CN113454763A - 使用牺牲性掩模的选择性蚀刻 - Google Patents

使用牺牲性掩模的选择性蚀刻 Download PDF

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CN113454763A
CN113454763A CN202080014795.5A CN202080014795A CN113454763A CN 113454763 A CN113454763 A CN 113454763A CN 202080014795 A CN202080014795 A CN 202080014795A CN 113454763 A CN113454763 A CN 113454763A
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silicon
regions
metal
reactant
sacrificial mask
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丹尼尔·彼得
李达
游正义
亚历山大·卡班斯凯
卡蒂·纳尔迪
萨曼莎·西亚姆华·坦
李英熙
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Lam Research Corp
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Lam Research Corp
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Abstract

提供相对于较低含氧硅区域而选择性地蚀刻氧化硅区域的方法。牺牲性掩模相对于氧化硅区域而选择性地沉积在较低含氧硅区域上。原子层蚀刻相对于较低含氧硅区域上的牺牲性掩模选择性地蚀刻氧化硅区域。

Description

使用牺牲性掩模的选择性蚀刻
相关申请的交叉引用
本申请要求于张2019年2月14日申请的美国专利申请No.62/805,474的优先权，其通过引用合并于此以用于所有目的。
技术领域
本公开内容涉及在半导体晶片上形成半导体装置的方法。更具体地，本公开内容涉及氧化硅(SiO2)的选择性蚀刻。
背景技术
在形成半导体装置方面，氧化硅可相对于其他含硅区域被选择性地蚀刻，反之亦然。
发明内容
为了实现上述且根据本发明的目的，提供了用于相对于较低含氧硅区域而选择性地蚀刻氧化硅区域的方法。牺牲性掩模相对于该氧化硅区域而选择性地沉积于该较低含氧硅区域上。原子层蚀刻相对于该较低含氧硅区域上的该牺牲性掩模而选择性地蚀刻该氧化硅区域。
在另一方面，提供了用于相对于如具有OH表面终端的SiOCN、SiN或金属氧化物的较高含氧区域而选择性地蚀刻硅或SiN区域的方法。牺牲性掩模相对于该硅或SiN区域而选择性地沉积于该较高含氧区域上。相对于该较高含氧区域上的该牺牲性掩模，选择性地蚀刻该硅或SiN区域。
下文将在本公开内容的详细描述中并结合以下附图来更详细地描述本公开内容的这些以及其他特征。
附图说明
本公开内容以示例而非限制性方式于附图的图中进行说明，其中相似附图标记代表相似组件，其中：
图1为一实施方案的高阶流程图。
图2A-C为根据一实施方案处理的结构的示意性截面图。
图3为另一实施方案的高阶流程图。
图4A-D为根据图3实施方案处理的结构的示意性截面图。
具体实施方式
