TWI636501B - 使用水蒸氣處理將材料層從基材移除的方法 - Google Patents
使用水蒸氣處理將材料層從基材移除的方法 Download PDFInfo
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- TWI636501B TWI636501B TW101141568A TW101141568A TWI636501B TW I636501 B TWI636501 B TW I636501B TW 101141568 A TW101141568 A TW 101141568A TW 101141568 A TW101141568 A TW 101141568A TW I636501 B TWI636501 B TW I636501B
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- substrate
- water vapor
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- 238000004380 ashing Methods 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
- H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
-
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
- C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
- H01L21/31116—Etching inorganic layers by chemical means by dry-etching
- H01L21/31122—Etching inorganic layers by chemical means by dry-etching of layers not containing Si, e.g. PZT, Al2O3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31144—Etching the insulating layers by chemical or physical means using masks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
- H01L21/76814—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Plasma & Fusion (AREA)
- Drying Of Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
本發明的實施例大體上關於透過使用水蒸氣電漿處理而移除及/或清洗上面配置有不同材料層的基材表面的方法。一個實施例中,清洗基材表面的方法包括以下步驟:將基材定位至處理腔室中,該基材具有介電層,該介電層配置在該基材上並且在該基材上形成多個開口;將配置在該基材上的該介電層暴露至水蒸氣,該水蒸氣是被供應進入該腔室中而在該水蒸氣中形成電漿;將該腔室中的製程壓力維持在約1托至約120托之間;以及清洗形成在該基材上的該接觸結構。
Description
本發明的實施例大體上關於從半導體基材移除材料層的方法,更特定而言,是關於使用水蒸氣電漿處理從半導體基材移除硼碳層的方法。
一般透過形成一系列介電層與導電層以建立由介電材料所分隔的導電層三維網絡,而製造積體電路與半導體元件的互連結構。該互連結構可透過使用例如鑲嵌結構而製造,在該鑲嵌結構中,諸如低k介電層的介電層形成在一或多個導電插塞或次層頂上。為了對導電次層形成電連接,介電質經圖案化與蝕刻而界定穿過該介電層的介層窗開口。當在介電層中形成開口時,經常使用光阻層或硬光罩層協助將特徵及/或開口轉移至介電層中。在介電層內形成開口使一部分的導電線暴露。因此,可靠地形成這些互連特徵是確保個別基材上及每一晶粒中形成的元件之品質、性能與可靠度的重要因素。
積體電路與半導體元件的市場持續需要更快的電路系統與更大的電路密度,例如,在單一晶片上納入數百萬個
