)」用來指示任何製程氣體，其參與自表面上移除材料或沉積材料至表面上之反應。處於「激發態(excited state)」的氣體所描述之氣體中的至少某些氣體分子處於震動激發態、游離態及/或離子化態。氣體可為兩種以上氣體的組合。術語「溝槽(trench)」或「間隙(gap)」被使用於本文各處，且並非暗示蝕刻之幾何形狀具有高水平縱橫比。自表面之上方觀看，溝槽及間隙可呈現圓形、卵形、多邊形、矩形或各種其他形狀。
在已揭示若干具體實施例之後，熟習此項技術者將認識到，在不偏離所揭示之具體實施例之精神的情況下可使用各種修改、替代構造及等效物。另外，未描述若干熟知的製程及元件以避免不必要地混淆本發明。因此，上文描述不應視為限制本發明之範疇。
在提供一範圍之值之情況下，除非本文另有明確指定，應理解亦特定地揭示彼範圍之上限與下限之間的每一中間值，精確度為至下限單位的十分位。將涵蓋在陳述範圍中之任一陳述值或中間值與在彼陳述範圍中之任一其他陳述值或中間值之間的每一較小範圍。此等較小範圍之上限及下限可獨立地包括於該範圍中或排除於該範圍之外，且在界限中任一者、沒有任一界限或兩界限皆包括於該等較小範圍中之每一範圍亦涵蓋於本發明內，其受所陳述範圍中任何特定排除之界限管轄。在所陳述範圍包括該等限制中一者或兩者之情況下，亦包括排除彼等包括之限制中一者或兩者之範圍。
如本文及隨附申請專利範圍中所使用，除非本文另有明確指定，否則單數形式「一(a)」、「一(an)」及「該(the)」包括複數指示物。因此，例如，參照「一製程」包括複數個該等製程，且參照「該前驅物」包括參照一或多個前驅物及熟習此項技術者熟知之其等效物，等等。
又，當在本專利說明書中及下文申請專利範圍中使用字彙「包含(comprise)」、「包含(comprising)」、「包括(include)」、「包括(including)」及「包括(includes)」時，意欲指定陳述之特徵、整數、組件或步驟之存在，但其不排除一或多個其他特徵、整數、組件、步驟、動作或群組之存在或添加。
100、200、300．．．方法
102~108、202~206、302~308．．．流程步驟
400．．．系統
402．．．前開式晶圓盒
404．．．機器人手臂
406．．．低壓保持區
408a~408f．．．處理腔室
410．．．第二機器人手臂
500．．．基材處理腔室
510．．．遠端電漿系統
511．．．氣體入口總成
512．．．第一通道
513．．．第二通道
520．．．腔室電漿區域
521．．．蓋體/導電頂部區域
524．．．絕緣環
526．．．長度
550．．．穿孔的最小直徑
551．．．凹陷容積
553．．．開孔隔板/噴灑頭
555．．．小孔
556．．．穿孔
570．．．基材處理區域
可藉由參照本專利說明書的其它部分及圖式來實現對所揭示之實施例之特性及優點的進一步瞭解，其中在多個圖式之間使用相似的元件符號來指出類似的組件。在某些例子中，子標號與元件符號有關且伴隨著連字號，以表示多個類似組件中之一。當提及一元件符號而未載明現存的子標號時，其意指所有此等多個類似組件。
第1圖為流程圖，其繪示根據本發明之具體實施例的用以製作共形介電層之經選擇步驟。
第2圖為流程圖，其繪示根據本發明之具體實施例的用以形成具有可選擇的光學特性之共形介電層的經選擇步驟。
第3圖為流程圖，其繪示根據本發明的具體實施例的用以於間隙中形成介電層的經選擇步驟。
第4圖顯示根據本發明的具體實施例之基材處理系統。
第5A圖顯示根據本發明的具體實施例之基材處理腔室。
第5B圖顯示根據本發明的具體實施例之基材處理腔室的噴灑頭。
100．．．方法
102~108．．．流程步驟

Claims (22)