本公开内容现在将参考如附图中所示的一些示例性实施方案作详细描述。在以下描述中，阐述了许多具体细节，以提供对本公开内容的透彻理解。然而，对于本领域技术人员而言，显而易见，可以在没有这些具体细节中的一些或全部的情况下实施本公开内容。在其他情况下，众所周知的工艺步骤和/或结构不再详细描述，以免不必要地使本公开内容难以理解。
图1是实施方案的高阶流程图。提供具有氧化硅区域的结构(步骤104)。图2A是具有氧化硅区域204的结构200的部分的示意性截面图。在该示例中，结构200还具有硅氧碳氮化物(SiOCN)区域208以及硅(Si)区域212。硅区域212可以为晶体或多晶、或非晶硅。SiOCN材料包括氮氧化硅(SiON)、碳氧化硅(SiOC)、碳氮化硅(SiCN)、有机氧化硅(SiOCHx)(后段工艺(BEOL)低k)、氮化硅(SiN)、以及碳化硅(SiC)。SiOCN区域208以及Si区域212被指定为较低含氧硅区域，因为它们具有低于氧化硅区域204的氧浓度。
牺牲性掩模相对于氧化硅区域204而选择性地沉积于较低含氧硅区域208、212上(步骤108)。在该实施方案中，含碳牺牲性掩模选择性地沉积于较低含氧硅区域208、212上。在一示例中，氧化硅区域204、SiOCN区域208和Si区域212的表面用0.5％氟化氢(HF)水溶液清洁。氟化氢可以为气态或水溶液。可使用具有氩(Ar)、氦(He)或氢(H2)的预等离子体处理，以进一步清洁并活化SiOCN区域208和Si区域212。通过提供50-500瓦射频(RF)功率，使5-50sccm甲烷(CH4)、0-200sccm H2以及50-500sccm氩(Ar)的沉积气体形成为等离子体。压强维持在5-150毫托。提供0-200伏特的偏压功率。图2B是已沉积牺牲性掩模216后的结构200的部分的示意性截面图。沉积工艺在氧化硅区域204上选择性地沉积比在SiOCN区域208和Si区域212上薄的牺牲性掩模。如果需要较厚的牺牲性掩模216，则预等离子体处理和掩模沉积可循环地重复多次。在其他实施方案中，惰性气体Ar可以其他惰性气体(例如氦、氖、氙或氪)代替。
使用原子层蚀刻选择性地蚀刻氧化硅区域204(步骤112)。在该实施方案中，原子层蚀刻提供六氟-2-丁炔(C4F6)的反应物气体。C4F6在该氧化硅区域204上方选择性地形成沉积层。清扫掉反应物气体，并提供Ar的活化气体。Ar活化沉积层，从而导致沉积的氟蚀刻氧化硅区域204。原子层蚀刻工艺可重复多个循环。图2C是完成原子层蚀刻后的结构200的截面图。在此示例中，氧化硅区域204被部分地蚀刻，且牺牲性掩模216已被蚀刻掉。选择性掩模沉积(步骤108)和选择性地蚀刻氧化硅区域204(步骤112)可重复(步骤116)直到充分地蚀刻氧化硅区域204。
在无选择性掩模沉积(步骤108)的情况下，选择性地蚀刻氧化硅区域204(步骤112)将显著地蚀刻SiOCN区域208和Si区域212。通过提供选择性掩模沉积(步骤108)，氧化硅区域204的蚀刻(步骤112)的选择性被显著地改善。