部件。所以,積體電路部件的尺寸縮小,且用於製造此類部件的材料的選擇變得愈來愈重要。例如,在積體電路上的部件之間提供導電路徑的低電阻率的金屬互連件(諸如銅與鋁)現在需要在金屬互連件之間有低介電常數層(例如具有≦4的介電常數),以提供絕緣的金屬間層,以減少相鄰金屬線之間的電容耦合,從而在相同線寬下實現可靠的性能。
習知上用作介電層的低k材料在除其他材料之外特別包括無摻雜的矽玻璃(USG)、氟摻雜的矽玻璃(FSG)、碳摻雜的二氧化矽(SiOC)以及聚四氟乙烯,這些材料沉積成基材上的膜。將導電層形成於蝕刻所界定的介電層上之前,期望清洗介電膜的頂表面以移除殘餘的污染物,諸如來自蝕刻及/或灰化製程的原生氧化物及/或有機材料。移除污染物減少待沉積的導電層之介面處的接觸電阻及/或防止所述介面處的黏著損失。
預清洗程序可用於在沉積導電層之前從介電膜表面移除污染物。然而,習知的用於預清洗介電層的清洗製程(諸如濕式清洗製程或其他製程)可能會在後續的導電層沉積之前損害或再度濺射介電膜表面,或者在處理腔室中生成不想要的帶電荷粒子。就此而言,藉由使用習知技術清洗的低k介電膜可能造成膜的劣化及缺陷。此外,碳摻雜的低k材料傾向經歷碳空乏或「k損失」,其中低k材料的介電常數在暴露至清洗程序所用的電漿後增加。於是,清洗程序後,非期望的串擾以及RC延遲變得更加嚴重。
再者,對於用於使特徵及/或開口轉移進入介電層的
光阻層及/或硬光罩層而言,期望有適合的移除製程清洗或移除該光阻層及/或硬光罩層,而不損害下面的介電層,或不負面地造成介電層中的膜劣化與缺陷。例如,已證實硼碳膜(諸如硼碳層)相較於非晶形碳在蝕刻製程期間用作為硬光罩時具有更卓越的圖案化性能。但是,硼碳膜不容易剝除。用於移除硼碳膜的過度劇烈的電漿移除製程可能導致腐蝕半導體基材上亦常見的介電材料、暴露的金屬表面或嵌入的金屬,從而非期望地導致劣化元件結構且導致元件性能失效。
此外,當電路密度增加以用於下一代元件時,互連件(諸如介層窗、溝槽、開口、觸點、閘極結構與其他特徵)以及互連件間介電材料的寬度減少至45 nm與32 nm之尺寸,然而介電層的厚度維持實質上恆定,於是增加了特徵的深寬比,這些特徵諸如深接觸結構、複雜的高k、金屬閘極膜堆疊及/或三維記憶體堆疊與類似物。許多傳統清洗製程具有從次微米結構移除殘餘物的難處,該次微米結構中,深寬比超過4:1或具有畸零的幾何形狀。
因此,需要一種移除或清洗基材表面的改良方法。
本發明的實施例大體上關於透過使用水蒸氣電漿處理而移除殘餘物及/或清洗上面配置基材表面的方法。一個實施例中,用於清洗基材表面的方法包括以下步驟:將基材定位至處理腔室中,該基材具有介電層,該介電層配置在該基材上並且在該基材上形成多個開口;將配置在該基材上的該介電層暴露至水蒸氣,該水蒸氣是被供應進入該腔室中而在
該水蒸氣中形成電漿;將該腔室中的製程壓力維持在約1托至約120托之間;以及清洗形成在該基材上的該接觸結構。
另一實施例中,用於清洗基材表面的方法包括以下步驟:於腔室中定位具有介電層的基材,該介電層配置在該基材上;將該介電層暴露至水蒸氣,該水蒸氣被供應進入該腔室而在該水蒸氣中形成電漿;控制該介電層的表面具有低於約40度的溼潤角;以及從該基材清洗該介電層。
於再一實施例中,用於清洗處理腔室的方法包括以下步驟:提供具有含硼碳的殘餘物的處理腔室,該等殘餘物形成於該處理腔室的內部;供應水蒸氣進入該處理腔室以在該水蒸氣中形成電漿,該水蒸氣是由耦接至該處理腔室的水蒸氣生成器所生成;以及從該處理腔室移除該等含硼碳的殘餘物。
100‧‧‧處理腔室
101‧‧‧側邊/壁
102‧‧‧真空泵
106‧‧‧電源
110‧‧‧控制器
112‧‧‧CPU
114‧‧‧支援電路
116‧‧‧記憶體
118‧‧‧訊號匯流排
120‧‧‧噴頭
122‧‧‧底壁
124‧‧‧頂部
124‧‧‧頂部
126‧‧‧內部空間
128‧‧‧口孔
130‧‧‧氣體分配盤
132‧‧‧基材處理系統
138‧‧‧匹配網路
140‧‧‧RF源
150‧‧‧支撐底座
152‧‧‧水蒸氣生成系統
170‧‧‧加熱器元件
172‧‧‧溫度感測器
190‧‧‧基材
191‧‧‧表面
200‧‧‧方法
202-206‧‧‧步驟
304‧‧‧開口
306‧‧‧硬光罩層
308‧‧‧材料層
310‧‧‧表面
312‧‧‧含碳殘餘物
316‧‧‧側壁
402‧‧‧第一液體前驅物
404‧‧‧第二液體前驅物
502‧‧‧基材
504‧‧‧場效電晶體
506‧‧‧介電層
508‧‧‧特徵