  1. 一種於一基材處理腔室中之一基材處理區域中形成一共形含矽與氮層於一經圖案化基材上的方法，該方法包含下列步驟：將一無碳含矽與氮前驅物與一自由基-氮前驅物混合，其中藉由接觸該自由基-氮前驅物而主要地激發該無碳含矽與氮前驅物；以及於該經圖案化基材上沉積具有一共形層厚度之一共形含矽與氮層。
  2. 如申請專利範圍第1項所述之方法，其中於該共形含矽與氮膜沉積期間，該基材處理區域中之一共形沉積壓力低於或約為200mTorr(毫托)。
  3. 如申請專利範圍第1項所述之方法，其中於該共形含矽與氮膜沉積期間，該基材之一共形沉積溫度低於或約為200℃。
  4. 如申請專利範圍第1項所述之方法，其中該共形層厚度低於或約為20nm。
  5. 如申請專利範圍第1項所述之方法，進一步包含下列 步驟：藉由使該含矽與氮層暴露至臭氧，將該含矽與氮層轉化為一含矽與氧層。
  6. 如申請專利範圍第1項所述之方法，其中該無碳含矽與氮前驅物包含一矽烷基胺。
  7. 如申請專利範圍第6項所述之方法，其中該矽烷基胺包含N(SiH3)3。
  8. 如申請專利範圍第1項所述之方法，其中該自由基-氮前驅物係在與該無碳含矽與氮前驅物混合之前，使用一電漿自一含氮與氫氣體所產生。
  9. 如申請專利範圍第8項所述之方法，其中該含氮與氫氣體包含選自由氨、N2及H2所組成之群組中之一氣體。
  10. 如申請專利範圍第1項所述之方法，其中該共形含矽與氮層包含一無碳Si-N-H層。
  11. 如申請專利範圍第1項所述之方法，其中藉由使該含 矽與氮層暴露至一含氧氣氛，將該共形含矽與氮層轉化為一氧化矽層。
  12. 如申請專利範圍第11項所述之方法，其中該含氧氣氛包含選自由氧氣、臭氧以及水蒸汽所組成之群組中之一或多種氣體。
  13. 一種形成具降低的體積收縮率之一含矽層的方法，該方法包含下列步驟：移轉含有一間隙之一基材；於該基材上沉積一共形含矽與氮層，其中該共形含矽與氮層具有一共形性；以及於該共形含矽與氮層上沉積一可流動的含矽與氮層，其中該含矽層包含該共形含矽與氮層以及該可流動的含矽與氮層二者。
  14. 如申請專利範圍第13項所述之方法，進一步包含下列步驟：於一含氧氣氛中加熱該含矽層，以增加氧含量，其中該含矽層保留沉積於該間隙中之該無碳含矽與氮層之約85%以上之體積。
  15. 如申請專利範圍第13項所述之方法，其中該共形含矽與氮層之該共形性大於或約為80%。
  16. 如申請專利範圍第13項所述之方法，其中該共形含矽與氮層係藉由一含矽與氮前驅物與一自由基-氮前驅物之反應沉積於該基材上，其中該自由基-氮前驅物對該矽與氮前驅物提供主導性激發。
  17. 如申請專利範圍第16項所述之方法，其中該含矽與氮前驅物包含N(SiH3)3，且該自由基-氮前驅物係形成自電漿-活化之NH3。
  18. 如申請專利範圍第14項所述之方法，其中該含氧氣氛包含O2、O3或H2O中之至少一者。
  19. 如申請專利範圍第13項所述之方法，其中該間隙中之該含矽層為實質上無空隙(void-free)。
  20. 如申請專利範圍第16項所述之方法，其中該含矽與氮層包含一Si-N-H層。
  21. 如申請專利範圍第13項所述之方法，其中該共形含矽與氮層包含一Si-N-H層。
  22. 如申請專利範圍第13項所述之方法，其中該基材間隙具有約50nm或更小之寬度。
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US20110217851A1 (en) 2011-09-08
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