在另一实施方案中，牺牲性掩模包括使用原子层沉积(ALD)工艺形成的含金属层。图3是另一实施方案的高阶流程图。抑制剂层的沉积可在含金属层沉积之前沉积。该含金属层可以为金属氧化物、金属碳化物、金属氮化物或其混合物。抑制剂及金属氧化物的这种沉积循环可被循环。提供具有氧化硅区域的结构(步骤304)。图4A是具有氧化硅区域404的结构400的部分的示意性截面图。在该示例中，结构400还具有硅氧碳氮化物(SiOCN)区域408和硅(Si)区域412。硅区域412可以为晶体或多晶、或非晶硅。SiOCN材料包括SiON、SiOC、SiCN、SiOCHx(BEOL低k)、SiN和SiC。SiOCN区域408和Si区域412被指定为较低含氧硅区域，因为它们具有低于氧化硅区域的氧浓度。在该实施方案中，氧化硅区域404、SiOCN区域408和Si区域412的表面用0.5％的HF水溶液清洁。氧化硅区域404、SiOCN区域408和Si区域412的表面用去离子水(DIW)冲洗。
抑制剂层相对于SiOCN区域408和Si区域412而选择性地沉积于氧化硅区域404上(步骤306)。在该示例中，抑制剂层(414)为自组装单层，其选择性地结合至表面硅醇基团上。抑制剂层的沉积可以在液体旋涂工艺或气相工艺中进行。抑制剂分子可以包括有机硅烷化合物，如：HMDS(六甲基二硅氮烷)、ODTS(十八烷基三氯硅烷)、FOTS(1H,1H,2H,2H-全氟辛基三氯硅烷)、烯烃(如：1-十八烯、1-辛烯、1-戊烯)。对于液体工艺，前体分子被溶解于有机非极性溶剂中。气相工艺利用分子的蒸气压。对于液相工艺，使用以下顺序：使用异丙醇(IPA)取代DIW，因其与前体的非极性溶剂不互溶。随后，带有前体的非极性溶剂取代IPA。分配前体直到实现氧化硅上的表面覆盖率。最后，前体被IPA取代，并使用标准IPA干燥进行干燥。IPA干燥可包括如前所述的干燥方法。描述于美国专利申请2017/0345681中的干燥方法可用于多种实施方案中。对于气相工艺，将衬底放置于加热基座上。温度可以为20-250℃。压强可为10毫托至30托。来自抑制剂的蒸气流过晶片，接着从室中清扫掉。例如水或氨气之类的催化剂可以流过晶片。该循环可重复直到获得所期望的膜。图4B是抑制剂层414已选择性地沉积在氧化硅区域404上方后的结构400的部分的示意性截面图。
牺牲性掩模相对于氧化硅区域404而选择性地沉积在较低含氧硅区域408、412上(步骤308)。在该实施方案中，利用原子层沉积工艺，以提供牺牲性掩模，其中抑制剂层414增加沉积的选择性。在该实施方案中，牺牲性掩模的选择性沉积(步骤308)包括金属前体沉积步骤(前体步骤)(步骤310)和反应物步骤(步骤312)的多个循环，以提供选择性原子层沉积工艺。在一些实施方案中，在金属前体沉积步骤(步骤310)与反应物步骤(步骤312)之间进行清扫。金属前体沉积步骤(步骤310)提供含金属前体沉积。
在含金属前体层已选择性地沉积在SiOCN区域208和Si区域412上之后，反应物形成含金属层，例如在反应物步骤(步骤312)中提供的金属氧化物、金属碳化物或金属氮化物。在多种实施方案中，反应物可以为含氧反应物，含氮反应物或含碳反应物。
抑制剂的选择性沉积减少了含金属层在氧化硅区域404上的沉积，使得更多金属氧化物、金属碳化物或金属氮化物沉积在SiOCN区域408和Si区域412上。抑制剂膜的表面密度决定防止沉积的时间有多长。相比于氧化硅区域404上的整个抑制剂层，抑制剂在SiOCN区域408和Si区域412上的部分沉积使得金属氧化物、金属碳化物或金属氮化物中的至少一者能较早生长。