570‧‧‧接觸結構
藉由參考實施例(一些實施例說明於附圖中),可獲得於上文中簡要總結的本發明之更特定的說明,而能詳細瞭解上述的本發明之特徵。然而應注意附圖僅繪示此發明的典型實施例,因而不應將該等附圖視為限制本發明之範疇,因為本發明可容許其他等效實施例。
第1圖描繪可用於操作此發明的設備的示意圖;第2圖描繪根據本發明的一個實施例的清洗製程的流程圖;第3A圖至第2B圖描繪根據第2圖之方法對併入硼摻雜之碳層的基材結構進行清潔的一系列示意剖面圖;
第4A圖至第4B圖是根據本發明一個實施例的與不同液體前驅物接觸的基材表面的剖面圖,該基材表面具有不同的溼潤角;以及第5圖是具有高深寬比特徵的複合結構的剖面圖,該等特徵形成在用於場效電晶體的接觸結構上,該複合結構可有在該複合結構上執行的水蒸氣電漿處理製程。
為了助於瞭解,如可能則使用相同的元件符號標注共通於該等圖式的相同元件。應考量在一個實施例中所揭露的元件與特徵可有利地併入其他實施例中,而無需進一步記載。
本發明的實施例大體上關於透過使用水蒸氣電漿處理而移除及/或清洗上面配置有材料層的基材表面的方法。一個實施例中,該材料層是含碳層。另一實施例中,該材料層是含硼碳層。又一實施例中,該材料層可以是如所需的任何適合的材料。該等方法可用於使用水蒸氣電漿處理而移除上面配置有材料層的基材表面。該材料層移除製程也可包括於移除材料層之前的視情況任選的含碳材料層移除製程。本發明的實施例可在Producer® SE或Producer® GT腔室中操作,該等腔室可購自美國加州Santa Clara的應用材料公司。應考量,其他腔室(包括其他製造商所生產的腔室)可受惠於在此描述的實施例。
第1圖是基材處理系統132的示意圖,該基材處理系統132可用於執行根據本發明實施例的清洗/移除製程。可
用於操作本發明的基材處理系統132的一個範例之細節描述於共同讓渡的美國專利6,364,954中,該專利於2002年4月2日頒發給Salvador等人。可用於操作本發明的系統之其他範例包括CENTURA®及Producer® SE或Producer® GT沉積系統,這些系統皆可購自美國加州Santa Clara的應用材料公司。應考量,其他處理系統(包括其他製造商所生產的處理系統)可適於操作本發明。
處理系統132包括處理腔室100,該處理腔室100耦接氣體分配盤130與控制器110。該處理腔室100大體上包括界定內部空間126的頂部124、側邊101以及底壁122。水蒸氣生成(water vapor generating(WVG))系統152耦接處理系統132,該水蒸氣生成系統152與處理腔室132內所界定的內部空間126流體連通。WVG系統152藉由催化O2與H2反應而生成超高純度的水蒸氣。或者,如需要,WVG系統152也可透過直接將水(H2O)氣化成的水蒸氣而生成水蒸氣。一個實施例中,H2與O2各自以範圍在約1 sccm至約30000 sccm之間的速率流進WVG系統152。在其中需要富含O2的水蒸氣的實施例中,將O2流設得高於H2流,反之亦然。一旦確定期望的H2/O2濃度,各流速可成比例地改變,而以相同或不同的H2/O2濃度調整向外流動的水蒸氣。
一個實施例中,WVG系統152具有襯有催化劑的反應器或催化劑匣筒,在該襯有催化劑的反應器或催化劑匣筒中,透過化學反應生成水蒸氣。該催化劑可包括金屬或合金,諸如鈀、鉑、鎳、前述金屬之組合以及前述金屬之合金。超
高純度的水在清洗製程中是理想的,以消除形成至下面介電層(該介電層配置在基材190上)的非期望的污染或純質。一個實施例中,為了防止未反應的H2向下游流動,使O2流過WVG系統152五秒。接著,使H2進入反應器約5秒。H2與O2之間的催化反應是瞬間的,所以水蒸氣在H2與O2抵達反應器後立刻生成。調節H2與O2流使濃度得以準確地被控制在1%至100%濃度的任一處,即水蒸氣可含有水、H2、O2或前述物質之組合。一個實施例中,水蒸氣含有水與O2。另一實施例中,水蒸氣含有水與H2。同樣,透過運用相同的氣流控制方法,也可調節水蒸氣的量,而每一次產生準確且可重覆的流動。當水蒸氣通常由將H2與O2流入反應器而生成時,可用另一氧源化合物補充或替代O2,所述氧源化合物諸如NO、N2O、NO2、N2O5、H2O2或O3。一個實施例中,如所需般,H2與N2O用於形成水蒸氣。可購得適合的WVG系統152,諸如位在美國加州Santa Clara的美國富士金公司的WVG以及位在美國加州Menlo Park的Ultra Clean Technology的CSGS(催化劑蒸氣生成器系統)。應注意,WVG系統152也可以是任何類型的能夠生成任何濃度的水蒸氣的設備。