在一实施方案中，金属氧化物、金属碳化物和金属氮化物中的至少一者为通过热ALD工艺沉积的二氧化钛。利用含Ti前体(步骤310)与作为反应物的氧化剂(步骤312)之间的循环工艺，以沉积二氧化钛。Ti前体可以为异丙醇钛(IV)、四(二乙基酰胺基)钛(IV)、四(二甲基酰胺基)钛(IV)、四(乙基甲基酰胺基)钛(IV)、四氯化钛。氧化剂可以为水(H2O)蒸气、氧(O2)、过氧化物(H2O2)或臭氧(O3)。图4C是牺牲性掩模416已被选择性地沉积在氧化硅区域404上方后的结构400的部分的示意性截面图。在该实施方案中，牺牲性掩模416的沉积去除了抑制剂层414。由于抑制剂层414，沉积工艺选择性地在氧化硅区域404上沉积比在SiOCN区域408和Si区域412上薄的牺牲性掩模416。如果需较厚的牺牲性掩模416，抑制剂层的选择性沉积(步骤306)和牺牲性掩模的选择性沉积(步骤308)可循环地重复(步骤316)。
在其他实施方案中，含金属前体可包含钨(W)、钼(Mo)、钛(Ti)、锆(Zr)、铅(Hf)、锑(Sb)、钒(V)、钽(Ta)、铝(Al)、钇(Y)或镍(Ni)。在多种实施方案中，至少一种金属氧化物、金属碳化物或金属氮化物牺牲性掩模可以为二氧化钛(TiO2)、二氧化锆(ZrO2)、二氧化铅(HfO2)、锑(SbO)、氧化钒(V2O3)、氧化钇(YO)、氧化钽(TaO)或氧化铝(Al2O3)中的至少一者。
在多种实施方案中，使用了HfO2的牺牲性掩模。在这样的实施方案中，含Hf前体(步骤310)以及作为反应物的氧化剂(步骤312)用于沉积二氧化铪。含Hf前体可以为叔丁醇铪(IV)、四(二乙基酰胺基)铪(IV)、四(二甲基酰胺基)铪(IV)、四(乙基甲基酰胺基)铪(IV)、四氯化铪中的至少一者。HfO2和TiO2比SiO2的蚀刻选择比分别为30:1和5:1。氧化剂可以是水(H2O)蒸气、氧(O2)、过氧化物(H2O2)或臭氧(O3)中的一或更多者。在多种实施方案中，在牺牲层为金属氮化物的情况下，反应物可以为氨(NH3)、联胺(N2H4)中的至少一者。在其他实施方案中，在牺牲层为金属碳化物的情况下，反应物可以是甲烷(CH4)、乙烯(C2H4)和乙炔(C2H4)中的至少一者。
在其他实施方案中，使用ZrO2的牺牲性掩模。在这样的实施方案中，将含Zr前体(步骤310)及作为反应物的氧化剂(步骤312)用于沉积ZrO2。含Zr前体可以是叔丁醇锆(IV)、四(二乙基酰胺基)锆(IV)、四(二甲基酰胺基)锆(IV)、四(乙基甲基酰胺基)锆(IV)、四氯化锆中的至少一者。氧化剂可以是水(H2O)蒸气、氧(O2)、过氧化物(H2O2)或臭氧(O3)中的一或更多者。
可利用专用的缺陷控制步骤，以清除氧化硅表面上的任何残留金属氧化物。这可以是基于三氯化硼(BCl3)的等离子体工艺，其在5-150毫托的压强下使用每分钟5-100标准立方厘米(sccm)的缺陷控制气体，BCl3、50-300sccm氯(Cl2)以及0-500sccm氦(He)。提供100-500瓦的RF功率。提供0-50伏特的偏压。
使用原子层蚀刻以相对于硅区域412和SiOCN区域408而选择性地蚀刻氧化硅区域404。由于原子层蚀刻相对于氧化硅区域选择性地蚀刻较低含氧硅区域，因此可以使用先前实施方案中所描述的原子层蚀刻。在该实施方案中，原子层蚀刻提供碳氟化合物(例如六氟-2-丁炔(C4F6)或八氟环丁烷(C4F8))的反应物气体。碳氟化合物在该氧化硅区域404上方选择性地形成沉积层。清扫掉反应物气体，并提供Ar的活化气体。Ar活化沉积层，从而导致沉积的氟蚀刻氧化硅区域404。原子层蚀刻工艺可重复多个循环。图4D是完成原子层蚀刻后的结构400的部分的示意性截面图。
随着半导体装置的不断收缩，特征之间的距离缩小，而光刻的边缘放置误差成为重要的问题。为了减轻这种情况，产业界已采用自对准方案，例如用于触点孔的蚀刻。在该方案中，触点孔的布置可以与栅极间隔物重叠。因此，触点氧化硅蚀刻需要对间隔物材料具有选择性。同时，材料预算在缩减。预算缩减增加了目标蚀刻相对于余者(未受影响的材料)的选择性要求。常规碳氟化合物(CxFy)/基于Ar的氧化硅ALE已呈现较高的材料选择性，但仍面临数十
Figure BDA0003213464320000061
的初始损耗。
另一方法是选择性沉积材料作为额外牺牲性掩模，以选择性地保护不应被蚀刻的材料。这在沉积工艺期间需要高选择性，使得待蚀刻的区域上没有材料成核。任何核都将构成后续蚀刻工艺的缺陷基础，因此是不可接受的。
多种实施方案提供了增进选择性成核延迟的表面处理。该表面处理可以包括抑制剂层。多种实施方案提供牺牲性掩模的材料选择性沉积。多种实施方案在牺牲性掩模的开口区域上提供缺陷控制。多种实施方案提供牺牲性掩模的开口区域的底层材料的选择性蚀刻。
选择适当的预处理能够基于反应位点的密度以区分材料而达到牺牲性掩模的选择性沉积。预处理可通过活化(如等离子体处理)或通过抑制剂去活化来增强反应位点。示例为自组装单层(气和液)相、聚合物或碳基抑制剂、原位预处理：氨(NH3)、联胺(N2H4)、氢(H2)、水(H2O)、过氧化物(H2O2)、氧(O2)、臭氧(O3)和气相反应。
牺牲性掩模的沉积取决于反应位点的密度，其通过选择除了沉积外还不或限制表面的化学改性的条件。
在其他实施方案中，可使用硅化物的牺牲性掩模。在一些实施方案中，氧化硅区域含有氧化硅并且可以具有额外掺杂物，但具有高于较低含氧硅区域的氧浓度。
在其他实施方案中，提供了用于相对较高含氧区域(如具有氢氧(OH)表面终端的SiOCN、SiN或金属氧化物)而选择性蚀刻硅或氮化硅(SiN)区域的方法。牺牲性掩模相对于硅或SiN区域而选择性地沉积在较高含氧区域上。硅或SiN区域相对于较高含氧区域上的牺牲性掩模而被选择性地蚀刻。在一些实施方案中，牺牲性掩模是基于金属氧化物的。金属氧化物选择性地沉积在较高含氧区域上。该金属氧化物可以是通过热ALD工艺沉积的氧化钛、氧化锆或氧化铪，其利用含Ti、Zr或Hf前体与氧化剂(用于沉积氧化钛，氧化锆或氧化铅)之间的循环工艺，其中氧化剂可为H2O蒸气、O2或O3。在一些实施方案中，牺牲性掩模在较高含氧区域上的沉积是通过表面处理来提高的。
尽管本公开内容已就几个示例性实施方案进行描述，但还存在落入本公开内容范围内的变更、修改、置换以及多种替代等同方案。还应注意，存在许多实施本公开内容的方法及设备的替代方式。因此，倾向于将以下权利要求解释为包括落入本发明真实精神及范围内的所有的这样的变更、修改、置换以及多种替代等同方案。

Claims (21)

1.一种用于相对于较低含氧硅区域而选择性地蚀刻氧化硅区域的方法，其包括：
a)相对于所述氧化硅区域，选择性地在所述较低含氧硅区域上沉积牺牲性掩模；以及
b)相对于所述较低含氧硅区域上的所述牺牲性掩模，以原子层蚀刻选择性地蚀刻所述氧化硅区域。
2.根据权利要求1所述的方法，其中重复步骤a和b多次。
3.根据权利要求1所述的方法，其中所述较低含氧硅区域是硅、碳化硅、氮化硅、氮氧化硅、碳氮化硅和硅氧碳氮化物中的至少一者。
4.根据权利要求1所述的方法，其还包括选择性地在所述氧化硅区域上沉积抑制剂层，其中所述牺牲性掩模是基于金属氧化物、金属碳化物或金属氮化物中的至少一者，其中金属氧化物、金属碳化物或金属氮化物中的所述至少一者选择性地沉积于所述较低含氧硅区域，同时通过所述抑制剂层来延迟在所述氧化硅区域上的沉积。