支撐底座150設置在腔室100的內部空間126中。該底座150可由鋁、陶瓷及其他適合材料製造。一個實施例中,底座150由陶瓷材料(諸如氮化鋁)所製造,該氮化鋁是適合用在高溫環境(諸如電漿製程環境)且不引發對底座150的熱損害的材料。底座150可在腔室100內透過使用舉升機構(圖中未示)於垂直方向上移動。
底座150可包括嵌入的加熱器元件170,該加熱器元件170適合用於控制底座150上所支撐的基材190的溫度。一個實施例中,可透過從電源106施加電流至加熱器元件170而電阻式加熱底座150。一個實施例中,加熱器元件170可由包覆在鎳鐵鉻合金(例如INCOLOY®)鞘管中的鎳鉻線所製成。由電源106所供應的電流是由控制器110調節,以控制加熱器元件170生成的熱,因此在任何適合溫度範圍的膜沉積期間將基材190與底座150維持在實質上恆定的溫度。另一實施例中,底座可維持在如所需的室溫。又一實施例中,底座150也可包括如所需之冷卻器(圖中未示),以將底座150冷卻於如所需的低於室溫的範圍。所供應的電流可經調整而選擇性將底座150之溫度控制在約攝氏100度至約攝氏780度之間,諸如介於約攝氏150度至約攝氏550度之間。
諸如熱偶之溫度感測器172可嵌在支撐底座150中,以用習知方式監視底座150之溫度。所測量的溫度由控制器110使用,以控制供應至加熱元件170之功率,而將基材維持在期望溫度。
真空泵102耦接通口,該通口形成於腔室100的壁101中。真空泵102用於維持處理腔室100中的期望氣壓。真空泵102也從腔室100排空後處理氣體以及製程副產物。
具有複數個口孔128的噴頭120耦接處理腔室100頂部124而位於基材支撐底座150上方。噴頭120的口孔128用於將製程氣體導入腔室100中。該等口孔128可具有不同尺寸、數目、分佈、形狀、設計與直徑,以助於各種製程氣
體的流動以用於不同的製程需求。噴頭120連接氣體分配盤130,而使各種氣體得以在製程期間供應至內部空間126。電漿是由離開噴頭120的製程氣體混合物形成,以強化製程氣體的熱分解,導致材料沉積在基材190的表面191上。
噴頭120與基材支撐底座150可形成一對在內部空間126中相隔的電極。一或多個RF源140透過匹配網路138提供偏壓電位至噴頭120,以助於在噴頭120與底座150之間生成電漿。或者,RF電源140與匹配網路138可耦接噴頭120、基材底座150,或耦接噴頭120與基材底座150二者,或耦接天線(圖中未示),所述天線配置在腔室100外部。一個實施例中,RF源140可提供頻率為約30 kHz至約13.6 MHz的約10瓦至約3000瓦之間。
控制器110包括中央處理單元(CPU)112、記憶體116與支援電路114,以用於控制製程順序及調節來自氣體分配盤130與WVG系統152的氣流。CPU 112可以是任何形式的通用電腦處理器,此通用電腦處理器可用於工業設施中。軟體常式可儲存在記憶體116中,諸如隨機存取記憶體、唯讀記憶體、軟碟或硬碟機或其他形式的數位儲存裝置。支援電路114以習知方式耦接CPU 112且可包括高速緩衝儲存器、時脈電路、輸入/輸出系統、電源與類似物。控制單元110與處理系統132之各部件之間的雙向通訊是透過多個訊號電纜所操縱,這些訊號電纜統稱訊號匯流排118,一些訊號匯流排118繪示於第1圖中。
第2圖繪示根據本發明一個實施例的方法200的製
程流程圖,該方法200用於移除配置在基材上的材料層。第3A圖至第3B圖是繪示根據方法200移除基材上形成之材料層(用作為硬光罩層)的順序的示意剖面圖。
方法200開始於步驟202,該步驟為在處理腔室中提供基材,諸如第1圖所描述的處理系統132中所配置的基材190。應考量可利用其他處理腔室,例如其他蝕刻腔室或沉積腔室,包括可由其他製造商所購得之腔室。如第3A圖所示,基材190可具有配置在該基材190上的材料層308。基材190可具有實質上平面的表面、不平坦的表面或具有結構形成在上面的實質上平面的表面。一個實施例中,材料層308可以是膜堆疊的一部分,所述膜堆疊是用於形成閘極結構、接觸結構、後端互連結構或淺溝槽隔離(STI)結構、高k/金屬閘極堆疊、三維(3D)記憶體堆疊或具有高深寬比、畸零或困難幾何形狀或小尺寸的任何適合的結構。在其中不存在材料層308的實施例中,該等結構可直接形成在基材190中
一個實施例中,材料層308可以是含碳的氧化矽(SiOC)與其他低k聚合物,所述含碳的氧化矽諸如為可購自應用材料公司的BLACK DIAMOND®介電材料,其他低k聚合物諸如為聚醯胺。其他適合的材料也包括如所需的氧化矽層、矽層、氮氧化矽層或氮化矽層或碳化矽層。又一實施例中,材料層308可包括一或多層用於製造半導體元件的其他介電材料。
透過利用視情況任選的硬光罩層306,材料層308可經圖案化或蝕刻而形成材料層308內的開口304(或所謂的
介層窗、溝槽、通道或其他適合的結構)。應注意在此所指的「開口」之用語包括具有開放區域的所有類型的結構,且該等開放區域形成在該等結構中,所述開放區域包括在島狀物之間的通道、所有類型結構之間的介層窗或類似物。在某些實施例中,基於不同的製程需求,可如所需般消除硬光罩層306。硬光罩層306保護材料層308的某些區域免受蝕刻,同時暴露材料層308的其他區域以受蝕刻而形成開口304,直到下面的基材190之表面310暴露為止。一些實施例中,光阻層(圖中未示)可配置在硬光罩層306上,以助於在材料層308中形成開口304。
一個實施例中,硬光罩層306是非晶形碳層、含碳層或硼碳層,上述層是由適合的習知沉積技術所形成,所述習知沉積技術諸如CVD、PVD、ALD、塗佈、離子佈植與類似技術。硼碳層含有硼與碳二者,且膜中硼對碳的原子比為約1:1至約3:1的範圍內。
在步驟204,將基材定位在支座上之後,將位在硬光罩層306上的含碳殘餘物312移除。如前文所論述,含碳殘餘物312於先前執行的蝕刻製程(其中硬光罩層做為蝕刻硬光罩)期間生成在硬光罩層306的上表面上。應注意,含碳殘餘物312也可形成或存在於硬光罩層306的側壁316上或開口304的底部310上。蝕刻期間,基材與基材上的硼碳硬光罩層306暴露至蝕刻劑,以將期望的圖案蝕刻至基材中,該蝕刻劑例如為含氟氣體,諸如C4F8。由於蝕刻製程期間生成碳與氟的聚合,蝕刻製程產生含碳殘餘物,該含碳殘餘物
也可包括矽及/或氧。含碳殘餘物312大體上是在硬光罩層移除製程之前移除,以容許更有效率地移除硼碳硬光罩層306。
一個實施例中,透過將含碳殘餘物312暴露至由含氟氣體、含氧氣體或前述氣體組合所形成的電漿,而從硬光罩層306表面移除含碳殘餘物312。例如,含碳殘餘物可透過使用電漿移除,該電漿由比為約100:1的氧氣與NF3所形成。電漿中期望的氟量隨含碳殘餘物312中存在的矽量增加。
含碳殘餘物移除製程期間,提供使用氧氣與NF3氣體的遠端生成的電漿至處理腔室,該電漿的流速為每300 mm的基材約1 sccm至約15000 sccm,例如約100 sccm至約5000 sccm。氧對NF3的比為約100:1至約1000:1。處理腔室內的壓力維持在範圍從約1毫托至約760托的範圍內的壓力(諸如約4毫托至約10托),同時基材維持在低於750℃的溫度。氧與NF3連同含碳殘餘物312進行反應,而形成揮發性化合物,該揮發性化合物從處理腔室排放。這樣的條件下,含碳殘餘物312以每分鐘約2000埃至每分鐘約10000埃之速率移除。應考量含碳殘餘物312可受過度蝕刻,以確保從基材表面移除。
在步驟206,從基材190移除含碳殘餘物312後,隨後透過在基材190上執行水蒸氣電漿處理製程,而移除硬光罩層306,如第3B圖中所示。電漿處理中生成的水蒸氣可有效地形成氧化劑(O‧)、還原劑(H‧)以及氫氧基團(OH)。相信氧之氧化劑可與來自硬光罩層的碳元素反應,而形成可從腔室排放的揮發性化合物(例如CO2),同時氫之還原劑
可與硬光罩層306中的硼(如果任何硼存在)反應,而形成隨後從腔室排放的揮發性化合物(例如B2H6)。由水蒸氣提供的氫氧基團(OH)與H2O成份可有效地隨著移除製程修飾表面性質,以便有效地助於來自氫氧基團的還原劑與氧化劑持續浸潤與吸收至硬光罩層中,並且強化移除製程的持續。例如,相信氫氧基團可有效地沿硬光罩層移除製程改變表面溼潤性能,因而有效地提供表面不同的溼潤能力。相信氫氧基團在與硬光罩層306反應時可減少溼潤角,因而導致膜表面變得更加親水,而助於從基材表面移除碳元素。親水表面可助於來自水蒸氣電漿的氫或氧離子滲透進入硬光罩層,因而有效地分解硬光罩層並且從基材表面移除硬光罩層。