5.根据权利要求4所述的方法，其中金属氧化物、金属碳化物或金属氮化物中的所述至少一者是利用包含有含金属前体步骤和反应物步骤的循环工艺通过原子层沉积工艺来沉积的。
6.根据权利要求5所述的方法，其中所述含金属前体步骤包括沉积含有钨、钼、钛、锆、铪、锑、钒、钽、铝、钇或镍中的至少一者的含金属前体。
7.根据权利要求5所述的方法，其中所述反应物步骤包括提供为含氧反应物、含氮反应物或含碳反应物中的至少一者的反应物。
8.根据权利要求5所述的方法，其还包括在所述含金属前体步骤与所述反应物步骤之间提供清扫。
9.根据权利要求5所述的方法，其中所述牺牲性掩模包括二氧化铪。
10.根据权利要求9所述的方法，其中所述含金属前体步骤包括沉积叔丁醇铪(IV)、四(二乙基酰胺基)铪(IV)、四(二甲基酰胺基)铪(IV)、四(乙基甲基酰胺基)铪(IV)、四氯化铪中的至少一者的含金属前体，且其中所述反应物步骤包括提供为水蒸气、氧、过氧化物或臭氧中的至少一者的反应物。
11.根据权利要求5所述的方法，其中所述牺牲性掩模包括二氧化锆。
12.根据权利要求11所述的方法，其中所述含金属前体步骤包括沉积叔丁醇锆(IV)、四(二乙基酰胺基)锆(IV)、四(二甲基酰胺基)锆(IV)、四(乙基甲基酰胺基)锆(IV)、四氯化锆中的至少一者的含金属前体，且其中所述反应物步骤包括提供为水蒸气、氧、过氧化物或臭氧中的至少一者的反应物。
13.根据权利要求5所述的方法，其中所述牺牲性掩模包括二氧化钛。
14.根据权利要求13所述的方法，其中所述含金属前体步骤包括沉积异丙醇钛(IV)、四(二乙基酰胺基)钛(IV)、四(二甲基酰胺基)钛(IV)、四(乙基甲基酰胺基)钛(IV)、四氯化钛的至少一者的含金属前体，且其中所述反应物步骤包括提供为水蒸气、氧、过氧化物或臭氧中的至少一者的反应物。
15.根据权利要求4所述的方法，其中所述选择性地沉积所述抑制剂层包括沉积自组装单层，所述自组装单层相对于所述较低含氧硅区域而选择性地沉积于所述氧化硅区域上。
16.根据权利要求4所述的方法，其还包括在沉积所述抑制剂层前，用氟化氢的气态或水溶液清洁所述氧化硅区域和所述较低含氧硅区域。
17.根据权利要求4所述的方法，其还包括在沉积所述牺牲性掩模后提供清洁。
18.根据权利要求4所述的方法，其还包括在沉积所述抑制剂层之后且在沉积所述牺牲性掩模之前提供预处理，其中所述预处理通过活化来增强所述较低含氧硅区域的反应位点或使所述抑制剂层去活化。
19.一种用于相对于如具有OH表面终端的SiOCN、SiN或金属氧化物的较高含氧区域而选择性地蚀刻硅或SiN区域的方法，其包括：
a)相对于所述硅或SiN区域，选择性地在所述较高含氧区域上沉积牺牲性掩模；以及
b)相对于所述较高含氧区域上的所述牺牲性掩模，选择性地蚀刻所述硅或SiN区域。
20.根据权利要求19所述的方法，其中所述牺牲性掩模包括金属氧化物，其中所述金属氧化物选择性地沉积于所述较高含氧区域上。
21.根据权利要求20所述的方法，其中所述金属氧化物包括利用含Ti前体与用于沉积所述氧化钛的氧化剂之间的循环工艺通过热ALD工艺沉积的氧化钛，其中所述氧化剂为水蒸气、氧、过氧化物或臭氧中的至少一者。
CN202080014795.5A 2019-02-14 2020-02-11 使用牺牲性掩模的选择性蚀刻 Pending CN113454763A (zh)

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