在第4A圖與第4B圖所繪的實施例中,第一液體前驅物402具有對基材表面190的高溼潤角α1(例如疏水表面),如第4A圖所示,此高溼潤角會造成第一液體前驅物402堆積與聚集在基材表面190上,而非吸收或滲透進入基材表面190而與配置在基材表面190上的膜層中的元素反應。相較之下,第二液體前驅物404具有對基材表面190的低溼潤角α2(例如親水表面),如第4B圖所示,此低溼潤角將會助於第二液體前驅物404反應、吸收且滲透進入基材190上配置的膜層中,因而有效地改善第二液體前驅物404與基材表面之間的元素反應,以從基材表面移除此膜層。因此,透過使用水蒸氣電漿製程移除硬光罩層306,水蒸氣電漿可有效地使硬光罩層306有親水表面,因而有效地改善硬光罩層306的清洗及/或移除效能。
一個實施例中,前驅物對基材表面的溼潤角(例如,當暴露至水蒸氣電漿時所控制的表面溼潤角)可被控制在約低於40度,諸如介於約0度至約40度之間,以維持良好的膜移除效能。
再者,也相信將製程壓力控制在中間的壓力工作狀態(諸如約1托至約120托之間)也可助於造成圖案是形成在更親水的表面中的基材表面,從而有助於硬光罩層306的清洗及/或移除效能。相信處理期間中間的壓力工作狀態可助於用期望方式控制製程條件。一個實施例中,水蒸氣電漿處理製程期間控制的製程壓力為1托至約120托,諸如約20托至約100托之間。在其中硬光罩層306上執行水蒸氣電漿移除的示範性實施例中,製程壓力可被控制在約40托至約70托之間。其中在含矽層(諸如氧化矽層,例如接觸結構中的氧化矽層)上執行水蒸氣電漿處理製程的另一示範性實施例中,製程壓力可被控制在約1托至約7托之間。
操作中,也可控制數個製程參數。一個範例中,可將水蒸氣以連續模式或脈衝模式生成而供應至處理腔室中。一個實施例中,可用連續模式以約5 sccm至約30000 sccm之間的流速生成水蒸氣送進處理腔室。可供應約5瓦至約5000瓦之間的RF功率至處理腔室,以分解水蒸氣而用於反應。腔室製程可被控制在低於約760托,諸如約1托至約150托之間。基材溫度可被控制在約攝氏0度至約攝氏760度之間。可將基材暴露至水蒸氣電漿達約1秒至約36000秒之間。
在其中以脈衝模式將水蒸氣供應至處理腔室中的實
施例中,可用每60秒持續約30秒之方式將水蒸氣以脈衝式送進製程中。工作週期可被控制在如所需的約1%至約100%。
此外,當在步驟206執行水蒸氣電漿處理製程的同時,也可將其他不同的氣體源供應至處理腔室中,以強化反應效能。一個範例中,水蒸氣含有水且進一步含有O2氣體。另一範例中,水蒸氣含有水且進一步含有H2氣體。尚有另一實施例,水蒸氣如所需般含有水且進一步含有O2與H2氣體。已發現添加氫增加硬光罩層306的移除速率,尤其是在含有更高硼濃度(相較於碳)的硼碳硬光罩層306中更是如此。已觀察到添加其他載氣(諸如氦氣、氬氣或氮氣)降低硼碳硬光罩層306的移除速率,同時改善蝕刻均勻度。另一實施例中,應考量水蒸氣可用於移除實質上不含硼的碳膜(諸如非晶形碳)。或者,應考量水蒸氣可用於剝除實質上不含碳的硼膜(諸如非晶形硼)。
其中含氧氣體也可與水蒸氣一併供應進入處理腔室而執行電漿處理製程的實施例中,應考量可在步驟206使用及與水蒸氣一併供應任何提供氧之化合物,以執行硼碳硬光罩層移除製程,該化合物諸如O2、N2O、CO2、NO或NO2。其中含氫氣體也可與水蒸氣一併供應進入處理腔室而執行電漿處理製程的實施例中,應考量在步驟206可使用任何提供氫的化合物,諸如H2、NH3或H2O2。應注意,不僅在此水蒸氣電漿處理製程中硬光罩層可為待移除之目標材料,在蝕刻期間可能形成而餘留在半導體元件中之結構(諸如接觸結構、金屬閘極結構或金屬接觸結構)上的所有其他蝕刻殘餘
物也可如所需用此水蒸氣電漿處理製程移除或清洗。
一個實施例中,應考量可由WVG系統152輸入或生成包括H2O2之非化學當量的氧與氫之組合,例如HxOy,其中x與y可以是大於1的整數或非整數。這樣的實施例中,可由WVG系統152生成一些過氧化氫。另一實施例中,應考量除了水蒸氣外,可提供如所需的氧氣、氦氣、氮氣、氬氣、一氧化二氮氣體及/或氫氣至製程氣體。
一個實施例中,當生成電容耦合水蒸氣電漿時,位於腔室內的基材190與噴頭120之間的間距可在約20密耳至約600密耳之範圍內。當在較高壓力(例如大於約7托)下處理較大體積的基材時(例如,當處理大面積基材時),基材之間減少的間距是有利的。當在大於約7托的壓力下處理基材時,減少的間距助於電漿的持續性。一個範例中,當在約30托處理基材時,介於基材與面板之間的間距可為約300密耳。在40托,基材與面板間的間距可在約240密耳至約270密耳範圍內。在約50托的壓力下,基材與面板之間的間距可低於200密耳。
應注意,可在設置以如步驟206所述般移除硬光罩層306的相同腔室中實行於步驟204執行的含碳殘餘物移除製程。另一實施例中,應考量步驟204可發生在分別的腔室(諸如蝕刻腔室)中,且可發生在將基材定位於執行步驟206的硬光罩層306移除製程所用的處理腔室之前。應注意,步驟204的製程可與步驟206的製程同時發生。換言之,當水蒸氣電漿處理是在處理腔室中執行時,不僅硬光罩層306被
移除(描述於步驟206),而且含碳殘餘物或副產物(描述於步驟204)也可被移除。因此,透過執行一個水蒸氣電漿製程,含碳殘餘物或副產物(描述於步驟204)以及硬光罩層306(描述於步驟206)可同時被移除。
一個實施例中,應考量步驟204的電漿與步驟206的水蒸氣電漿製程可為電容耦合或感應耦合以替代遠端生成,或除遠端生成之外還可為電容耦合或感應耦合。例如,應考量可由水蒸氣與惰氣生成電容耦合電漿。可用約5 sccm至約3000 sccm(諸如約4000 sccm)的流速將水蒸氣導至腔室。可用約5 sccm至約3000 sccm(諸如約1000 sccm)的流速將諸如氬氣或氦氣之惰氣提供至腔室。另一實施例中,應考量水蒸氣可如所需般經由原位蒸氣生成方式所生成。
在其中硼碳層及/或離子佈植製程後受摻雜的具有摻質的光阻層的實施例中,水蒸氣電漿製程200也可用於如所需般清洗或移除此類層。
一個實施例中,可利用水蒸氣電漿製程200清洗形成在介電層506中的接觸結構570,該接觸結構570具有特徵508,該等特徵508具有大於約20:1(諸如約100:1)的深寬比,該介電層506中的接觸結構570誠如基材502上的場效電晶體504上所配置的接觸結構,如第5圖所示。介電層506可以是含氧化矽層。其他用於介電層506的適合材料包括無摻雜的矽玻璃(USG)、硼矽酸鹽玻璃(BSG)、磷矽酸鹽玻璃(PSG)、硼磷矽酸鹽玻璃(BPSG)與前述玻璃之組合,而無摻雜的矽玻璃又諸如為氧化矽或TEOS。在此描述的示範
性實施例中,介電層506是無摻雜的矽玻璃(USG)層。一個實施例中,介電層506具有約3000 Å至約15000 Å之間之厚度,諸如約4000 Å至約12000 Å之間、例如約10000 Å。再者,也可利用水蒸氣電漿清洗介電層506之表面以及配置在接觸結構501上的場效電晶體504的表面,此述的表面經常是金屬矽化物層,該金屬矽化物層選自由矽化鎳、矽化鈷、矽化鎢、矽化鉭、矽化鈦與其他適合的金屬矽化物材料所構成的群組。一些實施例中,金屬矽化物層可具有配置在該金屬矽化物層上的氮化矽層,該氮化矽層做為蝕刻停止層。當形成在介電層506中的特徵508可能具有相當高的深寬比或具有難以清洗的幾何形狀時,透過使用水蒸氣電漿處理製程,可供應水蒸氣更深入特徵底部(例如介層窗/溝槽底部),以清洗基材表面,之後再進行後續的金屬沉積製程,諸如接觸預清洗製程或後蝕刻殘餘物清洗。相信電漿處理製程中供應的水蒸氣可具有極微的金屬氧化效應,因此易於維持低接觸電阻表面而擁有該表面上形成的後續金屬層,以完成接觸結構。
表面預清洗製程之後,在後續製程中,可稍後使用金屬材料填充或沉積特徵508,以於基材上形成互連結構。金屬材料的範例包括鎢(W)、氮化鎢(WN)、銅(Cu)、鈦(Ti)、鉭(Ta)、鋁(Al)、氮化鈦(TiN)、氮化鉭(TaN)或類似物。或者,製程200可用於清洗或移除如所需的其他結構以及一些非金屬污染物,所述其他結構諸如金屬閘極結構或任何其他適合的結構,所述非金屬污染物諸如氟、氯與
硫污染物。尚有另一實施例,製程200可用於進行表面鈍化、腔室壁鈍化或表面處理,以如所需將表面溼潤角在期望範圍內改變。在其中腔室壁包括Al2O3的實施例中,可執行製程200以保護腔室內部隔絕刺激性的化學物質,諸如氟元素。製程200也可進一步用於清洗基材晶邊剝除(bevel strip),包括針對硼膜、碳膜或含硼與碳的膜殘餘物的基材晶邊移除製程。
應注意,在某些例子中(在這些例子中,包括諸如沉積腔室與蝕刻腔室的所有類型處理腔室的處理腔室壁可能會在硼碳層、碳層或硼層沉積製程循環之後具有硼碳層堆積物、碳層堆積物或硼層堆積物或其他累積物),水蒸氣電漿製程200也可用於如所需般清洗或移除此類層。此外,在蝕刻製程或沉積製程的循環之後,水蒸氣電漿製程200也可助於腔室壁鈍化,或提供腔室壁保護。
此述的方法之優點包括:移除材料層或清洗基材表面而不至於損害位於基材上的材料層或下面的金屬層。移除及/或清洗方法透過變化電漿組成而使蝕刻速率(以及蝕刻均勻度)得以控制。應注意,如此述的水蒸氣電漿處理製程也可用於清洗所需的具任何材料的基材表面。
雖然前述內容係針對本發明之實施例,然而可不背離本發明基本範疇設計其他與進一步的本發明之實施例,且本發明之範疇由隨後的申請專利範圍所決定。
Claims (17)
- 一種清洗一基材之一表面的方法,包括以下步驟:將具有一接觸結構的一基材定位至一處理腔室中,該基材具有一介電層,該介電層配置在該基材上並且在該基材上形成多個開口,其中該等開口具有大於20:1的深寬比;將配置在該基材上的該介電層暴露至水蒸氣,該水蒸氣是被供應進入該腔室中而在該水蒸氣中形成一電漿;將該腔室中的一製程壓力維持在約1托至約120托之間;以及清洗形成在該基材上的該接觸結構。
- 如請求項1所述之方法,其中用於形成該接觸結構的該介電層是選自由無摻雜的矽玻璃(USG)、硼矽酸鹽玻璃(BSG)、磷矽酸鹽玻璃(PSG)、硼磷矽酸鹽玻璃(BPSG)與前述玻璃之組合所構成的群組。
- 如請求項1所述之方法,其中暴露該介電層之步驟進一步包含以下步驟:將該介電層的一表面控制成具有低於約40度的一溼潤角。
- 如請求項3所述之方法,其中暴露該介電層之步驟進一步包含以下步驟: 將該介電層的一表面改變成一親水表面。
- 如請求項1所述之方法,其中將該介電層暴露至該水蒸氣之步驟進一步包含以下步驟:連同該水蒸氣將一含氧氣體或一含氫氣體供應進入該腔室。
- 如請求項1所述之方法,其中暴露該介電層之步驟進一步包含以下步驟:施加介於約5瓦至約5000瓦之間的一RF功率,以在該水蒸氣中形成該電漿。
- 如請求項1所述之方法,其中暴露該介電層之步驟進一步包含以下步驟:使該介電層在暴露至該水蒸氣前先暴露至一含碳氟氣體。
- 如請求項1所述之方法,其中該水蒸氣是在氬氣、氦氣或氮氣的存在下生成。
- 如請求項1所述之方法,其中將該介電層暴露至該水蒸氣之步驟進一步包含以下步驟:以一脈衝模式供應該水蒸氣至該腔室。
- 如請求項1所述之方法,進一步包含以下步驟:將該基材溫度控制在約攝氏0度至約攝氏760度之間。
- 如請求項1所述之方法,其中形成在配置在該基材上的該介電層中的該等開口暴露一下面的接觸金屬或接觸金屬矽化物層或接觸氮化矽層。
- 如請求項11所述之方法,其中供應至該腔室的該水蒸氣清洗該接觸金屬或接觸金屬矽化物層或接觸氮化矽層,也清洗配置在該基材上的該介電層。
- 一種用於清洗一基材表面的方法,包括以下步驟:於一腔室中定位具有一介電層的一基材,該介電層配置在該基材上,該介電層在該基材上形成多個開口,其中該等開口具有大於20:1的深寬比;將該介電層暴露至水蒸氣,該水蒸氣被供應進入該腔室而在該水蒸氣中形成一電漿;控制該介電層的一表面具有低於約40度的一溼潤角;以及從該基材清洗該介電層。
- 如請求項13所述之方法,其中將該介電層暴露至水蒸氣之步驟進一步包含以下步驟: 將該腔室中的一製程壓力維持在約1托至約120托之間。
- 如請求項13所述之方法,其中將該介電層暴露至水蒸氣之步驟進一步包含以下步驟:施加一RF功率至水蒸氣。
- 如請求項13所述之方法,其中將該介電層暴露至水蒸氣之步驟進一步包含以下步驟:連同該水蒸氣將一含氧氣體及/或一含氫氣體流入該處理腔室中。
- 如請求項16所述之方法,其中該含氧氣體是選自由O2、N2O、CO2、NO與NO2所構成的群組,且該含氫氣體是選自由H2、H2O2與NH3所構成的群組。
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WO2013070570A1 (en) | 2013-05-16 |
JP6158199B2 (ja) | 2017-07-05 |
JP2015504239A (ja) | 2015-02-05 |
US9653327B2 (en) | 2017-05-16 |
KR102033707B1 (ko) | 2019-10-17 |
TW201330085A (zh) | 2013-07-16 |
KR20140089383A (ko) | 2014-07-14 |
US20120285481A1 (en) | 2012-11-15 |
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